Liquid Waste Tank Residuals Sampling- Quality Assurance ... · B10.7 Data Management Checklists and Forms .....80. Liquid Waste Tank Residuals Sampling- SRR-CWDA-2011-00117 Quality

SRR-CWDA-2011-00117 Revision 0

Liquid Waste Tank Residuals Sampling- Quality Assurance Program Plan

February 2012

Prepared by: Savannah River Remediation LLC Closure and Waste Disposal Authority Aiken, SC 29808

Prepared for U.S. Department of Energy Under Contract No. DE-AC09-09SR22505

Liquid Waste Tank Residuals Sampling- SRR-CWDA-2011-00117 Quality Assurance Program Plan Revision 0 February 2012

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REVISION SUMMARY

REV. # DESCRIPTION DATE OF ISSUE

0 Initial Submitttal 2/29/2012


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SECTION A PROJECT MANAGEMENT

A1 Title and Approvals

Title: Liquid Waste Tank Residuals Sampling-Quality Assurance Program Plan

Site Location: F- and H-Area Tank Farms Savannah River Site Aiken, South Carolina

Lead Organization: Savannah River Remediation LLC Closure and Waste Disposal Authority

Preparer: J. P. Pavletich Closure and Waste Disposal Authority Savannah River Remediation LLC 803-557-9355

Preparation Date: February 2012

r7912

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A2 Table of Contents

REVISION SUMMARY .............................................................................................................. 2

SECTION A PROJECT MANAGEMENT ............................................................................. 3

A1 Title and Approvals ......................................................................................................... 3

APPROVALS ................................................................................................................................ 4

A2 Table of Contents ............................................................................................................ 5

LIST OF FIGURES ...................................................................................................................... 8

LIST OF TABLES ........................................................................................................................ 8

ACRONYMS/ABBREVIATIONS .............................................................................................. 9

A3 Distribution List ............................................................................................................ 12

A4 Project Organization .................................................................................................... 13 A4.1 Key Individuals ........................................................................................................13 A4.2 Roles and Responsibilities .......................................................................................13 A4.3 Organization Responsible for Quality Assurance Program Plan Maintenance,

Updating and Distribution .......................................................................................14 A4.4 Organization Chart ...................................................................................................14

A5 Problem Definition/Background ................................................................................... 15 A5.1 Reason for the Study ................................................................................................15 A5.2 Explanation of Decisions and Actions to be Taken with the Information

Obtained ..................................................................................................................16 A5.3 Identification of Regulatory Information, Applicable Criteria, or Action Limits

that will Impact the Study .......................................................................................16

A6 Project/Task Description and Schedule ........................................................................ 17 A6.1 Summary of Work to be Completed ........................................................................17 A6.2 Project Schedule .......................................................................................................19 A6.3 Location of Study Area ............................................................................................19 A6.4 Resource Management .............................................................................................21

A7 Data Quality Objectives and Data Quality Indicators ................................................. 21 A7.1 Identification of Performance/Measurement Criteria ..............................................21 A7.2 Data Quality Indicators ............................................................................................37 A7.3 Data Quality Objectives Process ..............................................................................38

A8 Training and Certification ............................................................................................ 41

A9 Documentation and Records ......................................................................................... 41 A9.1 QAPP Distribution ...................................................................................................42 A9.2 Data Report Package ................................................................................................42 A9.3 Other Applicable Records and Documents ..............................................................46 A9.4 Project Information Retention ..................................................................................46 A9.5 Data Records Backup ...............................................................................................46


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SECTION B MEASUREMENT/DATA ACQUISITION .................................................... 47

B1 Sampling Process/Experimental Design ....................................................................... 47

B2 Sampling Methods ......................................................................................................... 50

B3 Sampling Handling and Custody .................................................................................. 52

B4 Analytical Methods ....................................................................................................... 54 B4.1 Identify Standard Operating Procedures ..................................................................55 B4.2 Identify Equipment and Instrumentation .................................................................55 B4.3 Specify Measurement Performance Criteria ............................................................55 B4.4 Identify Procedures to Follow When Failures Occur ..............................................55 B4.7 Provide Method Validation and SOPs for Nonstandard Methods ...........................62

B5 Quality Control Requirements ...................................................................................... 62 B5.1 Quality Control Samples ..........................................................................................63 B5.2 Quality Control Limit Exceedance and Corrective Action ......................................66 B5.3 Quality Control Statistical Analysis .........................................................................66

B6 Instrument/Equipment Testing, Inspection, and Maintenance ..................................... 67 B6.1 Identification of Field and Laboratory Equipment ..................................................67 B6.2 Identification of Equipment Testing Criteria ...........................................................68 B6.3 Availability and Location of Equipment Spare Parts ..............................................69 B6.4 Procedures for Inspecting Equipment Prior to Use ..................................................69 B6.5 Responsibility for Testing, Inspection and Maintenance .........................................69 B6.6 Equipment Deficiency Corrective Action ................................................................69

B7 Instrument Calibration and Frequency ........................................................................ 69 B7.1 Instruments, Equipment and Tools to be Calibrated and Frequency .......................69 B7.2 Calibration Performance and Documentation ..........................................................73 B7.3 Deficiency Resolution and Documentation .............................................................73

B8 Inspection/Acceptance Requirements for Supplies and Consumables.......................... 73 B8.1 Identification of Critical Supplies and Consumables ...............................................74 B8.2 Responsibility for Critical Supply and Consumables Acquisition ..........................74

B9 Data Acquisition Requirements (Non-Direct Measurement) ........................................ 74 B9.1 Identification of Data Sources .................................................................................75 B9.2 Intended Use of Information and Selection Rationale .............................................75 B9.3 Data Acceptance Criteria .........................................................................................75 B9.4 Identification of Key Resources/Support Facilities Needed ....................................76

B10 Data Management ......................................................................................................... 76 B10.1 Describe Data Management Scheme .......................................................................76 B10.2 Standard Record-Keeping Practices and Document Control System ......................78 B10.3 Data Handling Equipment/Procedures .....................................................................78 B10.4 Responsibility for Data Management ......................................................................79 B10.5 Process for Data Archival and Retrieval ..................................................................80 B10.6 Hardware and Software Configuration Acceptability ..............................................80 B10.7 Data Management Checklists and Forms ................................................................80


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SECTION C ASSESSMENT AND OVERSIGHT ................................................................ 81

C1 Assessment and Response Actions ................................................................................ 81

C2 Reports to Management ................................................................................................ 84

SECTION D DATA VERIFICATION AND USABILITY .................................................. 85

D1 Data Review and Verification ....................................................................................... 85

D2 Data Validation and Verification Methods ................................................................... 90 D2.1 Process for Data Validation .....................................................................................90 D2.2 Responsibilities for Verifying and Validating Project Data ....................................90 D2.3 Identify Issue Resolution Process ............................................................................91 D2.4 Identify Checklists, Forms and Calculations ...........................................................91

D3 Reconciliation with User Requirements ........................................................................ 91 D3.1 Procedures to Evaluate the Usability of the Data ....................................................91 D3.2 Limitations on Data Use ..........................................................................................93

REFERENCES ............................................................................................................................ 94

Attachment 1: Liquid Waste Tank Residuals Sampling: Chain-of-Custody Form ....... A.1-1

Attachment 2: Analytical Operating Procedures and Summary of Analytical Methods Used for Residuals Sample Analyses .................................................................... A.2-1

Attachment 3: Data Verification Checklists ....................................................................... A.3-1

Attachment 4: Records Checklists ...................................................................................... A.4-1

Attachment 5: Data Validation Procedures and Checklists ............................................. A.5-1


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LIST OF FIGURES

Figure A4-1: Functional Organization Structure for Liquid Waste Tank Residuals Sampling Program ......................................................................................................................................... 15

Figure A6-1: Liquid Waste Tank Residuals Sampling and Analysis Program Process .............. 18

Figure A6-2: General Layout of F-Area Tank Farm ................................................................... 20

Figure A6-3: General Layout of H-Area Tank Farm ................................................................... 21

Figure B1-1: Waste Tank Sampling and Analysis Planning Process .......................................... 48

Figure B2-1: Sample Collection Cup Being Placed in the Retrieval Basket ............................... 51

Figure B10-1: Data Management Scheme for Waste Tank Residual Sampling and Analysis ..... 77

Figure D1-1: Roles and Responsibilities for Waste Tank Characterization Implementing Procedure/Activity/Document ...................................................................................................... 86

LIST OF TABLES

Table A6-1: Tasks Scheduled for Each Waste Tank ................................................................... 19

Table A7-1: Typical Performance Measurement Criteria for Residuals Sample Analyses ......... 22

Table A9-1: Sample Analysis Report Content ............................................................................. 43

Table A9-2: Project Records, Record Copy Location, Retention Period, and Backup Schedule44

Table B1-1: Waste Tank Sampling Design ................................................................................. 49

Table B3-1: Sampling Methods and Sample Handling Requirements ........................................ 54

Table B4-1: Typical Laboratory Analytical Operating Procedures ............................................. 56

Table B5-1: Field Quality Control Samples ................................................................................ 65

Table B5-2: Laboratory Analytical Quality Control Indicators ................................................... 66

Table B6-1: Laboratory Instrument Maintenance ........................................................................ 68

Table B7-1: Laboratory Instrument Calibration Criteria ............................................................. 70

Table B8-1: List of Key Consumables and Acceptance Criteria ................................................. 74

Table C1-1: Liquid Waste Tank Residuals Sampling Program Planned Project Audits and Assessments .................................................................................................................................. 82

Table D1-1: Data and Associated Records Verified by SRR Engineering .................................. 87

Table D1-2: Data and Associated Records Verified by C&WDA .............................................. 88

Table D1-3: Data and Associated Records Verified by SRNL .................................................... 88

Table D3-1: Items and Activities Evaluated During the Data Quality Assessment .................... 92


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ACRONYMS/ABBREVIATIONS

AA Atomic Absorption AD Analytical Development ALARA As Low As Reasonably Achievable AOP Analytical Operating Procedure ARG Analyzed Reference Glass ASME American Society of Mechanical Engineers C&WDA Closure and Waste Disposal Authority CA Corrective Action CCB Continuing Calibration Blank CERCLA Comprehensive Environmental Response, Compensation, and Liability Act CM Closure Module CPC Characterization Project Coordinator COC Chain-of-Custody CQF Cognizant Quality Function CTF Cognizant Technical Function CTS Concentrate Transfer System DB Diversion Box DOE U.S. Department of Energy DOE-SR U.S. Department of Energy-Savannah River DQA Data Quality Assessment DQI Data Quality Indicator DQO Data Quality Objective E&CPT Environmental and Chemical Process Technology EDWS Electronic Document Workflow System EPA U.S. Environmental Protection Agency ESH&QA Environment, Safety, Health and Quality Assurance FE Fundamental Error FFA Federal Facility Agreement FTF F-Area Tank Farm FWHM Full Width at Half Maximum GCP General Closure Plan

HPGe Gamma High-Purity Germanium Detector Gamma Spectrometer and Associated Electronics

HRR Highly Radioactive Radionuclide HSWA Hazardous and Solid Waste Amendments HTF H-Area Tank Farm ICB Initial Calibration Blank ICP-ES Inductively Coupled Plasma - Atomic Emission Spectroscopy


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ICP-MS Inductively Coupled Plasma - Mass Spectroscopy ICV Independent Calibration Verification ISO International Organization for Standardization LCS Laboratory Control Standard LIMS Laboratory Information Management System LOAX Low Energy Photon/X-ray LOD Level of Detection LSC Liquid Scintillation Counting LWO Liquid Waste Organization LWTRS Liquid Waste Residuals Sampling LWTRSAPP Liquid Waste Tank Residuals Sampling and Analysis Program Plan LWTRS-QAPP Liquid Waste Tank Residuals Sampling-Quality Assurance Program Plan M&TE Measuring and Test Equipment MAC Material Acquisition Center MAPEP Mixed Analyte Performance Evaluation Program MARLAP Multi-Agency Radiological Laboratory Analytical Protocols MCP Measurement Control Program MDA Minimum Detectable Activity MDC Minimum Detectable Concentration MFPPTP Mixed Fission Product Proficiency Test Program MPC Measurement Performance Criteria MRP Management Requirements and Procedure MS&E Measurement Systems and Equipment NaI Gamma Sodium Iodide Detector Gamma Spectrometer and Associated Electronics PA Performance Assessment PHA Pulse-Height Analysis PIC Person-In-Charge N/A Not Applicable NA Not Applied to the Method for This Program NAA Neutron Activation Analysis NIST National Institute of Standards and Technology PM Project Manager PL Project Lead PMMD Procurement and Materials Management Department PP Pump Pit PSQ Principal Study Question QA Quality Assurance QAPP Quality Assurance Program Plan QC Quality Control


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r Correlation Coefficient R&D Research and Development RadCon Radiological Controls RCRA Resource Conservation and Recovery Act SA Special Analysis SCDHEC South Carolina Department of Health and Environmental Control SCO Shielded Cell Operations SET Sample Extraction Team SME Subject Matter Expert SOP Standard Operating Procedure SQL Structured Query Language SRNL Savannah River National Laboratory SRNS Savannah River Nuclear Solutions, LLC SRR Savannah River Remediation LLC SRS Savannah River Site SRSL Savannah River Standards Laboratory STAR Site Tracking, Analysis, and Reporting TBD To Be Determined TFO Tank Farm Operations TRAIN Training Records and Information Network TSA Technical System Audit TSAP Tank-Specific Sampling and Analysis Plan TTR Technical Task Request TTQAP Task Technical Quality Assurance Plan VOC Volatile Organic Compound WCS Waste Characterization System


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A3 Distribution List

LWTRS-QAPP Recipient

Organization Telephone Number

E-Mail How

Provided

David Hoel DOE-SR 803-952-8783 [email protected] Electronic

Jolene Seitz DOE-SR 803-208-6234 [email protected] Electronic & Hard Copy

Armanda Watson DOE-SR 803-952-8406 [email protected] Electronic

Jeffrey deBessonet SCDHEC 803-898-4157 [email protected] Electronic & Hard Copy

Nydia Burdick SCDHEC 803-896-0862 [email protected] Electronic

Shelly Wilson SCDHEC 803-896-8955 [email protected] Electronic

Robert Pope EPA Region 4 404-562-8506 [email protected] Electronic & Hard Copy

Martha Berry EPA Region 4 404-562-8533 [email protected] Electronic

Victor Franklin SRR Waste Determinations Director

803-557-9308 [email protected] Electronic & Hard Copy

Dan Wood SRR Waste Removal and Tank Closure

803-952-4395 [email protected] Electronic

Andy Tisler SRR Engineering 803-852-3470 [email protected] Electronic

Rudy Jolly SRR Engineering 803-557-6358 [email protected] Electronic & Hard Copy

Kim Hauer SRR C&WDA 803-957-9767 [email protected] Electronic

Steve Thomas SRR C&WDA 803-957-8960 [email protected] Electronic

Mark Mahoney SRR C&WDA 803-557-6588 [email protected] Electronic

Joe Pavletich1 SRR C&WDA 803-557-9355 [email protected] Electronic & Hard Copy

Robert Hinds SRR QA 803-208-7735 [email protected] Electronic

Mary Mcdaniel SRR QA 803-208-1429 [email protected] Electronic

Mary Flora SRNS 803-952-9153 [email protected] Electronic

Mike Griffith SRNS 803-557-6303 [email protected] Electronic

Sharon Marra SRNL 803-725-5891 [email protected] Electronic & Hard Copy

Robin Young SRNL 803-725-1631 [email protected] Electronic

Frank Pennebaker SRNL 803-725-6749 [email protected] Electronic

Scott Reboul SRNL 803-725-3737 [email protected] Electronic

Robin Dillman SRNL QA 803-725-5179 [email protected] Electronic 1 Designated Characterization Project Coordinator responsible for updating and distributing the LWTRS-QAPP

C&WDA Closure and Waste Disposal Authority DOE-SR U.S. Department of Energy-Savannah River EPA U.S. Environmental Protection Agency SCDHEC South Carolina Department of Health and Environmental Control SRR Savannah River Remediation LLC SRNL Savannah River National Laboratory SRNS Savannah River Nuclear Solutions, LLC QA Quality Assurance


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A4 Project Organization

A4.1 Key Individuals

Due to the extended time-period (i.e., greater than 10 years) anticipated to remove all the waste tanks from service, key individuals are not specified. Organizations may be restructured; priorities, budgets and schedules may change; and the workforce will adjust accordingly to best perform the operational closure of the waste tanks. Regardless, Savannah River Site (SRS) will always maintain a Quality Assurance Function independent of the performing organizations. Activities related to waste tank residuals sampling and analysis are currently the responsibility of the organizations listed below. Managers and their appointees will function within the organizations to implement the requirements of the Liquid Waste Tank Residuals Sampling and Analysis Program Plan (LWTRSAPP) and Liquid Waste Tank Residuals Sampling-Quality Assurance Program Plan (LWTRS-QAPP).

Program Management: Waste Removal and Tank Closure Waste Tank Sampling Management: SRR Engineering Waste Tank Sampling: Tank Farm Operations (TFO) Laboratory Analyses: Savannah River National Laboratory (SRNL) Regulatory Reporting: Savannah River Remediation LLC (SRR), Closure and Waste

Disposal Authority (C&WDA) (under Waste Determinations) Data Management: SRR and SRNL for their respective areas of responsibility Records Management: SRS for overall SRR Engineering, TFO, and C&WDA records

custody and maintenance Quality Assurance: SRR Quality Assurance (QA) for overall program reporting; SRNL

QA for laboratory analyses and reporting

A4.2 Roles and Responsibilities

C&WDA has the responsibility for maintaining, updating, and distributing the LWTRSAPP and LWTRS-QAPP as directed for SRR. The specific organizations involved will be responsible for activities and coordination under their area of operation. The specific organizations designate individuals to oversee sampling and analysis activities or interface with the other performing organizations. A brief description of the operational areas is provided below.

The Waste Removal and Tank Closure Project Manager (PM) will be responsible for the overall work scope, schedule, and budget.

The SRR Engineering Project Lead (PL) manages the interfaces with SRNL regarding sample analyses, and with TFO on the waste tank residual volume determinations, sample collection, sample shipment to SRNL, and documenting sampling activities.

TFO is responsible for residuals sampling, scheduling and planning, ensuring adequate safety and health support personnel are available, and that work is performed by trained personnel. The TFO Sample Extraction Team (SET) collects the samples and prepares them for transport to the laboratory.

The C&WDA Manager leads the preparation of various closure documents, such as the sample-location basis documents, compositing instructions, the waste-tank inventory determination


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report, special analyses (SAs) and closure modules (CMs). C&WDA also compiles and maintains the necessary office, field, and laboratory records in the Liquid Waste Organization (LWO) Document Library in addition to transmitting copies to the Electronic Document Workflow System (EDWS) which is the SRS records management and retention system.

The SRR and SRNL Cognizant Quality Function (CQF) oversee implementation of the QA/Quality Control (QC) actions in accordance with SRS 12Q Manual, Assessment Manual. In addition, the CQFs are responsible for approving the LWTSR-QAPP, including subsequent revisions. The SRR and SRNL CQFs are independent from the generation of data.

The SRNL Laboratory Manager will have ultimate responsibility for overall laboratory technical quality, cost control and laboratory personnel management including personnel training and qualification.

The SRNL PL serves as the principal point-of-contact for coordinating laboratory activities, records management, and for ensuring that the sample analyses meet the requirements in the LWTRS-QAPP, Task Technical Quality Assurance Plan (TTQAP), and Technical Task Request (TTR). The SRNL PL has the responsibility for compiling and verifying the laboratory data and records described in Section D that will be submitted to C&WDA for retention.

Additional information on the roles and responsibilities are presented in Section 2 of the LWTRSAPP. An organizational chart for the Liquid Waste Tanks Residuals Sampling Program is provided in Section A4.4.

A4.3 Organization Responsible for Quality Assurance Program Plan Maintenance, Updating and Distribution

C&WDA is responsible for LWTRS-QAPP maintenance, update and distribution. Cognizant Technical Functions (CTFs) within the participating organizations are responsible for implementation of the LWTRS-QAPP and identifying needed changes. The QAPP will be reviewed annually and revised at a minimum of every five years as required by South Carolina Department of Health and Environmental Control (SCDHEC) guidance. When QAPP updating becomes necessary, individuals from the approving organizations will review and agree upon any changes. The C&WDA Characterization Project Coordinator (CPC) will be responsible for preparing and distributing the updated document as described in Section A9.1.

A4.4 Organization Chart

The functional organization structure for the Liquid Waste Tank Residuals Sampling program is presented in Figure A4-1.


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Figure A4-1: Functional Organization Structure for Liquid Waste Tank Residuals Sampling Program

A5 Problem Definition/Background

Since the early 1950’s, the primary mission of the SRS had been to produce nuclear materials for national defense and deep space missions. A legacy of the SRS mission was the generation of liquid radioactive waste from chemical separations processes in both F and H Areas. Since the beginning of SRS operations, an integrated waste management system consisting of several facilities designed for the overall processing of liquid waste has evolved. Two of the major components of this system are the F-Area Tank Farm (FTF) and H-Area Tank Farm (HTF) located in F and H Area respectively, which are near the center of the site. The F- and H-Chemical Separations Facilities are the facilities in which plutonium, uranium, and other radionuclides were extracted from irradiated fuel and target assemblies using chemical separations processes. The liquid radioactive wastes resulting from these chemical separations processes were transferred to the FTF and HTF for waste storage, treatment, and disposition. The tank farms include waste tanks, evaporators, transfer line systems and other ancillary equipment. The FTF and HTF contain 22 and 29 waste tanks, respectively. In the FTF, two waste tanks have been operationally closed (Tanks 17 and 20). Others are in various stages of bulk waste removal, cleaning, residuals characterization, or physical isolation in preparation for removal from service. More information on the FTF/HTF is provided in Section A6.

A5.1 Reason for the Study

This LWTRS-QAPP has been prepared to establish the waste tank sampling and analysis quality program protocols necessary to characterize the residual materials. The characterization data is needed to support waste tank removal from service decisions.

The format and content of this document follows the SCDHEC “Guidance Document for Preparing Quality Assurance Project Plans (QAPPs) for Environmental Monitoring Projects/Studies” [DHEC_QAPP_Guide_09-2008] which is based on the U.S. Environmental Protection Agency (EPA) requirements as found in the EPA QA/G-5, Guidance for Quality Assurance Project Plans, and EPA QA/R-5, EPA Requirements for Quality Assurance Project


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Plans for Environmental Data Operations. These reference documents were used to establish a recognized process for characterizing the residual materials remaining in the waste tanks at the time of removal of service, even though the samples are not environmental compliance samples.

The U.S. Department of Energy (DOE) has a priority to first remove from service the waste tanks that do not meet the standards established in Appendix B of the SRS Federal Facility Agreement (FFA). Removal of these waste tanks from service reduces the risk of a potential release of radionuclides and chemicals to the environment and provides a stable form that is protective of human health and environment.

A5.2 Explanation of Decisions and Actions to be Taken with the Information Obtained

The residual waste tank material sampling and analyses generate the concentration data used to support the residual material inventory determination. The characterization data is used in analyses to demonstrate conformance with both qualitative and quantitative Federal and State performance objectives and allow DOE to make closure decisions related to waste tank removals from service. For FTF, the protocol DOE uses to remove waste tanks from service is given in the FTF Industrial Waste Water General Closure Plan (GCP), which has been approved by SCDHEC. [LWO-RIP-2009-00009] A similar HTF GCP is currently under development and will provide the protocol for HTF waste tank and ancillary structure removals from service. The characterization data for the radiological and hazardous constituents together with the residual volume determination are used to develop the waste tank-specific residuals inventory determination report.

A5.3 Identification of Regulatory Information, Applicable Criteria, or Action Limits that will Impact the Study

In support of environmental remediation activities at SRS, the DOE, EPA, and SCDHEC signed a FFA pursuant to Section 120 of the Comprehensive Environmental Response, Compensation, and Liability Act (CERCLA) and Sections 3008(h) and 6001 of the Resource Conservation and Recovery Act (RCRA), as amended by the Hazardous and Solid Waste Amendments of 1984 (HSWA) (usually jointly referred to as RCRA) and the Atomic Energy Act of 1954 as amended. The agreement became effective in August 1993. As part of this comprehensive agreement, DOE has committed to remove from service those waste tank systems that do not meet the standards set forth in Appendix B of the FFA. Appendix B of the FFA also defines the specific waste tank systems that are subject to the agreement. [WSRC-OS-94-42]

After completion of waste removal activities from individual waste tank systems, the waste tank systems will be operationally closed under the industrial wastewater permit that regulates their operation. SCDHEC will regulate the process of waste-tank system removal from service via applicable South Carolina law and regulation, and the SRS FFA. The use of the terms “operational closure” and “removal from service” are considered synonymous.


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This LWTRS-QAPP applies to the waste tank residuals sampling and analysis presented in the LWTRSAPP from the start of sampling through the Data Quality Assessment (DQA). [SRR-CWDA-2011-00050] This LWTRS-QAPP is not applicable to Tanks 5, 6, 18, or 19 that are currently undergoing removal from service sampling activities. These waste tank and other waste removal activities are governed by the SRS QA Program.

A6 Project/Task Description and Schedule

The objective of this LWTRS-QAPP is to describe the general procedures to sample and analyze waste tank residuals and the QA/QC requirements necessary to perform and document this work.

A6.1 Summary of Work to be Completed

Information determined in the field or directly from field measurements consists of:

The preliminary and final waste tank residual material volume, uncertainty estimate, and residuals distribution maps

Design of the sampling arrays necessary to represent the residual material populations Documentation of the sample collection locations and justification of any departures from

the initial sampling design Calculation of the volume-proportioning amounts for analytical sample compositing

Details on the methodology and approach used for sampling a waste tank are presented in the Liquid Waste Tank Residuals Sampling and Analysis Program Plan. [SRR-CWDA-2011-00050] The process followed to characterize waste tanks for removal from service decisions is summarized on Figure A6-1. The activity, organization responsible, and event initiating the scheduled activity start for each waste tank is summarized in Table A6-1.

Waste tank-specific sampling and analysis plans (TSAPs) are developed on a tank-by-tank basis to account for the actual residual material variations, waste tank usage history and material distributions encountered. The sampling plan design in each TSAP and associated QA/QC are consistent with the LWTRSAPP and LWTRS-QAPP. The analyte lists will be determined on a waste tank-specific basis and specified in the TSAPs that will be provided to SCDHEC.

A copy of the TSAP, reflecting any changes required by field conditions, will be provided to SCDHEC. SCDHEC will be given an update on waste tank sampling and analysis in progress at the liquid waste quarterly FFA meetings, or as needed. These meetings are documented in meetings minutes.

The characterization results are used to determine the analyte concentration in the residual material and are used in conjunction with the final residuals volume and uncertainty estimate to determine the total residual waste tank inventory. The inventory is evaluated in the SA that supports waste tank removal from service decisions.

Waste tank residuals sampling data and the subsequent residual characterizations that the data support are used as input to complex engineering computational models such as the SA and Performance Assessment (PA) to assess the long-term fate and transport of the chemical and radiological constituents in the environment. Waste tank residuals sampling is not performed for comparing residual concentrations against prescribed environmental limits and, as such, the samples to be taken and analyzed under this plan are not environmental compliance samples and are not used for environmental monitoring.


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Figure A6-1: Liquid Waste Tank Residuals Sampling and Analysis Program Process

Liquid Waste Residuals Sampling- SRR-CWDA-2011-00117 Quality Assurance Program Plan Revision 0 February 2012

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Table A6-1: Tasks Scheduled for Each Waste Tank

Waste Tank-Specific Task

Responsible Organization

Start Date Initiator (Waste Tank-Specific1)

Anticipated Date(s) of Completion1

Preliminary Volume Estimate

SRR Engineering Following approval to enter sampling and analysis phase

Two months after receiving approval to enter sampling and analysis phase

Sampling Plan Design C&WDA, SRR Engineering

Following receipt of preliminary volume estimate

One month after receipt of preliminary volume estimate

TSAP and TTR Preparation

SRR Engineering Following approval to start waste tank-specific sampling

Three months after approval to start waste tank-specific sampling

TTQAP Preparation SRNL Following receipt of TTR Two weeks after receipt of TTR

Sample Collection and Shipment

SRR Engineering, TFO

Waste tank-specific start date following approval of TSAP

Two months after start of sampling

Final Volume Determination and Uncertainty Estimate

SRR Engineering Volume and uncertainty finalized during sampling

At completion of sampling; volume and uncertainty used to finalize sample compositing instructions

Sample Preparation (drying, grinding, compositing)

SRNL Following sample receipt at laboratory

Two months after sample receipt

Sample Analysis and Reporting

SRNL Analyses begin after final compositing instructions received from C&WDA

Estimated nine months after composite samples are created

Statistical Analysis SRNL Following receipt of analytical results

Six weeks after receipt of final data

DQA C&WDA Following receipt of final characterization data

Three weeks after receipt of final characterization data and statistical analysis

Final Inventory Determination

C&WDA Following completion of DQA

Four weeks after completion of DQA

SA C&WDA Following determination of final waste tank inventory

Six months after final inventory determination

CM C&WDA Following determination of final waste tank inventory

Per schedule outlined in SCDHEC approved GCP

1 Dates are set for each waste tank to support FFA commitments

A6.2 Project Schedule

Waste tank-specific schedules will be generated to support the overall FTF/HTF closure program. The overall closure project schedule is driven by the Liquid Waste System Plan (SRR-LWP-2009-00001) as described in Section A6.4 in support of FFA commitments.

A6.3 Location of Study Area

The FTF is a 22-acre site containing 22 waste tanks, two evaporator systems, transfer pipelines, six diversion boxes (DBs), one catch tank, a concentrate transfer system (CTS) tank and three


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pump pits (PPs). Figure A6-2 shows the general layout of FTF. There are three major waste tank types in FTF that range in size from 750,000 gallons (Type I tanks) to 1,300,000 gallons (Type III/IIIA and Type IV tanks) and have varying degrees of secondary containment and intra-tank interferences, such as pumps, cooling coil networks, and roof support columns.

Figure A6-2: General Layout of F-Area Tank Farm

The HTF is an approximately 45-acre site containing 29 liquid waste storage tanks, three evaporator systems, transfer pipelines, eight DBs, one catch tank, two CTS tanks and 10 PPs. Figure A6-3 shows the general layout of HTF. There are four major waste tank types in HTF that range in size from 750,000 gallons (Type I tanks) to 1,030,000 gallons (Type II tanks) to 1,300,000 gallons (Type III/IIIA and Type IV tanks) and have varying degrees of secondary containment and intra-tank interferences, such as cooling coil networks and roof support columns.

Additional details on waste tank construction are provided in the LWTRSAPP in Section 1.2.


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Figure A6-3: General Layout of H-Area Tank Farm

A6.4 Resource Management

Overall waste tank removal from service priorities and schedules are highly dependent on funding from DOE and the success of waste removal and treatment activities. Resources necessary to accomplish the tasks governed by this LWTRS-QAPP are managed by SRR, the Liquid Waste contractor, and Savannah River Nuclear Solutions, LLC (SRNS), the Management & Operations contractor, for the DOE. The schedule documentation is published in the SRS Liquid Waste System Plan (SRR-LWP-2009-00001), which is updated annually and provided to SCDHEC. The FFA sets forth the schedule for waste tank removal from service activities. [WSRC-OS-94-42]

A7 Data Quality Objectives and Data Quality Indicators

A7.1 Identification of Performance/Measurement Criteria

The analytical measurements and associated Measurement Performance Criteria (MPC) typically used for waste tank residuals samples are summarized in Table A7-1 and are divided into two categories: 1) the chemical, physical, and Highly Radioactive Radionuclide (HRR) measurements for which enhanced MPCs are defined, and 2) additional radionuclides. The


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Table A7-1: Typical Performance Measurement Criteria for Residuals Sample Analyses

Method Analyte

Analytical Operating Procedure

(AOP)

Data Quality Indicator (DQI)1

Quality Control (QC) or Activity Used to Assess Performance

SRNL Measurement Performance Criteria (MPC)

Density measurements for sample material

Density R&D Directions Proper balance operation Daily mass check Masses measured for reference weight deviate from the established standard by <10%

Weight % solids Weight % R&D Directions Results for solid matrix reference material

Accuracy of results for matrix reference material (5% NaCl solution)

Weight % Solids measured for reference material deviate from the established value by <10%

Sample Preparation

Aqua regia dissolution of solids for elemental and radiochemical analysis

N/A ADS-2226

Extent of dissolution for elements suitable to be digested by aqua regia

Visual appearance of final digest solutions. Analytical results for LCS material digested by this method.

The final digest solution is clear (not cloudy). Any remaining insolubles are minor and white in color, and analytical results for key LCS constituents agree with the analyzed reference values.

Extent of contamination Analytical results for blank Analyte concentrations measured in blank are evaluated on a per element/isotope basis

Analytical results for solid matrix reference material

Accuracy of analytical results for solid matrix reference material

Major analyte concentrations measured for reference material deviate from the established concentrations by <20%

Alkali fusion dissolutions of solids for elemental and radiochemical analyses

N/A ADS-2502

Extent of dissolution for elements suitable to be digested by fusion

Visual appearance of final digest solutions. Analytical results for LCS material digested by this method.

The final digest solution is clear (not cloudy). Any remaining insolubles are minor and white in color, and analytical results for key LCS constituents agree with the analyzed reference values.

Extent of contamination Analytical results for blank Analyte concentrations measured in blank are evaluated on a per element/isotope basis

Analytical results for solid matrix reference material

Accuracy of analytical results for solid matrix reference material

Major analyte concentrations measured for reference material deviate from the established concentrations by <20% for elements relevant to fusion digestion


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Table A7-1: Typical Performance Measurement Criteria for Residuals Sample Analyses (Continued)

Method (See Table B4-1 for

instruments typically used) Analyte


(AOP)




Chemical Analyses

Inductively Coupled Plasma - Atomic Emission Spectroscopy (ICP-ES)

Ag, Al, B, Ba, Cd, Co, Cr, Cu, Fe, Mn, Mo, Ni, Pb, Sb, Sr, U, Zn

ADS-1573

Requested Detection Limit Data review Meets requested LOD

Accuracy/Bias Calibration Fit (correlation coefficient [r])

r≥0.995

Accuracy/Bias ICB ICB ≤ reporting limit

Accuracy/Bias CCB (continuing and closing)

CCB ≤ reporting limit

Accuracy/Bias ICV (initial and closing) 90-110% of true value

Accuracy/Bias Batch size limitation (before additional ICV)

20 Samples

Accuracy/Bias Internal Standard 80-120% Recovery

Accuracy/Bias LCS Example: ARG, 80-120% Recovery

Ion Chromatography for Anions

Fluoride, Chloride, Phosphate, Nitrite, Nitrate, Sulfate

ADS-2310


Accuracy/Bias Calibration Fit (r) r≥0.995




Accuracy/Bias ICV (initial and closing) 90-110% of true value


20 Samples

Accuracy/Bias Internal Standard NA

Accuracy/Bias LCS NA


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(AOP)




Chemical Analyses (Continued)

Atomic Absorption (AA) Spectroscopy

As, Se, Hg ADS-1557






Accuracy/Bias ICV (initial and closing) 80-120% Recovery


20 Samples

Accuracy/Bias Internal Standard NA

Accuracy/Bias LCS NA

Inductively Coupled Plasma -Mass Spectroscopy (ICP-MS)

Co-59 plus all masses between 82 and 244, except masses: 83, 115, 127, 129, 131-132, 188-190, 192, 199-202, and 209-229

ADS-1543






Accuracy/Bias ICV (initial and closing) 80-120% Recovery


20 Samples

Accuracy/Bias Internal Standard 80-120% Recovery

Accuracy/Bias LCS Example: ARG, 80-120% Recovery

HRR Analyses

Sr-90 Sr-90, Y-90 (by calculation)

ADS-2447, ADS-2424, ADS-2420, ADS-2407, R&D Directions

Requested Detection Limit Data review Meets requested MDA


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(AOP)




HRR Analyses (Continued)

Sr-90 (Continued) Sr-90, Y-90 (by calculation)


Precision, Accuracy/Bias Serial Dilution (each batch)

3σ overlap (σ determined from propagation of error for major sources of uncertainty for individual sample, i.e., counting statistics, standard certificate uncertainty, pipette uncertainty, calibration uncertainty in accordance with MARLAP guidelines)

Accuracy/Bias ARG (if dissolution, each batch)

<10% of that measured for sample analyte

Accuracy/Bias Laboratory Spike (each batch)

75-125% Recovery

Accuracy/Bias

Instrument Performance Check

HPGe Gamma for NAA of tracer

LSC for Sr-90 counting

See Table B7-1

Accuracy/Bias Internal Tracer (each sample; stable Sr)

Signal/noise ratio in final counts sufficient for quantification to meet the requested MDA

Accuracy/Bias Method Blank (each batch) <10% of that measured for sample analyte


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(AOP)





Tc-99 Tc-99

ADS-2424, ADS-2420, ADS-2445, ADS-2407, ADS-2462, R&D Directions




Accuracy/Bias Laboratory Spike (each batch)

75-125% Recovery

Accuracy/Bias


NaI Gamma detector for counting Tc-99m tracer

LSC for Tc-99 counting

See Table B7-1

Accuracy/Bias Internal Tracer (each sample, Tc-99m tracer)


Accuracy/Bias Method Blank <10% of that measured for sample analyte

I-129 with separation I-129 ADS-2420, ADS-2407, R&D Directions




Accuracy/Bias


HPGe Gamma for NAA of tracer

HPGe Gamma for I-129 counting

See Table B7-1

Accuracy/Bias Internal Tracer (each sample; stable iodide)




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(AOP)





Gamma Scan Cs-137, Cs-134

ADS-2420, R&D Directions




Accuracy/Bias Instrument Performance Check

HPGe Gamma See Table B7-1

Accuracy/Bias Method Blank (if dissolution, each batch)


U-233, 234, 235, 236

U-233, U-234, U-235, U-236

ADS-2449, ADS-1543, R&D Directions, results linked to ICP-MS for U-238





ICP-MS See Table B7-1


Np-237 Np-237

ADS-2420, ADS-2449, ADS-1543, R&D Directions, results linked to ICP-MS




Accuracy/Bias


HPGe Gamma or

ICP-MS

See Table B7-1

Accuracy/Bias Internal Tracer (each sample, Np-239)




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(AOP)





Pu-238/241 Pu-238, Pu-239+Pu-240, Pu-241

ADS-2402, ADS-2453, ADS-2449, ADS-2405, ADS-2424, R&D Directions


Precision, Accuracy, Bias Serial Dilution (each batch)

3σ overlap(σ determined from propagation of error for major sources of uncertainty for individual sample, i.e., counting statistics, standard certificate uncertainty, pipette uncertainty, calibration uncertainty in accordance with MARLAP guidelines)



Accuracy/Bias Laboratory Spike (each batch, Pu-238)

75-125% Recovery

Accuracy/Bias


LSC for Pu-241

Alpha PHA for Pu-238, Pu-239+240

See Table B7-1

Accuracy/Bias Internal Tracer (each sample Pu-236)



Gamma Scan Cs removed2

Al-26, Co-60, Sb-126,

Sb-126m, Sn-126, Eu-152, Eu-154, Np-239, Am-2412, Am-243

ADS-2420, R&D Directions








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(AOP)




Additional Radionuclide Analyses

Am/Cm

Am-241, Am-243, Am-242m, Cm-243, Cm-245, Cm-247, Cf-249, Cm-244, Cm-248

ADS-1543, ADS-2449, ADS-2405, ADS-2424, ADS-2420, ADS-2402, R&D Directions


Accuracy/Bias Internal Tracer (each sample, Am-243 or Am-241)


Accuracy/Bias


HPGe Gamma

Alpha PHA

ICP-MS

See Table B7-1


Ni-59/63 Ni-59, Ni-63

ADS-1573, ADS-2449, ADS-2405, ADS-2424, ADS-2420, ADS-2452, R&D Directions


Accuracy/Bias Laboratory spike (Ni-59 and Ni-63, each batch)

75-125% recovery

Accuracy/Bias


HPGe Gamma for Ni-59

LSC for Ni-63

ICP-ES for stable Ni

See Table B7-1

Accuracy/Bias Internal Tracer (each sample, stable Ni)




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(AOP)




Additional Radionuclide Analyses (Continued)

Se-79 Se-79



Accuracy/Bias


HPGe Gamma for NAA of tracer (Se)

LSC for Se-79

See Table B7-1

Accuracy/Bias Internal Tracer (each sample, stable Se)



Pm-147/Sm-151 Sm-151

ADS-2424, ADS-2407, ADS-2449, R&D Directions


Accuracy/Bias


HPGe Gamma for NAA of tracer (Sm)

LSC for Sm-151 and Pm-147

See Table B7-1

Accuracy/Bias Laboratory Spike (each batch, Sm-151)

75-125% Recovery

Accuracy/Bias Internal Tracer (each sample, stable Sm)




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(AOP)





Ra-226 Ra-226 ADS-2449, ADS-2420, R&D Directions




Accuracy/Bias Laboratory Spike (each batch, Ra-226)

75-125% Recovery

Accuracy/Bias Internal Tracer (each sample, stable Ra-224 from Th-228)



Pa-231 Pa-231



Accuracy/Bias


HPGe Gamma or

ICP-MS

See Table B7-1

Accuracy/Bias Internal Tracer (each sample, Pa-233)



Gross Alpha/Beta Gross Alpha, Gross Beta



Accuracy/Bias


LSC or Traveler Alpha/Beta Proportional Counter

See Table B7-1

Accuracy/Bias Matrix Spike (each sample counted by LSC)

75-125% Recovery



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(AOP)





Nb-94 Nb-94 ADS-2420, ADS-2449, R&D Directions




Accuracy/Bias Internal Tracer (each sample, Nb-95 from Zr-95)



K-40 K-40 ADS-2420, ADS-2449, R&D Directions





C-14

C-14 ADS-2424, R&D Directions



LSC See Table B7-1



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(AOP)


Quality Control (QC) or Activity Used to

Assess Performance



Th-229/230 Th-229 Th-230 Ac-227




Alpha PHA See Table B7-1

Accuracy/Bias Laboratory Spike (each batch, Th-228)

75-125% Recovery

Accuracy/Bias

Internal Tracer (each sample analyzed as paired samples, one spiked with Th-229 and one not spiked)


Accuracy/Bias Method Blank (each batch)


U-232 U-232



Accuracy/Bias


Alpha PHA

ICP-MS

See Table B7-1

Accuracy/Bias

Internal Tracer (each sample analyzed as paired samples, one spiked with U-233 and one not; or use intrinsic U-238)





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(AOP)



Assess Performance



Pu-242, 244 Pu-242 Pu-244

ADS-2449, ADS-1543, R&D Directions, results linked to Pu-238/241

Requested Detection Limit

Data review Meets requested MDA

Accuracy/Bias


ICP-MS, isotopic ratios applied to results from Pu-238/241 method

See Table B7-1



Cs-135 Cs-135

ADS-2420, ADS-2449, ADS-1543, R&D Directions, results linked to ICP-MS or Gamma PHA



Accuracy/Bias


HPGe Gamma

ICP-MS

See Table B7-1

Accuracy/Bias Internal Tracer (each sample, intrinsic Cs-137)




Zr-93 Zr-93 ADS-1543, ADS-2449, R&D Directions





Accuracy/Bias Internal Tracer (each sample, inherent Zr-91)





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(AOP)



Assess Performance



Pd-107 Pd-107 ADS-1543, ADS-2449, R&D Directions





Accuracy/Bias Internal Tracer (each sample)




Cl-36 Cl-36




Accuracy/Bias


Traveler Gas Flow Proportional Counter

HPGe Gamma for NAA of stable Cl

See Table B7-1

Accuracy/Bias Internal Tracer (each sample, stable Cl)




H-3 H-3 ADS-2424, ADS-2444, R&D Directions




LSC See Table B7-1




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(AOP)



Assess Performance



Pt-193 Pt-193




Accuracy/Bias

Instrument Performance Check HPGe Gamma ICP-ES for stable Pt

See Table B7-1

Accuracy/Bias Internal Tracer (each sample, stable Pt from ICP-ES)




1 Measurement uncertainty is used as a DQI and will be reported for radionuclides and reviewed by the data user to ensure that it meets the user needs. It will be addressed in the case narrative and in the DQA.

2 Am-241 is the only HRR measured in this analysis.

Notes: ARG Analyzed Reference Glass CCB Continuing Calibration Blank HPGe Gamma High-Purity Germanium Detector Gamma Spectrometer and associated electronics ICB Initial Calibration Blank ICV Independent Calibration Verification LCS Laboratory Control Standard LOD Level of Detection LSC Liquid Scintillation Counting MDA Minimum Detectable Activity MARLAP Multi-Agency Radiological Laboratory Analytical Protocols N/A Not Applicable NA Not applied to the method for this program NAA Neutron Activation Analysis NaCl Sodium Chloride NaI Gamma Sodium Iodide Detector Gamma Spectrometer and associated electronics PHA Pulse-Height Analysis r correlation coefficient R&D Research and Development


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additional radionuclides may require enhanced MPCs and they will be defined in the waste tank-specific analyte list presented in the TSAP and TTQAP. The MPCs will take into account that the methods are unique and are developed to accommodate the variable matrices and QC necessary to determine radionuclide concentrations in the waste tanks. Any radionuclides not on the waste tank-specific analyte list detected during the gamma spectroscopy analysis will also be reported.

A7.2 Data Quality Indicators

Typical data quality indicators (DQIs) are presented in Table A7-1 for chemical, physical, and radionuclide measurements. Additional DQIs and MPCs may be developed as needed by SRNL and C&WDA to deal with challenging radionuclides and difficult matrices.

The chemical analyses use standard methods and instrumentation, but due to the complex matrixes, analyses can be difficult. As an example, As Low As Reasonably Achievable (ALARA) issues restrict the amount of material that can be used for analysis. The QA measures for the chemical analyses are shown in Table A7-1.

Many of the radiochemical methods require that radionuclides be separated chemically from their sample matrix and purified before measurement. During chemical separation, some of the analyte radionuclide may be lost due to sample transfer, evaporation, or incomplete chemical precipitation or extraction reactions. Losses are particularly prevalent during aggressive separation processes that are necessary to remove highly-radioactive species from the matrix prior to quantifying very low radionuclide activities or confirming radionuclide absence. With the complex matrices encountered with waste tank closure samples, these losses are often sample-specific and highly variable. For quantitative analysis, it is necessary to correct the observed instrument responses for these losses for each analytical sample whenever possible. Corrections are made using compounds that are stable (carriers) or radioactive (tracers). The ratio of the carrier or tracer recovered to the amount added is the recovery, or yield.

In accordance with Multi-Agency Radiological Laboratory Analytical Protocols (MARLAP), guidelines, the major sources of uncertainty receive the most focus during uncertainty calculations. The major sources of error are propagated to calculate a sample-specific uncertainty, which is reported (1) with the sample result. For situations where the propagated error is below 5%, the reported uncertainty is conservatively assigned to be 5%.

For radioanalytical measurements, the measurement uncertainty is calculated based on the uncertainty associated with a variety of possible sources:

Uncertainty in standard preparation Uncertainty in tracer preparation Uncertainty in sample preparation Counting uncertainty for the analyte peak(s) and associated background(s) Counting uncertainty for the tracer peak and associated background Uncertainty in detector calibration Other

Evaluations of uncertainties for each individual sample are carried out and a combined measurement uncertainty is reported with each analytical result. While all possible sources of


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measurement uncertainty are evaluated, the most significant sources receive the most stringent focus. Inordinate effort is not expended on the evaluation of small components of uncertainty when much larger components are known to dominate. In general, the uncertainty propagation for sources of error considered significant is carried out as described in MARLAP Section 19.4, Example 19.9. [EPA 402-B-04-001C] The calculations are performed using spreadsheets originated and maintained in accordance with ADS-WI00023, “Spreadsheet Quality Control for Analytical Development Section.” The spreadsheets are part of the analytical records maintained in the laboratory.

In accordance with MARLAP, acceptance limits for yields should be specified in some manner. The required yields for carriers and tracers are not defined numerically; rather, they are based upon their quantification above the minimum detectable concentration (MDC) or minimum detectable activity (MDA). As the instrument’s signal to noise ratio worsens, the uncertainty in the reported result increases due to counting statistics and error propagation. A low yield will increase the overall measurement uncertainty and decrease the effective detection capability. Provided the tracer recovery provides a tracer signal that is quantifiable above the MDC or MDA, and the low yield does not increase the reported analyte MDA to a value that exceeds the customer-requested MDA, the tracer recovery is considered acceptable. The propagated measurement uncertainty increases as the tracer recovery (and signal) decreases. This increase in analysis uncertainty caused by low yield is reflected in the uncertainty reported with the result.

For metals and anions, control charting is used to determine analytical uncertainties. For Inductively Coupled Plasma - Atomic Emission Spectroscopy (ICP-ES) and Ion Chromatography the reported uncertainties would be a minimum of 10%. For Atomic Absorption (AA) and Inductively Coupled Plasma - Mass Spectroscopy (ICP-MS), the reported uncertainties would be a minimum of 20%. For radiologicals, the uncertainties are quantified as described in this section.

In the DQA, the analytical uncertainty will be evaluated against the measurement uncertainty between the analysis in triplicate measurements for each sample. In general, the analytical uncertainty should be less than the uncertainty between the triplicate measurement results, indicating the analytical uncertainty does not need to be taken into account separately. The measurement uncertainty for each analyte is calculated by dividing the standard deviation of the mean by the square root of n, where n is the number of replicate samples analyzed.

A7.3 Data Quality Objectives Process

Consistent with the DOE Guide 435.1-1 and EPA/240/B-06/001, the seven-step Data Quality Objectives (DQOs) development process was followed to identify the type, quantity, and quality of characterization data needed to support the FTF/HTF waste tank removal from service activities. Details on the development of the DQOs are provided in Chapter 3 of the LWTRSAPP. [SRR-CWDA-2011-00050] The DQO process is summarized below.

The scope of the DQOs is outlined in the following statements:

The DQO process will only address the sampling plan design and sample analyses for waste tank residual materials.


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The waste tank system within the footprint of the waste tank is the sampling and analysis action boundary. These DQOs will not address any closure actions associated with contaminated soil or ancillary tank farm equipment.

A7.3.1 State the Problem

Based on the intent and commitments of DOE and compliance with relevant and appropriate guidelines listed in the FTF and HTF PAs [SRS-REG-2007-00002, SRR-CWDA-2010-00128], the problem to be addressed can be written as:

Provide residual tank material characterization (concentrations) that enable residual material inventory determinations to support tank closure decisions.

The Principal Study Question (PSQ) that addresses the problem statement follows:

Do the sample analyses provide the necessary concentration data to support the residual inventory determination?

A7.3.2 Identify the Decision

Waste tank residual sampling is not performed for measuring residual concentrations against prescribed environmental limits. The characterization data is used to determine the residual inventory, which is then compared in the SA to the inventory used in the PA and to support operational closure decisions.

This LWTRS-QAPP is designed to support the waste tank residual sampling and analysis documented in the LWTRSAPP. This LWTRS-QAPP is not applicable to Tanks 5, 6, 18, or 19 that are currently undergoing residuals characterization sampling and analysis activities.

A7.3.3 Identify Inputs to the Decision

Four types of data are required to address the problem statement and the decision statement for the waste-tank material characterization to enable waste tank closure decisions:

Radionuclide concentrations Chemical constituent concentrations Sample densities Residual volume data

Residual volume data, sample densities, and concentrations are used to determine the constituent inventory in the residual material.

A7.3.4 Define the Study Boundaries

The spatial boundary defined in the LWTRSAPP is the waste tank system within the footprint of the waste tank. This would include the waste tank annular space for applicable waste tanks. Samples of the waste tank residuals will be collected after SCDHEC, EPA, and DOE reach mutual agreement that DOE can proceed to the sampling and analysis phase. Other than additional drying resulting from waste tank ventilation system operation and radioactive decay, minimal changes in concentration are expected to occur in the residual material after the temporary cessation of waste removal and before sample analysis.


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A7.3.5 Develop an Analytical Approach and a Decision Rule

For the LWTRSAPP PSQ, if the necessary concentration data are not obtained, the operational closure decisions may be impacted and alternative actions to finalize the residuals inventory may be necessary. If necessary, any required action will be decided on a case-by-case basis in consultation with the appropriate regulatory authorities.

A7.3.6 Specify Limits on Decision Error

The probability of determining an incorrect waste tank-specific inventory is related to inaccuracies in the volume determination and in the representative sampling and analysis of the residual materials.

The residual mapping and volume estimation process is intended to not only determine the residual volume and uncertainty in the volume estimate; it also looks for areas of possible heterogeneity. The sampling plan design requires a sufficient number of samples of adequate size from the segments present in the residual material for the sample compositing. Incomplete sampling and/or insufficient material recovery could impact the data usability for the waste tank inventory determination. Those impacts would need evaluation before the waste tank-specific sampling finishes so that steps could be taken to ensure that the sampling representativeness and completeness goals are met.

Uncertainty in the residuals final volume determination is incorporated into the sample compositing as described in Appendix A of the LWTRSAPP. However, the usability of a large uncertainty in the volume determination would need to be evaluated for its impact on the inventory determination.

The samples are complex mixtures of particulate material, and their analysis is influenced by the Fundamental Error (FE) of sampling that originates from the particulate material size, shape, chemical properties and other physical factors. FE can be controlled by meeting the required material conditions as described in Appendix A of the LWTRSAPP.

Historical data from the Waste Characterization System (WCS) that tracks individual waste tank receipts and removals, gives a general accounting of the radionuclide and chemical inventory for a waste tank at the time the system is updated. This data is used to develop the waste tank-specific analyte lists, and not for inventory determinations. Conservative assumptions in the WCS would not necessarily impact the waste tank-specific inventory since that is determined using the actual analytical data for the residuals sampling.

The inventory determination could be affected by analytical uncertainties related to interferences and the overwhelming of minor constituents by large amounts of other constituents all of which would influence the method detection limits. Precision and accuracy criteria for the acceptance of the data are presented in Table A7-1. Recoveries for some of the minor radionuclides may introduce a large uncertainty in the measured concentration that will need evaluation in the DQA. The DQA will also review the DQIs and evaluate any nonconformities for impacts on the data.

The decision error (i.e., errors in the inventory) resulting from the uncertainties described above is difficult to quantify. Since the inventory determination is an estimation problem, and the data generated is limited by what material can be collected and by analytical success,


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data uncertainties do not necessary result in data rejection. When data uncertainties are recognized, or cannot be quantified, the impact is evaluated and typically biased towards conservatism.

A7.3.7 Optimize the Design for Obtaining Data

The basis for the sampling approach for residuals characterization is presented in Appendix A of the LWTRSAPP. The residual material areas remaining after waste removal activities have ceased are delineated into segments based on similarity, appearance, or possible heterogeneity. The material within each segment is then randomly sampled. This stratified random sampling with volume-proportional compositing will be used to characterize the residual material. The material distribution and volume will be used to design the three sampling arrays, and to calculate a volume-proportional mass needed from each of the five sample locations per array for compositing. The approach was statistically evaluated and determined that the built-in variations in the volumetric proportions produced valid statistical sampling results for the concentrations of residual material. [SRNL-STI-2011-00323]

The waste tank-specific sampling design and sampling locations will be developed based on the residual material volume and distribution and documented in the sample location determination report and TSAP.

A8 Training and Certification

Site 4B Manual, Training and Qualification Program Manual, implements a training and qualification program meeting DOE requirements that is tailored to SRS operations. SRNL and SRR personnel receive training applicable to their technical area and job requirements in accordance with 4B Manual. Training history records are documented and maintained in a SRS database, the Training Records and Information Network (TRAIN). The date for re-training is tracked by TRAIN, and an employee is not permitted to perform a task if their training has expired.

SRNL personnel are qualified to perform tasks through a combination of training (on-site and off-site), education and experience. On-site training consists of a combination of classroom and computer-based training as well as on-the-job training. SRNL utilizes subject matter experts (SMEs) and technical analysts who are qualified for each of the activities for which they are responsible. All training is up-to-date as specified in each worker’s Automated Qualification Matrix and is documented in TRAIN.

The SET members will be experienced in the operation of the appropriate sampling equipment and other requirements for sampling FTF/HTF waste tank systems. They will be familiar with the applicable sampling procedures and work instructions as well as appropriate SRR and SRS procedures and policies.

A training program will be implemented for the waste tank mappers to minimize uncertainty in the volume determination and ensure consistency for the lifetime of the project.

A9 Documentation and Records

The documentation for the waste-tank characterization program will be generated, reviewed, and approved by the organizations discussed in Section 2 of the LWTRSAPP.


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Records will be processed in accordance with existing SRS and SRR site-wide requirements as described in 1B Manual, Procedure 3.31, Records Management. QA records will be processed in accordance with 1Q Manual, Procedure 17-1Q, Quality Assurance Records Management. Preparation and processing of any controlled documents required will be in accordance with 1B Manual, Procedure 3.32, Document Control.

In addition to the SRS document control requirements described above, the SRR Engineering and SRNL PL are responsible for preparing and submitting these respective field and laboratory records inventories for the records described in Section D. The Records Inventories may be stand-alone documents, compilations of records, or specified hardcopy locations.

A9.1 QAPP Distribution

The C&WDA CPC is responsible for preparation and distribution of the LWTRS-QAPP to the recipients on the Section A3 distribution list. The CPC is also responsible for conducting the annual LWTRS-QAPP review, soliciting comments for incorporation, and preparing revisions. If changes are extensive, the LWTRS-QAPP will be revised. If only minor changes are made, the revisions may be distributed using change pages. A revisions list and/or pages with track change bars will be used to indicate changed material. Revisions will be sent to the recipients by the method shown on the Section A3 distribution list.

A9.2 Data Report Package

Laboratory Information Management System (LIMS) reports generated from SRNL Analytical Development (AD) contain final analytical results with reported uncertainty and the analytical method used by AD. Information on results or the analytical method is provided to the Environmental and Chemical Process Technology (E&CPT) SME.

Once the data are received by the E&CPT SME, the SME compiles and reviews the data and prepares a Sample Analysis Report for submission to SRR. The elements and organization of a technical report are provided in E7 Manual, Conduct of Engineering, Procedure 3.60, Technical Reports.

Drafts of these reports are reviewed by independent E&CPT SMEs using the technical report design-check process in place at SRNL for all baseline facility studies. [E7 Manual, Procedure 2.60, WSRC-IM-2002-00011] The sample analysis reports are reviewed using the key elements of a design check:

Review of analytical/experimental approach Mathematical check Review for correct use of analytical/experimental input Review of the justification for assumptions Review of the reasonableness of output Cross-check of data for accuracy of transcription Validation of results against blanks and other quality indicators Qualification of data, as appropriate

Once the checks are complete, the E&CPT SME forwards the draft reports to selected SRNL and SRR managers and professionals for review and comments. The E&CPT SME addresses


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comments to the satisfaction of the reviewers and obtains approval signatures from appropriate SRNL and SRR managers and professionals prior to issuing the final Sample Analysis Report.

An associated Analytical Record Summary package with tracking sheets for recording the associated QC analytical information, associated laboratory notebooks with the Research and Development (R&D) directions, LIMS numbers, descriptions of analytical problems, etc., will be compiled as the analyses are conducted. The package will serve as a traceability tool to recover the underlying raw analytical data if necessary and will be made available for data verifiers and the data quality assessor for use in their reviews. The package will be a reference document for the Sample Analysis Report and will be filed in the EDWS.

Table A9-1 summarizes the content of a Sample Analysis Report. The report will be submitted in hard copy and electronic formats by SRNL. The associated laboratory records will be retained as described in Table A9-2.

Table A9-1: Sample Analysis Report Content

Item Content

Introduction Briefly describes the project and requested work and references the associated work control documents.

Sample Receipt and Composite Sample Preparation

Describes the sample receipt condition (including any photographs) and COC, sample material preparation steps, and composite sample creation records and calculations.

Sample Analysis

Lists the digestion and analytical methods for the analyses used for each analyte. Includes a case narrative that describes the analyses, any analysis or instrument problems, interferences affecting results, failure to reach requested MDCs, MDAs, QC failures and resolution, etc. for radionuclide and chemical analyses.

Sample Results

Presents the results of the analyses with standard deviation and 1σ % uncertainty as appropriate, tracer recoveries as appropriate, and results of the associated QC sample analyses. The results will include the data verification checklists and records, and reference the associated Analytical Record Summary package.

Note: COC Chain-of-Custody


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Table A9-2: Project Records, Record Copy Location, Retention Period, and Backup Schedule

Project Record

Description

Generated and Submitted to

Records Management by

Record Copy

Location

Records Retention

Period Backup Schedule

Procedures, AOPs, and SOPs

SRR Engineering, SRNL, C&WDA

EDWS Lifetime of Facility Daily site server back-up for record metadata and optical image

Training and Qualification Records

SRR, SRNL EDWS Two years after last course session

Daily site server back-up for record metadata and optical image

LWTRSAPP and LWTRS-QAPP

C&WDA EDWS 75 years Daily site server back-up for record metadata and optical image

Tank Mapping Methodology

SRR Engineering EDWS 75 years Daily site server back-up for record metadata and optical image

Preliminary Residuals Volume Estimate Report


Sample Location Determination Report

SRR Engineering, C&WDA

EDWS 75 years Daily site server back-up for record metadata and optical image

TSAP SRR Engineering EDWS 75 years Daily site server back-up for record metadata and optical image

Sampling Work Package

SRR Engineering EDWS Lifetime of Facility Daily site server back-up for record metadata and optical image

Sample Location Verification Document


COC SRR Engineering EDWS 75 years Daily site server back-up for record metadata and optical image

Final Residuals Volume Determination and Uncertainty Estimate Report


Photographs and Videos

SRR Structural Authority & Inspection

SRR Structural Authority & Inspection

Permanent

Photos and any written description stored digitally on site server and backed-up daily.

Videos retained and converted to DVD after 1 year; DVDs stored in fireproof cabinet.

TTR SRR Engineering EDWS 75 years Daily site server back-up for record metadata and optical image


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Table A9-2: Project Records, Record Copy Location, Retention Period and Backup Schedule (Continued)

Project Record

Description



Record Copy

Location

Records Retention


TTQAP SRNL EDWS Permanent Daily site server back-up for record metadata and optical image

Scientific Notebooks relative to sampling (including R&D directions)

SRNL EDWS Permanent Daily site server back-up for record metadata and optical image

Laboratory M&TE calibration records; Instrument Logbooks

SRNL SRNL Service Life of

M&TE/Instrument Temporary storage within SRNL facility

LIMS Reports: Including final analytical results with reported uncertainty and analytical method used

SRNL LIMS 5 years Daily site server back-up for LIMS

Radionuclide Data Package: including prep sheets, computer printouts, calculations, and instrumentation QC check

Chemical Data: See LIMS Reports

Analytical Record Summary (for Radionuclide and Chemical Analyses)

SRNL

Radionuclide: Laboratory Files

Chemicals: LIMS

Analytical Record Summary: EDWS

Radionuclide: 5 years

Chemicals: 5 years

Analytical Record Summary: Permanent

Radionuclide: Fire suppression, monitored facility

Chemicals: See LIMS Report

Analytical Record Summary: Daily site server back-up for record metadata and optical image

Sample Analysis Report: Including Data Verification Records

SRNL EDWS Permanent Daily site server back-up for record metadata and optical image

Data Validation Checklists (TBD)

C&WDA, SRNL EDWS Permanent Daily site server back-up for record metadata and optical image

Data Validation Report

Third-Party Validator EDWS 75 years Daily site server back-up for record metadata and optical image

DQA C&WDA EDWS 75 years Daily site server back-up for record metadata and optical image


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Table A9-2: Project Records, Record Copy Location, Retention Period and Backup Schedule (Continued)

Project Record

Description



Record Copy

Location

Records Retention


Assessments and Audits

SRR QA, SRNL QA STAR 5 years Daily site server back-up

CA Reports and Resolution (if applicable)

SRR, SRNL STAR 5 years Daily site server back-up

Notes: CA Corrective Action M&TE Measuring and Test Equipment SOP Standard Operating Procedure STAR Site Tracking, Analysis, and Reporting TBD To Be Determined

A9.3 Other Applicable Records and Documents

Records and document retention practices at SRS are described in Section A9.4.

A9.4 Project Information Retention

As a Federal facility, SRS generated records are required to be identified and maintained consistent with DOE requirements and National Archives and Records Administration guidelines for identification, protection, retention, and storage. Established site-wide information management infrastructure and processes provide for records retention, storage and protection. Backups of electronic information management systems occur daily as routine information technology practice. SRS records are managed and maintained in accordance with 1B Manual Procedure 3.31, Records Management. Both SRR and SRNL comply with this procedure. In accordance with Procedure 3.31, records created in support of waste tank residuals sampling and analysis as described in various sections of this document will be retained as listed in Table A9-2.

A9.5 Data Records Backup

See Section A9.4.


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SECTION B MEASUREMENT/DATA ACQUISITION

Waste tank residuals will be collected and analyzed for a specific list of analytes to generate the data necessary to satisfy South Carolina and DOE requirements for removing FTF/HTF waste tanks from service. None of the data collected or generated is for informational purposes. All of the data is necessary to determine the final waste tank residuals inventory, although, within limits, allowances for missing samples or insufficient material recovery can be made. Because of the difficulty, high cost, and ALARA issues, resampling to collect additional material would be unlikely.

Because the final residual material composition, volume, distribution, and accessibility in a waste tank can be highly variable, the sampling plan design, sampling methods used, and analytical success can be highly variable. Any departures from the original sampling plan caused by sampling location inaccessibility or equipment limitations will be described in the final TTR or TSAP, and DQA. Analytical problems will be documented in the case narrative of the Sample Analysis Report from the laboratory. The DQA will address any impacts on the data produced by departures from the planned sampling and analysis.

B1 Sampling Process/Experimental Design

Waste Tank Residual Sampling

Sample collection and analysis will be designed to satisfy the DQOs by implementing the stratified random sampling with volume-proportional compositing approach. The sampling and analysis planning process and decisions are shown on Figure B1-1 and described in LWTRSAPP Section 4.1. The basis for the sampling approach to minimize sampling error and capture the possible variability in the residual materials is described in LWTRSAPP Appendix A.

The sample planning process evaluates waste tank-specific material distribution variables such as low-volume conditions, area accessibility, or presence of annular materials to determine the samples necessary to characterize the residual material present. The characterization information will be used to determine the residual waste tank inventory to support waste tank removal from service decisions.

The waste tank characterization objective is to determine the radionuclide and chemical concentrations in the waste tank residuals. To accomplish the objective, samples will be collected where the material is present, and not on a systematic grid pattern. In order to represent any possible material heterogeneity, multiple locations will be sampled to create composite samples for analysis. The material sampled (location) will be represented in the composite sample using a volume-proportioning scheme.

Table B1-1 provides a general description for the type(s) and number of samples expected for waste tank residual materials. The general sampling approach uses three arrays, each with five sample locations, to produce three composite samples for laboratory analysis. If sufficient material thickness is present in an area, depth sampling may be appropriate to characterize the residuals. Additional details on the sample location determination and compositing are contained in the LWTRSAPP Appendix A and Section 4.1.


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Figure B1-1: Waste Tank Sampling and Analysis Planning Process


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Table B1-1: Waste Tank Sampling Design

Sample Location ID

Matrix Depth Analytical

Group Concentration

Level

Number of Samples

(identify field duplicates)

Sampling SOP Reference

Rationale for Sampling Locations

Specific to waste tank being sampled

Solids

Variable, depending on thickness of material. Depth samples will be collected if sufficient thickness is present in an area.

Radionuclides and Chemical constituents

Variable

Three composite samples per waste tank (Five locations sampled per composite) No field duplicates are planned

N/A, Training requirements for the SET team is defined in Section A8. And specific procedures required are developed on a waste tank-specific basis and defined in the work package.

Stratified random as explained in the LWTRSAPP Appendix A


Fluids N/A

Radionuclides and Chemical constituents TBD for waste tank-specific situation

Unknown None anticipated TBD for waste tank-specific situation

TBD for waste tank-specific situation


Cooling coils, primary liner

Material surface and residual layer if present


Unknown No further material samples anticipated




Material in waste tank annular space



Unknown TBD for waste tank-specific situation




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No fluid sampling is anticipated since the waste tanks are normally air-dried before sampling occurs. No additional cooling coil or steel liner sample collection is planned. If material is present in a waste tank annular space, it may require sampling. If necessary, the sampling approach, sampling method and analyte list for fluids or non-solids materials will be developed for the waste tank-specific conditions and detailed in the TSAP. The inventories for these materials will be evaluated in the final waste tank inventory determination report.

Any impacts resulting from sampling plan departures (inaccessible areas, insufficient sample material collection) will be described and evaluated in the DQA described in Section D3 and described in the associated waste tank CM.

Sample shipments to the laboratory will be scheduled to minimize worker exposure during sample packing, to accommodate space restrictions in the transport container, and to accommodate receipt in the laboratory Shield Cell Operations (SCO) facility.

B2 Sampling Methods

Sample collection in the waste tanks is complicated by waste tank top access restrictions, interior obstructions, and radiological conditions. Residual material distribution and accessibility, worker exposure risk, and sampling equipment capabilities are evaluated during the sampling plan design phase and used to develop the TSAPs and evaluate the best methods to representatively sample the residual material. Because of the specialized and still evolving nature of this sampling, Standard Operating Procedures (SOPs) have not been developed. However, special sampling tools and their applications are developed as needed on a waste tank-specific basis. The TSAPs and work packages developed for individual waste tank samplings contain the details for sample locations, sample naming and numbering, collection method, and material handling. Key equipment, facilities, and support personnel are identified in Section B9.4.

Accessibility of the areas requiring sampling largely dictates the method of sample collection. If the sampling area is directly beneath a waste tank riser, a sampling tool on the end of a pole could be used. To sample remote areas of a waste tank, a robotic crawler is typically used. This method requires practice and careful planning to avoid tangling or snagging control cables and possibly special tools such as ramps, to negotiate over obstacles such as cooling coils.

Special sample collection devices have been developed for use with the robotic crawler. In general, these are open-top stainless steel cups with a flared scoop opening. The cups are approximately 1.5 inches in diameter and 3 to 4 inches long with an approximate volume of 150 to 200 milliliters. The cups have a quick release device for attachment and release from the robotic sampling arm of the crawler. The cups are single-use items and are cleaned after fabrication and before use by wire wheel buffing and water rinsing to remove any particulate matter. The sample cups are pre-labeled for the samples to be collected and lowered into the waste tank using a special “basket”. The 5-inch diameter basket can contain up to three sample cups, and the cups are kept vertical by insertion into short plastic pipe sections attached to the inside bottom of the basket. Figure B2-1 shows a sample cup being placed into a two container sample basket. The basket is tethered to the access opening and if necessary, is moved step-wise by the crawler until the sample location is reached. The appropriately labeled sample cup is removed from the basket and scraped several times through the material at the sample location to


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fill the cup. A camera on the crawler is used to verify the container label and to visually estimate the amount of material recovered. Depending on the thickness of the material at the sample location, several scrapes may be needed to fill the cup. Ideally, between 20 and 40 grams of material are collected at each location.

Figure B2-1: Sample Collection Cup Being Placed in the Retrieval Basket

When sufficient material has been collected, the cup is inserted back into the basket and preparations are made to collect the next sample. When sampling is completed, the basket is moved back to the access riser and lifted out of the waste tank. The sample basket is placed into a plastic bag, which is sealed and placed inside a specially designed plastic carrier tube. The plastic tube is inserted into a cloth carrying bag, which is in turn suspended inside the transport cask. The sample identifications are written on the outside of the cloth carrying bag before the plastic carrying tube containing the samples is placed inside. The sampling process continues until all the planned samples are collected.

Early residual material sampling attempts used sample cups fitted with weighted, self-closing tops that proved problematical. The pivot rod for the tops crossed the cup opening and was found to block residual material flakes and chunks from entering the cup. Material would also foul the pivot action and jam the top half-closed between scrapes, hampering additional material collection. Often, no visual estimate of the cup contents was possible with the tops jammed, or closed, and collection might be stopped before the desired amount of material was recovered. Considering the drawbacks of the self-closing design, an open-top sample cup design is currently used. To minimize any impacts of any cross-contamination, samples from different sampling areas are not put into the same sample basket. During retrieval and transport, care is exercised to minimize jostling, and to keep the basket vertical so that the materials do not spill or bounce out of their containers. Furthermore, the sample compositing approach and large analyte concentrations in the material would also override the potential impacts of any minor cross contamination.

The entire sampling process is observed and recorded using the on-board crawler camera and may be supplemented by still photographs or other camera systems deployed during waste tank sampling. A sample collection document is prepared at the end of waste tank sampling to verify and document the actual sample locations and samples collected. Loss of the on-board camera does not necessarily end sampling operations with that crawler. If the in-tank camera can provide sufficient visual coverage, sampling will continue.


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Any problems encountered during the sampling will be communicated to the SRR Engineering PL, and the impacts and resolution will be discussed with the responsible parties from SRR Engineering, C&WDA, and TFO. The decisions reached will be documented in the sample collection records, memorandums, or by updating the TTR or TSAP. Any deviations from the sampling plan will be documented in the sample collection records and in updates to the TSAP. If necessary, corrective actions will be implemented according to the corrective action process described in Section C.

Because of the high sample activity, special handling and transport procedures are required as described in LWTRSAPP Section 4.1.8. Sample preservation limitations are discussed below in Section B3.

At the laboratory, the samples will be thoroughly dried, ground, sieved, homogenized, and eventually composited to make the samples for analysis. The sample density is measured in the “as received” material, again after drying, and in final composite sample. As described in the LWTRSAPP Section 5.1, after the final residual volume is determined, a memo detailing the composite sample creation instructions will be sent to the laboratory. The memo will become an attachment to the TTR.

Special compositing instructions to account for sampling problems, such as low sample recovery or inability to collect sample(s), will be addressed in the instructions to the laboratory in the form of a TTR or a subsequent TTR revision. If necessary, the explanation and justification may be documented in a separate report. The impact on the final residual characterization results will be evaluated in the DQA.

As the project progresses, “lessons learned” will be used to develop and modify the sampling tools and procedures for effective sampling. At some stage, SOPs may be developed for waste tank sampling activities. The LWTRSAPP and LWTRS-QAPP will be updated to reflect any changes or SOPs implemented.

B3 Sampling Handling and Custody

Sample collection will be performed and documented using procedures described in the SET work package. The SET team leader (Person-In-Charge [PIC]) is responsible for recording the required information and filing the completed records with the SRR Engineering PM. The entire in-tank sampling process is observed and recorded using the on-board crawler camera and may be supplemented by still photographs or other camera systems deployed during waste tank sampling. A sample location verification document is prepared at the end of waste tank sampling to document the actual sample locations and samples collected.

Assuming the sampling approach using three arrays with five samples per array can be applied to a waste tank having three residual material areas to be sampled, the samples would be identified using the following four character scheme:

1. The waste tank where the sample was collected (5 for Tank 5).

2. The residual material area of the waste tank where the sample is collected. This is based on the preliminary mapping and sample plan design (e.g., A, B, C).

3. The sample set number (e.g., 1, 2, or 3), which corresponds to the array and uniquely identifies the samples supporting the same composite sample.


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4. If more than one sample per array will be collected in an area, another identifier (i.e., a, b, or c) would be added to correspond to the 1st, 2nd, or 3rd sample collected for the respective array in that waste tank area.

For example, the sample identification for a sample collected for Tank 5, which represents the 3rd sample collected for the 2nd composite sample set in Area B would be designated as 5-B2c. That sample identification would be marked on the exterior of the carrier tube into which the wrapped sample basket is placed after removal from the waste tank.

The sample identification will be permanently marked on the sample container large enough to be visible with the video camera while sampling with the robotic crawler. The crawler operator will use the sample container labeled for the corresponding sample location. Verification will be made using photography and documented in the sample location determination document prepared by SRR Engineering.

Shipping containers are surveyed by Radiological Controls (RadCon) personnel before use to verify they are within contamination limits. The exterior of the overpack containers holding samples are surveyed before placement inside the shipping container. Sample transport is described in LWTRSAPP Section 4.1.8.

Sample custody is tracked using a chain-of-custody (COC) that will be incorporated into the existing CST Sample Manual. [SW11.1-SAMPLE] A COC form is under development and will be provided as Attachment 1 in a future update of this LWTRS-QAPP. Transportation shipping documents also record the material transfer from the waste tank farm to the SCO as described in Section 4.1.8 of the LWTRSAPP. Actual verification of the sample identifications is performed when the containers are placed in the hot cell and can be examined. Sample receipt in the SCO is documented on a sample receipt form in accordance with L7.7 Manual, Procedure 1.15, SRNL Receipt of Radioactive Material. The laboratory will log in the samples and use internal tracking and LIMS procedures to track material and aliquots for analysis.

Once activated in LIMS, each sample aliquot is assigned a unique sample identification number that is correlated to a sample identification number provided by the E&CPT SME. The E&CPT identification number is a unique identifier created by the SME after compositing multiple original waste tank samples into a single sample. The new identification can be traced to SRR sample identification numbers through the records maintained in the SCO hot cells by the E&CPT SME.

AD tracks the customer-requested due dates and progress of analyses through LIMS and/or the AD Sample Management database as well as the SRNL schedule tracking software. Sample progress reports are available through database queries and are reviewed regularly by SRNL personnel and management.

Because of the radiological conditions that will be encountered, activities relating to the sampling, sample handling, and characterization of waste tank residual materials will be done in accordance with requirements and procedures of the SRS 5Q Manual, Radiological Control Manual, to minimize worker exposure. Table B3-1 summarizes the sample handling requirements.


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Table B3-1: Sampling Methods and Sample Handling Requirements

SOP Abbreviated

Name Method Analyte Matrix

Container Type/Sample

Volume

Preservation and Holding

Time

N/A Scrape or core sampling

Defined in work packages

Radioisotopes and chemicals

Solids Stainless steel/variable

N/A

N/A Sampling with the crawler

Defined in work packages

Radioisotopes and chemicals

Solids Stainless steel/150 ml

N/A

Sample preservation in the field is not possible because the high activity of the samples prohibits direct handling of the sample containers and residual materials. Temperature control is also not possible due to the size and construction of the shipping cask used for sample transport and the limited space availability inside the shielded cells. As a result, sample preservation is not feasible until the samples have been received and processed at the laboratory.

Per discussion with Stephen Burdick of SCDHEC in December 2011, and documented in the LWTRS-QAPP review comments (DHEC_01-17-2012), it was decided that sample preservation would have minimal benefit for residual materials. The materials have been in a highly radioactive, caustic and temperature-elevated environment for many years. During the waste removal campaigns prior to sampling, the solids have been agitated and washed numerous times with oxalic acid, supernatant, and/or water and sometimes given a final water rinse before the waste tank and residual solids are dried using heated air. Whatever physical changes and chemical compound degradations have taken place to that point far exceed any changes that might occur at ambient temperature after sample removal from the waste tank.

There are no known sample preservation requirements for these residual materials. They are not analogous to soil; however, the aqua regia digestion preparation step can be considered equivalent to acidification with nitric acid to pH less than 2, which is typically used for metal and radiological analyses of soil.

It was also determined in the discussion with Stephen Burdick of SCDHEC in December 2011 (DHEC_ 01-17-2012), that soil sample holding times are also not applicable for these materials. However, most sample preparation and analysis can be performed within 180 days of the acidification; the usual holding time requirement for metal and radiological analyses of soil. It is unlikely that the 28-day holding time for nitrate/nitrite and the 4ºC and 28-day holding time requirements for mercury and sulfate analyses will be met due to the sample handling requirements.

Key resources, individuals, and facilities to support the residuals sampling project are presented in Section B9.4.

B4 Analytical Methods

SRNL utilizes Analytical Operating Procedures (AOPs), designated as Technical Reference Procedures, coupled with R&D directions for their analytical work. Both types of documents are written by SRNL SMEs. The procedures describe routine activities or generalized instructional


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material while the R&D directions provide customized instruction for the completion of matrix-specific preparations by well-trained personnel. The waste tank residual analyses require special protocols to reduce worker exposure and meet the complex analytical requirements for some radioisotope measurements.

B4.1 Identify Standard Operating Procedures

Procedures are peer-reviewed and approved by management while R&D directions are prepared by technical experts that decide if review is required. These procedures and R&D directions are based on widely-accepted protocols, such as EPA for chemical methods and MARLAP for radioanalytical methods, and allow flexibility to analyze these residual material matrices to meet project expectations. Additional technical or quality requirements will be specified in a technical task document (TTR or TTQAP).

Examples of some of the analytical methods and corresponding instrumentation are presented in Table B4-1. The typical AOPs and summary method descriptions used for typical residual material analyses are included in Attachment 2. The actual method utilized for future sample analyses cannot be predetermined due to the complex nature of the sample matrices. A significant amount of method development may take place as the samples are analyzed. The complete details for each analysis used are contained in the final data packets referenced in LIMS, and detailed in the case narrative of the Sample Analysis Report.

B4.2 Identify Equipment and Instrumentation

Equipment and instrumentation typically used for the sample analyses are listed in Table B4-1.

B4.3 Specify Measurement Performance Criteria

Specific MPC typically used for the analyses are listed in Table A7-1. Refer to Section A7.2 for additional discussion of MPCs and DQIs.

B4.4 Identify Procedures to Follow When Failures Occur

Noncompliant work includes occurrences outside of specified limits. Equipment failures or concerns are reviewed, evaluated for significance, and resolved by the SME. When appropriate and feasible, reanalysis may be performed, as determined by the SME. Radiochemistry instrument failures are noted via a combination of documentation steps in the instrument log book and instrument history file. For chemical analyses, the task supervisor documents failures in the instrument’s maintenance laboratory notebook.

Instruments or equipment that have generated suspect data are tagged, segregated, or otherwise controlled to prevent use until repaired and recalibrated, if required. The SME is responsible for evaluating the validity of any sample results and a course of action for instrument repair or servicing.


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Table B4-1: Typical Laboratory Analytical Operating Procedures

Analyte Grouped by Method

Listed Procedures/ AOPs

Revision Number

Method Reference

Typical Instrument

MDC1 Performance Criteria

Ag, Al, B, Ba, Cd, Co, Cr, Cu, Fe, Mn, Mo, Ni, Pb, Sb, Sr, U, Zn

ADS-1573 2 N/A ICP-ES Requested in TTR

See Table A7-1 R&D Directions N/A N/A N/A

Fluoride, Chloride, Phosphate, Nitrite, Nitrate, Sulfate

ADS-2310 0 N/A Dionex ICS3000

with Ion Chromatograph Requested in TTR

See Table A7-1

R&D Directions N/A N/A N/A

As, Se, Hg ADS-1557 5 N/A

VGA-77 with AA Spectrometer Requested

in TTR See Table

A7-1 R&D Directions N/A N/A N/A

All masses between 82 and 244, except masses: 83, 115, 127, 129, 131-132, 188-190, 192, 199-202, 209-229 and Co-59

ADS-1543 5 N/A ICP-MS

Requested in TTR

See Table A7-1 R&D Directions N/A N/A N/A

Ni-59, Ni-63

ADS-2424 7 N/A LSC

Requested in TTR

See Table A7-1

ADS-2405 6 N/A N/A

ADS-2449 4 N/A N/A

ADS-2420 6 N/A HPGe Gamma (low energy)

ADS-2452 2 N/A N/A

ADS-1573 2 N/A ICP-ES

R&D Directions, yield linked to ES

N/A N/A N/A


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Table B4-1: Typical Laboratory Analytical Operating Procedures (Continued)



Revision Number

Method Reference

Typical Instrument


Se-79

ADS-2447 4 N/A LSC

Requested in TTR

See Table A7-1

ADS-2424 7 N/A N/A

ADS-2420 6 N/A N/A

ADS-2407 8 N/A HPGe Gamma

R&D Directions 2 N/A N/A

Cs-134 ADS-2420 6 N/A HPGe Gamma Requested

in TTR See Table


Sr-90, Y-90

ADS-2447 4 N/A N/A

Requested in TTR

See Table A7-1

ADS-2424 7 N/A LSC


ADS-2407 8 N/A N/A

R&D Directions 2 N/A N/A

Tc-99

ADS-2424 7 N/A LSC

Requested in TTR

See Table A7-1

ADS-2445 4 N/A N/A

ADS-2407 8 N/A N/A

ADS-2462 0 N/A NaI Gamma


Sm-151, Pm-147

ADS-2424 7 N/A LSC

Requested in TTR

See Table A7-1


ADS-2449 4 N/A N/A



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Revision Number

Method Reference

Typical Instrument


Pu-238, Pu-239+Pu-240, Pu-241

ADS-2453 2 N/A N/A

Requested in TTR

See Table A7-1

ADS-2449 4 N/A N/A

ADS-2405 6 N/A N/A

ADS-2424 7 N/A LSC

ADS-2402 5 N/A Alpha PHA Chambers


Am-241, Am-243, Am-242m, Cm-243,Cm-244, Cm-245, Cm-247,Cm-248, Cf-249


Requested in TTR

See Table A7-1

ADS-2449 4 N/A N/A

ADS-2405 6 N/A N/A




Ra-226

ADS-2449 4 N/A N/A Requested

in TTR See Table

A7-1 ADS-2420 6 N/A HPGe Gamma


Pa-231


Requested in TTR

See Table A7-1

ADS-2405 6 N/A N/A

ADS-2449 4 N/A N/A



I-129

ADS-2420 6 N/A HPGe Gamma (low energy) Requested

in TTR See Table

A7-1 ADS-2407 8 N/A HPGe Gamma



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Revision Number

Method Reference

Typical Instrument


Al-26, Co-60, Sb-126, Sb-126m, Sn-126, Eu-152, Eu-154, Am-241, Am-243

ADS-2420 6 N/A HPGe Gamma Requested

in TTR See Table


Nb-94


in TTR See Table

A7-1 ADS-2449 4 N/A N/A


K-40


in TTR See Table

A7-1 ADS-2449 4 N/A N/A


C-14 ADS-2424 7 N/A LSC Requested

in TTR See Table


Th-229, Th-230, Ac-227

ADS-2449 4 N/A N/A

Requested in TTR

See Table A7-1

ADS-2405 6 N/A N/A



U-232


Requested in TTR

See Table A7-1

ADS-2449 4 N/A N/A

ADS-2405 6 N/A N/A



U-233, U-234, U-235, U-236

ADS-2449 4 N/A N/A

Requested in TTR

See Table A7-1


R&D Directions, results linked to ICP-MS

N/A N/A N/A


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Revision Number

Method Reference

Typical Instrument


Pu-242, Pu-244

ADS-2449 4 N/A N/A

Requested in TTR

See Table A7-1


R&D Directions, results linked to Pu-238/241

N/A N/A N/A

Cs-135

ADS-2449 4 N/A N/A

Requested in TTR

See Table A7-1



R&D Directions, results linked to ICP-MS or Gamma PHA

N/A N/A N/A

Np-237


Requested in TTR

See Table A7-1

ADS-2449 4 N/A N/A


R&D Directions, results linked to ICP-MS if necessary

N/A N/A N/A

Zr-93

ADS-1543 5 N/A ICP-MS Requested

in TTR See Table

A7-1 ADS-2449 4 N/A N/A


Pd-107

ADS-1543 5 N/A ICP-MS Requested

in TTR See Table

A7-1 ADS-2449 4 N/A N/A



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Revision Number

Method Reference

Typical Instrument


Cl-36

ADS-2424 7 N/A LSC

Requested in TTR

See Table A7-1


ADS-2405 6 N/A Traveler Alpha/Beta Proportional Counter

or equivalent


H-3

ADS-2424 7 N/A LSC Requested

in TTR See Table

A7-1 ADS-2444 5 N/A N/A


Pt-193

ADS-1573 2 N/A ICP-ES

Requested in TTR

See Table A7-1

ADS-2449 4 N/A N/A


R&D Directions, yield is linked to ICP-ES

N/A N/A N/A

1 MDC limits requested/desired to meet project needs. MDC limits will vary based on the actual sample matrix and cannot be determined in advance.


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B4.7 Provide Method Validation and SOPs for Nonstandard Methods

Due to the uniquely complex and variable nature of the waste tank residual materials, standard method validation procedures cannot be routinely applied for these analyses.

Typical analytical methods and instruments are listed in Tables A7-1 and B4-1. AOPs and summaries of typical analytical methods are included in Attachment 2. These AOPs and methods, with modifications as needed for variation of matrix and radionuclide content, will be those used for future waste tank residual material analyses. In cases where waste tank characterization requires additional analyte-specific performance criteria, the requirements will be specified in TTRs, TSAPs, and TTQAPs.

SRNL SMEs may supplement the AOPs with additional specific implementing information for the method procedures in R&D directions.

R&D directions are developed and managed in accordance with SRNL L1 Manual, Procedure 7.26, Work Control Document. Situations arising where the requested analyte resolution or detection limits may be impacted are documented, and the Waste Removal and Tank Closure PM and SRR Engineering are informed. Flowcharts showing general separation processes that may be used for specific radionuclide analyses are available upon request.

B5 Quality Control Requirements

Procedures at SRS are written instructions used to guide administrative, management, and technical activities. All procedures are intended to implement quality policies contained in SRS 1Q Manual. Procedures are reviewed at least every five years for technical, operational, administrative, safety, and QA information. Additional specific technical and quality requirements desired by the customer may be specified in TTRs.

For residuals samples, matrix spikes for risk-driving constituents are often impractical, since these constituents are normally radionuclides present at such high concentrations that the spike quantities would need to be on the order of a curie or more. Additionally, residuals samples contain some of the nuclides that are traditionally used as tracers in environmental samples, making use of those tracers ineffective. Due to the difficulty of waste tank sampling and ALARA concerns, replicate samples are not collected and analyzed; however, replicate aliquots of individual samples are analyzed (usually in triplicate) to provide precision information on the analytical methods.

Alternative QA measures are also utilized in SRNL to assure confidence in the analytical results. Included among these measures are hybrid analysis techniques utilizing independent measurement techniques, addition of spikes after sufficient dilution of the sample such that the spike quantity would dominate, and usage of alternative spike/tracer materials. As appropriate, laboratory blanks, laboratory replicates, lab control spikes, and serial dilutions are also used as part of the routine QA/QC protocols. Such approaches are method specific and refined to assure analytical adequacy for a given waste tank residual matrix and constituent. An overview of typical QC samples used for the residuals sample analyses are listed in Table A7-1.

For chemical measurements, the analytical methods are qualified by a prior method detection limit study per AD procedures, statistical evaluation of control-charted standards, and validation for a few analytes by performance evaluation studies (e.g., Mixed Analyte Performance


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Evaluation Program [MAPEP]). Each batch of samples contains appropriate blanks and QCs to verify acceptable instrument performance. In some cases, the results obtained from two different instruments are compared to judge acceptability of the reported data (e.g., metal concentrations measured by ICP-ES and ICP-MS on separate aliquots from different types of dissolution).

For radioanalytical methods, the preparative work needs to be customized (in the form of R&D directions) for the specific waste tank matrix due to the highly-variable composition of the waste tanks. Following customized method protocols, the samples are typically traced (spiked) with a non-target radionuclide or chemical species so that each sample preparation, when possible, can be corrected for the losses that occur during multiple preparative steps. Each batch of samples also contains blanks (such as the Analyzed Reference Glass [ARG] sample), serial dilutions, and spiked samples, as feasible, to verify preparative and analytical performance. In some cases, data from two or more instruments is combined to obtain the tracer recovery, spike recovery, and yield-corrected sample results.

B5.1 Quality Control Samples

QC is assured for each method through a combination of blanks, spikes, duplicates, serial dilutions, reference standards, and control charting, as applicable for the technique. A sample batch size is 20 samples or less and for the chemical analyses, QC samples are typically placed at the beginning and end of the batch. For radiological analyses, the QC samples are randomly inserted into the batch run. For chemical or radiological analyses, additional QC samples may be placed within the batch as required by the method as described in Table A7-1.

Raw sample material is used when the analysis technique and sample dose rates allow. Otherwise, samples are digested in the shielded cells to provide digestates that are transferred to the AD lab modules for chemical and selected radioanalytical analyses. During the digestion in the cells, matrix appropriate sample blanks are prepared as a negative control to monitor for sample cross-contamination. The blank is carried through the complete sample preparation and analytical procedures.

As an alternative to matrix and laboratory control spikes, SRNL may analyze a well-characterized ARG sample. The ARG standard is also dissolved along with the samples in the shielded cells and carried through the complete sample preparation and analytical procedures. The ARG contains oxides of Al, B, Ca, Fe, K, Li, Mn, Na, Ni, Si, and Ti as major components. The oxides of Ba, Cr, Cu, Mg, P, Sr, Zn, and Zr are minor components.

For the elemental methods (ICP-ES and ICP-MS), the matrix appropriate cell blank and ARG sample constitute the batch QC. The analysis QC introduced at the instrument includes the initial and continuing calibration verifications (blanks and check standards). Both the ICP-ES and ICP-MS utilize internal standards added to each sample, blank, and standard to monitor and/or correct for sample matrix effects.

For some radioanalytical methods (examples include Sr-90 and Pu isotopes), radionuclides are separated from other interfering radionuclides, as needed, using separation techniques applied to the digestates from the shielded cells. In these cases, either solid aliquots are analyzed as negative batch controls to determine if cross-contamination is an issue in the cell or tedious preparations are performed in the SCO on the original solid samples. The ARG cannot function as a positive control because it does not contain radionuclides. During the separation process in


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AD radiological containment units, additional controls are added, as feasible, to the sample batch to monitor losses in the separation steps, monitor potential contamination, and assess matrix effects. These controls include tracers to provide yield, blank spikes for spike recovery, and serial dilutions for matrix effects.

For many other radionuclides, SRNL cannot analyze aliquots of the digested sample dilutions because the process would dilute the sample too much to meet SRR-requested detection limits. For a few radionuclides, such as for C-14 and Tc-99, a digestion would volatilize some of the target analyte and bias the measurement. In these cases, solid aliquots are weighed in the shielded cells or AD radiological containment units, thereby allowing a larger starting mass to be dissolved and processed though separations. As described previously, the same types of QC samples are used at the outset of these sample preparations.

Reference materials, such as vendor-supplied elemental standards (e.g., Cr, Fe, Hg, etc.) and radiochemical standards (e.g., Pu-236, Sr-90, etc.) used in SRNL are uniquely identified and of sufficient accuracy to meet the requirements of the customer, SRR, and the requirements of 1Q Manual, Procedure 2-7, QA Program Requirements for Analytical Measurement Systems. Reference materials are procured from external suppliers and are traceable to a national or international standard (National Institute of Standards and Technology [NIST], for example). Purchased reference materials require a Certificate of Analysis from the manufacturer, if available. In the case of radioactive sources used in calibration, an allowance is made for the correction of the assigned value due to the half-life of the source.

Standards from reference materials are prepared and analyzed with customer samples to calibrate or verify control of the measurement system and analytical instrumentation. Reference material working solutions are prepared from stock solutions, all of which are within their expiration dates. Standard preparation records are maintained in analytical notebooks and indicated traceability to purchased stocks or neat compounds, reference to the method of preparation, date of preparation, expiration date, and preparer initials.

SRNL participates in several performance testing programs. SRNL analyzes samples distributed biannually for the MAPEP as required by the DOE. Participation in the MAPEP routinely tests gamma pulse-height analysis (PHA), ICP-ES, ICP-MS, and AA methods. In the past, the MAPEP sample was submitted as a single-blind performance testing sample and analyzed for gross alpha and gross beta analysis; the results were not reported formally to MAPEP but were compared to the published acceptable results from the MAPEP website by an independent third party. The reported gross alpha and gross beta results were both within the documented acceptance range for the MAPEP. In addition to participation in the MAPEP, blind samples are routinely analyzed for International Organization for Standardization (ISO) 17025 continued accreditation. The SRNL ISO 17025 performance testing program utilizes blind, pedigreed standards or documented performance testing samples which are analyzed using ISO-accredited procedures. The ISO 17025 performance testing matrix has been used for gross alpha and gross beta analysis by gas flow proportional counting, gamma PHA, gross alpha and gross beta by liquid scintillation counting (LSC), Sr-90 separation and analysis, plutonium separation and analysis, ICP-ES, and ICP-MS. In addition, the radiochemistry laboratory participates in an EPA-sponsored Mixed Fission Product Proficiency Test Program (MFPPTP). [SRNL-STI-2011-00557] The MFPPTP primarily tests gamma PHA, with a focus on gamma spectral


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interpretation for non-routine matrices. It also tests gross alpha and gross beta by LSC, and tritium separation and analysis.

Details on field and laboratory analytical QC samples are included in Tables B5-1 and B5-2, respectively.

Table B5-1: Field Quality Control Samples

Item DQI Frequency

Field Blank Contamination (Accuracy/Bias) Evaluates contamination introduced during sampling

None are planned due to the impracticality of blank collection inside a waste tank.

Equipment Blank Contamination (Accuracy/Bias) Evaluates contamination introduced during sampling

N/A; all sampling equipment is fabricated out of stainless steel and cleaned prior to use. The concentration of residual material analytes greatly exceeds any potential trace contamination introduced during sampling.

VOC trip blank Contamination (Accuracy/Bias) Evaluates contamination introduced during sampling

If VOC samples are collected, one per trip will be utilized.

Field Duplicates Precision None planned. Most samples are analyzed in triplicate for most analytes.

Note: VOC Volatile Organic Compound


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Table B5-2: Laboratory Analytical Quality Control Indicators

Item DQI Frequency

Method Blank Accuracy/Bias As required by method listed in Table A7-1

Instrument Blank Accuracy/Bias As required by method listed in Table A7-1

Lab Duplicates Precision As required by method listed in Table A7-1

Internal Standards Precision, Accuracy/Bias As required by method listed in Table A7-1

Matrix Spikes Bias As required by method listed in Table A7-1

Surrogate Spikes Bias As required by method listed in Table A7-1

QC Sample Bias As required by method listed in Table A7-1

Instrument Performance Check Sensitivity/Accuracy/Bias As required by method listed in Table A7-1

Initial Calibration Accuracy As required by method listed in Table A7-1

Continuing Calibration or Calibration Verification Checks

Accuracy As required by method listed in Table A7-1

Serial Dilution Precision/Accuracy/Bias As required by method listed in Table A7-1

Laboratory Spikes Accuracy/Bias As required by method listed in Table A7-1

Internal Tracer Accuracy/Bias As required by method listed in Table A7-1

Performance Testing Samples Accuracy/Bias For participation in the MAPEP, MFPPTP performance testing programs, and ISO 17025 accreditation process

B5.2 Quality Control Limit Exceedance and Corrective Action

Noncompliant work includes Quality Control Limit Exceedances. Any noncompliant issues are reviewed, evaluated for significance, and resolved by the SME. When appropriate and feasible, reanalysis may be performed, as determined by the SME.

Some reanalyses may be necessary, but those may occur because the batch QC samples indicate a problem with the batch, the radioanalytical separation prescribed in the R&D direction was unsuccessful, or the customer’s desired detection limit was not reached in the original analysis. In these cases, the data is not reported to the customer until the issues are resolved.

Appropriate corrective actions will be taken, and their adequacy verified and documented in response to the identified findings. 1B Manual, Procedure 4.23, Corrective Action Program, identifies the requirements of the corrective action.

B5.3 Quality Control Statistical Analysis

Calibration checks for radionuclide and chemical analyte measurement techniques are performed on a routine interval, from daily to weekly depending on the method. The results of the calibration checks are used to ensure measurement accuracy. The data from the calibration checks are compiled and are available for end users.


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If statistics are applied other than those listed in Table A7-1, then the calculations are documented in the Data Verification Checklist. The Data Verification Checklist will be provided as Attachment 3 to a future QAPP update.

B6 Instrument/Equipment Testing, Inspection, and Maintenance

Analytical measurements at SRNL are performed on instruments that are managed according to the 1Q Manual, Procedure 2-7, QA Program Requirements for Analytical Measurement Systems or Procedure 12-1, Control of Measuring and Test Equipment. Typically, the more complex instruments are covered by Procedure 2-7 as analytical Measurement Systems and Equipment (MS&E) while balances, thermocouples, and temperature controllers are covered by Procedure 12-1 as Measuring and Test Equipment (M&TE).

B6.1 Identification of Field and Laboratory Equipment

Field equipment used for waste tank residuals sampling consists of the robotic crawler and associated sample cups and sampling basket. If appropriate, push-core, or scrapers attached to poles, may be used. The types of sampling equipment that are typically used are described in Section 4.1.3 of the LWTRSAPP.

Except for the vendor-provided crawler platform, all sampling equipment is fabricated as needed by SRR Tank Farm Maintenance. The crawler platform is modified by SRR Tank Farm Maintenance to accommodate cameras, lights, and robotic sampling arm requirements for use in the waste tanks. All sampling equipment is checked before it is inserted into the waste tank being sampled.

All analytical instruments are properly maintained, inspected, and cleaned. SRNL SMEs may perform routine maintenance and adjustments as needed to ensure reliable analytical results. Alternatively, a service contract from a vendor may be in place to regularly service instrumentation. An instrument history log or file is maintained by the SME for analytical instrumentation. Detailed information on instrument maintenance is documented in accordance with the instrument Technical Reference Procedure. The instrument manufacturer’s manuals are also typically kept available as in-laboratory references. Instrumentation subject to maintenance is presented in Table B6-1.


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Table B6-1: Laboratory Instrument Maintenance

Instrument Type of Maintenance Frequency Parts

Needed/Location Person

Responsible

Laboratory Balance

Various

Annual calibration with daily mass check of proper operation

Weight sets obtained from SRNL M&TE

SME

ICP-ES See ADS-1573 As needed- minimally once per month

Torch, nebulizer, spray chamber, tubing

SME or maintenance call

ICP-MS See ADS-1543 As needed- minimally once per month

Torch, nebulizer, spray chamber, tubing, cones


Ion Chromatograph

Various As needed based on daily QC results

Columns, tubing, suppressors


AA Various As needed based on daily QC results

Torch, nebulizer, lamps, tubing


Gamma Counters NaI Gamma


Spare electronics, Spare Dewars

SME, may send to vendor for repair or maintenance call

LSC

Various (i.e., preventive maintenance cleaning, troubleshooting, etc.)

As needed, minimally twice per year

Vendor; as part of maintenance contract

Maintenance contract

Traveler Alpha/Beta Proportional Counter


If needed, ordered from vendor


Alpha PHA Chambers

Various As needed based on QC and background results

Pumps, spare electronics, spare detectors


B6.2 Identification of Equipment Testing Criteria

Field sampling equipment is fabricated as needed by SRR Tank Farm Maintenance. The equipment is also tested by SRNL for compatibility and manageability using the remote handling equipment in the SCO facility. If necessary, the design is adjusted to accommodate SRNL SCO facility limitations.

The laboratory instrument MPCs are listed in Table A7-1. Failure to meet the MPCs for blank or QC sample analysis may require an evaluation of the instrument by the SME. Laboratory instruments or equipment that have generated data that is suspect are tagged, segregated, or otherwise controlled to prevent use until repaired and recalibrated, if required. The SME is


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responsible for evaluating the validity of any sample results and a course of action for instrument repair or servicing.

B6.3 Availability and Location of Equipment Spare Parts

Field sampling equipment is fabricated as needed by SRR Tank Farm Maintenance.

Spare parts, equipment, and consumable laboratory materials are obtained through the SRNL procurement system according to 1Q Manual, Procedure 7-2Q, Control of Purchased Items and Services. When feasible, spare parts and equipment redundancy are maintained to minimize lost productivity in the event of equipment problems.

B6.4 Procedures for Inspecting Equipment Prior to Use

See Section B7.1.

B6.5 Responsibility for Testing, Inspection and Maintenance

Field sampling equipment is tested and inspected by SRR Engineering and TFO before use in a waste tank. Due to the difficulty of decontamination, most equipment is for single use, and is properly disposed of, after that use. The high radiation fields in a waste tank slowly degrade the robotic crawler’s optical and electrical systems. Due to the high crawler cost, and if judged to still be serviceable, crawlers may be decontaminated and reused.

All laboratory analytical instruments are properly maintained, inspected, and cleaned. As shown on Table B6-1, SRNL SMEs may perform routine maintenance and adjustments to instruments as needed to ensure reliable analytical results. Alternately, a service contract from a vendor may be in place to regularly service instrumentation. An instrument history log or file is maintained by the SME for analytical instrumentation.

B6.6 Equipment Deficiency Corrective Action

All field sampling equipment is inspected and tested prior to use. Any defective part or system on the crawler is repaired and retested before insertion into a waste tank for sampling.

At SRNL, noncompliances include any equipment behavior outside of specified limits. Any noncompliant issues are reviewed and evaluated for significance with the SRNL PM, and if necessary, the CQF, and resolved by the SME. The SME is responsible for evaluating the validity of any sample results and a course of action for instrument repair or servicing. When appropriate and feasible, reanalysis may be performed, as determined by the SME.

B7 Instrument Calibration and Frequency

B7.1 Instruments, Equipment and Tools to be Calibrated and Frequency

Field radiation monitoring equipment requires routine calibration. RadCon personnel will be responsible for determining and using the correct radiation monitoring equipment and performing and documenting the required tests and calibrations. All work will be conducted, and documented in accordance with the 5Q Manual, Radiological Control Manual, requirements.

Table B7-1 identifies the laboratory instrument calibration criteria.


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Table B7-1: Laboratory Instrument Calibration Criteria

Instrument Calibration Procedure

Frequency of Calibration

Acceptance Criteria CA Person

Responsible

Laboratory Balance

Daily check with standard weights

Annually <10% deviation from standard weight

Various SME

ICP-ES ADS-1573 Daily <10% deviation from known value of standard

Various SME

ICP-MS ADS-1543 Daily <20% deviation from known value of standard

Various SME

AA ADS-1557 Daily <20% deviation from known value of standard

Various SME

Ion Chromatograph

ADS-2310 Weekly <10% deviation from known value of standard

Various SME

HPGe Gamma ADS-2420

Efficiency verified yearly

Energy, efficiency, and FWHM undergo daily check

Background obtained monthly

Energy: 0.5keV (warning); 1.0keV (action)

Efficiency: Statistical analysis during set-up, 2σ (warning); 3σ (action) [Determination of σ is detector specific, see procedure for various approaches]

FWHM: Statistical analysis during set-up. 2σ [standard deviation/mean] (warning); 3σ (action)

Various (decay correct, electronics adjustment, etc.)

Corrective actions are documented in instrument history files and log books

SME

Gamma Detective

ADS-2462

Daily verification of energy calibration and FWHM

Energy: 1.5keV (warning); 2.0keV (action)

FWHM: Statistical analysis during set-up to obtain mean. Difference between daily check and mean is used. 2keV(warning), 3keV (action)

Various (decay correct, electronics adjustment, etc.)

Corrective actions are documented in history files and log books

SME


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Table B7-1: Laboratory Instrument Calibration Criteria (Continued)

Instrument Calibration Procedure

Frequency of Calibration

Acceptance Criteria CA Person

Responsible

LSC ADS-2424

Baselines established at set-up or during maintenance from vendor. Efficiencies (C-14 and tritium) and background are verified each day prior to use.

If daily efficiency check differs from baseline mean by >3%, an action notice will be issued.

If background differs from mean by >4 standard deviations, an action notice will be issued.

Various (wipe vials, wipe chamber, contact vendor for maintenance, etc.).

Corrective actions are documented in instrument history files and log books.

SME or vendor

Traveler Alpha/Beta Proportional Counter

ADS-2405

Alpha and beta efficiencies are calibrated at set-up or during maintenance (as needed). Efficiencies are verified each day prior to use.

Mean and standard deviation of efficiencies determined during set-up or post maintenance.

Difference between mean and daily check is determined. (2 standard deviation difference is warning, 3 standard deviation difference is action)

Various (adjust gas flow, clean standard, decay correct standard, etc.).

Corrective actions are documented in instrument history files and log books.

SME or vendor

Alpha PHA Chambers

ADS-2402

Energy calibrated during set-up.

Mean and standard deviation of efficiency determined during set-up.

Energy and efficiency verified each week prior to use. Background obtained monthly.

Energy: 0.1keV

Efficiency: Difference between mean and check value determined and compared to standard deviation from set-up; the control limit is at 3 standard deviations

Various (change foil in chamber, change detector, change electronics, etc.)

Corrective actions are documented in instrument history files and log books

SME

Note: FWHM Full Width at Half Maximum


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All laboratory equipment and instrumentation is maintained in accordance with Technical Reference Procedures and the appropriate 1Q Manual procedure to ensure proper operation. Traceability is ensured by calibration with a national or international standard. As appropriate, instrumentation is checked with reference materials from varying lots or manufacturers on a batch basis.

As specified in 1Q Manual, Procedure 2-7, SRNL MS&E instrumentation is managed by a Measurement Control Program (MCP), which encompassed the procedures and activities used to ensure that the measurement process generated measurements of sufficient quality for their intended use. For each system, a documented MCP is established and implemented for determining, maintaining, and assuring the accuracy and precision of measurements involving MS&E. The SMEs are responsible for evaluating and documenting MS&E requirements via procedures and a Measurement Control Plan to ensure that a systematic approach is utilized and that the appropriate degree of control and/or verification is accomplished based upon the complexity of the system and the consequences of failure.

SRNL calibrates and verifies analytical instrumentation by analyzing NIST-traceable standards, when available, containing known concentrations of target analytes. The calibration procedures and frequencies are described in the Technical Reference Procedures.

All SRNL instruments undergo an initial calibration process prior to the analysis of samples. The frequency of the initial calibration process varies, but the initial calibration is repeated when instrument configuration or maintenance impacts detection capability or instrument response or when a corrective action is needed to resolve a QC failure. For example, the ICP-ES and ICP-MS are calibrated daily prior to sample analysis while the efficiency calibration for gamma spectrometers are verified on an annual basis. All chemical analysis and radioanalytical instruments are calibrated per the specified frequency.

Subsequent to the initial calibration but prior to analysis of samples on a specific workday, SRNL instruments are checked with a calibration check standard for all chemical analysis and radioanalytical instruments, except alpha spectrometers are checked to verify calibration on a weekly basis. If commercially available and economically feasible, the initial calibration check standard is prepared from a lot that is different from that used to prepare the calibration standards. All instruments, except the alpha spectrometers, are checked with an initial calibration verification prior to analysis of samples; the alpha spectrometers are checked on a weekly basis.

For the chemical analysis instruments, including the ICP-ES and ICP-MS, the instruments are checked after sample analysis has commenced for a specific workday with a continuing calibration verification standard or independent calibration standard. The SME determines at what point in the batch sequence the continuing calibration blank and standard is analyzed.

M&TE is used for acceptance, calibration, measurement, gauging, testing, and/or inspection. SRNL M&TE is calibrated by the Savannah River Standards Laboratory (SRSL), which maintains ISO 17025 accreditation for numerous calibration methods. M&TE is calibrated at prescribed intervals and is labeled with an equipment identification number and the expiration date for the calibration.


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SRNL balances are calibrated annually by SRSL. At the time the calibration certificate is issued, the balance is labeled with its M&TE identification number, date of calibration, date of next calibration due, and identification of the metrologist performing the calibration.

American Society for Testing and Materials Class 1 weights are used for calibration verification before use on each working day the balance will be in operation. Weights are calibrated either annually, or, in the case of weights used in radiological containment units or the shielded cells, assigned a three year expiration date, at which time the weights are discarded. At the time of calibration, the weight set is labeled with its M&TE identification number, date of calibration, date of next calibration due, and identification of the metrologist performing the calibration. The results of before-use balance checks are recorded either in a laboratory notebook or electronically.

Pipettes may be managed as M&TE or MS&E at the discretion of the SME. M&TE electronic pipettes are calibrated every six months, using purchased pipette calibration software. M&TE pipettes are verified with an accuracy check by weight on each working day the pipette is used. Tolerance limits for accuracy checks are standardized for commonly used verification volumes.

MS&E electronic pipettes are determined by the SME to demonstrate sufficient control within the measurement system. These pipettes are verified by the instrument recovery of the QC standards prepared with the pipette. Thermocouples and temperature controllers are calibrated by SRSL at a frequency determined by the SME against a NIST-traceable standard.

B7.2 Calibration Performance and Documentation

An instrument history log or file is maintained by the SME for analytical instrumentation. Detailed information on instrument maintenance is documented per the Technical Reference Procedure.

B7.3 Deficiency Resolution and Documentation

Deficiencies and resolution are described in B6.6.

B8 Inspection/Acceptance Requirements for Supplies and Consumables

Reference materials, such as vendor-supplied elemental standards (e.g., Cr, Fe, Hg, etc.) and radiochemical standards (e.g., Pu-236, Sr-90, etc.) used in SRNL are uniquely identified and of sufficient accuracy to meet the TTR requirements of the customer, SRR, and the requirements of 1Q Manual, Procedure 2-7. Suppliers are prequalified for procurement, and materials are inspected upon receipt to verify material traceability.

Reference materials are procured from external suppliers and are traceable to a national or international standard. Purchased reference materials require a Certificate of Analysis from the manufacturer, if available. For some radioanalytical methods, radionuclide reference materials are not available.

In the case of radioactive sources used in calibration, an allowance is made for the correction of the assigned value due to the half-life of the source.

Standards from reference materials are prepared and analyzed with customer samples to calibrate or verify control of the measurement system and analytical instrumentation. Reference material


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working solutions are prepared from stock solutions, all of which are maintained within their expiration dates.

The integrity of reference materials is ensured by separation from incompatible materials and/or minimizing exposure to degrading environments or materials. Reference materials are stored in accordance with manufacturer’s recommendations and separately from samples. They are labeled with expiration dates, where applicable. The containers are also labeled with unique identifiers that are traceable to the preparation documentation.

Standard preparation records will be maintained in analytical notebooks with indicated traceability to purchased stocks or neat compounds, reference to the method of preparation, date of preparation, expiration date, and preparer initials.

B8.1 Identification of Critical Supplies and Consumables

The sample crawler requires substantial lead-time for purchasing from an outside vendor. Other sampling equipment is fabricated onsite on an as needed basis. The SRNL procurement system and ordering routines relies on timely input from the staff to meet laboratory supply needs. The key consumables and acceptance criteria are shown in Table B8-1.

Table B8-1: List of Key Consumables and Acceptance Criteria

Item Vendor Acceptance Criteria

Handling/Storage Conditions

Responsibility for Inspection

Versatrak 450™ TTC sample crawler

Inuktun Services Ltd.

Proper operation of modified crawler is verified before deployment in waste tank

The crawler should be maintained in Class B or higher storage

SRR Engineering

Laboratory supplies and consumables

Various Specified by procurement contract

As required by laboratory AOPs User

B8.2 Responsibility for Critical Supply and Consumables Acquisition

The SRR Engineering PM is responsible for purchasing any vendor-supplied equipment and coordinating on-site equipment modification and fabrication as needed with TFO. All equipment is inspected and tested before insertion into a waste tank.

All SRNL supplies are obtained using the Procurement and Materials Management Department (PMMD) Material Acquisition Center (MAC). The MAC controls the acquisition, order verification, temporary storage, staging, and delivery of commercially available items and services.

B9 Data Acquisition Requirements (Non-Direct Measurement)

Non-direct measurement data that is used to support the waste tank residuals characterization includes historical information on waste tank contents and the residual material volume determination and uncertainty estimate.


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B9.1 Identification of Data Sources

Historical data from the WCS, that tracks individual waste tank receipts and removals, was used to develop the waste tank inventories for the FTF/HTF PA modeling. The WCS gives a general accounting of the radionuclide and chemical inventory for a waste tank, at the time the system is updated. This data is used to develop the analyte list for waste tank-specific characterization.

After the agreement to temporarily cease waste removal has been reached, a residual material distribution and volume mapping effort is performed by an experienced team of SRR Engineering and C&WDA engineers. The height (thickness) of residual material is estimated for waste tank floor areas and input into a Microsoft Excel spreadsheet that calculates the volume for that area. At the end of the mapping, the total volume is calculated. As part of the final volume determination, an uncertainty estimate is also developed for the volume as described in the Tank Mapping Methodology document. [SRR-LWE-2010-00240] The uncertainty in the volume estimate is incorporated into the composite sample creation as described in Appendix A of the LWTRSAPP. [SRR-CWDA-2011-00050]

B9.2 Intended Use of Information and Selection Rationale

The general radionuclide and chemical inventory for a waste tank from the WCS is used to develop the analyte list for waste tank-specific characterizations. This allows the analyte list to be tailored for the expected residual material constituents based on the waste tank usage history.

The residuals mapping and volume determination is necessary to implement the sampling plan, described in Section 4 of the LWTRSAPP, in order to representatively characterize the residual waste tank materials. The final volume determination and uncertainty estimate are used to determine the analytical sample compositing instructions as described in Appendix A of the LWTRSAPP. [SRR-CWDA-2011-00050]

The analyte measurements, residual volume determination, and uncertainty estimate are the key inputs used to establish the actual individual waste tank inventory. That individual waste tank inventory is then compared to the inventory used in the respective waste tank farm PA by way of an SA. The SA uses the actual inventory for demonstration of compliance with the project performance objectives.

B9.3 Data Acceptance Criteria

The chemical and radionuclide data from the WCS are used only to develop the waste tank-specific analyte lists. The concentrations in the WCS are not specific enough to be used for final material characterization.

The preliminary residual volume estimate is subsequently reviewed by the SRR Engineering and C&WDA mapping team engineers. Using additional photographic evidence collected with the crawler camera during waste tank sampling, residual material areas are re-evaluated until all parties are in agreement on the final volume, and a final volume determination report is issued. As part of the review process, the uncertainty associated with the mapping process is estimated. The process is described in the Tank Mapping Methodology report. [SRR-LWE-2010-00240] The uncertainty in the volume estimate is incorporated into the composite sample creation as described in Appendix A of the LWTRSAPP. [SRR-CWDA-2011-00050]


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B9.4 Identification of Key Resources/Support Facilities Needed

Key resources for sampling the waste tank residuals include:

Trained personnel from SRR Engineering and C&WDA for residual material mapping and volume estimation, and designing the sampling plan

Personnel from TFO to construct, procure, and/or modify sampling equipment to collect the residual material for analysis

Personnel from TFO to operate the specialized sampling equipment (i.e., crawler) for material collection, transfer the samples from the waste tank to the 8-ton cask, and transport the cask to the SCO

Trained personnel from RadCon for screening materials and personnel involved with sample collection, transfer, and transport

The SCO facility where the 8-ton cask is received and opened, and staff that open the actual sample containers to initially process the sample material

Trained laboratory staff that perform the chemical and radiological analyses and verify the analytical data

Data quality assessors to evaluate the usability of the data for project decisions

B10 Data Management

None of the data collected or generated is for informational purposes. All of the data is necessary to determine the final waste tank residuals inventory.

B10.1 Describe Data Management Scheme

The data management scheme for waste tanks sampling and analysis is shown in Figure B10-1. The preliminary residual volume estimate is used as the basis to design the sampling plan and generate the TTR, TSAP, and subsequently the TTQAP. The samples are collected and locations documented. Sample transport to, and receipt at the laboratory, is tracked using SRS transportation records and a COC. The final residuals volume and uncertainty estimate is used to generate the compositing instructions for the samples. If the laboratory data review and verification determines that the data did not meet the acceptance criteria, the client will be contacted and a data validation may be performed to investigate the cause. In some cases, the laboratory may not be able to meet a requested detection limit, and the client will document the acceptance of that data. In the case of other acceptance criteria failures, a reanalysis using additional experimental process development may be necessary. When all data issues have been resolved, and the data verified, the laboratory will issue a Sample Analysis Report.


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Figure B10-1: Data Management Scheme for Waste Tank Residual Sampling and Analysis


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Laboratory records documenting the sample preparation and analyses will be stored and maintained per the requirements of 1B Manual Procedure 3.31, Records Management. Laboratory records are stored and retained as described in Section A9.4.

SRR Engineering and C&WDA will review the sample results. C&WDA will perform a DQA to determine the data usability. If the data is determined to be unusable, a reanalysis may be requested or other alternatives to resolve the issue will be explored. When all data issues have been resolved, C&WDA will use the data in decision documents.

QA records will be processed in accordance with 1Q Manual, Procedure 17-1, Quality Assurance Records Management.

B10.2 Standard Record-Keeping Practices and Document Control System

Appropriate records are processed into the EDWS. The field and laboratory records that document the waste tank residuals sampling are presented in Figure D1-1.

SRNL maintains written and electronic documentation needed to support analytical results by several means. This documentation includes laboratory notebooks and logbooks, R&D directions, sample submission forms, instrument data sheets, and control charts. Analytical and sample preparation methods used for each sample are documented. All analytical results reported to SRR are stored electronically in the AD LIMS system, which is backed up regularly. Written records generated are legible and made with indelible ink. Records are stored and retained as described in Section A9.4.

B10.3 Data Handling Equipment/Procedures

SRR uses a Lotus Notes-based system to store electronic copies of documents in the LWO Document Library. Records are scanned and input into the system and linked using standardized menu-based classification criteria for archiving and searching. Certain record types are also electronically transferred to the EDWS system for storage and retention. EDWS is a custom application built on the Documentum Platform and is used to manage records for SRS. It is maintained by Information Technology Services according to the 12B1 Manual, Information Technologies Policies, Procedures, Standards, and Guidelines, which requires the routine preventative and regular maintenance on the component of an information system. EDWS is a Class C application available 24/7 and is mirrored to another site server to ensure backup in a disaster recovery scenario. Prior to the final transfer of records into EDWS, the classification and other indexing criteria are validated.

SRNL utilizes two electronic databases to manage the information associated with samples. The first is a customized Filemaker Pro Sample Management database designed to allow customers to generate a travel copy, which provides a variety of parameters including sample identification, the requested analytical methods, sample hazards, turnaround time requirements, and initial weight and final volume of any digested samples. The database tracks the location of the sample at all times within AD lab modules and documents how and when the sample residue is disposed.

The second database is an Oracle Structured Query Language (SQL) LIMS system which has features commonly found in other laboratory LIMS systems. Via an electronic link with the Sample Management database, the LIMS is able to capture relevant customer information about the sample without data re-entry. The LIMS is the official repository for the measurements on


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the individual aliquots for each of the analytical methods. The LIMS contains a cross reference to the laboratory notebook that contains the R&D directions used to prepare samples for a method. For radiochemical and chemical analyses, a packet containing the R&D directions, preparation sheets, instrument printouts, spreadsheet identification, and traceability to all instruments utilized for the analysis (e.g., pipettes, balances, counting instruments) is prepared to support the Sample Analysis Report, data verification, data validation, and DQA.

The LIMS software in use has been developed in accordance with ISO 9001 quality system guidelines. Each LIMS user is required to sign on with a unique username and password. The AD organization appoints a LIMS Manager who is responsible for the management of the LIMS software. The LIMS Manager also executes appropriate updates and revisions to the LIMS software in accordance with AD procedures and maintains a service contract with the software vendor.

AD sample results are entered into the LIMS system either manually or using an automated results entry program. As each result is entered, an automated routine sends an electronic message to forward the data to the identified customer. Any subsequent change to a LIMS result generates an audit trail entry, documenting the reason for the change.

Analytical calculations are performed using spreadsheets which are governed by ADS-WI00023, Spreadsheet Quality Control for Analytical Development Section. Spreadsheets used repeatedly containing calculations that do not change are created and assigned a revision number. The calculation cells are protected (locked) or results are verified by an alternate calculation. The spreadsheet is validated using test data or hand calculations performed by a CTF familiar with the subject matter to ensure the correct result is obtained when the spreadsheet is used. The spreadsheet validation is documented in writing. Any changes to the spreadsheet are performed by the CTF or a designee and documented by the CTF or a designee.

Single-use spreadsheets are often utilized because of the varying types of calculations required with many of the analytical methods. Single-use spreadsheets are controlled as follows.

The CTF reviews and verifies all calculations, and signs and dates the printed spreadsheet containing the calculations

The spreadsheet, and the calculations, are then peer reviewed by a SME who signs and dates the printed spreadsheet

Reference data may be used to verify correct spreadsheet operation and output and to check for transcription and transformation errors

Data outputs to the Sample Analysis Report are reviewed and verified as described in Section A9.2.

B10.4 Responsibility for Data Management

Data management consists of compiling and controlling the data generated during the waste tank residuals sampling and analysis effort. All data is reviewed by the responsible SRR Engineering or SRNL PL for completeness and accuracy before use, distribution, or storage.

Records are managed using the processes in accordance with existing SRS/SRR site-wide requirements as described in 1B Manual, Procedure 3.31, Records Management. QA records are


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processed in accordance with 1Q Manual, Procedure 17-1, Quality Assurance Records Management. Preparation and processing of any controlled documents required is in accordance with 1B Manual, Procedure 3.32, Document Control. Additional details are presented in Section D.

B10.5 Process for Data Archival and Retrieval

C&WDA receives the SRR Engineering and SRNL Record Inventory document. The C&WDA Records Custodian scans and enters the inventories into the LWO Document Library and forwards the originals to the SRS EDWS.

SRNL is responsible for compiling and storing the laboratory analytical records and documentation associated with the sample analysis per SRS requirements and their records control procedures. The Records Inventory will either provide the necessary report numbers or listing of logbook locations to recover analytical information, if needed.

B10.6 Hardware and Software Configuration Acceptability

SRS maintains the EDWS system described in Section B10.3 in accordance with the requirements of DOE Order 200.1A, Information Management Program, and DOE Order 243.1A, Records Management Program.

In addition to EDWS, SRR uses the LWO Document Library to store and access records necessary to support the waste tank removals from service. The LWO Document Library is a Lotus Notes-based system and records are input as electronic files. Records required by contract for long-term storage are automatically forwarded to the EDWS.

SRNL utilizes a LIMS designed to store data about customer samples and the tests performed on them. The LIMS software in use has been developed in accordance with ISO 9001 quality system guidelines. Each LIMS user is required to sign on with a unique username and password. The AD organization appoints a LIMS Manager who maintains responsibility for the management of the LIMS software. The LIMS Manager also executes appropriate updates and revisions to the LIMS software in accordance with AD procedures and maintains a service contract with the software vendor.

LIMS data may be output in a variety of customer reports utilizing various query options. The LIMS data is stored on a secure server and is regularly backed up on electronic storage media.

AD sample results are entered into the LIMS either manually or using an automated results entry program. As each result is entered into LIMS, an automated routine spawned an electronic message to forward the data to the identified customer. Any subsequent change to a LIMS result generated an audit trail entry, documenting the reason for the change.

B10.7 Data Management Checklists and Forms

The basic records generated to support the waste tank residuals sampling are identified in Figure D1-1 and Tables D1-1 through D1-3. These records checklists are being developed for the content and compilation of these documents for subsequent filing and will be provided as Attachment 4 in a future QAPP update.


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SECTION C ASSESSMENT AND OVERSIGHT

C1 Assessment and Response Actions

Table C1-1 lists the types of assessment activities conducted and the approximate frequency. The table also identifies the individual(s) or organizations responsible for conducting assessments, other possible participants in the assessment process, describes how and to whom assessment information will be reported, and identifies the authority ultimately responsible for the implementation of corrective actions. The assessments are all independent assessments - conducted by organizations/personnel that are not directly responsible for performance of the work.

Issues identified during assessment and oversight activities are identified, documented, and managed to resolution according to the SRS Corrective Action (CA) Program, 1B Manual, Procedure 4.23, Corrective Action Program, using the Site Tracking, Analysis, and Reporting (STAR) database. Verification of corrective actions to prevent recurrence is performed by SRR QA. The CA Program (American Society of Mechanical Engineers [ASME] NQA-1 compliant) manages issues in a tailored manner based on the significance of the issue and includes the following elements:

Issue identification Significance determination Issue evaluation CA development CA closure verification CA effectiveness review

If the situation so warrants, a “Stop Work” may be issued by QA. The situation is investigated by the appropriate organization and resolved using 1B Manual, Procedure 4.23 before the stop work is closed by QA and work is allowed to resume.


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Table C1-1: Liquid Waste Tank Residuals Sampling Program Planned Project Audits and Assessments

Assessment Type

Frequency Organization Individual Receiving

Assessment Report and Notification of Deficiencies

Timeframe of Notification

Person(s) Responsible for Implementing CA

CA Documented

Field Sampling TSA (Internal - Independent)

Next waste tank following LWTRS-QAPP implementation then, every other year

SRR QA

Waste Removal & Tank Closure Director,

C&WDA Manager, SRR Engineering PM, SRR QA Manager

Audit Report - Nominal 15 days after completion of TSA

SRR Engineering Manager

STAR system

On-Site Analytical TSA (Internal - Independent)


SRNL QA


C&WDA Manager, SRR Engineering Manager, SRNL Laboratory Manager, SRR QA Manager, SRNL QA Manager

Audit Report - Nominal 15 days after completion of TSA

C&WDA Manager, Laboratory Manager

STAR system

Data Review (Internal - Independent)


SRR QA


C&WDA Manager, SRR Engineering Manager, SRNL Laboratory Manager, SRR QA Manager, SRNL QA Manager

Assessment Report - Nominal 15 days after completion of assessment

C&WDA Manager, Laboratory Manager

STAR system

Management System Review (Internal - Independent)

Initial assessment approximately 6 months after second waste tank sampled in accordance with the LWTRS-QAPP. Thereafter, approximately every 3 years, possibly as part of an SRR Facility Evaluation Board assessment program

Director, SRR Contractor Assurance

SRR President and CEO, Waste Removal & Tank

Closure Director, SRNL Laboratory Manager, ESH&QA Manager, SRNL QA Department

Manager

Assessment Report - Nominal 30 days after completion of assessment


Laboratory Manager STAR system

Note: ESH&QA Environment, Safety, Health and Quality Assurance TSA Technical System Audit


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Types of Assessments and Audits

Following QAPP implementation, the types and frequencies of assessments and audits specified in Table C1-1 will be performed and continue throughout the duration of the waste tank residuals sampling program.

Readiness Review

A Readiness Review is not applicable to the waste tank residuals sampling as it does not represent startup or continued use of a facility, process, or activity, and it is not an initial startup or recovery/return to service project. Waste tank sampling and sample analysis are not new activities for the SRS. Periodic assessments of specific tasks for LWTRS will be addressed in other assessment types.

Field Sampling Technical System Audit (TSA)

A TSA of the field activities will be performed to assess conformance with the LWTRSAPP and LWTRS-QAPP for field activities related to waste tank residual mapping and volume determination, sample location determination, sample collection and handling through shipment to the SCO facility.

On-Site Analytical TSA

A TSA of SRNL analytical procedures will be performed during which M&TE, personnel qualification and training, analytical methods and procedures, general laboratory procedures, sample handling and tracking, data reporting, data handling and management, data control, and data review procedures will be checked for conformance with the LWTRS-QAPP.

Off-Site Laboratory TSA

Not applicable to LWTRS. No off-site laboratory support will be used due to the high activity and unique nature of the waste tank residual samples. If off-site laboratory capability becomes possible, a TSA will be conducted to check for conformance with the LWTRS-QAPP.

Split Sampling and Analysis Audit

Not applicable to LWTRS. Due to the high activity and unique nature of the waste tank residuals samples, it is not possible to send split samples to an off-site laboratory for independent analysis. If off-site laboratory capability becomes possible, a split sampling and analysis audit may be conducted.

Performance Test Sample Tracking and Analysis

Not applicable to LWTRS. There is no performance evaluation program for the unique high-activity waste solids matrix found in SRS waste tanks. Performance test sample analyses routinely performed by SRNL for participation in other programs are described in Section B5.2.

Data Review

An assessment will be performed of the data review process, including a review of the sampling analysis verification, sampling and analysis validation, and data quality (usability) assessment steps, to ensure that the process conforms to the procedures specified in the LWTRS-QAPP and is effective.


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Management System Reviews

Management system reviews are performed in accordance with the SRS 1B Manual, Management Requirements and Procedures, to ensure the effectiveness of the structure, plans, and procedures related to quality.

C2 Reports to Management

The results of the assessments and audits identified in Table C1-1 are documented by the organization performing the assessment. Assessment report copies that include description of any identified deficiency are distributed as identified in Table C1-1. The organization performing the assessment will initiate a STAR item in accordance with 1B Manual, Procedure 4.23, Corrective Action Program, as described in C1.

Detailed integrated schedules are maintained on residual waste sampling and analysis and related activities to remove waste tanks from service. Schedules are reviewed weekly with SRR and SRNS management. The status updates include, but are not limited to:

Schedule performance Results for previous activities Planned activities Problems Status of any corrective actions


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SECTION D DATA VERIFICATION AND USABILITY

The data verification and usability determinations take place after data collection and generation are completed to substantiate that the data are known and of sufficient quality to support waste tank removal from service decisions. Data are considered known when all components associated with the generation are thoroughly documented, and such documentation is verifiable and defensible.

D1 Data Review and Verification

Sample Collection Data and Records

Roles and responsibilities for document generation, reviews, and approvals are described in Section 2.4 of the LWTRSAPP. As shown on Figure D1-1, there are numerous entities involved with the review of each document and the underlying data supporting the various documents.

Data and associated records generated during the residuals sampling are reviewed by the sampling team PIC and by the SRR Engineering PL for completeness and accuracy. The SRR Engineering PL is responsible for compiling the appropriate field records and verifying calculations related to the residual volume determination. Data and associated records related to sample collection that are reviewed and verified by SRR Engineering are listed in Table D1-1. Any comments or discrepancies identified during the internal or external organizational reviews are resolved before the reports are finalized.

The C&WDA PL coordinates the reviews and comment resolution for the C&WDA generated documents shown on Figure D1-1. Data and associated records that are reviewed and verified by C&WDA are listed in Table D1-2.

Analytical Data

The analytical data generated by SRNL is 100% verified through internal processes to assess and document the data quality and to identify any anomalies. Because all analytical data is essential, the laboratory often implements extreme measures to perform the analyses to the requested MPCs. Due to the difficulty in obtaining samples, it is not expected that any samples will be rejected. However, sample analysis issues will be discussed in the case narrative rather than flagged. The data verification is not started until the analyses are completed to the extent of practicality. Anomalous data is identified and the need for an in-depth validation is evaluated by the SRNL, SRR Engineering, and C&WDA PLs. The data quality assessor is notified of the anomalies and resolution. All analytical data will be included and evaluated in the DQA.


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Figure D1-1: Roles and Responsibilities for Waste Tank Characterization Implementing Procedure/Activity/Document


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Table D1-1: Data and Associated Records Verified by SRR Engineering

Record Information Verified Supporting Information

Preliminary Residuals Volume Estimate Report

Maps produced and calculations of estimated volume

Photographs and videos, spreadsheet for volume estimation

TTR The analyte list and the final sample locations, sample compositing instructions

Earlier TTR revisions, justification and documentation for revisions

Sample Location Determination Report

That the initial selection criteria is explained and documented. Methodology in LWTRSAPP is followed or departure explained.

The preliminary residual material distribution and volume

TSAP

The final sample locations, sample identifications, (sample depth if necessary), approximate volumes needed, and sample analyte lists.

Earlier TSAPs, justification and documentation for revisions

Sampling Work Package Completeness of work package and sign-offs, COC and transport records.

TTR and TSAP to generate work package

TTQAP That the analytes, MPC, and QA/QC measures requested for the sample analyses have been provided

TTR, earlier TTQAPs, justification and documentation for revisions

Final Residuals Volume Determination and Uncertainty Estimate Report

Final maps produced and calculations of final volume and estimated uncertainty

Photographs and videos, spreadsheet for volume estimation


That the correction action has been resolved and documented

Documentation (reports) of occurrences requiring corrective action


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Table D1-2: Data and Associated Records Verified by C&WDA


TSAP

The final sample locations, sample identifications (sample depth if necessary), approximate volumes needed, and sample analyte lists.

Earlier TSAPs, justification and documentation for revisions

TTQAP That the analytes, MPC, and QA/QC measures requested for the sample analyses have been provided.

TTR, earlier TTQAPs, justification and documentation for revisions

Analytical Sample Compositing Instructions

Final residual material volume determination and uncertainty estimate, calculation of the compositing amounts for sample creation.

This is an attachment to the TTR

Sample Analysis Report

Analyses, uncertainties, recoveries, as appropriate, are reported. Case narrative and data verification checklists are complete and adequate for the DQA.

Requirements in the LWTRS-QAPP, TTR, and TTQAP




Table D1-3: Data and Associated Records Verified by SRNL


TTQAP The analyte list, MPC, and QA/QC measures for the sample analyses and report contents are specified.

LWTRS-QAPP, TTR

Sample Analysis Report

Analytical results and uncertainties for sample analyses. QC sample analytical results. Blank, spike and control sample results. Trip blanks, if applicable1. Compositing instructions. Case narrative. Data verification checklists.

TTQAP, TTR, Analytical Record Package

Analytical Record Package

Analysis records, checklists with associated logbooks, preparation logs, QC sample information, calibration records, instrument records, and notes on analytical problems.

TTQAP, TTR




Note: 1 A trip blank will be used if VOC sampling is conducted.


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Data and associated records that are reviewed and verified by SRNL are listed in Table D1-3. SRNL verifies 100% of the analytical results through internal reviews to ensure completeness, correctness, and conformance/compliance of each data set against the method or procedural specifications. The analytical data are verified by evaluating the conformance of the specific data set with the DQIs, MPCs, and other criteria listed in Section A7. A statistician from the Applied Computational Engineering and Statistics section of SRNL performs a simple statistical analysis on the data to calculate the sample mean and standard deviations of the composite sample concentrations and the 95% upper confidence limit for the true mean concentrations when there are measurements above the detection limits. Tests for heterogeneity of the measurement variances are also performed if there are enough measurements above the MDCs or MDAs.

The analytical data are entered into data reduction software by a qualified laboratory professional who reviews batch QC samples for acceptable results. The data are then verified for completeness and correctness by an independent qualified laboratory professional prior to reporting to the SRNL PL. Any anomalies, QC problems, or other analytical issues that could affect data quality are noted and discussed in the case narrative section of the Sample Analysis Report.

The SRNL PL examines the reported data to ensure that all the required analytes are present and were analyzed according to the requirements of the LWTRS-QAPP. QC data are examined for completeness and adherence to the DQI and MPC. This review also evaluates any necessary corrective actions that were taken when the analysis QC did not meet the LWTRS-QAPP or method requirements. The laboratory is responsible for ensuring that the QC requirements have been met and will document in the Sample Analysis Report that the data verification was performed. After exhausting all analytical approaches, any analytical data failing to meet the requirements of the LWTRS-QAPP will also be discussed in the Sample Analysis Report case narrative. The SRNL PL coordinates and reviews the final documentation and reports associated with sample characterization.

The analytical data verification checklists and case narrative including a discussion of any anomalies or QC problems occurring during the analyses, is sent to the data quality assessor. Depending on the nature of the impact of any discrepancies identified, an evaluation may be conducted by the involved parties to determine if reanalysis, resampling, or some other course of action is required. A validation of anomalous data going back to the raw data may also be performed by an independent reviewer to identify the source of the problem. The verification decision and/or validation finding is appropriately documented and evaluated as part of the DQA.

Records management is described in Section A9.4 and is conducted in accordance with 1B Manual, Procedure 3.31, Records Management.

The data verification checklists will specify and document the elements and requirements reviewed during the data verification steps by each organization to ensure consistency for the life of the project. These checklists will be provided as Attachment 3 in a future LWTRS-QAPP update.


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D2 Data Validation and Verification Methods

The process for data verification is described in Section D1. The process for data validation is described below.

D2.1 Process for Data Validation

For the Liquid Waste Tanks Residuals Sampling Program, data validation will be performed on every tenth waste tank for a limited suite of radionuclides and chemicals similar to the validation performed for the Tanks 18 and 19 Data Quality Summary Report. [SRR-CWDA-2011-00150] The choice of analytes to be validated will be determined at the time of validation but will include at least four radionuclides from the HRR list and one metal as was done for the Tanks 18 and 19 validation. Validation may also be performed if any anomalies are discovered during the data verification or DQA steps. Validation will be performed by an independent evaluator using the data validation procedures and checklists developed as part of the LWTRS-QAPP implementation. For data validation “independent evaluator” is defined as a person not directly involved in the data generation (both laboratory analysis or data verification steps), the DQA, or data usability evaluation steps.

When data validation is performed following QAPP implementation, it will use data validation procedures similar to those used by the DOE at the Hanford DOE Site for similar waste tank residual material samples. The validation will use data validation checklists specifically developed for the waste tank residuals sampling program. These procedures and checklists are currently under development and will be provided as Attachment 5 in a future LWTRS-QAPP update.

The data validation will include a check on:

Completeness of the data Proper sample collection documentation and transport procedures, including COC Documentation of sample material compositing and preparation for analyses Documentation of the required QC measures during analyses Documentation of all analytical results and verification Traceability of the analytical data generated in the Sample Analysis Report to specific

waste tank sample locations

If any apparent data anomalies or departures from the LWTRS-QAPP requirements are identified during the data verification process, they may be validated by an independent evaluator. The validator may require investigation down to the level of raw analytical data, material receipt records, and field records, as necessary, to resolve the issue. The subsequent data validation report documenting the findings will be distributed to the organizations involved and to the data quality assessor.

D2.2 Responsibilities for Verifying and Validating Project Data

Data verification is the responsibility of the organizations involved with the residuals characterization as described in Section D1.

The laboratory data validation will be performed by an independent evaluator not involved with data generation, DQA, or usability evaluation; possibly by a contracted independent third party.


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The results will be reviewed by laboratory and project personnel. The validator will be identified in the DQA.

Final verification of the entire project data assemblage, including laboratory data, is the responsibility of the C&WDA CPC.

D2.3 Identify Issue Resolution Process

Any problems, errors, or omissions discovered during the data verification by the organization involved will be transmitted verbally or by e-mail to the respective PM, and if impactive of the data, to the data quality assessor. The respective PL will be responsible for taking appropriate actions to resolve the issue such as requiring a data validation or implementing a CA.

Any problems discovered during the data validation will be transmitted verbally or by e-mail by the validator to the SRR Engineering and SRNL PLs and to the data quality assessor. Additional information or clarification will be requested to resolve the issue. The final validation report will be sent to the SRR Engineering and SRNL PLs, and the data quality assessor. Preliminary results may also be transmitted by email or by phone in advance of the final validation report. The data qualifiers used will be based on those used in the EPA functional guidelines for data validation.

D2.4 Identify Checklists, Forms and Calculations

The basic records necessary to document residuals sampling and analysis are presented in Figure D1-1. The data verification checklists will be provided as Attachment 3 in a future LWTRS-QAPP update. Records checklists to support the data verifications shown in Tables D1-1 through D1-3 are under development and will be provided as Attachment 4 in a future LWTRS-QAPP update. Data validation procedures and validation checklists are under development and will be provided as Attachment 5 in a future LWTRS-QAPP update.

D3 Reconciliation with User Requirements

D3.1 Procedures to Evaluate the Usability of the Data

The respective PLs shall ensure that the data collected address the requirements to characterize the waste tank residual materials. This includes the data verification and validation. The DQA is part of this evaluation. The DQA documents problems and corrective action throughout the waste tank-specific residuals sampling and discusses results that appear to be anomalous and the impact on the usability of the data. Because of the nature of the project, all data is expected to be of the same quality and will be used. Any unexpected or additional uncertainties will be accounted for in the final data use.

For anomalies or conflicting data generated during the field sampling or laboratory analyses, the appropriate records are checked, and the record generator is contacted to resolve the issue. If resolution cannot be reached, the affected parties and the data quality assessor consult to determine the extent of the impact and the appropriate course of action. The issue is documented in the appropriate field record and evaluated in the DQA.

The laboratory results are reviewed before data are verified to determine whether all samples and analyses have been performed as required. If an analytical result does not meet all user requirements specified in the TTR and LWTRS-QAPP, the result is investigated as far as


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necessary to determine where the problem arose. The analytical results are reported only after the investigation is complete and all verification criteria not met are explained in the Sample Analysis Report.

The DQA (usability report) assesses the suitability of the data to meet the project DQOs described in Section A7 and to meet the MPCs specified in Table A7-1. Elements evaluated during the DQA are shown in Table D3-1.

Table D3-1: Items and Activities Evaluated During the Data Quality Assessment

Item/Activity Evaluation Criteria

Data Deliverables Check compliance with the TTR for deliverables

Data Departures How did any analytical deviations (i.e., not reaching MDCs, not being able to quantify an analyte) impact the usability of the data? Did the data meet the MPCs?

Sampling Locations Were all the necessary samples collected? Were there any adjustments or departures from the planned locations and how did they affect the characterization? How well did the sampling design perform?

Insufficient Sample Mass Recovery

Was sufficient material recovered from all sample locations to meet compositing and sample analysis requirements? If not, what is the impact on the analytical results and residual characterization?

Representativeness Did the composite samples represent the residual material to allow estimates of the concentrations?

Completeness What is the impact of any missing samples, analytes, or analyses?

Comparability Ensure that the data collection for the residual volume determination and uncertainty estimate are acceptable.

Critical Samples Were the critical analytes defined in the TSAP and TTQAP provided?

Holding Times N/A

QC Samples Did any QC samples fail the acceptance criteria and what is the impact on the affected analytical results?

Data Validation If performed, what do the data validation results indicate regarding data defensibility?

Visual Data Inspection Inspection of the plotted data for inconsistencies.

Statistical Evaluations

The overall uncertainty will be evaluated by testing for homogeneity between the composite samples. The data set will be examined for outliers and their impacts on the statistics. The underlying statistical assumptions will be tested.

Data Restrictions Describe how data that does not meet the MPCs will be handled.

Usability Decision Discuss how data may or may not be sufficient for use in the decision-making process (i.e., inventory determination).

Usability Summary Discuss and compare overall precision, accuracy/bias, representativeness, comparability, and completeness. Describe the limitations on the project data use if the DQIs are not met.


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To evaluate uncertainty, the considerations in the DQA focus on:

Anomalies in the sample collection, transport, and preparation steps that may influence the material properties and increase the sampling error and the results from validation attempting to resolve anomalies.

The individual composite sample analysis measurements will be used to determine the statistics, mainly averages, for the composite samples.

The total uncertainty will be used for calculating the confidence limits on the statistics calculated for the composite samples. As the uncertainty increases, so will the confidence limits.

The measurement uncertainties will be evaluated against each composite sample’s variation to determine if this variation totally accounts for the measurement uncertainty. The variation between the multiple measurements of an individual composite sample is expected to vary more than the analytical uncertainty. In this case, no adjustment would be needed. In the case where the analytical uncertainty is greater than the variation between the multiple measurements of an individual composite sample, a greater variability would need to be reflected in the total uncertainty, and ultimately reflected in the confidence limits.

An additional evaluation of the uncertainty would be a review for outliers in the data. The influence of any outliers on a data set would need to be considered before using the data.

D3.2 Limitations on Data Use

Data usability for residuals characterization is evaluated and documented during the DQA as described above. It is anticipated that all data will be used, and the uncertainties arising from sampling or analytical problems will be taken into account for the final waste tank inventory determination, which is outside the scope of this LWTRS-QAPP.


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REFERENCES

Note: References identified as (Copyright) were used in the development of this document, but are protected by copyright laws. No part of those publications may be reproduced in any form or by any means, including photocopying or electronic transmittal in any form by any means, without permission in writing from the copyright owner.

1B Manual, Management Requirements and Procedures, Savannah River Site, Aiken, SC, December 15, 2011 (Table of Contents).

1B Manual, Procedure 3.31, Management Requirements and Procedures (MRP), Records Management, Savannah River Site, Aiken, SC, Rev 9, October 26, 2011.

1B Manual, Procedure 3.32, Management Requirements and Procedures (MRP), Document Control, Savannah River Site, Aiken, SC, Rev 7, July 30, 2003.

1B Manual, Procedure 4.23, Corrective Action Program, Savannah River Site, Aiken, SC, Rev 6, January 3, 2011.

1Q Manual, Procedure 12-1, Control of Measuring and Test Equipment, Savannah River Site, Aiken, SC, Rev. 16, October 14, 2011.

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1Q Manual, Procedure 2-7, QA Program Requirements for Analytical Measurement Systems, Savannah River Site, Aiken, SC, Rev. 8, December 17, 2008.

1Q Manual, Procedure 7-2, Control of Purchased Items and Services [NQA-1 2008/2009a], Savannah River Site, Aiken, SC, Rev. 20, October 14, 2011.

1Q Manual, Quality Assurance Manual, Savannah River Site, Aiken, SC, December 15, 2011 (Table of Contents).

4B Manual, Training and Qualification Program Manual, Savannah River Site, Aiken, SC, February 2, 2011 (Table of Contents).

5Q Manual, Radiological Control Manual, Savannah River Site, Aiken, SC, January 1, 2010 (Table of Contents).

12B1 Manual, Information Technology Policies, Procedures, Standards, and Guidelines (U), Savannah River Site, Aiken, SC, May 6, 2011.

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ASME NQA-1 (Copyright), Quality Assurance Requirements for Nuclear Facility Applications, The American Society of Mechanical Engineers, New York, NY, March 14, 2008.


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DHEC_01-17-2012, Quality Assurance Program Plan, Revision A and the Liquid Waste Tank Residuals Sampling and Analysis Program Plan, Revision 0A, South Carolina Department of Health and Environmental Control, Columbia, SC, January 17, 2012.

DHEC_QAPP_Guide_09-2008, Guidance Document for Preparing Quality Assurance Project Plans (QAPPs) for Environmental Monitoring Projects/Studies, South Carolina Department of Health and Environmental Control, Office of Quality Assurance, State Park, SC, Rev. 1.1, September 2008.

DOE G 435.1-1, Implementation Guide for use with DOE M 435.1-1, U.S. Department of Energy, Washington DC, July 9, 1999.

DOE O 200.1A, Information Management Program, U.S. Department of Energy, Washington DC, December 23, 2008.

DOE O 243.1A, Records Management Program, U.S. Department of Energy, Washington DC, February 3, 2006.

E7 Manual, Procedure 2.60, Technical Reviews, Savannah River Site, Aiken, SC, Rev. 13, March 1, 2010.

E7 Manual, Procedure 3.60, Technical Reports, Savannah River Site, Aiken, SC, Rev. 4, July 1, 2004.

EPA 402-B-04-001C, Multi-Agency Radiological Laboratory Analytical Protocols Manual (Final) Volume III: Chapter 18-20 and Appendix G, U.S. Environmental Protection Agency, Washington DC, July 2004, http://www.epa.gov/radiation/marlap/manual.html#voliii Accessed February 6, 2012.

EPA/240/B-06/001, Guidance on Systematic Planning Using the Data Quality Objectives Process, U.S. Environmental Protection Agency, February 2006.

L1 Manual, Procedure 7.26, Conduct of Research & Development (R&D) - Work Control Document, Savannah River National Laboratory, Aiken, SC, Rev. 1, November 10, 2009.

L7.7 Manual, Procedure 1.15, SRNL Receipt of Radioactive Material, Savannah River National Laboratory, Aiken, SC, Rev. 8, March 17, 2011.

LWO-RIP-2009-00009, Industrial Wastewater General Closure Plan for F-Area Waste Tank Systems, Industrial Wastewater Construction Permit #17,424-IW, Savannah River Site, Aiken, SC, Rev. 3, January 24, 2011.

SRNL-STI-2011-00323, Technical Review of the Method of Constructing Composite Samples with Uncertain Volumetric Proportions, Savannah River Site, Aiken, SC, Rev. 0, May 2011.

SRNL-STI-2011-00557, SRNL Quality Assurance & Quality Control Summary for Tanks 18 and 19 Liquid Waste Tank Residuals Samples (LWTRS), Savannah River Site, Aiken SC, Rev 0, September 26, 2011.

SRR-CWDA-2010-00128, Performance Assessment for the H-Area Tank Farm at the Savannah River Site, Savannah River Site, Aiken, SC, Rev. 0, March 2011.


Page 96 of 96

SRR-CWDA-2011-00050, Liquid Waste Tank Residuals Sampling and Analysis Program Plan, Savannah River Site, Aiken, SC, Rev. 1, January 2012.

SRR-CWDA-2011-00150, Savannah River Site F-Area Tank Farm Tanks 18 and 19 Data Quality Summary Report, Savannah River Site, Aiken, SC, Rev 1, February 2012.

SRR-LWE-2010-00240, Tank Mapping Methodology, Savannah River Site, Aiken, SC, Rev 0, October 2010.

SRR-LWP-2009-00001, Liquid Waste System Plan, Savannah River Site, Aiken, SC, Rev. 16, December 2010.

SRS-REG-2007-00002, Performance Assessment for the F-Tank Farm at the Savannah River Site, Savannah River Site, Aiken, SC, Rev. 1, March 31, 2010.

SW11.1-SAMPLE, Section 7.2, CST Sample Manual, Savannah River Site, Aiken, SC, Rev 13, September 27, 2011 (Table of Contents)

WSRC-IM-2002-00011, Savannah River National Laboratory Technical Report Design Check Guidelines, Savannah River Site, Aiken, SC, Rev. 2, August 2004.

WSRC-OS-94-42, Federal Facility Agreement for the Savannah River Site, Savannah River Site, Aiken, SC, August 16, 1991.


Page A.1-1 of A.1-1

Attachment 1: Liquid Waste Tank Residuals Sampling: Chain-of-Custody Form

To Be Determined


Page A.2-1 of A.2-1

Attachment 2: Analytical Operating Procedures and Summary of Analytical Methods Used for Residuals Sample Analyses

Provided Electronically (See Attached CD)


Analytical Operating Procedures

Analytical Development SectionAnalytical Operating Procedures

Manual: L16.1Procedure: ADS-1543

Volume 2 Revision: 5Inductively Coupled Plasma – Mass Spectrometer Elemental and Isotopic Analysis for Aqueous Liquid SamplesPlasmaquad II RADICPMSMajor Revision

Effective Date: 06/29/11Type-Category: Technical Page: 1 of 29

Electronic Approval on File:

Author/Task Supervisor: __________________________L. C. Johnson

Peer Reviewer: __________________________M. A. Jones

ADS Spectroscopy & SeparationsGroup Manager __________________________

C. M. Gregory

ADS Procedure Coordinator __________________________M. S. Hanks

Procedure: ADS-1543Inductively Coupled Plasma – Mass Spectrometer Elemental and Isotopic Analysis for Aqueous Liquid SamplesPlasmaquad II RADICPMSMajor Revision

Revision: 5Page: 2 of 29

1.0 INTRODUCTION

1.1 Purpose

The purpose of this procedure is to provide a basic operating format for the Rad Plasma Quad II Inductively Coupled Plasma Mass Spectrometer (ICPMS). The instrument is used to analyze liquid samples for support of site processes as well as research and development efforts being performed to support these processes.

1.2 Scope

This procedure describes the minimum requirements for the use of the ICPMS for the quantitative analysis of elements or isotopes in aqueous solutions at low concentrations (µg/L to low mg/L), or for the semi-quantitative measurement of inorganic elements and isotopes in aqueous solutions. There are different modes of operation, such as scan, peak jump, and isotope ratio.

The Task Supervisor reviews the requested analysis to determine if it is suitable for the instrument. Problems such as the matrix interference, high concentrations of interfering elements and oxide interference may require the sample be directed to other analytical techniques.

The solution to be analyzed must be in the form of an aqueous liquid with few or no insoluble particles present. Dissolved elements will be determined in heterogeneous samples, once they are filtered and acidified, except in the case of analyses for iodide which are performed in an alkaline matrix. Upon request,total elements can be determined after appropriate digestion procedures are performed.

Organic samples may be analyzed under certain conditions, with the direction of the task supervisor or technical personnel. The matrix for iodide analyses is a 5% proprietary tertiary amine reducing solution and its use for these analyses is outlined below.



2.0 GENERAL INFORMATION

2.1 Definitions and Abbreviations

1. Scan - This mode of operation collects data for a complete spectrum containing information for all the isotopes within the mass range selected. Data is collected for large number of points (20 per peak), so that the peak shape is defined for each isotope and the area under the peak is integrated.

2. Peak Jump -

3.

In this mode, the mass spectrometer is used to collect data for isotopes of interest. This mode often used when analyses are being performed on a few analytes in low concentrations.

Quantitative

4.

- A set of external calibration standards containing the analytes of interest are used for calibration. The standards cover the range of concentrations expected in the sample.

Semi-Quantitative

5.

- A plot of mass against sensitivity yields a relatively smooth curve, this response could be used to calibrate the instrument to provide semi quantitative data.

Qualitative-

3.0 PRECAUTIONS AND LIMITATIONS

Collect data over the complete mass range and visually examine the spectra for the presence or absence of analytes.

3.1 Safety

1. The plasma source emits strong ultraviolet (UV) radiation, which can cause permanent eye damage. Do not look directly at the source unless it is viewed through UV absorbing material. Although the UV shield is interlocked to prevent its removal during plasma operation,

2. Concentrated nitric acid is an extremely corrosive and toxic chemical that must be handled with care. The acid irritates all parts of the respiratory tract and is corrosive to the skin and other tissues, especially the eyes.

do not remove the UV shield if the plasma is on. Ensure the instrument is in the Vacuum Ready state and power down the RF generator with the Power On/Off switch on the front of the RF generator if the UV shield is to be removed and hands-on work is to be performed in the torch box.

Dilutions of concentrated acids (>3molar) whether samples or pure acid shall be performed in a hood with the sash pulled below chin level while wearing safety glasses with side shields and a lab coat. If the hood sash cannot be lowered or used for face protection goggles and a face shield



shall be worn. Due to a portion of the torso being exposed even with the hood sash lowered a lab apron shall also be worn over a lab coat.

3. High voltages are associated with the radio frequency (RF) generators, controllers, and the posterior, enclosed portion of the torch box.

4. Troubleshooting and/or hands-on work inside the front portion of the torch box shall not be performed under any circumstances while the RF generator is powered up. (See Section 5.11, Torch Box Maintenance/Adjustment/Alignment, below).

Electrical work on these parts shall not be performed while they are powered up, except by vendor’s service representative or a qualified electrical worker who understands the schematics, circuitry, and electrical hazards of the instrument. If only mechanical work is being performed on any of these parts be they shall be powered down and disconnected, where possible, so as to avoid any contact with RF and/or electrical energy.

5. A lab coat, safety glasses with side shields, and chemical gloves shall be worn when handling open containers of samples and/or chemicals.

6. The proprietary tertiary amine reducing solution concentrate, CFA-C thatis used for iodide analyses is corrosive and toxic and the preparation/dilution of this material for subsequent use in analyses is to beperformed in a hood as prescribed in Section 3.1, No. 2, above.

4.0 PREREQUISITES

4.1 Description of Method

The Inductively Coupled Plasma Mass Spectrometer (ICPMS) provides multi-element analyses of aqueous solutions based on the measurement of atomic species from their ions created in the plasma. Liquid samples are nebulized and the aerosol transported to argon plasma. In the high temperature plasma (~10,000 K) metallic species are ionized. The ions generated by the plasma enter the mass spectrometer through a sampling cone set near the end of the plasma. The ions are separated by a quadrapole mass filter and focused on a detector. The detector in this instrument is a channeltron. It can provide ion count or an analog signal. These ions are detected by an electron multiplier. The signal from the detector is amplified, measured, and stored in a multi-channel analyzer. These measurements are used to calibrate the instrument, perform sample analyses, and display spectra.



4.2 Quality Control

1. Instrument Calibration

A. Mass Calibration

B.

- The instrument is mass calibrated on a regular basis. Mass and detector cross calibrations are performed using a multi-element standard that contains lithium and uranium, the two elements necessary to perform the mass calibration properly. Refer to the ThermoElectron software manual regarding mass and detector cross calibrations.

Analytical Calibration for Concentration Measurements

2. Measurement Control Program

-For elemental quantification the instrument is calibrated for each analyte of interest by preparing and analyzing a series of standards containing known concentrations of the analyte(s) of interest. Semi-quantitative and qualitative analyses can also be performed when deemed adequate by all parties involved.

The rad ICPMS is a part of a measurement control system as defined by Manual 1Q, Procedure 2-7. The rad ICPMS measurement control program is designed to provide a method to monitor the performance of the ICPMS measurement system, and it provides a graded to approach to establish the quality of the data appropriate to the task requirements. These requirements are negotiated between Analytical Development Section and the customer. The requirements are subsequently documented in task plans.



A. For routine quantitative analyses a blank and calibration standards are analyzed prior to a set of samples.

B. QC or check standards are analyzed after the initial calibration and after a set of samples, as specified by the task supervisor. These standards are prepared from standards from a lot different from the calibration standards, or they are prepared from standards procured from another manufacturer. Check standards are used to verify the calibration; hence their concentration should fall within the range of the calibration standards. The results of the analysis of the check standard shall be within the limits set by the task supervisor.

C. Pipets used to measure samples and standards are part of the Measurement Systems and Equipment (MS&E) program.

4.3 ManufacturerICP Mass Spectrometer, (ICP-MS)Model Number: PlasmaQuad II, PQS-995Fisons System Number 20259Location - 773A B067Thermo Electron5225 Verona RdMadison, WI 53711608-276-6373800-642-6538



4.4 Reagents

1. Argon Gas (Ar) – Ultra High purity >

2.

99.99%

Nitric Acid (HNO3)

3.

- Used for the preparation of standards and for sample processing must be ultra-high purity grade or equivalent.

CFA-C Reducing Solution

4.

– Proprietary tertiary amine reducing solution that is diluted to a concentration of 5% vol/vol and subsequently used for the preparation of standards and the dilution of samples for iodide analyses. The concentrate is purchased from Spectrosol in Warwick, NY. Phone no. 845-987-1300.

De-ionized water

5.

- Prepared by passing water through a mixed bed of cation and anion exchange resins. This ultra-pure water must be used for the preparation of dilute acids used to make calibration and check standards as well as diluting samples.

Stability Check Solution

6.

- A multi-element solution used daily to determine the stability of the instrument.

Calibration Standard Stock Solutions

7.

- The standard stock solutions are purchased or prepared form ultrahigh purity grade chemicals. All standards should be NIST traceable, or in compliance with QAP 2-7. For the quantitative analysis of an individual element, the instrument will be calibrated for the analyte, by preparing a standard curve for that analyte. For the quantitative analysis of multi-elements standards can be prepared either from a multi-element stock standard or by combining stock standards of the individual analytes of interest.

Internal standard

8.

- An analyte, not present in samples or standards, that is put in standards and samples in a known concentration in order to account for signal or enhancements that may be caused by sample matrices and/or instrument variability.

Check Standard

9.

- An independent standard defined as a standard with the same analytes as the standard used for calibrating the instrument, but from a different source or lot.

Blank solution

5.0 PROCEDURE

- The acid matrix used for the calibration standard with the selected concentration of internal standard.

5.1 Instrument Set-up



1. Turn the chiller on and ensure the temperature is set at 6oC.

2. Turn the argon on at the outlet side of the regulator.

3. Turn on the instrument computer.

4. Check the auto-sampler to make sure it is on.

5. Make sure the instrument effluent and sampler tip rinse tubes are in the instrument effluent bottle.

5.2 Turning the Instrument on Automatically

1. Once the computer has booted up and the system operating software has been initialized, press the Instrument button (See Figure 1 below).

Figure 1 – Initial Screen



2. Press the Control tab.

Figure 2 –Start up Screen (with Instrument in Operate Mode)

3. Press the Standby button (see Figure 2 above) and acknowledge the window asking if the instrument is to be placed into the Standby mode. (During this stage of start-up the gases will be automatically turned on, the torch ignited, and the expansion chamber evacuated.) If the torch does not ignite properly the first time it is recommended that the instrument be returned to the Vacuum state and the process of placing it into the Standby mode repeated. If the Standby mode is not achieved a second time it is recommended that the manual process be used to place the instrument into the Standby mode be used.

4. Once the Standby mode has been achieved, as signified by the button turning green, press the Operating button (See Figure 2 above) andacknowledge the window asking if the instrument is to be placed into the Operating mode. (During this stage of start-up the slide valve to the quadrapole is opened and the detector is started.)

5. Once the torch is ignited and the slide valve is opened and operating properly allow a minimum of thirty minutes, preferably 60 minutes, for the instrument to warm up.



5.3 Turning the Instrument on Manually

1. With the instrument in the Vacuum mode, press the Aux. and Cool gas button (see Figure 2 above) and allow the gases to come on.

2. Press the Nebulizer gas button (see Figure 2 above) and allow the system to go through start-up and purge.

3. Press the Nebulizer gas button again to turn the nebulizer gas off and allow the system to go through the process of turning off the gas to the nebulizer.

4. Once the nebulizer pressure has reached zero, press the RF button (see Figure 2 above) to ignite the torch.

5. Once the torch ignites press the Expansion pump button (see Figure 2 above) to start the vacuum pump.

6. Press the Nebulizer gas button and allow the nebulizer gas to achieve its proper setting.

7. The system is now in the Standby mode, as signified by the Standby button being green.

8. Press the Operate button (see Figure 2 above) to open the slide valve and turn on the multiplier.

9. The system is now in the Operate mode and should be allowed at least thirty minutes (sixty minutes are preferable) for warm-up.

5.4 Tuning Ion Lenses to Optimize Sensitivity

1. Once the instrument has been allowed sufficient time to warm up, place the sample uptake tube into a stability check solution which contains the element indium, which is used to “tune” the instrument.

2. Press the Technician button and then press the Real-Time Display tab (See figure 3 below).



Figure 3 – Technician and Real-Time Display

3. Press the Start button (See Figure 3 above) and check the list of elements to ensure mass 114.9 is selected. (Other elements may be selected by entering the desired mass into the mass column and enabling its display by right clicking the mouse, selecting Column Visibility, and Enable, then checking the Enable and View boxes.

4. Maximize the signal using the following sequence:

A. Adjust each of the Aux, Cool, and Neb gas flow controls until a maximum signal is achieved.

B. Adjust the voltages on the lens stack by adjusting the following lens stack controls: L1, L2, L3, L4, Extraction Lens, Collector, and Pole



Bias until the maximum signal and a stability that averages 2% or less, approximately.

5. If tuning difficulties are encountered, consult the operating manuals for the instrument for more details. (These manuals are located in the laboratory).

5.5 Stability Check

1. Press the Experiment button (See Figure 3 above).

2. Select: Open an existing experiment (See Figure 4 below).

Figure 4 – Experiment Selection Window

3. A window containing experiments will appear. Select from the list of experiments select either PJ Stab Check or Stab Check on Auto, depending on whether the analyses to be run are to be run in the peak jumping or scanning mode.

4. Press the Sample List tab (See Figure 5 below).



Figure 5 – Experiment Set-up Tabs

5. Enter the date into the Label cell and check the Report Block and select the respective row (See Figure 6 below).

Figure 6 – Sample List



6. Press the Queue button and acknowledge the windows that appear.

7. Once the experiment begins, press the Results tab, select the Numerical tab, and when the spreadsheet appears select the Analyte ICPS tab at the bottom of the sheet. The data will be automatically entered into the spreadsheet for each analyte.

8. Upon completion of the experiment acknowledge the two windows and review the data. The Relative Standard Deviation (RSD) for the analytes should be equal to or less than 5%. If the RSD is greater than 5% for a given analyte the Task Supervisor has the authority to approve the Stability Check or request the Stability Check be re-run and/or the instrument re-tuned prior to re-running the Stability Check.

5.6 Experiment Set Up

There are several means for setting up experiments. They may be developed either by starting from a blank experiment or by using a previous experiment as a template (See Figure 4 above).

1. Blank Experiment

A. Select: Create a new blank experiment.

B. Select the analytes desired by clicking each on the periodic table that appears. In order to select the default isotope simply double click on the analyte in the chart. To select additional isotopes of an analyte click on the analyte and select the desired isotopes when the window containing the various isotopes appear (See Figure 7 below).

Figure 7 – Isotope Selection



C. Once all the analytes/isotopes have been selected press the Internal Standard tab and select the analyte to be used as the internal standard by selecting the analyte of choice and pressing the arrow key to add it as an internal standard. Enter the concentration of the internal standard and select the units from the Tools menu. (See Figure 8 below).

Figure 8 – Internal Standard Selection

(with Indium selected at a concentration of 25 ug/L)

D. Press the Instrument Parameters tab, press the Configurations Editor tab, and select either the Default (Automated with sample changer) or Manual mode by double clicking on the respective cell (See Figure 9 below). If the automated mode is to be used initialize the sample changer by pressing the Initialize button. Once the sample changer has been initialized, press the Go to Rinse Station button.



Figure 9 – Instrument Configurations

E. Press the Timings tab and enter the Uptake time as directed by the Task Supervisor. Also, enter the wash time between samples if directed by the Task Supervisor.

F. Press the Mass Calibration tab and right click the mouse to bring up a drop down menu. Select: Import Mass Calibration. Select themost current Mass Calibration and press the Import button.

G Repeat the process with the Detector Cross Calibration.

H. Press the Calibration Method tab and select the method (Fully Quantitative, Standard Addition, etc.) by clicking on the arrow on the right hand side of the cell (See Figure 10 below).



Figure 10 – Calibration Method

I. Select Blank ICPS from the Blank Subtraction column (See Figure 10 above).

J. Press the Sample List tab and enter the blanks, calibration standards, check standards, and samples and their respective dilutions into the spreadsheet (See Figure 11 below). If the sample changer is to be used, verify the positions of the samples versus the positions on the list.



Figure 11 – Completed Sample List

K. Press the Fully Quantitative Concentrations tab and enter the concentrations for the respective analytes/isotopes (see Figure 12 below).



Figure 12 – Fully Quantitative Concentrations

L. Press the Sample List tab next to the Fully Quantitative Concentrations tab to return to the list of standards and samples.

M. Press the Queue button and acknowledge the two windows that appear to initiate the experiment.

N. Once the analyses of the blank and calibration standards have been completed check the calibrations curve by pressing the Results tab. The calibration curve should be the first window to appear (see Figure 13 below for an example).



Figure 13 – Completed Calibration Curve

O. The sample results, including check standards, should be monitored as the experiment progresses. This is accomplished by pressing the Numerical Results tab and pressing the Analyte Dilution Concentration tab at the bottom of the spreadsheet (See Figure 14 below).



Figure 14 – Analyte Dilution Concentration Results

P. Once the experiment is complete press the Reports tab and select the desired criteria for the report. Normally this is only the Analyte Dilution Concentration. The press Update Report to generate the report (See Figure 15 below).



Figure 15 – Report Generation

Q. Press the Printer tab to print a copy of the report.

5.7 Standard Preparation

Standards are to be prepared from NIST traceable standards. Normally, calibration standards used for analysis are prepared from a 1 mg/L standard that is prepared from a 10, 100 or 1,000 mg/L stock standard. The concentrations of calibration and check standards shall be designated by the task supervisor. Normal standard preparations are as follows:

NOTE: The 1mg/L and 100 ug/L working standards noted below shall be prepared daily.

For routine analyses all standard dilutions are made with 2%vol/vol nitric acid according to the following steps.



1. Prepare a 1mg/L, working calibration standard by pipetting into a clean, dry sample tube pipette 0.1 mL each of 100 mg/L solutions A, B, and C that have been designated for calibration.

2. Pipet 9.70mL 2% vol/vol nitric acid into the bottle containing the volumes dispensed in step 1, above. Cap the tube and thoroughly mix by shaking the tube.

3. Prepare a 100 ug/L, working calibration standard by pipetting 1 mL of thecompleted solution from step 2, above into a clean, dry sample tube.

4. Pipet 9.00mL 2% nitric acid into the tube containing the solution dispensed in step 3, above. Cap the bottle and thoroughly mix by shaking the tube.

5. Prepare a 1 mg/L working check standard by pipetting into a clean, dry sample tube, 0.1 mL each of solutions A, B, and C that have been designated for use as a check standard.

6. Prepare a sufficient volume of 5 mg/L internal standard solution by pipetting the specified volumes of standard into a volumetric flask and diluting to the mark with2% nitric acid.

7. The normal calibration scheme of blank, 1, 10, 25, and 50 ug/L solutions are prepared from the 1 mg/L and 100 ug/L working calibration standards and check standards are prepared from the 1mg/L working check standard according to the following:

a. Blank – Pipet 0.050 mL of the 5mg/L internal standard solution into a clean, dry tube followed by pipetting 9.95 mL 2% nitric acid. Cap and shake to effect mixing.

b. 1 ug/L Calibration Standard – Pipet the following into a clean, dry tube: 0.050 mL of 5 mg/L internal standard, 0.100 mL of 100 ug/L working calibration standard, and 9.85 mL 2% nitric acid. Cap and shake to effect mixing.

c. 10 g/L Calibration Standard – Pipet the following into a clean, dry tube: 0.050 mL of 5 mg/L internal standard, 1.00 mL of 100 ug/L working calibration standard, and 8.95 mL of 2% nitric acid.

d. 25 ug/L Calibration Standard – Pipet the following into a clean, dry tube: 0.050 mL of 5 mg/L internal standard, 0.250 mL of 1 mg/L working calibration standard, and 9.70 mL of 2% nitric acid. Cap and shake to effect mixing.



e. 50 ug/L Calibration Standard – Pipet the following into a clean, dry tube: 0.050 mL of 5 mg/L internal standard, 0.500 mL of 1 mg/L working calibration standard, and 9.45 mL of 2% nitric acid. Cap and shake to effect mixing.

f. 25 ug/L Check Standard – Pipet the following into a clean, dry tube: 0.050mL of 5 mg/L internal standard, 0.250 mL of 1 mg/L working check standard, and 9.70 mL of 2% nitric acid. Cap and shake to effect mixing.

For iodide analyses all standard dilutions are made with 5%vol/vol CFA-CReducing Solution according to the following steps.

1. Prepare a 1 mg/L working calibration standard by pipetting 0.1 mL of the 100 mg/L NIST traceable iodide standard designated for calibration into a clean, dry sample tube followed by pipetting 9.90 mL of 5% CFA-C solution. Cap the tube and mix thoroughly by shaking.

2. Prepare a 100 ug/L working calibration standard by pipetting 1.0 mL of the 1 mg/L working calibration standard, as prepared above, into clean, dry sample tube followed by pipetting 9.00 mL of 5% CFA-C solution. Cap the tube and thoroughly mix by shaking.

3. Prepare a 1 mg/L working check standard by pipetting 0.1 mL of the 100 mg/L NIST traceable iodide standard designated for use as check standard into a clean, dry sample tube followed by pipetting 9.90 mL of 5% CFA-C solution. Cap the tube and mix thoroughly by shaking.

4. The normal calibration scheme of blank, 0.5, 1, 10, and 25 ug/L solutions are prepared from the 1 mg/L and 100 ug/L working calibration standards and check standards are prepared from the 1 mg/L working check standard according to the following:

a. Blank – Pipet 0.050 mL of the 5 mg/L internal standard solution into a clean, dry tube followed by pipetting 9.95 mL 2% nitric acid. Cap and shake to effect mixing.

b. 0.5 ug/L Calibration Standard – Pipet the following into a clean, dry sample tube: 0.050 mL of 5 mg/L internal standard solution, 0.05 mL of the 100 ug/L working calibration standard, and 9.90 mL 5% CFA-Csolution. Cap and shake to effect mixing.

c. ug/L Calibration Standard – Pipet the following into a clean, dry tube: 0.050 mL of 5 mg/L internal standard, 0.100 mL of 100 ug/L working calibration standard, and 9.85 mL 5% CFA-C solution. Cap and shake to effect mixing.



d. 10 g/L Calibration Standard – Pipet the following into a clean, dry tube: 0.050 mL of 5 mg/L internal standard, 1.00 mL of 100 ug/L working calibration standard, and 8.95 mL 5% CFA-C solution. Cap and shake to effect mixing.

e. 25 ug/L Calibration Standard – Pipet the following into a clean, dry tube: 0.050 mL of 5 mg/L internal standard, 0.250 mL of 1 mg/L working calibration standard, and 9.70 mL of 5% CFA-C solution. Cap and shake to effect mixing.

f. 5 g/L Check Standard – Pipet the following into a clean, dry tube: 0.050mL of 5 mg/L internal standard, 0.050 mL of 1 mg/L working check standard, and 9.90 mL of 2% nitric acid. Cap and shake to effect mixing.

5.8 Sample Preparation and Pre-Analysis Scans

1. In order to determine the approximate concentration of the desired analyte(s), make a significant dilution (1,000X – 10,000X) of the sample which includes the desired concentration of internal standard. (using the specified diluent – 2% nitric for routine analyses and 5% CFA-C for iodide analyses).

2. Using a previously prepared scan experiment, scan the sample along with a calibration standard (as designated by the task supervisor). Determine the proper sample dilution to stay within the calibration range (as designated by the task supervisor) by comparing the integrated counts per second of the sample with the integrated counts per second of the calibration standard. (For high salts (>4 molar) a dilution of 1000X, or higher, is preferred due to the suppression of the signal of the analyte and the internal standard caused by the high salts).

3. Based on the results of the scans prepare the proper dilutions such that the concentration of the analyte(s) does not exceed the concentration of the maximum calibration standard, as designated by the task supervisor.



5.9 Calculations

Final results are calculated by the instrument software when the respective dilution factors are entered into the sample list. Using scientific notation where necessary, the results are rounded to two or three significant figures (as directed by the task supervisor).

5.10 Instrument Shutdown

1. Once analyses have been completed, allow the instrument to rinse with DI water for a minimum of 5 minutes by placing the sample probe in a container of DI water or by moving the probe to the rinse station via software commands. After running iodide analyses the system is to be rinsed with 5% CFA-C for a minimum of 15 minutes followed by a minimum rinse of 30 minutes with DI water.

2. Upon completion of the rinse press the Instrument Button, followed by the pressing of the Control tab (see Figure 2).

3. Press the Standby button and acknowledge the subsequent window.

4. Once the Standby mode has been achieved, press the Vacuum ready button and acknowledge the subsequent window.

5. Turn off the chiller and shut off the argon supply at the regulator.

6. Close out the PlasmaLab software and shut down the computer.

5.11 Torch Box Maintenance/Alignment/Adjustment

NOTE: The load coil surrounding the end of the torch carries significant radio frequency (RF) power when the plasma is operating. Prior to any work in which the load coil can be contacted either directly or indirectly, the following precautions shall be taken prior to doing any work in the torch box.

1. Ensure instrument is in Vacuum Ready state as indicated by a green indicator button on the Instrument Control of the instrument software.

2. Power down the RF generator by pressing the white Power On/Off switch. The switch for the RF generator for the torch box is located just below the torch box in the upper right hand portion on the front of the instrument panel. This switch has a cover associated with it that must be lifted in order to use the switch. Allow



thirty minutes for any stored energy to drain before commencing work on anything in the torch box.

3. Remove the UV shield in front of the torch only after verifying that the instrument is in Vacuum Ready and there are NO lights or read-outs visible on the front of the RF panel.

4. Proceed with extreme caution when inserting devices near the load coil. Non-conducting tools are recommended for use in this area, when possible.

5. Once all work has been completed replace the UV shield, power up the RF generator, and re-ignite the plasma via the prescribed routine.

6. Most of the sample handling components in the torch box are glass and should be handled so as to avoid breakage. Do not exert undue pressure on these components, i.e. spray chamber, elbow, torch, and nebulizer, when working with them as they can break exposing someone to injury. Chemical resistant gloves shall be worn in the event any portion of the sample handling system is disassembled in order to the potential for exposure to chemical hazards.

5.12 Routine Instrument Maintenance

1. Cone Replacement

A. Power down RF generator using Power On/Off switch on front of RF generator panel.

. When cones are replaced the following pre-requisites shall be met prior to commencing work:

B. Allow thirty minutes for any stored energy in the RF generator to drain before commencing work.

C. After thirty minutes, unbuckle the torch box and push back and place chock between torch box and front of translation table to hold box in position.



(1) Using the vendor supplied cone tool, remove the outer retainer ring and the outer sampler cone. Carefully remove the graphite gasket so as to avoid scratching the surface where the gasket is mounted. Using the other end of the cone tool remove the inner skimmer cone.

(2) Securely mount a new skimmer cone using the cone tool.

(3) Place a new graphite gasket in position, place the new sampler cone in position and hold in position while securing with the retainer ring. Secure the ring with the cone tool.

(4) Slide the torch box into place and re-buckle.

(5) Replace UV shield.

(6) Turn on power to RF generator and begin normal instrument start-up sequence

2. Oil Change for Vacuum Pumps

A Instrument must be in Vacuum Ready.

B. Remove the front panel covering the vacuum pumps.

C. Don lab coat and chemical gloves (safety glasses are a pre-requisite for entry into lab).

D. Place a shallow pan below the drain plug of the pump.

E. Using an Allen wrench of the proper size remove the oil drain plug at the bottom of the pump.

F. Using the same Allen wrench, loosen the oil filler plug at the top of the pump until oil flows from the drain plug.

G. Once the oil has drained from the pump replace the drain plug making sure it is adequately tightened so as to avoid leaking.

H. If not already removed, remove the oil filler plug, insert a funnel, and slowly add new oil pausing to examine the fill level on the front of the pump. Once the level of new oil has reached ½ - ¾ full replace the filler plug.



I. Thoroughly clean up any spilled oil. Pour the used oil into a polyethylene bottle of sufficient size and label the bottle. (Submit a sample of the oil for rad screen for subsequent disposal in the appointed used oil drum.)

J. Replace the cover panel and lock in place.

K. Resume normal operations of instrument.

NOTE: No other maintenance activities are performed by SRNS employees without an assessment, documentation and mitigation of the hazards via a Job Hazards Analysis with all interested parties involved with the analysis.

6.0 REFERENCES

1. Jarvis, K. E., Gray, A. L., and Houk, R. S., Inductively Coupled Plasma Mass Spectrometry

2. Holland, G., and Eaton, A. N.,

, Blackie & Son LTD, 1992.

Applications of Plasma Source Mass Spectrometry

3. Holland, G., and Eaton, A. N.,

, Thomas Graham House, 1991.

Applications of Plasma Source Mass Spectrometry II

4. TJA Solutions VG PlasmaLab Reference Guide, Issue 1.05, July 2000

, Thomas Graham House, 1993.

5. Job Hazard Analysis for Non-Routine Maintenance on the ICPMS-974,

7.0 RECORDS

Results are sent to the customer via an e-mail report. The experiment, the data work-up spreadsheet, and the report spreadsheet are saved on the designated server in a folder with the customer’s name. The designation of the server with the folder name as well as the person or persons to whom the results were reported are entered into the ADS LIMS.

8.0 ATTACHMENTS

None

SAVANNAH RIVER NATIONAL LABORATORY Manual: L16.1 ANALYTICAL DEVELOPMENT SECTION Procedure: ADS-1554 ADS ANALYTICAL OPERATING PROCEDURES Revision: 7 Page: 1 of 19 TECHNICAL REFERENCE Effective Date: 5/15/2008 Procedure for Operating Varian Approved by: SPECTRAA-880 Atomic Absorption Spectrometer (U) APPROVAL ON FILE AD Manager MAJOR REWRITE 1.0 PURPOSE

This procedure provides instructions for the operator of the Varian SpectrAA-880.

2.0 SCOPE

This method describes the requirements for the use of atomic absorption for the analysis of metals in aqueous solutions at low concentrations (trace levels) (µg/L to mg/L). The samples should be in the form of a liquid with no solid particles present. Routinely, only dissolved metals will be determined in heterogeneous samples, once they have been filtered and acidified.

3.0 PRECAUTIONS/LIMITATIONS

3.1 Safety

NOTE: All SRS, SRNL, and AD safety rules apply.

3.1.1 Material Safety Data Sheets (MSDS) for the reagents associated with this procedure can be accessed electronically through WSRC Shrine Home Page.

3.1.2 Concentrated hydrochloric acid is an extremely corrosive and

toxic chemical that must be handled with great care. The acid will produce burns, ulcerations, scarring on the skin, and mucous membranes (mouth and respiratory tract). Eye contact may result in reduced vision or blindness.

3.1.3 Concentrated nitric acid is an extremely corrosive and toxic

chemical that must be handled with great care. The acid irritates all parts of the respiratory tract and is corrosive to the skin and other tissues, especially the eyes.

3.1.4 Read, understand and comply with the Safety Practices of

Varian SpectrAA-880 section of the operating manual.

SAVANNAH RIVER NATIONAL LABORATORY Manual: L16.1 ANALYTICAL DEVELOPMENT SECTION Procedure: ADS-1554 ADS ANALYTICAL OPERATING PROCEDURES Revision: 7 Page: 2 of 19 TECHNICAL REFERENCE Effective Date: 5/15/2008

3.1.5 Operation of this instrument involves the use of compressed gases, flames, and hazardous materials including corrosive fluids and flammable liquids. Improper or careless use of the instrument can create explosion hazards, fire hazards, or other hazards that can result in serious injury to personnel.

3.1.6 Exhaust system must be operational before work is performed.

Fumes emitted from the flame and the vapor generation apparatus (VGA) can be hazardous to personnel.

3.1.7 The instrument is plumbed to building air, nitrous oxide, and

acetylene compressed gases for flame operation. The acetylene must be atomic absorption grade (99.6%) and substitutes cannot be used. No other gases, e.g. oxygen or oxygen enriched air, shall be used in conjunction with the acetylene because use of this type of oxidant can lead to an explosion. For VGA operation, use only inert gases such as nitrogen or argon.

3.1.8 If gas leaks are suspected, immediately turn off the

instrument and leak check the hoses and gas connections.

3.1.9 Never leave the flame unattended. For flame determinations, always operate the instrument, with the flame shield closed and the sample compartment panel in place.

3.1.10 Use standard plastic residue containers for instrument

residue. Do NOT use glass vessels because they can shatter if a flashback occurs.

3.1.11 Organic solvents with densities less than 0.75 g/mL cannot be

used. Samples with matrices comprised of these types of solvents cannot be analyzed directly; they must be subjected to dissolution. Low density, organic solvents can create flashbacks or explosion hazards. If organic solvents with densities greater than 0.75 g/mL are used the drain tubing for the instrument effluent must be solvent resistant nitrile rubber.

3.1.12 All sample and acid preparations, where the initial or

resulting concentrations are >3 M for acids and >4 M for bases shall be performed in a hood, as noted in the JHA in Attachment C of this procedure.


3.1.13 pH adjustments of analytical residues shall be performed in a fume hood.

4.0 PREREQUSITE ACTIONS

None

5.0 PERFORMANCE

5.1 General Information

5.1.1 Description of Method

In direct aspiration atomic absorption spectroscopy, a sample is aspirated and atomized in a flame. A light beam from a hollow cathode lamp, whose cathode is made of the element to be determined, is directed through the flame into a monochromator, and on to a detector that measures the amount of light absorbed. Absorption depends upon the presence of free unexcited ground state atoms in the flame. Since the wavelength of the light beam is characteristic for only the metal being determined, the light energy absorbed by the atoms in the flame is a measure of the concentration of that metal in the sample. This principle is the basis of atomic absorption spectroscopy.

5.1.2 Data Quality

As a matter of routine, check standards shall be used as a means of verifying the calibration of the instrument as well as validating the data generated from the application of the calibration curve. Check standards shall be prepared from a NIST traceable standard different from the standard used to prepare the calibration standards. (This standard may be from a different manufacturer, or it may be from the same manufacturer of the calibration standard but from a different lot.) The concentration of this standard is normally at the midpoint of the calibration range. For most elements, results from the analysis of a check standard shall not exceed + 5% of the nominal value of the check standard (exception – cesium + 10%). During the course of an analysis a check standard shall be analyzed after every 10 samples or for each set of samples of a similar matrix type, whichever is more frequent. A check


standard shall also be analyzed at the completion of an analytical run. The task supervisor may prescribe other methods such as duplicate samples, replicates, and/or sample spikes for data validation when these techniques are requested as a part of a special analytical plan or if the task supervisor determines that they are needed.

5.1.3 Quality Control

A calibration curve shall be generated with the Varian SpectrAA software for each element analyzed for a given series of samples. The calibration curve shall be generated using a reagent blank, and a minimum of two standards of different but known concentrations. The standard from which the calibration standards are prepared shall be traceable to the National Institute of Standards and Technology (NIST). The calibration shall be verified by a check standard prepared from an independent, NIST traceable standard. (See section 5.1.2)

5.1.3.1 Instrument Calibration – The number and concentration of the calibration standards shall be established by the task supervisor and used for routine analyses unless the task supervisor specifies changes. Calibration standards shall be prepared from a working standard which is a dilution of the NIST traceable, stock (1,000, 100, or 10 mg/L) standard. The task supervisor shall specify the concentration of the working standard. The working standard is normally prepared by pipetting the appropriate volume of the stock standard into a 100 mL volumetric containing several milliliters of deionized distilled water, adding 2 mL concentrated nitric acid, and diluting to volume with deionized distilled water. The standard is then transferred to a new polyethylene or PTFE fluorocarbon container to which is affixed a label containing the name and concentration of the element, date of preparation, and the analyst’s initials. The number (a minimum of two) and the concentration of the calibration standards to be prepared from the working standard for routine analyses are dependent on the element of interest and shall be defined by the task supervisor and outlined in this procedure. Working


standards for cesium, sodium, and potassium are to be prepared as needed, and calibration standards shall be made monthly, at a minimum.

5.1.3.2 Calibration Blank – A blank containing all of the

reagents in volumes comparable to the volumes used in the preparation of the calibration shall be incorporated into the calibration scheme.

5.1.3.3 Method Detection Limits – The task supervisor should

annually determine the detection limits for each of the various elements to be analyzed by Atomic Absorption. The calculated Method Detection Limit (µg/mL) is determined by multiplying the standard deviation of 10 blank measurements (water) by 5 and dividing the product by the slope (mv/µg/mL) of the calibration curve for that analyte. The slope is be determined by measuring in triplicate the intensity (mv) of a 1-10 µg/mL analyte solution. This analyte intensity reading should be corrected for the blank intensity value. Each measurement must be performed as though it were a separate sample. Additional method detection limits for these elements in different matrices may also be determined by direct measurements.

5.1.3.4 Analysis of Duplicate Samples – This technique requires

the analysis of two separate but equal sample aliquots that have been diluted identically. These dilutions are then analyzed within the same calibration regimen. The relative percent differences (RPD) for each component are calculated using the following equation.

RPD = |S - D|(S + D)/2 x 100

where: S = First sample value D = Second sample value (duplicate).

A control limit of ± 20% for RPD shall be used for sample values greater than 5 times the method


detection level (MDL) for the AA Method. RPD is not calculated for concentrations less than 5 times MDL.

5.1.3.5 Analysis of Replicates – Replicate analysis technique

involves multiple analyses of a single aliquot that has been appropriately diluted for analysis. These analyses may be performed under the same or different calibration regimens. The relative percent differences (RPD) for each component are calculated using the following equation.

RPD = |S - R|(S + R)/2 x 100

where: S = First sample value R = Second sample value (replicate). A control limit of ± 20% for RPD shall be used for sample values greater than 5 times the method detection level (MDL) for the AA Method. RPD is not calculated for concentrations less than 5 times MDL.

5.1.3.6 Registered Notebooks - At the direction of the Task

Supervisor, all quality control data, instrument status data, records of preventive maintenance and instrument repair and analyst training will be kept in bound notebooks registered with SRTC Records.

5.1.4 Manufacturer

AA Spectrophotometer Model: SpectrAA-880 Varian Instrument Group 1-800-926-3000

5.1.5 Equipment

SpectrAA-880 Volumetric flasks Pipettes Sample and reagent poly bottles


5.1.6 Reagents

The date should be recorded on the bottles of chemicals, standards, and reagents as they are received to track their age. Prepared standards and reagents should be labeled with the name of the standard, date of preparation, and the analyst's initials. The labeling should also contain the hazards associated with material. Acids used in the preparation of standards and for sample processing must be ultrahigh purity grade or equivalent. Reagent grade acids can be used for cleaning glassware and plastic sample containers. Hydrochloric Acid (12 M HCl) - Concentrated (sp. gr. 1.19) Nitric Acid (15 M HNO3) - Concentrated (sp. gr. 1.41) Deionized Water - Use ultra-pure deionized water for the preparation of all reagents, calibration standards, and as dilution water. This is available from systems such as the Millipore Milli-Q system. Before dispensing Milli-Q water make sure the resistivity reading of the water is 18 Mohms/cm or higher. If the resistivity does not increase to 18 Mohms/cm after 15 minutes of recirculation, replace the ion exchange cartridges. Building deionized water does not meet this specification and shall not be used. Stock Standard Solutions - These may be purchased or prepared from ultrahigh purity grade chemicals or metals. All standard solutions must be NIST traceable.

5.2 Scope and Application

Metals in solution may be readily determined by atomic absorption spectroscopy. The method is simple, rapid, and applicable to a large number of metals in drinking, surface and saline waters, and domestic and industrial wastes. While drinking waters free of particulate matter may be analyzed directly, domestic and industrial wastes require processing to solubilize suspended material. Sludges, sediments and other solid type samples may also be analyzed after proper pretreatment. For more details see references 1-3.


5.3 Operating Procedure The following is an outline of the procedure for operating the Varian

SpectrAA-880. Additional details of the instrument operation can be found in the Varian software and hardware manuals. These manuals are located in the laboratory.

5.3.1 Preliminary Settings on the SpectrAA-880

5.3.1.1 Ensure the working area is clear of all hazardous

materials including corrosive liquids and flammable solvents.

5.3.1.2 Ensure that the instrument chimney is fitted. Ensure

that the collector hood is correctly positioned above the instrument chimney.

5.3.1.3 Ensure that the correct burner is installed. Ensure that

the pressure relief bung is correctly fitted to the spray chamber.

5.3.1.4 Secure the drain tube to the liquid trap outlet and locate

the tube properly in the drain vessel. Fill the trap with deionized water. Make sure the drain vessel is empty.

5.3.1.5 Close the flame shield. Always wear your safety

glasses.

5.4 Instrument Startup Note: This instrument is controlled by “Windows” based software and there are numerous ways to traverse through the menus in order to run a series of analyses. 5.4.1 Turn on the AA system in the following order: Instrument,

computer, monitor, and printer. The AA system and the specific hollow cathode lamp should have a warm-up time of approximately 15-20 minutes.

5.4.2 Allow MS Windows software to completely boot the system. 5.4.3 Once all the desktop icons have appeared on the computer

monitor screen, double click on the SpectrAA icon and wait for the Varian AA instrument software to load.


5.4.4 Customer Worksheet Creation

5.4.4.1 The Varian AA instrument software should be displayed on the computer monitor screen. From this window there are four options to select from: Worksheet, Reports, Administrator, and Exit. Select “Worksheet.” To create a customer worksheet a series of windows and menus will follow.

• Once the “Worksheet” option has been selected the

Load Worksheet window will appear on the screen. There are three options to select from: New, New from, and Open. Select “New from…”

• The next window to appear will be New Worksheet From Worksheet menu. In this window there will be several items to select from, the symbol of various elements (Na, K, Cs, Hg, etc.) and the file names of previous customer runs. From this menu highlight the symbol of the element to be analyzed with the mouse. Click “OK.”

• The Name Worksheet window will appear on the screen next. To create the customer’s worksheet, type in the customer’s name in the name blank using the following format: date (mm-dd-yy), customer’s name (last, first). Next, type in the analyst name in the analyst blank. And finally any comments related to the samples being analyzed can be entered into the comment blank. When finished click “OK.”

5.4.4.2 At this point the Instrument analysis window with the

customer’s worksheet should be displayed on the computer monitor screen. At the top of the screen there are four tabs to select from: Filing, Develop, Labels, and Analysis. Select the “Labels” tab.

• In the Labels window select the appropriate blank

and type in the appropriate information (check standard, reagent blanks, sample ID, etc.) in the order they will be analyzed.

• Once all the information has been entered this will


complete the customer’s worksheet. 5.4.4.3 At the top of the screen select the “Analysis” tab. This

will bring the system back to the instrument analysis window.

5.5 Signal Optimization and Igniting the Flame

5.5.1 Before igniting the flame, the following must be satisfied:

5.5.1.1 Spray chamber pressure relief bung must be in place. 5.5.1.2 Liquid trap must be above the level mark. Looking at

the water level from the outside, the level should be just below the drain outlet. The sensor in the liquid trap will shut down the flame if the liquid level falls below the required level. Also, the sealing gasket must be positioned correctly in the liquid trap. Arrows on the float should be pointing up.

5.5.1.3 The appropriate gases, acetylene, air, and nitrous oxide,

must be pressurized to the spectrophotometer. The gases need to be valved open at the cylinder station and subsequently valved open at the instrument for the following pressures:

Acetylene: 15 (range 7-15 psi) Air: 60 (range 35-65 psi) Nitrous Oxide: 60 (range 35-65 psi)

5.5.2 Check/Install the appropriate burner head, N2O/acetylene or

air/acetylene, for the gases being used for the analyses and optimize its position (described below).

Note: For burner heads, the vertical and horizontal adjustments can be made either through the software or manually. Generally, the optimum height for the burner head for most elements is 5 mm below the optical path, but the optimal position will depend on the analyte (element) of interest. Reasonable optimization of the burner position, for most elements, can be performed using a white card that has a centering symbol, e.g., a cross or circle, positioned at 5 mm from the bottom edge of the card. Place the card mid-length on the burner head with the centering mark over the flame slit and adjust the burner horizontally and vertically so that the light


beam is centered on the white card. Note: The burner head should be cleaned before every use to remove any salts or debris deposited on and in the burner head slit. This can be accomplished by slipping the white alignment card into the slit of the burner head and gently moving the card up and down and back and forth. The burner head should then be gently wiped with a damp tissue followed by gently wiping with a dry tissue to remove any residues. Note: A cleaning wire is to be inserted into the nebulizer opening, and a cleaning wire is to be passed through the capillary tubing that is attached to the nebulizer so as to remove impediments. Note: When finished analyzing samples the SpectrAA should rinse, with flame ignited, for 5-10 minutes to reduce the amount of salt deposit and buildup on and in the burner head slit.

5.5.3 Press the ignite button on the SpectrAA and keep it depressed until the flame ignites. Note: The flame, while aspirating distilled, deionized water or any liquid solution should be allowed to stabilize for at least 5 minutes prior to calibration. This will keep the burner head cool and operating properly. If necessary, or desired, check the uptake using a 10 or 25 mL graduated cylinder. The uptake should be approximately 7 ± 1 mL/min.

5.5.4 Analyte Signal

5.5.4.1 There are several options to choose from on the left side of the instrument analysis window: Select, Optimize, Start, Stop, Read, and Help. Select “Optimize.”

5.5.4.2 Select “Ok” on the Optimize window. The Flame

Optimization window will appear. Select the “Optimize Lamps” option. Wait for the turret to rotate to the hollow cathode lamp corresponding to the element selected for analysis.

5.5.4.3 The lamp should be allowed to warm up for at least 5

minutes to stabilize before calibrating and performing analyses.


5.5.4.4 Once the lamp has stabilized select the “Rescale” option. On the scale to the left in the Optimize Lamps window the green signal bar and the readout below the scale should be between 0.9 and 1.1. If the readout is not within this range, select the “Rescale” option again. If it is still not within the range, contact the Task Supervisor for corrective action.

5.5.4.5 Once the lamp has been optimized select the “Optimize

Signal” and then the “Inst. Zero” option.

5.5.4.6 The instrument is now optimized. Select “Ok” on the Flame Optimization window and “Cancel” on the next window (Optimize) that appears on the screen to return to the instrument analysis window.

5.6 Calibration and Sample Analysis

5.6.1 Select “Start” from the options on the left side of the instrument

analysis window. After selecting Start, there will be a series of interactive windows that will appear on the screen.

5.6.2 Select “Ok” to the Confirm window to prepare for standard Zero.

Once selected the instrument will be zeroed with the distilled, deionized water being aspirated into the system.

5.6.3 From this point forward the software will ask the operator to

present various solutions (cal zero, calibration standards, check standards, reagent blanks and samples) to the instrument.

5.6.4 Place the aspirating tube into the solution the interactive

window is asking for and select “Read.”

5.6.5 The instrument will take three readings and ask for the next solution.

5.6.6 Should it become necessary to repeat an analysis, the following

steps are applicable:

5.6.6.1 Click the “Pause” button. 5.6.6.2 Click the “Stop” button.

5.6.6.3 Highlight the cells associated with the sample/standard


to be re-analyzed.

5.6.6.4 Click the “Read” button.

5.6.6.5 Click the “OK” button and allow the instrument to perform the analysis.

5.6.6.6 If the results are acceptable click the “OK” button.

5.6.7 If a third analysis of a sample/standard is required the following steps should be followed:

5.6.7.1 Click the “Start” button. 5.6.7.2 Click the “Cancel” button. 5.6.7.3 Click the “Stop” button. 5.6.7.4 Highlight the cells associated with the sample to be re-

analyzed.

5.6.7.5 Click the “Read” button. 5.6.7.6 Click the “OK” button.

5.6.8 Once satisfactory results are achieved for the sample/standard

in questions the automatic run is continued by following the steps outlined below:

5.6.8.1 Click the “Stop” button. 5.6.8.2 Click the “Start” button. 5.6.8.3 Click the “Cancel” button. 5.6.8.4 Click the “Continue” button.

5.6.9 Continue with the automatic run until the final sample, blank or

standard entered on the worksheet has been analyzed.

5.7 Instrument Shutdown - Flame Note: The flame will not automatically shut off. 5.7.1 Aspirate distilled, deionized water for at least 5 minutes after a

run has been completed.


5.7.2 Press the "Flame Off" button on the AA instrument to shut down the flame.

5.7.3 Using the Windows shut down the computer. 5.7.4 Turn off the spectrophotometer.

5.8 Reports

5.8.1 After the final sample, blank or standard entered into the

customer worksheet has been analyzed a hardcopy report will be automatically printed. The resulting data shall be reviewed by the CTF prior to being reported.

5.8.2 After instrument shutdown enter customer results on the LIMS. 5.8.3 Standard preparation:

• 100 mg/L (ppm) potassium (K) working standards:

Pipette 10 mL of 1000 mg/L (ppm) potassium (K) NIST treaceble stock standard into a 100 mL volumetric flask, and dilute to the mark with 0.3 M HNO3. The working calibration standard and the working check standard solutions shall be prepared from two different lots from the same manufacturer, or they shall be prepared from stock solutions from different manufacturers.

• 1.0 mg/L (ppm) potassium (K) calibration and check

standards:

Pipette 1.0 mL of the 100 mg/L (ppm) potassium (K) working standard prepared above into a 100 mL volumetric flask and dilute to the mark with the 1600 mg/L (ppm) cesium solution prepared in step 5.11.1.

• 1.5 mg/L (ppm) potassium (K) calibration standard: Pipette 1.5 mL of the 100 mg/L (ppm) potassium (K)

working standard prepared above into a 100 mL volumetric flask and dilute to the mark with the 1600 mg/L (ppm) cesium solution prepared in step 5.11.1.

5.8.4 Prepare each unknown potassium sample by diluting a 1 mL


aliquot of unknown with 4 mL of 2000 ppm cesium stock solution. If additional dilution(s) of this original dilution is required, all subsequent dilutions are to be made with the 1600 ppm cesium.

5.8.5 Set up the instrument for analysis by following the directions in

section 5.4 of this procedure.

5.9 Analytical Residue Disposal

5.9.1 Solidification of High Chloride Rad AA Residues for Disposal in Solid Waste

Note: The adjustment of the pH of the residues should be done well in advance of being mixed with the absorbent so the residues can cool to room temperature after the adjustment of the pH. 5.9.1.1 In addition to the required lab coat, safety glasses, and

two pair of rad gloves, a face shield and plastic/rubber apron should be worn, and if feasible to do so, use the horizontal hood sash for additional splash protection.

5.9.1.2 In a radiological hood, carefully transfer

approximately 250 mL of high chloride residue from a storage bottle into a 1 L beaker that has had a stirring bar inserted.

5.9.1.3 Insert a portable pH meter that has been calibrated to

pH 7 into residue and determine pH of residue. Use sodium hydroxide solution or nitric acid to adjust the pH of the residue to 5 – 10. If the solution becomes hot, allow the solution to cool to near room temperature before transferring to a storage bottle. Making sure the solution has cooled, pour the pH-adjusted solution into a 2 L bottle and repeat steps 1 – 3 until the 2 L bottle is filled. Never add the hot solution to the absorbent. Always allow the pH – adjusted solution to cool to room temperature before adding to absorbent.

5.9.1.4 Thoroughly check the integrity of the side and bottom


seams of a medium to large sized, radiological, poly bag to ensure the seams will not fail. Then add approximately 750 grams of the specified absorbent (No Char A660) to the bag. (Note: A 250 mL beaker completely filled roughly equal to 250 grams of absorbent.)

5.9.1.5 Line a small paint pail with the rad bag containing the

750 grams of absorbent.

5.9.1.6 Pour approximately 1000 mL (approximately ½ of the volume of a 2 L bottle) of pH adjusted residue, which is at or near ambient temperature, to the absorbent in the bag and paint pail.

5.9.1.7 Carefully remove the bag from the pail, carefully close

the mouth of the bag with one hand, and carefully mix the liquid and absorbent by gently kneading the outside of the bag to effect solidification.

5.9.1.8 Inspect the contents of the bag to determine if any free

liquid is present. If liquid is present, carefully, so as to avoid any absorbent coming out of the hood, add 100-200 more grams of absorbent to the bag and carefully lift the bags containing the absorbent and liquid from the pail and manually mix the contents to remove any free liquid.

5.9.1.9 Should any free liquid remain after mixing add an

additional 100 – 200g of absorbent and repeat the mixing.

5.9.1.10 Repeat steps 6 – 9 for the remaining 1,000 mL in the

residue bottle.

5.9.1.11 Once all free liquid has been absorbed, twist and tape shut using the J-seal technique.

5.9.1.12 Place the taped bag in a bag used for hood waste.

5.9.1.13 Repeat the necessary steps for any additional residues


requiring disposal.

5.9.2 Adjustment of pH and Disposal of Non-Radiological, High Chloride Residues to Trade Waste Stream in D-0101

Note: The adjustment of the pH of the residues should be done well in advance of their disposal so the residues can cool to room temperature after the adjustment of the pH. 5.9.2.1 In a chemical hood with sash lowered below chin level

transfer approximately 500 mL of residue to a 1 liter beaker. Insert a magnetic stirring bar and the stirrer on slowly until a vortex of about one-fourth the depth of the liquid is achieved.

5.9.2.2 These solutions are quite acidic, therefore, carefully

add sodium hydroxide solution dropwise to the liquid in the beaker, checking the pH with each addition. Continue to slowly add the sodium hydroxide until a pH between 5 – 8 is achieved. If a pH above 8 is achieved slowly and carefully add either untreated, acidic residue or nitric acid dropwise until the specified pH range is obtained.

5.9.2.3 Once the desired pH is achieved and the temperature

has cooled sufficiently transfer the residue to a 2 liter, polyethylene bottle.

5.9.2.4 Continue to adjust the pH of the residues and

transferring the residues to 2 liter bottles until the pH of all the residues have been adjusted. Place the 2 liter bottles containing the residues with the pH adjusted aside and allow them to cool to room temperature.

5.9.2.5 Once the bottles containing the residues with the

proper pH have reached room temperature, in a non-rad hood, transfer 4 liters of the residue to the wide-mouth carboy equipped with a valve.

5.9.2.6 Place the carboy containing the residue to be disposed


in a 5 gallon bucket for transport to D-0101.

5.9.2.7 Don lab coat and chemical gloves.

5.9.2.8 Remove the carboy from the transport bucket and place on the back portion of the ledge of the sink.

5.9.2.9 Turn on the tap water to achieve a full stream (make sure the water flows while the residue is being discharged into the sink.)

5.9.2.10 Slowly open the valve on the carboy until a stream no

larger than the diameter of a pencil (approximately 9 mm) is achieved. As the level of residue falls in the carboy the valve opening may be increased but the diameter of the stream must not get larger than the diameter of a pencil.

5.9.2.11 Allow the entire contents of the carboy to drain into

the sink. Should there be any residue in the carboy when flow from the carboy valve ceases pour the residual liquid down the drain and rinse the carboy with tap water; disposing of the rinsate in the drain with the tap water flowing.

5.9.2.12 After the carboy has been emptied flush the sink and

drain by allowing the tap water to continue to run until at least 5 gallons has been discharged from the tap (at least 5 minutes of flushing.)

5.9.2.13 Turn off the tap water.

5.9.2.14 Cap the carboy, place it in the bucket and return it to

its designated storage place in B-133. 5.10 Calculations

5.10.1 Elemental concentrations are calculated by the Varian SpectrAA-880 software using current calibration data.

5.10.2 If dilutions were performed, the appropriate factor must be

applied to sample values.


5.10.3 Analytical results must be reported to three significant figures. 5.10.4 Units must be clearly specified.

5.11 Preventive Maintenance

5.11.1 Refer to the manufacturer’s manual for preventive

maintenance. 5.11.2 Record all preventive maintenance and instrument repair

actions in the registered AA Log Book when directed to do so by the Task Supervisor.

5.11.3 Check the sample introduction system and torch assembly

daily for any noticeable problems - collapsed tubing, clogged burner head, clogged nebulizer, etc.

6.0 RECORDS

None 7.0 REFERENCES

1. Welz. B., Atomic Absorption Spectrometry, VCH, 1985. 2. Dean, J.A. and Rains, T.C., Flame Emission and Absorption

Spectrometry, Marcel Dekker, 1969. 3. Alkemade, C. Th. J, and Hermann, TR., Fundamentals of Analytical

Flame Spectroscopy, John Wiley Sons, 1979. 4. Varian SpectrAA 880 Operation Manual

8.0 ATTACHMENTS

None.

SAVANNAH RIVER NATIONAL LABORATORY Manual: L16.1 ANALYTICAL DEVELOPMENT Procedure: ADS-1557 ANALYTICAL OPERATING PROCEDURES Revision: 5 Page: 1 of 24 TECHNICAL REFERENCE Effective Date: 5/15/2008 Procedure for Cold Vapor/Hydride Approved by: Generation Atomic Absorption (U) APPROVAL ON FILE AD Manager ______________________________________________________________________________ 1.0 PURPOSE

This procedure provides instructions for performing analyses using the VGA-77 vapor generator attachment that accompanies the Varian SpectrAA-880 Atomic Absorption Spectrophotometer.

2.0 SCOPE The VGA-77 vapor generator attachment is a mechanical device that attaches to the Varian SpectrAA-880 Atomic Absorption Spectrophotometer. The VGA-77 provides a means for the mixing and reaction of reagents with a sample followed by the liberation, via a liquid/gas separator, of the gaseous form of the analyte.


3.1 Safety

NOTE: All SRS, SRNL, and AD safety rules apply. 3.1.1 A reference file of material safety data sheets (MSDS) on all

the hazardous chemicals associated with this method is available. Review the MSDS on all chemicals prior to handling.

3.1.2 Mercury vapors and many of the element-hydrides are toxic.

Precautions must be taken to avoid their inhalation. The system must be vented to a fume hood, exhaust vent, or the vapor passed through an absorbing medium, such as: • Equal volumes of 0.1M KMnO4 and 10% H2SO4 or • 0.25% iodine in a 3% KI solution.

3.1.3 Read and understand Safety Practices of the Varian

SpectrAA880 in the operating manual.

SAVANNAH RIVER NATIONAL LABORATORY Manual: L16.1 ANALYTICAL DEVELOPMENT Procedure: ADS-1557 ANALYTICAL OPERATING PROCEDURES Revision: 5 Page: 2 of 24 TECHNICAL REFERENCE Effective Date: 5/15/2008

3.1.4 Operation of these instruments involves the use of compressed gases, and hazardous materials including corrosive fluids and flammable liquids. Improper or careless use of the instrument can create explosion hazards, fire hazards, or other hazards that can result in serious injury to personnel.

3.1.5 Exhaust system must be operational before work is performed.

Fumes emitted from the vapor generation system can be hazardous to personnel.

3.1.6 If gas leaks are suspected, immediately turn off the

instrument and leak check the hoses and gas connections. 3.1.7 Never leave the flame unattended. For flame determinations,

always operate the instrument, with the flame shield closed and the sample compartment panel in place. In some cases for the vapor generation operation, the flame shield and sample compartment panel must be removed. Hazardous, ultraviolet radiation can be emitted by the hollow cathode lamps, therefore, wear only approved safety glasses to protect eyes from the ultraviolet radiation.

3.1.8 The instrument is to be used only with air, nitrous oxide, and

acetylene compressed gases for flame operation. Use of oxygen or oxygen enriched air as the oxidant can result in an explosion. Use only atomic absorption grade acetylene (99.6% purity). For VGA operation, use only inert gases such as nitrogen, argon, or air.

3.1.9 If organic solvents are used, the drainage tubing for the waste

must be solvent-resistant nitrile rubber. Also, solvents with densities less than 0.75 cannot be used; these can create flashbacks or explosion hazards.

3.1.10 This procedure requires the use of acids > 3M and/or bases

> 4M which are considered concentrated in section 5 of Procedure 26 in Manual 8Q. These materials are corrosive and are to be prepared using the personal protective equipment also prescribed in section 5 of Procedure 26 in the 8Q Manual. Acids and bases that meet or exceed the specified description as concentrated are to be handled/prepared in a


hood, the use of which is outlined in section 6 of Procedure 26 in Manual 8Q.

4.0 PREREQUISITE ACTIONS


The system consists of a SpectrAA-880 Atomic Absorption Spectrophotometer with hollow cathode lamps for arsenic, mercury, and selenium, a vapor generation accessory (VGA) having a peristaltic pump, reaction coil, liquid/gas separator which is coupled to flow-through quartz cell designated for either As, Se, or Hg. This atomic absorption procedure is a physical method based on the ability of the arsenic and selenium to form volatile, covalent hydrides with “nascent” hydrogen. These gaseous hydrides are separated from the original sample matrix thereby enriching the analyte element, and thus reducing and sometimes completely eliminating interference. In the acidified sample the ionic element bonds with hydrogen provided by sodium borohydride thereby forming an element-hydride gas. The element-hydride gas is swept into a flow-through cell positioned in the path of the light beam emitted by a hollow cathode lamp where the amount of light absorbed by the gaseous element is measured by the spectrophotometer. The mercury method takes advantage of mercury being volatile when it is reduced to its elemental state. The mercury in an acidified sample is reduced to elemental mercury in a reaction with a solution of stannous chloride. The gaseous elemental mercury is then transported into a flow-through cell positioned in the path of the light beam emitted by a hollow cathode lamp where the amount of light absorbed by the gaseous element is measured by the spectrophotometer. In each case the absorbance is then translated into element concentration.

4.2 Data Quality

4.2.1 Scope and Application

This method describes the requirements for the use of atomic absorption and the vapor generation accessory for the analysis


of the elements, arsenic, mercury and selenium, in aqueous solutions at low concentrations (µg/L to mg/L). Included are standard and sample preparation procedures, descriptions of possible elemental interference, required operating conditions, and quality control procedures. This basic vapor generation technique for the volatile elements arsenic, mercury, and selenium is similar to methods outlined in the Standard Methods for the Examination of Water and Wastewater,1 the Test Methods for the Analysis of Solid Waste,2 the DOE Site Survey Manual,3 and the EPA Contract Laboratory Program.4 However, this procedure is only suitable for research and development samples, since it does not follow all of the requirements for compliance for regulated sample analysis.

4.3 Quality Control

Calibration Frequency - A calibration curve must be prepared for each element run for a series of samples with a minimum of a reagent blank and two NIST traceable standards.

4.4 Manufacturer

AA Spectrophotometer Model: SpectrAA-880 Varian Instrument Group 1-800-926-3000 Vapor Generation Accessory (VGA) Model: VGA-77 Varian Instrument Group 1-800-926-3000

4.5 Equipment

SpectrAA-880 VGA-77 Volumetric flasks Pipettes


Sample and reagent poly bottles Pump tubing

4.6 Reagents

The date that chemicals, standards, and reagents are received should be written on the bottle to track their age. Prepared standards and reagents should be labeled with the name of the standard, date of preparation, and the analyst’s initials. Acids used in the preparation of standards and for sample processing must be ultrahigh purity grade or equivalent. Ultra-pure acids from GFS Chemicals, Seastar Chemical, and Fisher Scientific are acceptable. Reagent grade acids can be used for cleaning glassware and plastic sample containers but must be rinsed with ultra-pure (deionized) water several times. Ultra-pure Deionized Water – This available from systems such as the Barnstead or Millipore Milli-Q de-ionizing systems. Before dispensing water make sure the resistivity reading of the water is 18 Mohms/cm or higher. If the resistivity does not increase to 18 Mohms/cm after 15 minutes of re-circulation, replace the ion exchange cartridges. Building deionized water does not meet this specification and should not be used. Hydrochloric Acid (12 M HCl) (Ultra-Pure) – Concentrated (sp. gr. 1.19) 10 M Hydrochloric Acid – In a fume hood, add 833 mL ultra-pure HCl to 167 mL ultra-pure deionized water, cap the container, and swirl to complete mixing. 8.75 M Hydrochloric Acid – In a fume hood, add 729 mL ultra-pure HCl to 271 mL ultra-pure deionized water, cap the container, and swirl to complete mixing. 7.0 M Hydrochloric Acid – In a fume hood, add 583 mL ultra-pure HCl to 417 mL ultra-pure deionized water, cap the container, and swirl to complete mixing. 5.0 M Hydrochloric Acid – In a fume hood, add 417 mL ultra-pure HCl to 583 mL water, cap the container, and swirl to complete mixing. Nitric Acid (16 M HNO3) (Ultra-Pure) - Concentrated (sp. gr. 1.41)


0.3 M Nitric Acid – In a fume hood, add 19 mL ultra-pure HNO3 to 981 mL ultra-pure deionized water, cap the container, and swirl to complete mixing. Sodium Hydroxide (NaOH) – Reagent grade pellets. Sodium Borohydride (NaBH4) – 95% Powder. Potassium Iodide (KI) – Reagent grade crystals. 20% Potassium Iodide – In a clean, dry 125 mL poly bottle weigh 20+0.1g KI. Add 100mL ultra-pure deionized water, insert magnetic stirring bar, and agitate on magnetic stirrer until KI is dissolved. Stannous Chloride (SnCl2Tin II Chloride) – Reagent grade crystals. 25% Stannous Chloride – In a fume hood, add 20 mL concentrated ultra-pure HCl to 80 mL ultra-pure deionized water, cap, and swirl to mix. Add 25+0.1 g stannous chloride to the solution, insert a magnetic stirring bar, place on magnetic stirrer and stir until stannous chloride is dissolved. Potassium Permanganate (KMNO4) – Reagent grade crystals. 5% Potassium Permanganate – To a 100mL volumetric flask containing approximately 50mL ultra-pure deionized water add 5+0.05g potassium permanganate, dilute to mark with ultra-pure deionized water, insert a magnetic stirring bar, place on magnetic stirrer, and mix until potassium permanganate is dissolved. Potassium Persulfate (K2S2O8) – Reagent grade crystals. 5% Potassium Persulfate – To a 100mL volumetric flask, containing approximately 50mL ultra-pure deionized water, add 5+0.05 g potassium persulfate, dilute to mark with ultra-pure deionized water, insert a magnetic stirring bar, place on magnetic stirrer, and mix until potassium persulfate is dissolved. Sodium Chloride (NaCl) – Reagent grade crystals. Hydroxylamine Hydrochloride – Certified ACS grade. 6% Sodium Chloride/6% Hydroxylamine Hydrochloride – To a 100 mL volumetric flask, containing approximately 50mL ultra-pure deionized water, add 6+0.05 g sodium chloride and 6+0.05 g hydroxylamine hydrochloride, dilute to mark with ultra-pure deionized water, insert a magnetic stirring bar, place on magnetic stirrer, and mix until solids are dissolved.


Standard Stock Solutions – These may be purchased or prepared from ultrahigh purity grade chemicals or metals. These stock standards shall be NIST traceable, and all calibration and check standards solutions shall be prepared from these stock standards, as outlined below for each element.

5.0 PERFORMANCE

5.1 Basic Methods For Vapor Hydride Generation Trace-Level Technique

NOTE: AA Instrument Operating Parameters - The Varian

SpectAA-880 AA instrument operating parameters for start up, calibration standards and verification, blanks, analyzing duplicates and replicates, check standards can be located in procedure ADS-1554.

Complete instructions for setting up and operating the VGA-77 are covered in the VGA operating manual. Since vapor generation is a trace-level technique, it is very important that the VGA system is meticulously cleaned after use and maintained in first-class condition. Instruction for cleaning, general maintenance, and replacement of individual components are given in the VGA operating manual. 5.1.1 Arsenic

The arsenic in the samples must be in the inorganic form, otherwise acid digestion will be necessary. Ensure that arsenic present as As (V) in standards and samples has been reduced to As (III)

by the action of potassium iodide at a concentration of

1% w/v. Reduction will take about thirty minutes at room temperature. The reduction can also be carried out at 50 oC in about four minutes. Standards, reagents, and samples solutions should be prepare as follows:

1 mg/L Working Standard(s) – In a fume hood, pipet 2 mL ultra-pure concentrated nitric acid into a 100 mL volumetric flask containing approximately 50 mL ultra-pure deionized water. Dilute to the mark with ultra-pure deionized water, stopper the flask and invert several


times to mix. Transfer contents to a bottle with a label that contains element name, concentration, date of preparation, and the initials of the person preparing. Repeat to produce a 1 mg/L working check standard. Calibration Standards – Prepare these solutions in a fume hood. 0.0025 mg/L Calibration Standard – Add approximately 25 mL 7 M HCl to a 50 mL volumetric flask, pipet 0.125 mL of the 1 mg/L stock calibration standard into the flask. Pipet 5 mL 20% KI solution and dilute to the mark with 7 M HCl, stopper, and mix contents. 0.0050 mg/L Calibration Standard – Add approximately 25 mL 7 M HCl to a 50 mL volumetric flask, pipet 0.250mL of the 1mg/L stock calibration standard into the flask. Pipet 5mL 20% KI solution and dilute to the mark with 7 M HCl, stopper, and mix contents.

0.0075 mg/L Calibration Standard – Add approximately 25 mL 7 M HCl to a 50 mL volumetric flask, pipet 0.375 mL of the 1mg/L stock calibration standard into the flask. Pipet 5 mL 20% KI solution and dilute to the mark with 7 M HCl, stopper, and mix contents. Check Standard – Prepare this solution in a fume hood. 0.0050mg/L Check Standard – Add approximately 25mL 7M HCl to a 50mL volumetric flask, pipet 0.250mL of the 1mg/L check standard. Pipet 5mL 20% KI solution and dilute to the mark with 7mL HCl, stopper, and mix contents. Note: The calibration and check standards may be made in larger volumes as long as the proper proportions are maintained. Reductant Container: 0.6% NaBH4; 0.5% NaOH; 10% KI

Prepare by weighing, into a clean, dry 250 mL, poly bottle, 1.5+0.05 g sodium borohydride, 1.25+0.05 g sodium hydroxide, and 25+0.1 g potassium iodide. Add 250 mL ultra-pure deionized water, insert magnetic stirring bar, and place on magnetic stirrer and stir until all solid ingredients are dissolved. Once solids are


dissolved transfer to reductant bottle on hydride module.

Acid Container: Fill with 10 M HCl.

Where arsenic and selenium are both to be determined from the same sample separate hydride systems are to be used because any KI present from arsenic analyses will affect the selenium analyses.

5.1.2 Selenium

Se (VI) is not quantitatively recovered by hydride generation and must be reduced to Se (IV). It may be necessary to prepare the samples in 7 M HCl acid, heat at 95ºC for about 10 minutes and cool to room temperature before analysis.

1 mg/L Working Standard(s) – In a fume hood, pipet 2mL ultra-pure concentrated nitric acid into a 100mL volumetric flask containing approximately 50mL ultra-pure deionized water. Pipet 0.100 mL of the 1,000mg/L stock selenium standard designated for calibration into the flask. Dilute to the mark with ultra-pure deionized water, stopper the flask and invert several times to mix. Transfer contents to a bottle with a label that contains element name, concentration, date of preparation, and the initials of the person preparing. Repeat to produce a 1mg/L working check standard. Calibration Standards – Prepare these solutions in a hood. 0.0050 mg/L Calibration Standard – In a fume hood, approximately 25 mL 7 M HCl to a 50 mL volumetric flask, pipet 0.250 mL of the 1 mg/L working selenium calibration standard into the flask. Dilute to the mark with 7 M HCl, stopper, and mix. 0.0075 mg/L Calibration Standard – In a fume hood, add approximately 25 mL 7M HCl to a 50mL volumetric flask, pipet 0.375 mL of the 1 mg/L working selenium calibration standard into the flask. Dilute to the mark, with 7 M HCl, stopper, and mix.


0.0100 mg/L Calibration Standard – In a fume hood, add approximately 25 mL 7 M HCl to a 50mL volumetric flask, pipet 0.375 mL of the 1 mg/L working selenium calibration standard into the flask. Dilute to the mark with 7 M HCl, stopper, and mix. Check Standard 0.075 mg/L Check Standard – In a fume hood, add approximately 25 mL 7 M HCl to a 50 mL volumetric flask, pipet 0.375 mL of the 1mg/L working selenium check standard into the flask. Dilute to the mark, with 7 M HCl, stopper, and mix. Reductant Container: 0.6% NaBH4; 0.5% NaOH Prepare by weighing, into a clean, dry 250 mL, poly bottle, 1.5+0.05 g sodium borohydride and 1.25+0.05 g sodium hydroxide. Add 250 mL ultra-pure deionized water, insert magnetic stirring bar, and place on magnetic stirrer and stir until all solid ingredients are dissolved. Once solids are dissolved transfer to reductant bottle on hydride module. Acid Container: Fill with 10 M HCl.

5.2 Mercury Determination by Cold Vapor AA with the VGA-77

Information: The cold vapor mercury technique is a flameless atomic absorption procedure that is a physical method based on the absorption of radiation at 253.7 nm by mercury vapor. Ionic mercury is reduced to the elemental state and liberated as a gas. The elemental vaporous mercury is separated from solution, via a liquid/gas separator, and passed through a flow-through cell positioned in a path of light of specific wavelength generated by a hollow cathode lamp. The amount of light absorbed by the elemental mercury vapor is then converted to concentration. 5.2.1 Standard Preparation

10.0 mg/L Working Standard(s) – Carefully pipet 1.0 mL of the 1000 mg/L stock calibration standard into a 100 mL volumetric flask containing approximately 50 mL 0.3 M nitric acid. Dilute to the mark with 0.3 M nitric acid, stopper, the flask and mix.


Transfer contents to a bottle with a label that contains element name, concentration, date of preparation, and the initials of the person preparing. Repeat to produce a 10 mg/L working check standard.

Calibration Standards: 0.0025 mg/L Calibration Standard – Pipet 0.125 mL of the 10.0 mg/L working calibration standard into a 50 mL volumetric flask containing approximately 25 mL of 0.3M nitric acid. Dilute to mark with 0.3 M nitric acid, stopper the flask, and mix. 0.0050 mg/L Calibration Standard – Pipet 0.250 mL of the 10.0 mg/L working calibration standard into a 50 mL volumetric flask containing approximately 25 mL of 0.3 M nitric acid. Dilute to mark with 0.3 M nitric acid, stopper the flask, and mix.

0.0075 mg/L Calibration Standard – Pipet 0.375 mL of the 10.0 mg/L working calibration standard into a 50 mL volumetric flask containing approximately 25 mL of 0.3 M nitric acid. Dilute to mark with 0.3 M nitric acid, stopper the flask, and mix.

Check Standard: 0.0050 mg/L Check Standard – Pipet 0.250 mL of the 10.0 mg/L working check standard into a 50 mL volumetric flask containing approximately 25 mL of 0.3 M nitric acid. Dilute to mark with 0.3 M nitric acid, stopper the flask, and mix.

5.3 Sample Preparation and Analysis of Samples Containing Organics

This sample preparation method is applicable to drinking, surface, and saline waters, domestic and industrial wastes, soils, sediments, bottom deposits, and sludge. In addition to inorganic forms of mercury, organic mercurials may also be present. These organo-mercury compounds will not respond to the cold vapor atomic absorption technique unless they are first broken down so that the mercury is


liberated as mercury ions. Potassium permanganate oxidizes many of these compounds, but recent studies have shown that a number of organic mercurials, including phenyl mercuric acetate and methyl mercuric chloride, are only partially oxidized by this reagent. Potassium persulfate has been found to give near a 100% recovery when used as the oxidant for these compounds. Therefore, a persulfate oxidation step following the addition of the permanganate has been included to insure that organo-mercuric compounds, if present, will be destroyed so as to produce mercuric ions. A heat step is required to oxidize methyl mercuric chloride when present in or spiked into a natural system. 5.3.1 Module Reagents:

Reductant Container – 25% Stannous chloride. Acid Container – 5 M HCl.

5.3.2 Begin preparing a blank by pipetting 10 mL 0.3 M nitric acid into a labeled, clean, dry centrifuge tube.

Note: It may be necessary to prepare multiple blanks.

5.3.3 Begin preparing calibration standards by pipetting 10 mL of

each standard into a clean, dry centrifuge tubes that have been labeled with the respective standard concentrations.

5.3.4 Begin preparing a check standard by pipetting 10 mL of the

check standard into a labeled, clean, dry centrifuge tube. 5.3.5 Pipet 10 mL of each sample into their respectively labeled

centrifuge tubes. For solid or semi-solid (sludge/slurry) samples weigh 6+0.1 g sample in a labeled, clean, dry centrifuge tube.

5.3.6 In a hood add the following to all the vials:

Liquid Samples: Solid and Semi Solid Samples: 0.500 mL concentrated 2.0 mL concentrated sulfuric acid. sulfuric acid.

0.200 mL concentrated 1.00 mL concentrated nitric acid. nitric acid.


1.5 mL potassium 6.00 mL potassium permanganate permanganate solution solution

NOTE: Filter the sample if directed to do so by the task

supervisor and record in the logbook. Use a 10 mL syringe and a 0.45 micron Gelman Filter or equivalent.

5.3.7 Allow solutions to stand for 15 minutes, making sure the purple color persists. If color does not persist add up to 5 - 1.5 mL aliquots of the potassium permanganate solution, if color does not persist for 15minutes after 5 the addition of 5 – 1.5 mL aliquots of permanganate consult the task supervisor. Once the color persists for 15 minutes, continue as outlined below.

5.3.8 Add the following to the samples.

Liquid Samples Solid and Semi-Solid Samples 1.00 mL potassium 4.00 mL potassium persulfate solution persulfate solution

5.3.9 Heat for a minimum of two hours in a water bath maintained at

95°C± 3 °C and then allow to cool to room temperature. 5.3.10 In a hood, add sodium chloride-hydroxylamine hydrochloride

solution dropwise and mix until the permanganate color is destroyed.

5.3.11 Immediately add 2 mL of concentrated nitric acid and then:

Liquid Samples Solid & Semi-Solid Samples Dilute to 30 mL with Weigh to 30.0± 0.1 gram with deionized water. deionized water into the

sample vial.

5.4 Instrument Start-up Note: This instrument is controlled by ”Windows” based

software and there are numerous ways to traverse through the menus in order to run a series of analyses.


5.4.1 Turn on the AA system in the following order: Instrument, computer, monitor, and printer. The AA system and the specific hollow cathode lamp should have a warm-up time of approximately 15-20 minutes.

5.4.2 Allow MS Windows software to completely boot the system.

5.4.3 Once all the desktop icons have appeared on the computer

monitor screen, double click on the SpectrAA icon and wait for the Varian AA instrument software to load.

5.4.4 Customer Worksheet Creation

5.4.4.1 The Varian AA instrument software should be displayed on the computer monitor screen. From this window there are four options to select from: Worksheet, Reports, Administrator, and Exit. Select “Worksheet.” To create a customer worksheet a series of windows and menus will follow.

• Once the “Worksheet” option has been selected the

Load Worksheet window will appear on the screen. There are three options to select from: New, New from, and Open. Select “New from…”

• The next window to appear will be New Worksheet From Worksheet menu. In this window there will be several items to select from, the symbol of various elements (As, Se, Hg, etc.) and the file names of previous customer runs. From this menu highlight the symbol of the element to be analyzed with the mouse. Click “OK.”

• The Name Worksheet window will appear on the screen next. To create the customer’s worksheet, type in the customer’s name in the name blank using the following format: date (mm-dd-yy), customer’s name (last, first). Next, type in the analyst name in the analyst blank. And finally any comments related to the samples being analyzed can be entered into the comment blank. When


finished click “OK.”

5.4.4.2 At this point the Instrument analysis window with the customer’s worksheet should be displayed on the computer monitor screen. At the top of the screen there are four tabs to select from: Filing, Develop, Labels, and Analysis. Select the “Labels” tab.

• In the Labels window select the appropriate blank

and type in the appropriate information (check standard, reagent blanks, sample ID, etc.) in the order they will be analyzed.

• Once all the information has been entered this will

complete the customer’s worksheet.

5.4.4.3 At the top of the screen select the “Analysis” tab. This will bring the system back to the instrument analysis window.

5.5 Signal Optimization and Igniting the Flame for Arsenic and

Selenium Analyses 5.5.1 Before igniting the flame, the following must be satisfied:

5.5.1.1 Spray chamber pressure relief bung must be in place. 5.5.1.2 Liquid trap must be above the level mark. Looking at

the water level from the outside, the level should be just below the drain outlet. The sensor in the liquid trap will shut down the flame if the liquid level falls below the required level. Also, the sealing gasket must be positioned correctly in the liquid trap. Arrows on the float should be pointing up.

5.5.1.3 The appropriate gases, acetylene, air, and nitrous

oxide, must be pressurized to the spectrophotometer. The gases need to be valved open at the cylinder station and subsequently valved open at the instrument for the following pressures:


Acetylene: 15 (range 7-15 psi) Air: 60 (range 35-65 psi) Nitrous Oxide: 60 (range 35-65 psi) 5.5.1.3 Check/Install the air/acetylene burner head, place the

mount the flow-through for the gases being used for the analyses and optimize its position (described below).

Note: For burner heads, the vertical and horizontal

adjustments can be made either through the software or manually. Generally, the optimum height for the burner head for most elements is 5 mm below the optical path, but the optimal position will depend on the analyte (element) of interest. Reasonable optimization of the burner position, for most elements, can be performed using a white card that has a centering symbol, e.g., a cross or circle, positioned at 5 mm from the bottom edge of the card. Place the card mid-length on the burner head with the centering mark over the flame slit and adjust the burner horizontally and vertically so that the light beam is centered on the white card.

Note: The burner head should be cleaned before every

use to remove any salts or debris deposited on and in the burner head slit. This can be accomplished by slipping the white alignment card into the slit of the burner head and gently moving the card up and down and back and forth. The burner head should then be gently wiped with a damp tissue then followed by gently wiping with a dry tissue to remove any residues.

Note: A cleaning wire is to be inserted into the

nebulizer opening, and a cleaning wire is to be passed through the capillary tubing that is attached to the nebulizer so as to remove any impediments.


Note: When finished analyzing samples the SpectrAA

should rinse, with flame ignited, for 5-10 minutes to reduce the amount of salt deposit and buildup on and in the burner head slit.

5.5.1.5 Press the ignite button on the SpectrAA and

keep it depressed until the flame ignites. Note: The flame, while aspirating distilled, deionized

water or any liquid solution should be allowed to stabilize for at least 5 minutes prior to calibration. This will keep the burner head cool and operating properly. If necessary, or desired, check the uptake using a 10 or 25 mL graduated cylinder. The uptake should be approximately 7 ± 1 mL/min.

5.5.2 Analyte Signal

5.5.2.1 There are several options to choose from on the left side of the instrument analysis window: Select, Optimize, Start, Stop, Read, and Help. Select “Optimize.”

5.5.2.2 Select “Ok” on the Optimize window. The Flame

Optimization window will appear. Select the “Optimize Lamps” option. Wait for the turret to rotate to the hollow cathode lamp corresponding to the element selected for analysis.

5.5.2.3 The lamp should be allowed to warm up for at least 5 minutes to stabilize before calibrating and performing analyses.

5.5.2.4 Once the lamp has stabilized select the “Rescale”

option. On the scale to the left in the Optimize Lamps window the green signal bar and the readout below the scale should be between .900 and 1.100. If the readout is not within this range, select the “Rescale” option again. If it is still not within the range contact the


Task Supervisor for corrective action. 5.5.2.5 Once the lamp has been optimized select the “Optimize

Signal” and then the “Inst. Zero” option

5.5.2.6 The instrument is now optimized. Select “Ok” on the Flame Optimization window and “Cancel” on the next window (Optimize) that appears on the screen to return to the instrument analysis window.

5.6 Signal Optimization for Mercury

5.6.1 The mercury analytical technique does not require a flame; it

is a cold vapor technique, therefore when the Hg lamp is selected the flame cannot be ignited.

5.6.2 Place the mounted mercury absorption cell onto the burner

head. 5.6.3 Make sure the Hg lamp is selected, and allow a minimum of

5 minutes for lamp warm-up.

5.6.4 Optimize the beam passing through the cell by using the manual adjustments on the instrument and noting the increase or decrease in signal displayed on the Optimization window of the software.

5.6.5 Perform the optimization of the signal as noted above in the

instructions for arsenic and selenium.

5.7 Calibration and Sample Analysis 5.7.1 Select “Start” from the options on the left side of the instrument

analysis window. After selecting Start, there will be a series of interactive windows that will appear on the screen.

5.7.2 Select “Ok” to the Confirm window to prepare for standard Zero.

Once selected the instrument will be zeroed with the distilled, deionized water being aspirated into the system.

5.7.3 From this point forward the software will ask the operator to

present various solutions (cal zero, calibration standards, check


standards, reagent blanks and samples) to the instrument. 5.7.4 Place the aspirating tube into the solution the interactive

window is asking for and select “Read.” 5.7.5 The instrument will take three readings and ask for the next

solution.

5.7.6 Should it become necessary to repeat an analysis, the following steps are applicable:

5.7.6.1 Click the “Pause” button.

5.7.6.2 Click the “Stop” button.

5.7.6.3 Highlight the cells associated with the

sample/standard to be re-analyzed.


5.7.6.5 Click the “OK” button and allow the instrument to perform the analysis.

5.7.6.6 If the results are acceptable click the “OK” button.

5.7.6.7 If a third analysis of a sample/standard is required the

following steps should be followed:

5.7.6.8 Click the “Start” button.

5.7.6.9 Click the “Cancel” button.


5.7.6.11 Highlight the cells associated with the sample to be re-analyzed.


5.7.6.13 Click the “OK” button.


5.7.7 Once satisfactory results are achieved for the sample/standard in questions the automatic run is continued by following the steps outlined below:


5.7.7.2 Click the “Start” button.

5.7.7.3 Click the “Cancel” button.

5.7.7.4 Click the “Continue” button.

5.7.8 Continue with the automatic run until the final sample, blank or

standard entered on the worksheet has been analyzed.

5.8 Preventive Maintenance

5.8.1 Refer to the manufacturer’s manual for preventive maintenance. 5.8.2 Record all preventive maintenance and instrument repair

actions in the registered AA Log Book when directed to do so by the Task Supervisor.

5.8.3. Daily check the sample introduction system and torch assembly

for any noticeable problems - collapsed tubing, clogged burner head, clogged nebulizer, etc.

5.9 Analytical Residue Disposal 5.9.1 Solidification of High Chloride Rad AA Residues for

Disposal in Solid Residue

Note: The adjustment of the pH of the residues should be done well in advance of being mixed with the absorbent so the residues can cool to room temperature after the adjustment of the pH.

5.9.1.1 In addition to the required lab coat, safety glasses, and

two pair of rad gloves, a face shield and plastic/rubber apron should be worn, and if feasible to do so, use the horizontal hood sash for additional splash protection.


5.9.1.2 In a radiological hood, carefully transfer approximately

250 mL of high chloride residue from a storage bottle into a 1L beaker that has had a stirring bar inserted.

5.9.1.3 Insert a portable pH meter that has been calibrated to pH 7 into residue and determine pH of residue. Use sodium hydroxide solution or nitric acid to adjust the pH of the residue to 5 – 10. If the solution becomes hot, allow the solution to cool to near room temperature before transferring to a storage bottle. Making sure the solution has cooled, pour the pH-adjusted solution into a 2 L bottle and repeat steps 1 – 3 until the 2L bottle is filled. Never add the hot solution to the absorbent. Always allow the pH-adjusted solution to cool to room temperature before adding to absorbent.

5.9.1.4 Thoroughly check the integrity of the side and bottom

seams of a medium to large sized, radiological, poly bag to ensure the seams will not fail. Then add approximately 750 grams of the specified absorbent (No Char A660) to the bag. (Note: A 250 mL beaker completely filled roughly equal to 250 grams of absorbent.)

5.9.1.5 Line a small paint pail with the rad bag containing the

750 grams of absorbent.

5.9.1.6 Pour approximately 1000 mL (approximately 1/2 of the volume of a 2 L bottle) of pH adjusted residue, which is at or near ambient temperature, to the absorbent in the bag and paint pail.

5.9.1.7 Carefully remove the bag from the pail, carefully close

the mouth of the bag with one hand, and carefully mix the liquid and absorbent by gently kneading the outside of the bag to effect solidification.

5.9.1.8 Inspect the contents of the bag to determine if any free liquid is present. If liquid is present, carefully, so as to avoid any absorbent coming out of the hood, add 100 – 200 more grams of absorbent to the bag and carefully


lift the bags containing the absorbent and liquid from the pail and manually mix the contents to remove any free liquid.

5.9.1.9 Should any free liquid remain after mixing add an additional 100 – 200 gms of absorbent and repeat the mixing.

5.9.1.10 Repeat steps 6 – 9 for the remaining 1,000 mL in the residue bottle.

5.9.1.11 Once all free liquid has been absorbed, twist and tape

shut using the J-seal technique. 5.9.1.12 Place the taped bag in a bag used for hood waste.

5.9.1.13 Repeat the necessary steps for any additional residues

requiring disposal.

5.9.2 Adjustment of pH and Disposal of Non-Radiological, High Chloride Residues to Sink in D-0101

Note: The adjustment of the pH of the residues should be

done well in advance of their disposal so the residues can cool to room temperature after the adjustment of the pH.

5.9.2.1 In a chemical hood with sash lowered below chin level transfer approximately 500 mL of residue to a 1 liter beaker. Insert a magnetic stirring bar and the stirrer on slowly until a vortex of about one-fourth the depth of the liquid is achieved.

5.9.2.2 These solutions are quite acidic, therefore, carefully add sodium hydroxide solution dropwise to the liquid in the beaker, checking the pH with each addition. Continue to slowly add the sodium hydroxide until a pH between 5 – 8 is achieved. If a pH above 8 is achieved slowly and carefully add either untreated, acidic residue or nitric acid dropwise until the specified pH range is obtained.

5.9.2.3 Once the desired pH is achieved and the temperature has cooled sufficiently transfer the residue to a 2 liter, polyethylene bottle.


5.9.2.4 Continue to adjust the pH of the residues and transferring the residues to 2 liter bottles until the pH of all the residues have been adjusted. Place the 2 liter bottles containing the residues with the pH adjusted aside and allow them to cool to room temperature.

5.9.2.5 Once the bottles containing the residues with the proper pH have reached room temperature, in a non-rad hood, transfer 4 liters of the residue to the wide-mouth carboy equipped with a valve.

5.9.2.6 Place the carboy containing the residue to be disposed in a 5 gallon bucket for transport to D-0101.

5.9.2.7 Don lab coat and chemical gloves. 5.9.2.8 Remove the carboy from the transport bucket and place

on the back portion of the ledge of the sink. 5.9.2.9 Turn on the tap water to achieve a full stream (make

sure the water flows the while the residue is being discharged into the sink).

5.9.2.10 Slowly open the valve on the carboy until a stream no larger than the diameter of a pencil (approximately 9 mm) is achieved. As the level of residue falls in the carboy the valve opening may be increased but the diameter of the stream must not get larger than the diameter of a pencil.

5.9.2.11 Allow the entire contents of the carboy to drain into the sink. Should there be any residue in the carboy when flow from the carboy valve ceases pour the residual liquid down the drain and rinse the carboy with tap water; disposing of the rinsate in the drain with the tap water flowing.

5.9.2.12 After the carboy has been emptied flush the sink and drain by allowing the tap water to continue to run until at least 5 gallons has been discharged from the tap (at least 5 minutes of flushing).

5.9.2.13 Turn off the tap water. 5.9.2.14 Cap the carboy, place it in the bucket and return it to

its designated storage place in B-133.


6.0 RECORDS

None

7.0 REFERENCE

7.1 Standard Methods for the Examination of Water and Wastewater, 16th Edition, 303 F. Determination of Mercury by the Cold Vapor Technique, pp. 171-173, APHA, AWWA, WPCF, 1985.

7.2 EPA (U.S. Environmental Protection Agency), Test Methods for

Evaluating Solid Waste, SW-846, Cincinnati, Ohio.

7.3 DOE (U.S. Department of Energy), The Environmental Survey Manual, DOE/EH-0053, Washington, DC.

7.4 EPA (U.S. Environmental Protection Agency), USEPA Contract

Laboratory Program, SOW. 12/87, Las Vegas, NV. 7.5 Varian SpectAA Operation Manual

8.0 ATTACHMENTS None

SAVANNAH RIVER NATIONAL LABORATORY Manual: L16.1 ANALYTICAL DEVELOPMENT Procedure: ADS-1573 AD ANALYTICAL OPERATING PROCEDURES Revision: 2 Page: 1 of 51 TECHNICAL REFERENCE Effective Date: 09/30/10 _____________________________________________________________________________________________

Radioactive and Non-Radioactive Approved by: Sample Analysis on the Leeman Prodigy Inductively Coupled Plasma Approval on File Emission Spectrometer (U) AD Manager 1.0 Purpose The purpose of this procedure is to establish the requirements for the use of

inductively-coupled plasma atomic emission spectroscopy (ICP-ES) for the analysis of metals in radioactive and non-radioactive aqueous solutions at low concentrations (g/L to mg/L).

2.0 Scope

This procedure applies to the analysis of research and development samples. Results obtained from use of this procedure do not meet requirements for compliance or regulated sample analysis reporting. This procedure applies to the following instrument: Model Number: Prodigy DV ID Number: 6048 Install Number: 63169 Teledyne Leeman Labs 6 Wentworth Drive Hudson, NH 03051 (800) 533-6267


MDL - Method Detection Limit. The minimum concentration detectable in a solution. MDLs are matrix-dependent and emission line specific. RCRA - Resource Conservation and Recovery Act. Defines eight elements as potentially hazardous and defines the maximum TCLP leachate concentration. The ICP-ES typically analyzes five of the eight (Ag, Ba, Cd, Cr and Pb.) TCLP - Toxic Characteristic Leaching Protocol. The leachate solutions are analyzed for the RCRA hazardous elements.


CTF - Cognizant Technical Function TA - Technical Analyst ADSLIMS - Analytical Development Section Laboratory Information Management System

2.2 Responsibilities 2.2.1 Cognizant Technical Function

The Chemist assigned to the Leeman Prodigy is the

Cognizant Technical Function (CTF).

The CTF is responsible for implementing the MS&E controls (1Q Manual, QAP 2-7); the selection and establishment of calibrations, calibration standards, calibration frequency, calibration ranges, acceptable uncertainties, electronic calibration records, reviewing and approving extensions of shelf lives, calibrations as well as designation of MS&E support equipment e.g. pipettes.

The CTF is responsible for data generated by the ICP-ES. The CTF is responsible for ensuring data is reviewed and

approved. The CTF is responsible for reviewing data generated by

the ICP-ES when an out-of-calibration condition is discovered, in order to ascertain when the instrument may have malfunctioned and determine the validity of the data generated by the instrument since the previous calibration.

The CTF, or designee, is responsible for the maintenance,

repair, and operation of the ICP-ES. The CTF, or designee, is responsible for training new

Technical Analyst(s).


The CTF is responsible for qualifying trained Technical

Analysts on the ICP-ES and applicable methods. The CTF is responsible for coordinating the procurement

of new components (i.e. autosampler, spray chamber) for the ICP-ES.

The CTF is responsible to ensure that standards used for

calibrating and verifying control of measurement systems shall be traceable as described in Manual 1Q, QAP 2-7.

2.2.2 Technical Analyst

The Technical Analyst (TA) assigned to the Leeman

Prodigy is responsible for operating the ICP-ES in accordance with approved procedures.

The TA is responsible for performing calibrations and

analyzing samples and instrument check standards. The TA is responsible for recording MS&E related

information in appropriate notebooks and/or logbooks. The TA is responsible for the preparation of calibration

standards and ordering chemicals and spare parts. The TA is responsible for disposing of waste and residue.

3.0 Precautions/Limitations

FOLLOW the ADD radiation safety guidelines (L1, Procedure 2.32)

Follow the ADD laboratory safety guidelines (8Q, Procedure 26) Hazard Assessment Package # SRNL-ADD-l4000-2009-00002 identified the

hazards listed in the table below and the corresponding hazard controls.


Identified Hazard Hazard Control

2 % Nitric acid preparation – contact with or spill of concentrated nitric acid

Prepare 2% nitric acid in hood with face shield and safety goggles, lab apron, neoprene or thick mil nitrile gloves, face shield, lab coat and use spill response per Manual 8Q Procedure 26.

Standards preparation – contact with or spill of 2 % HNO3 and 0.1 % HF

Prepare standards in a secondary containment tray or container with lab coat, safety glasses, and thin mil nitrile gloves.

Samples preparation, sample loading on auto-sampler, and waste handling – radioactive potentially containing HF and HNO3

Pay attention to limited-use pipets, which are labeled. Prepare samples in hood with safety glasses/side shields, lab coat and yellow gloves. Also don lab apron, neoprene or thick mil nitrile gloves, face shield and splash goggles when handling HF samples per Manual L1, Procedure 3.20. Follow safe radiological practices per Manual L1, procedure 2.32. Follow current SRWP guidelines. Use spill/contact response per Manual 8Q, Procedure 26 and Manual L1, Procedure 3.20.

Peristaltic pump pinch points Use caution when engaging peristaltic pump.

UV light/Rf power exposure and potential glass breaking during torch assembly maintenance

Switch instrument off and unplug prior to maintenance and optimization. Torch housing interlocks are also present as engineering controls. Don yellow gloves, labcoat, safety glasses/side shields per SRWP. Use care when handling glass. Do not use metal objects on the RF coil or torch.

Disposition of torch assembly components – handling beryllium contaminated waste

Torch assembly is labeled in accordance with Manual L1, procedure 3.24. Perform waste handling in accordance with Manual L1, procedure 3.24.

Auto-sampler maintenance – potential for chemical spill

Don yellow gloves, labcoat, safety glasses/side shields per SRWP and check for leaks in tubing and change if necessary.


Water spill, pinch points, and head injury during chiller maintenance

Perform rad screen on water before changing; check for leaks in tubing; don leather gloves in addition to lab coat and safety glasses; be mindful of head placement using proper position techniques.

3.1 Emergency Shutdown If conditions exist that warrant the immediate shutdown of the ICP-ES

(e.g. lab evacuation), press the red plastic button on the spectrometer housing (below green button on instrument outside of hood).

3.2 Method Hazards

3.2.1 The plasma source emits strong ultraviolet (UV) radiation, which can cause permanent eye damage. Do not look directly at the source unless it is viewed through the UV absorbing material mounted in the viewing window of the metal box that contains the torch.

3.2.2 High voltages exist inside the radio frequency (RF) power

generator and other parts of the spectrometer. Do not open the spectrometer or the power supply unless qualified to do so by the CTF.

3.2.3 Concentrated nitric acid is an extremely corrosive and toxic

chemical that must be handled with great care. The acid irritates all parts of the respiratory tract and is corrosive to the skin and other tissues, especially the eyes (see MSDS 9587-1).

3.2.4 For samples with high tritium content (up to 12 curies/L) to be

analyzed, follow special safety precaution instructions per the Special Radiological Work Permit and pre-job briefing for these analyses.

4.0 Prerequisite Actions

4.1 Calibration Frequency and Status


The instrument should be calibrated each day samples are analyzed, as needed. Calibrations must be confirmed prior to reporting results. Calibration status is established and maintained via analysis of instrument check standards (a) after calibration and (b) after a batch of samples is analyzed. For more details see the Quality Assurance and Quality Control section (See 5.1.5) and the Instrument Operation section (See 5.2).

4.2 Training Requirements

4.2.1 During training, all ADS analysts must work under direct technical supervision or under the guidance of another qualified analyst. It will be the CTF’s responsibility to decide when the analyst is suitably instructed and experienced to operate the instrument.

4.2.2 Qualification as an ICP-ES technician shall be documented by

an approved training method.

4.2.3 Advanced training offsite short courses, such as those offered by the American Chemical Society or the Society for Applied Spectroscopy, can be required of the technician. The need for this type of advanced training will be left to the discretion of the CTF. A technician operating the instrument will be required to use computers, to operate the instrument, to enter data and information on the LIMS, and may be required to prepare reports (using Microsoft Word) and to prepare data for direct transfer to the LIMS (using Microsoft Excel).

5.0 Performance


The Inductively Coupled Plasma Emission Spectrometer (ICP-ES) provides multi-elemental analyses of solutions. Measurements are based on atomic emission from excited atoms and ions. Liquid samples are nebulized. The aerosol produced is transported to an argon plasma. The plasma is created and sustained by coupling a radio frequency (RF) signal to the argon gas. In the high temperature plasma (10,000 K) atomic species are excited to higher energy states resulting in characteristic atomic and ion line emission. The spectra


are dispersed through a grating spectrometer (polychromator). The intensities of the lines, which are directly proportional to analyte concentration, are monitored by a Large Programmable Array Detector (L-PAD). The photocurrents from the L-PAD are processed, quantified and controlled by a computer system. The primary detection scheme for the Leeman Prodigy is a 0.80 Spectrometer with/L-PAD detector. For simultaneous detection, the L-PAD can be used for many elements commonly found in SRNL/SRS samples. These wavelength positions were selected by SRNL subject-matter-experts for optimum sensitivity and selectivity. Ag, Al, B, Ba, Ca, Cd, Ce, Co, Cr, Cu, Fe, Gd, K, La, Li, Mg, Mn, Mo, Na, Ni, P, Pb, Si, Sn, Sr, Ti, U, Zn, and Zr. Detection limits for the elements are generally in the ppb range, but vary with the emission line selected and the sample matrix. The choice of wavelengths used will depend on the complexity of the matrix, sensitivity needed and amount of sample available. The CTF is the final judge on analytical wavelengths.

The Leeman Prodigy ICP-ES is operated using Windows compatible software on an IBM-compatible personal computer (PC).

5.1.1 General Limitations

General Precautions: Do not run organic samples without prior authorization of

the CTF. Check for solids in samples and filter if necessary. If sample

is filtered, indicate in the sample ID by following the LIMS number with “f”.

Colored samples are to be run after dilution. Evaluate the sample following guidance of Attachment 8.1,

Sample Collection, Preservation and Preparation. Listed waste samples (i.e. F006-listed) including RPP

material must have all waste collected (including the effluent that normally goes to the High Activity Drain) and returned to the customer.

5.1.2 Interference Effects

Several types of interference may be present in the ICP-ES:


Spectral Interference is an increase or decrease in intensity

caused by spectral overlap from a matrix or plasma wavelength (either atomic or molecular). Interferences can result from nearby unresolved wavelengths (either atomic or molecular), altered background contribution from changing plasma conditions or increases in stray light from high concentration elements. Background correction, which is used for trace analysis when possible with the ICP-ES, corrects for spectral changes in the background. Spectral overlap from unresolved wavelengths is corrected using Interelement Correction factors (IECs), which correct for interference based on the measured intensity of the interfering species at a second wavelength.

Physical Interference is an increase or decrease in sample

nebulization or transport, which alters the measured wavelength intensity. Physical effects are commonly found when analyzing samples, which contain high quantities of dissolved solids and/or acid concentrations. Internal standards, typically Y or Sc, can be used with the Leeman Prodigy ICP to compensate for these effects. In those instances when a sample extinguishes the plasma, the sample introduction system may require purging as described on Attachment 8.2, Troubleshooting. Consequently, the suspect sample may require additional dilution. Commonly used dilution factors are listed on Attachment 8.3 in order to facilitate this process.

Chemical Interference is an increase or decrease in measured

intensity caused by molecular compound formation, ionization of elements, and solute vaporization effects. These effects are not typically found with ICP. However, if observed they can be minimized by matrix matching. Further improvements can be obtained by careful selection of operating conditions (e.g. incident power, observation position, etc.) by buffering of the sample, matrix matching, and standard addition procedures. These types of interferences can be highly dependent on matrix type and the specific analyte element of interest.


5.1.3 Detection Range Limits

Minimum Detection Limit (MDL) - The minimum detection limit for an element/wavelength must be determined, as directed by the CTF. Attachment 8.4, ICP-ES Method Detection Limits, lists typical MDLs for routine elements on the Leeman Prodigy.

The MDL is routinely determined by multiplying by ten the

standard deviation of ten blank measurements after calibrating the instrument in a particular matrix. Each blank measurement must be performed as though it were a separate sample. An MDL is normally measured in 2-5% HNO3.

MDL = 10 X conc)

(conc)- Standard deviation of ten blank measurements in units of either mg/L or g/L.

MDLs can also be determined for specific matrices by measuring a blank and standards spiked with the matrix. When directed by the CTF, an alternate approach may also be utilized to determine an MDL using the calibration and QC intensities obtained during an analysis. Each time the MDL for an element is determined, the resulting number (in mg/L) shall be kept on the ICP-ES server. The MDL files are controlled by the inclusion of a revision number and are matrix specific.

Linearity Ranges - The normal linearity range for analytes in an undiluted sample is from the MDL to 10 mg/L or maximum linear concentration, whichever is lower in the diluted sample.

Line Intensities Lines presenting a low intensity during

the analysis of a standard are typically calibrated using higher concentrations of standard (e.g. Sulfur). Drift in the apparent concentration of the blank for a low intensity line should not be a concern if the drift is comparable to the


detection limit (which is higher than for more sensitive lines).

5.1.4 Quality Assurance and Quality Control

5.1.4.1 MS&E Components

A series of pipettes, component parts of the Leeman Prodigy ICPES system, are identified via their unique serial numbers in the MS&E/Maintenance History logbook. Prior to use, the pipette is checked via weighing DDI H2O on a calibrated balance. Weighing result must be within 1% of the maximum volume for that pipette. If the pipette is out of the acceptable limit contact the CTF.

5.1.4.2 Registered Notebooks

At the direction of the CTF, the following are kept in a bound registered MS&E history notebook: Unique ID of pipets incorporated as part of the

RADICPES MS&E system, instrument status data, records of preventive maintenance and instrument

repair.

5.1.4.3 Calibration Standards

The instrument is calibrated for each analyte to be quantified. A standard curve for that element is generated using standard solutions with varying concentrations and a calibration blank. Mixed calibration standard solutions are prepared by combining appropriate volumes of the stock solutions in Class A #5680 volumetric flasks, or equivalent. Stock standard solutions shall be traceable to NIST standards or in compliance with QAP 2-7. Purchased multi-element standard solutions should be replaced when beyond the manufacturer’s expiration date. (Extending the use of calibration stock standards


beyond the expiration date is accomplished via procedure 1Q, QAP 2-7.) The number of calibration standards and their concentration depends on the specific element and its estimated concentration in the samples. The lowest concentration in a calibration standard is not to be lower than the Minimum Detection Limit (MDL) for that element. The number and concentration of standards should be approved by the CTF for prior to analysis. The calibration blank should contain the appropriate acid(s) and/or other materials used for sample preparation and the calibration standards.

After receiving replacement calibration stock standards, the stock solutions should be analyzed separately to determine possible spectral interferences and to detect the presence of impurities. Care should be taken when preparing any mixed standards that the elements are compatible and stable.

Prepare the mixed calibration standard solutions and transfer to a clean LDPE (low-density polyethylene) bottle. Freshly mixed standards should be prepared only as needed with the realization that concentration can change on aging. Fresh calibration standards should be prepared monthly (every 30 days). The 30 day shelf life may be adjusted if faster degradation has been confirmed, the material is consumed, or the CTF directs otherwise. If continuity of data is better served to use a calibration standard solution beyond 30 days, contact the CTF for approval. Purchased multi-element standard solutions contain typical calibration standard analytes. To facilitate analyzing a large variety of samples several custom mix standards are used. The elements contained in each mix vary depending upon vendor determined combinations.

Note: The specific analyte combinations and matrices used in an analysis are method-specific.


All standard combinations should be approved by the CTF before use. In the situation when a standard is not commercially available, elemental concentrations must be established by an acceptable laboratory method e.g. radiological counting, mass spectrometry, etc.

5.1.4.4 Data Validation (Quality Control)

5.1.4.4.1 Quality Control (QC) standards are analyzed

for routine samples. The QC standard is made from independent dilutions of stock standards that originate from a lot number different from the calibration standards. Other sources of stock standards may be utilized when directed to do so by the CTF. For the purchased multi-element standard solutions, the respective QC standards may be made from independent dilutions of single element stock standard solutions or as directed by the CTF. This material should be matrix matched to the calibration standards and should include the elements specified by the CTF from the customer requirements. QC standards originating from the same lot as the calibration standards may be used at the discretion of the CTF if a measurement from an independent source is made at least once during the analysis.

5.1.4.4.2 QC standard results are acceptable when the

results are within +10% of the listed values (prepared concentration). If the results are outside the QC limits, indicating calibration drift (or an “out-of-calibration condition”), consult the CTF.


5.1.4.4.3 Analyze the calibration blank before the QC

standard(s), as directed by the CTF. (This is the same material used for instrument calibration.).

The results should be low ppb (< ~1/3 of MDL). Results higher than this may need to be reviewed with the CTF.

5.1.4.4.4 Analyzing the QC standard(s)

QC standards are to be run such that they bracket sets of samples. This is accomplished by running the QC standards: after the calibration, every 10 to 15 samples or with every

group of samples, and at the end of the samples to be run with

that particular method Note: High concentrations of analyte may require flushing of the system and analysis of a blank after the last sample before “closing” QC standard.

5.1.4.4.5 All calibration and QC data results are

electronically stored on an Analytical Development controlled server. The server is backed up nightly. Because quality assurance requires that the Manufacturer, Expiration Date, Lot #, and dilution/matrix information be traceable on the solutions used for these measurements, documenting will be done via recording in the MS&E History notebook.

Note: EPA protocols dictate additional QC that is outside the scope of this procedure. Customer assisted Quality Assurance can be performed by acquiring these QC standards


and providing directions in a Task Plan on how to implement their use.

5.1.4.5 Traceability

Traceability of reported analytical results is documented via the pipets assigned to this MS&E system, unique LIMS sample number, and personnel identified in the electronic record stored on the ADS file server.

5.1.5 Reagents

Acids typically used in the preparation of standards and for sample processing must be ultrahigh purity grade or equivalent. Redistilled acids from Seastar Chemical, Seattle, WA are acceptable examples. Reagent grade acids can be used for cleaning glassware and sample containers.

5.1.5.1 Nitric Acid (16 M HNO3) - Concentrated (sp gr 1.41).

5.1.5.2 Deionized Water - Prepared by passing distilled or

potable water through a mixed bed of cation and anion exchange resins. Use deionized distilled water for the preparation of all reagents, calibration standards, and as dilution water. The purity of this water must be equivalent to ASTM Type II reagent water of Specification D 11931. This is available from the Millipore Milli-Q system.

Note: Building-distilled water "as is" does not meet this specification and should not be used unless it has been deionized through the Milli-Q system.

Before using the Milli-Q water make sure the resistance reading of the water on the LED meter is greater than 10 M/cm. Normal operation is in the 14-18 M range. Replace the ion exchange cartridges when the digital display indicates and allow water to run through the system until the display reads 18.2.


5.1.5.3 Calibration Standard Stock Solutions - These solutions

may be purchased or prepared from ultrahigh purity grade chemicals or metals. All standards should be NIST traceable or in compliance with QAP 2-7.

5.2 Operational Steps

5.2.1 Instrument Start-up

5.2.1.1 Instrument and computer power remains on at all

times. If power is off during start-up, consult either the CTF or a Leeman representative.

5.2.1.2 Turn on the monitor.

5.2.1.3 From the windows operating system, double click on

the Salsa.exe icon and click “OK” when prompted for a password.

5.2.1.4 Click on Method and Open in order to open an ICP method.

5.2.1.5 Highlight the method of choice and click OK.

5.2.1.6 If the prompt Opening Method Lines Updating from

Library appears, then

Click OK and proceed to step 5.2.1.7, else Proceed to step 5.2.1.7.

5.2.1.7 Click on the Method tab (found at the bottom of the

navigation panel as shown in Figure A-1).

5.2.1.8 Expand method by clicking on the + symbol.

5.2.1.9 Click on the Instrument Control line (listed on the


navigation panel as shown on Attachment 8.6, Figure A-1).

5.2.1.10 Click on Air in the Autosampler control box (found on

the Instrument Control screen as shown on Attachment 8.6, Figure A-1) in order to raise the uptake sipper tube.

CAUTION!

USE CAUTION WHEN ENGAGING PERISTALTIC PUMP

DUE TO PINCH POINTS

5.2.1.11 Connect the sample tubing (black-black or equivalent) and residue tubing (red-red or equivalent) around the peristaltic pump and close the levers.

5.2.1.12 Replenish and place the rinse reservoir underneath

the sample uptake tube.

5.2.1.13 From the Instrument Control screen (Attachment 8.6, Figure A-1), click on Rinse in the Autosampler control box in order to return the uptake sipper tube to the rinse reservoir.

5.2.1.14 On the Instrument Control screen (Attachment 8.6,

Figure A-1), click on Autostart and wait 40 seconds. The plasma will automatically ignite after this 40 seconds interval.

5.2.1.15 If the plasma does not remain lit, press the

Extinguish button next to Autostart. Repeat step 5.2.1.14. If the plasma does not sustain after repeating this step, contact the CTF.

5.2.1.16 Observe the plasma, uptake and drain tubing. If any

of these are unstable, press the Extinguish button and start again at step 5.2.1.14.


5.2.1.17 Allow the system to stabilize for thirty minutes at

these conditions before running calibrations or sample analyses. Conditions for normal operation are shown in 5.2.2.1.

5.2.1.18 After at least 30 minutes, select Standards and cup

33 from the pull-down cursors available in the Autosampler box and click Cup Fig. A1. This will send the uptake sipper tube to the position plasma solution (~10 ppm Mn in 2% nitric acid) in cup 33 on the standards rack (Attachment 8.6, Figure A-2).

5.2.1.19 Select the Auto-align function located on the shortcut

toolbar (Attachment 8.6, Figure A-3). 5.2.1.20 Click on Auto Align in the Auto Wavelength

Alignment box in order to automatically align on the Hg Reference Lamp (Attachment 8.6, Figure A-4).

5.2.1.21 After about a minute when the “Hg Ref alignment

fragment finished, acceptance required to continue” statement appears (Attachment 8.6, Figure A-4), highlight “Hg Ref” line (Attachment 8.6, Figure A-4) and view the dx and dy parameters.

5.2.1.22 If the dx and dy parameters are not between -4 and +4

(0 is optimum for both dx and dy), then Contact CTF, else Accept the Hg reference alignment and close the

Auto Wavelength Alignment box. 5.2.1.23 Click on the Radial option (Attachment 8.6, Figure A-

1) and the Position Plasma button (Attachment 8.6, Figure A-1) in order to peak the plasma on the intermediate Mn wavelength or wavelength of choice in the radial mode.

5.2.1.24 Select Mn 257.610 r (where r is for radial mode) or

the wavelength of choice from the scroll-down menu


located on the Position Source box and click on Peak Plasma (Attachment 8.6, Figure A-5). This will position the plasma in the radial mode. The minimum signal of Mn 257.610 r in the radial mode for 10 ppm Mn is 100,000 counts.

5.2.1.25 After the position plasma is complete (about one

minute), click on Close (Attachment 8.6, Figure A-5).

5.2.1.26 Click on the Axial option (Attachment 8.6, Figure A-1) and the Position Plasma button (Attachment 8.6, Figure A-1) in order to peak the plasma on the intermediate Mn wavelength or wavelength of choice in the axial mode.

5.2.1.27 Select Mn 257.610 (notice absence of “r” for radial) or

the wavelength of choice from the scroll-down menu located on the Position Source box and click on Peak Plasma (Attachment 8.6, Figure A-6). Note that the title in the window top must agree with the large bold print inside of the window (Attachment 8.6, Figure A-6). This will position the plasma in the axial mode. The minimum signal of Mn 257.610 in the axial mode for 10 ppm Mn is 1,000,000 counts.

5.2.1.28 After the position plasma is complete (about one

minute), click the Close button (Attachment 8.6, Figure A-6) and click on the “Rinse” button in the Autosampler box on the Instrument Control screen (Attachment 8.6, Figure A-1) in order to return the uptake sipper tube to the rinse reservoir.

5.2.2 Instrument Set-up Conditions (typical – as seen on screen shown in Attachment 8.6, Figure A-1).

5.2.2.1 At top of window: Power: 1.2 kW

Coolant gas flow: 19 L/min Auxiliary gas flow: 0.5 L/min Nebulizer gas flow: 32 psi


Pump flow rate: 1.1 mL/min Camera status: Connected; -45 ºC Within the window: Purge setting: Low

5.2.2.2 The above conditions are set for normal operation of

the instrument in most cases. However, there are occasions where other conditions will be used. These situations include analysis of alkali elements, halides and organic solutions. Consult the CTF prior to use under non-routine conditions.

5.2.3 Calibration and Analysis

5.2.3.1 Calibration and analysis are performed by using the

QC Automation function on the method tab along with the Run Sequence function on the sequence tab. Sequence files can be generated on pre-existing methods. Method generation will be discussed in Section 5.2.4. A complete understanding of the method is not needed to generate a sequence or perform an analysis.

5.2.3.2 On the Method tab, select the QC Automation line on

the navigation panel (Attachment 8.6, Figure A-7). 5.2.3.3 Check the appropriate boxes on the QC Automation

screen in order to select the calibration and QC standards of choice as depicted on Attachment 8.6, Figure A-7.

5.2.3.4 Select the Analysis tab at the bottom of the

navigation panel and click on Analysis on the Analysis screen (Attachment 8.6, Figure A-8).

5.2.3.5 Select New off the list of choices on the Analysis pull-

down menu and type today’s date (0-00-00) as shown on Attachment 8.8, Figure A-8. This will create a new daily analysis chapter.

5.2.3.6 Click OK to accept the new analysis chapter and


click on Results tab on the Analysis screen (Attachment 8.8, Figure A-8). This will allow results viewing during analysis.

5.2.3.7 Select the Sequence tab at the bottom of the

navigation panel (Attachment 8.6, Figure A-8). 5.2.3.8 Type the sample IDs to include the dilution factors on

the sequence editor and click Update (Attachment 8.6, Figure A-2). This will include the sample rack in the sequence. NOTE: An internal standard blank is placed in position 1 of the sample rack as a typical practice.

5.2.3.9 Review the sequence listed on the navigation panel to

ensure appropriate calibration and QC standards and sample identifications, etc. (Attachment 8.6, FigureA2).

CAUTION!

MOST SAMPLES ARE RADIOACTIVE AND COULD

CONTAIN HNO3 OR HF, FOLLOW SAFETY GUIDELINES THAT ARE SPECIFIED IN SECTION 3.0

OF THIS PROCEDURE

5.2.3.10 Load the standards and sample racks in accordance with the racks diagram on the sequence screen (Attachment 8.6, Figure A-2).

5.2.3.11 Click on Run Sequence on the sequence screen.

5.2.3.12 If the warning condition, the following subarrays

overlap . . . . continue?, appears, then click Yes.

5.2.3.13 Select analysis tab on the navigation panel. The Results menu will be available to view results during a run.


5.2.3.14 The method can be saved as a precaution at any point

while setting up for calibration and analysis. Select the method tab on the navigation panel and click on Method from the menu bar (Attachment 8.6, Figure A-9).

5.2.3.15 The calibration curves can be reviewed at any point

during a calibration and analysis. Select the method tab on the navigation panel and click on the plus symbol next to the Element Selection line on the navigation panel. Click on the wavelength of choice and click on the Calibration tab on the displayed wavelength screen. The Rho coefficient (acceptable is >0.995) and calibration curve levels are displayed for review on this screen. (Attachment 8.6, Figure A-10).

5.2.4 Method Creation

A method is a program, which contains all pertinent information for analysis. To create a method one must define:

The element(s) to determine, The wavelength(s) by element The standards and their concentrations The rinse time between subsequent samples The transfer time from sample to plasma The plasma conditions for the instrument Method Creation is an advanced topic which is not required

for analysis. See Attachment 8.7 for procedure for Method creation

5.2.5 Calibration Frequency

The instrument requires a minimum of a daily calibration unless directed by the CTF, for each method. A previously created calibration curve may be confirmed for subsequent use by the analysis of a blank as well as the check standards required in the method of interest. The desired minimum value for the correlation coefficient for each element should be 0.995. If analysis of the check does not meet the + 10% requirement, re-calibrate. However, a method may require calibration more


frequently. If the system is left idle for extended time periods, drift can occur and the calibration should be re-checked by analyzing for all elements using a blank and the QC standards. Data is recorded and stored in the following manner (refer to Attachment 8.6, Figure A-11):

The appropriate Report Spec is loaded on the analysis tab and Report menu with the Load function.

The results of choice are selected by clicking on the appropriate boxes listed on the navigation panel on the analysis tab.

The results are exported in CSV format by clicking the CSV button on the Report menu.

All data is in an Excel export file titled with the sample identification, date and time of analysis.

The export files are archived on the ICP server for CTF review.

Section 5.1.4 outlines the requirements for frequency and acceptance of QC and Blank results.

5.2.6 Analytical Waste and Residue

CAUTION!

THE RESIDUE IS RADIOACTIVE AND COULD CONTAIN HNO3 OR HF, FOLLOW SAFETY GUIDELINES THAT ARE

SPECIFIED IN SECTION 3.0 OF THIS PROCEDURE

Discard all analytical waste and residue according to proper procedures. (L1)

5.2.6.1 Standards

Discard any RCRA standards containing the following RCRA metals in concentrated (1,000 ppm) form according to CTF instructions:


As Ag Ba Cd Cr Pb Se

5.2.6.2 Samples

Discard diluted sample material and excess standard solution according to CTF instructions.

5.2.6.3 Listed Waste Samples Listed waste samples (i.e. F006-listed) must have all

waste collected (including the effluent that normally goes to the High Activity Drain) and returned to the customer

5.2.7 Calculations

The software is NOT set up to automatically calculate elemental concentrations with adjustments for the weights and volumes of digestions and dilutions. Post-processing of the concentrations with the dilution factors prior to reporting are done by the CTF or designee.

5.2.8 Preventative Maintenance

5.2.8.1 At the direction of the CTF, record all preventive

maintenance and instrument repair actions in the registered MS&E ICP History/Maintenance Log Book. The Leeman Software provides a basic maintenance schedule.

CAUTION!

USE CAUTION WHEN REPLACING PERISTALTIC PUMP TUBING DUE TO PINCH POINTS


5.2.8.2 Daily Check the sample introduction system and torch

assembly for any noticeable problems - collapsed tubing, cracked torch, clogged nebulizer, etc.

Replace peristaltic pump tubing, as needed. Check Peri pump tension.

CAUTION!

USE CAUTION WHEN REPLACING CHILLER WATER

DUE TO PINCH POINTS AND POTENTIAL FOR WATER SPILL AND HEAD INJURY

5.2.8.3 Monthly Check drain tubing. Replace chiller and camera water, as needed.

CAUTION!

USE CARE WHEN HANDLING THE TORCH BOX

ASSEMBLY GLASS COMPONENTS DUE TO POSSIBLE GLASS BREAKING

5.2.8.4 As needed or as directed by CTF

Replace nebulizer (6-9 months max). Replace or clean torch (as needed). Replace side view mirror Clean lens between spectrometer and torch box Check condition of all tygon tubing connecting

torch with argon gas. Replace where necessary.

It should be noted that the torch box assembly is never opened without first de-energizing the unit, which is accomplished by pressing the red button on the spectrometer and switching the breaker to the “off” position on the separate power supply unit. Further


upkeep on the instrument will be maintained through regular PM service visits, which are covered under the service agreement. Record all pertinent information from vendor visit in MS&E History Logbook.

6.0 RECORDS

6.1 Raw Data A customer may request a copy of all the raw data. Long-term data

storage is the customer’s responsibility. Record copy of raw data is stored on the ADS file server and backed up daily.

6.2 Quality Control Data

Quality Control data, including diagnostics information, is stored on the ADS file server and backed up daily.

6.3 Results Printouts “Information Only” file copies of all results transmitted to customers

are maintained in the ICP laboratory. Electronic record copy is maintained on the ADS file server.

6.4 Data Control, Electronic Records, and Software

6.4.1 LIMS Carefully review the data for errors and concentrations above

the linearity ranges that are defined by the CTF or supervision. Sequential dilutions may be needed.

If the samples were submitted in solid form, the digestion

dilution factor (DF) will be addressed by the CTF. For volumetric dilutions, the aliquot is entered on the Wt. column of the sequence editor, whereas the total volume is entered on the Vol. Column of the Sequence editor (Attachment 8.6, Figure A-2). The report will generate non-dilution corrected instrument results with the appropriate dilution factors included.

Report the samples as complete and results reported to the


customer on the ADS Laboratory Information Management System (LIMS). Enter results promptly. All samples analyzed during a work week should be entered into the LIMS database by the close of the last business day of that week. A typical entry would read “to (customer name), (date), (electronic file reference)”.

6.4.2 Electronic Records Periodically, typically monthly, confirm the backup of analytical

results onto a file server followed by a purge of old files from the IBM-compatible PC computer that controls the ICP-ES.

6.4.3 Software Software validation is indirectly demonstrated by the results

obtained with the QC standards and comparison of the results for submitted analytical reference materials to the known values.

7.0 References

7.1 Annual Book of ASTM Standards, Part 31. 7.2 Teledyne Leeman Labs Prodigy/Prism ICP High Dispersion ICP

Manual, May 2006, Leeman Reference: 61 7.3 L1 Manual, Procedure 4.19, “Laboratory Notebooks and Logbooks.

8.0 Attachments

8.1 Sample Collection, Preservation, and Preparation 8.2 Troubleshooting 8.3 Commonly-Used Dilution Factors 8.4 ICP-ES Method Detection Limits (Expected Performance of Leeman

Prodigy) 8.5 Method Development 8.6 Figures A-1 to A-17


Attachment 8.1 Sample Collection, Preservation and Preparation

Page 1 of 2

8.1.1 Sample Collection

It is the customer's responsibility to ensure that representative samples are collected and stored in properly cleaned containers. This is especially important for the ultratrace determination of toxic heavy metals. Glass containers are not recommended for sample storage or submitted to AD by the customer for ICP analyses.

For the determination of trace elements, contamination and loss are prime concerns. Dust in the laboratory environment, impurities in reagents and impurities on laboratory apparatus which the sample contacts are all sources of potential contamination. Sample containers can introduce either positive or negative errors in the measurement of trace elements by (a) contributing contaminants through leaching or surface desorption, and (b) by depleting concentrations through absorption. Thus, the collection and treatment of the sample prior to analysis requires particular attention. Laboratory glassware including the sample bottle (whether polyethylene, polypropylene, or FEP-fluorocarbon) should be thoroughly washed with detergent and tap water, soaked for 30 min in HNO3(1+1), rinsed with deionized water, soaked for 30 min. in HCl (1+1), and finally rinsed thoroughly with deionized water. Containers, precleaned using EPA protocols, are commercially available from I-Chem Research, Hayward CA.

Note: If it can be documented through an active analytical quality control program using spiked samples and reagent blanks, that certain steps in the cleaning procedure are not required for routine samples, those steps may be eliminated.

8.1.2 Sample Preservation It is the customer's responsibility to properly preserve their

samples before they are submitted to ADS.


Attachment 8.1 Sample Collection, Preservation and Preparation

Page 2 of 2 8.1.3 Sample Preparation for Solid Samples

One of several dissolutions e.g. sodium peroxide fusion, closed-vessel microwave digestion, will be required for total element determination of most solids or slurries with high percentage suspended solids.


Attachment 8.2 Troubleshooting

Page 1 of 2

8.2 Troubleshooting Troubleshooting discussed in this procedure is limited to adjustments

on the sample introduction system; all other troubleshooting is beyond the scope and needs technical supervision.

8.2.1 Sample Introduction System

8.2.1.1 If the plasma is extinguished when the nebulizer flow

is turned on: Run the pump for one minute prior with the sipper

uptake tube in the air position. Immerse the sipper uptake tube in rinse solution.

(Check tip of tubing - cut Teflon tube at angle if required.)

Restart the plasma by following directions in section 5.2.1.

8.2.1.2 If the plasma extinguishes during a run, check

connections for air leaks at: Nebulizer gas inlet Nebulizer o-ring seals Drain joint Joint between torch and spray chamber

8.2.1.3 If the plasma is uneven in shape (resulting in low

profile intensities or other problems), do the following: Turn off the plasma and check the alignment of the

torch relative to the coil. The torch is positioned in the center of the coil, 2 mm from air block.

Turn off the plasma and check that the injector tube is concentric with the torch body (if using the HF resistant system). If the tube is not concentric, disassemble it and reposition concentric within the torch body.


Attachment 8.2 Troubleshooting

Page 2 of 2

8.2.1.4 If no spray is coming from the nebulizer (or leakage into the catch vessel on the line from the pump to the nebulizer), do the following:

Check the connection between the pump tubing and the nebulizer tubing. Check the nebulizer for plugs. If plugged, replace the nebulizer.

Check the tube connections at the peristaltic pump, check that the tubing is not pinched in the connectors.

Note: The tubing connection between the peristaltic pump and the nebulizer is contained in an overflow container vial to catch liquid if the nebulizer clogs.

8.2.2. RF Generator

8.2.2.1 If the torch will not light or arcing occurs while trying

to light the plasma, do the following:

Check the sample introduction system for air leaks as described above.

If torch still will not light, insert another sample introduction system and try to ignite plasma again.

If torch still will not light, contact technical supervision, problem is probably related to power supply.

8.2.2.2 If salt buildup or torch erosion is noted, change torch

as necessary.

8.2.3. Spectrometer

If problems occur in the spectrometer, contact technical personnel.


Attachment 8.3 Commonly-Used Dilution Factors

Dilution mL 2-5% HNO3

Sample Aliquot

5-ppm Internal Standard

Total Volume

10X 8.00 1 mL

1 mL 10 mL

20X 8.50 0.5 mL

1 mL 10 mL

25X 8.60 0.40 mL

1 mL 10 mL

40X 8.75 0.25 mL

1 mL 10 mL

100X 8.90 0.10 mL

1 mL 10 mL

1,000X 8.91 0.10 mL of10X

0.990 mL 10 mL

100X 8.10 1.00 mL of 10X

0.900 mL 10 mL

40X 6.75 2.50 mL of 10 X

0.750 mL 10 mL

25X 5.40 4.00 mL of 10X

0.600 mL 10 mL

20X 4.50 5.00 mL of 10X

0.500 mL 10 mL

1.0 mL of 1000 ppm standard diluted to 100.0 mL = 10 ppm

0.1 mL of 10 ppm standard diluted to 100.0 mL = 10 ppb


Attachment 8.4 ICP-ES Method Detection Limits (Expected Performance

of Leeman Prodigy ICP-ES)

Element

Wavelength (nm)

MDL* (mg/L)

Element

Wavelength (nm)

MDL*

(mg/L)

Aluminum 308.215 0.060 Molybdenum 202.032 0.011

Barium 230.424 0.003 Nickel 231.604 0.011

Boron 208.959 0.009 Phosphorus 214.914 0.050

Cadmium 226.502 0.001 Potassium 766.490 0.019

Calcium 393.366 0.008 Silicon 251.611 0.018

Cerium 413.380 0.050 Silver 328.068 0.017

Chromium 205.552 0.004 Sodium 589.592 0.04

Copper 324.754 0.003 Strontium 460.733 0.013

Cobalt 228.615 0.005 Tin 189.926 0.020

Iron 259.940 0.003 Titanium 334.940 0.002

Lanthanum 408.672 0.010 Zinc 213.856 0.005

Lead 220.353 0.013 Zirconium 339.198 0.004

Lithium 670.784 0.001

Magnesium 279.553 0.001

Manganese 257.610 0.002

*Refer to the Leeman ICP-ES MDL electronic file to obtain the experimentally determined MDL. Results are obtained using procedure described in section 5.1.3 unless noted.

Additional elements are available upon request.


Attachment 8.5 Method Development

Page 1 of 3

8.5 Method Development

8.5.1 Click the method tab on the navigation panel (Attachment 8.6, Figure A-1).

8.5.2 Click on Method from the menu bar and select New from the

pull-down menu. (Attachment 8.6, Figure A-9).

8.5.3 On the pop up dialog box that appears, type the method’s name into the method name field and today’s date (0-00-00) in the analysis chapter field and click on the OK button to accept.

8.5.4 In the navigation panel the method name appears with a small

box to its left. Click on the box in order to expand the method tree and click on the Element Selection line on the navigation panel to display the Periodic Table of elements (Attachment 8.6, Figure A-12).

8.5.5 On the Periodic chart, click on the element of choice.

Immediately the two tables at the top of the display will be populated. In the left table the wavelengths that are available in the line library are displayed. Click on the line of choice, after which the spectral information for nearby interferents are listed on the right table (Attachment 8.6, Figure A-13).

8.5.6 Click Add Line button in order to use this wavelength. Once

selected, the wavelength appears on the navigation panel under the Element Selection line (Attachment 8.6, Figure A-13).

8.5.7 Line selection is an important part of method development.

Good line selection requires significant ICP-ES background; thus, help from a subject-matter-expert is advised. General suggestions for line selection include:

Choose the most sensitive wavelength.

Examine the interference table of the selected wavelength(s) to look for interference in the matrix.



Page 2 of 3

Choose an alternate wavelength if interference is suspected for a given matrix.

8.5.8 In order to add standards for the new method, click on the

Standards/MSA line on the navigation panel. A screen for naming the method’s standards is displayed (Attachment 8.6, Figure A-14).

8.5.9 Click on the Add Standard button and in the resultant dialog

box, type the desired title for the Standard Name and type the desired concentration for the Default concentration. Click OK to accept and note that the right table is populated with all lines set at the default concentration (Attachment 8.6, Figure A-14).

8.5.10 Click on the standard of choice, which is listed in the Standard

name box, and select the Line on the Standard lines box in order to change the default concentration of a given standard (Attachment 8.6, Figure A-14).

8.5.11 Click on the Internal Standards line on the navigation panel in

order to set a wavelength as the internal standard (Attachment 8.6, Figure A-15)

. 8.5.12 Click on the Quality Control Checks line on the navigation

panel in order to set up QC standards (Attachment 8.6, Figure A-16).

8.5.13 In order to establish desired QC checks, click on Add QC

(Attachment 8.8, Figure A-16). After a QC name has been entered, click on Check Standard title at top of QC list. This will cause the Check Standard Line to populate. Select check marks only for elements in the QC standard that was highlighted (Attachment 8.6, Figure A-16).



Page 2 of 3

8.5.14 Click on the Analytical Parameters line on the navigation panel

in order to set up parameters for the method (Typical or default settings are illustrated on Attachment 8.6, Figure A-17). It should be noted that the uptake time is the time it takes for the sample to reach the plasma. It depends primarily on the length of tubing used for sample introduction. This time, along with the rinse and integration times, should be determined experimentally. Consult the CTF for accurate Uptake and Rinse times.

8.5.15 Save the method as described on step 5.2.3.14.


Attachment 8.6 Figures A-1 to A-16

Pages 1 of 15

Figure A-1: Instrument Control Screen.

Method tool bar

Navigationpanel

AutosamplerPump

Auto Start

PositionPlasma

Rinse Air

RadialAxial

Settings

Purge options



Pages 2 of 15

Figure A-2: Sequence Tab

RunSequence

Sequence Editor UpdateTypical

Sequence

Cup 33 Cup 1 Cup 1 Cup 44


Attachment 8.6 Figures A-1 to A-16 Pages 3 of 15

Figure A-3: Shortcut Tool Bar. Auto-align


Figure A-4: Auto Wavelength Alignment for Hg Reference

Auto-align

Accept

HgReference

dxdy



Pages 4 of 15

Figure A-5: Position Plasma for Radial

Figure A-6: Position Plasma for Axial

Typical Radial PeakWavelength

Peak Plasma

Typical Axial PeakWavelength

Peak Plasma

Radial Radial

Close

Axial

Close



Pages 5 of 15

Figure A-7: QC Automation Screen

QC Automation

CalibrationStandards

PeriodicQC Analysis

FinalQC Analysis



Pages 6 of 15

Figure A-8: Analysis Tab

Results

OK



Pages 7 of 15

Figure A-9: Method Save



Pages 8 of 15

Figure A-10: Calibration review

CalibrationElement Selection

Wavelength of choice

Calibration R2



Pages 9 of 15

Figure A-11: Report Menu

Analysis Tab

Load Function

Result Selection

ReportSpec

Report Menu Tab



Pages 10 of 15

Figure A-12: Element Selection

Method Tree



Pages 11 of 15

Figure A-13: Line selection

Lines Added

Available Lines for Element

Interferences per Element



Pages 12 of 15

Figure A-14: Standards setup

Standard Choice Add Standard

Line Choice ConcentrationAdjustment



Pages 13 of 15

Figure A-15: Internal Standards

Internal Standard

I. S. Corrected

Internal Standard



Pages 14 of 15

Figure A-16: Quality Control Standards

QC Title

ConcentrationAdjustment



Pages 15 of 15

Figure A-17: Analytical Parameters

Integration Rinse

Uptake

SAVANNAH RIVER NATIONAL LABORATORY Manual: L16.1 ANALYTICAL DEVELOPMENT Procedure: ADS - 2226 ANALYTICAL OPERATING PROCEDURES Revision: 9 Page: 1 of 8 TECHNICAL REFERENCE Effective Date: 10/22/2009 MAJOR REWRITE

1

Aqua Regia Dissolution of Sludge Approved by: for Elemental Analysis (U) APPROVAL ON FILE AD Manager _____________________________________________________________________________ 1.0 PURPOSE

This procedure describes the aqua regia dissolution method.

2.0 SCOPE Aqua regia (the common chemical name for a 3:1 by volume mixture of

concentrated HCl and HNO3) is an effective method for dissolving waste tank sludge samples. The resulting solution is analyzed for elemental and radionuclide composition. Sludge dissolution is the sample preparation step required before elemental analysis by Inductively Coupled Plasma-Atomic Emission Spectroscopy (ICP-AES), Atomic Absorption Spectroscopy (AAS), and Inductively Coupled Plasma Mass Spectroscopy (ICP-MS). Radiochemistry and nuclear counting techniques are also performed on the dissolutions. This procedure is applicable to both actual radioactive sludge from the waste tanks and non-radioactive synthetic sludge that simulates waste tank sludge compositions; both materials have been successfully dissolved using this process.

The aqua regia method is broadly applicable to many sample types and can

be applied to different type samples per the technical judgment of the Task Supervisor.

The aqua regia dissolution is commonly used concurrently with a sodium

peroxide/sodium hydroxide fusion dissolution (for brevity, it will be referred to as the sodium peroxide fusion method in this document) to dissolve sludge for subsequent analysis. The sodium peroxide fusion dissolution is discussed in a separate procedure.


3.1 Safety Precautions

3.1.1 HCl and HNO3 are strong, corrosive acids that cause serious chemical burns. Perform the entire procedure in a fume hood,


2

glove box, or shielded cell. Avoid contact with skin and breathing vapors.

3.1.2 Protective clothing for performing the procedure in a fume

hood shall consist of:

Safety glasses or goggles Face shield (not required if the hood sash can be lowered

below the face and neck). The face shield is used while working with concentrated acids. After addition of water to create a more dilute solution, use of the face shield is no longer required.

Nitrile gloves Lab coat Rubber or plastic apron

3.1.3 Teflon® pressure vessels, which can build up significant

pressure upon heating, are used in this procedure. Two controls are used to prevent over-pressurization: pressure relief valves on the vessels and over-temperature control on the ovens.


None

5.0 PERFORMANCE 5.1 General Information

5.1.1 Method Description

The dissolution conditions can be modified per the technical judgment of the Task Supervisor. The following is a general description of the method that is applicable to the preponderance of SRNL samples.

Approximately 0.25 g of dried sludge are mixed with 12 mL of aqua regia (9 mL concentrated HCl and 3 mL concentrated HNO3) in a Teflon container used for microwave oven


3

dissolutions. The container is sealed and placed in a drying oven controlled at 115 ± 5 °C. The mixture is heated for two hours after the temperature equilibrates to 115 ± 5 °C and then removed from the oven. After the solution cools for at least 30 minutes, the sample is diluted to 250 mL. This solution may then be directly analyzed or diluted further and then analyzed per the technical judgment of the Task Supervisors in charge of spectroscopic and radiochemistry methods.

5.1.2 Data Quality

Limitations and Interferences:

Most sludge components that comprise at least 0.5 weight percent can be determined with good precision (5% relative standard deviation or better) by using the aqua regia dissolution. The procedure dilutes solid samples by a factor of about 1000 fold (0.25 g of solid sample to 250 mL of solution). However, if sensitivity is a problem for some elements, a smaller dilution factor may be used. By diluting the original dissolution to 100 mL or less, an improvement in sensitivity can be achieved. This approach should be used when minor components (< 0.5 wt. %), such as noble metals, are to be determined.

Most sludge elements can be determined equally well from either the aqua regia or the sodium peroxide fusion dissolution method. However, select elements can only be measured after one or the other of the dissolutions. Na and Zr must be determined from the aqua regia dissolution because they are introduced in the sodium peroxide fusion method. K should also be determined from the aqua regia dissolution because some batches of sodium peroxide contain K as an impurity. The aqua regia dissolution should also be used for elements such as As, Cd, Hg, Os, P, Rb, Re, Te, and Se that may have appreciable volatility at high temperatures, and subsequently may be partially lost in the sodium peroxide fusion upon heating at 675°C. The aqua regia procedure is performed in a sealed Teflon vessel to retain volatile elements. If volatile elements do not have to be measured, the method may be


4

carried out in a non-pressurized vessel. However, this practice is discouraged since the corrosive acid fumes can escape and attack the metal surfaces of hoods, glove boxes and shielded cells. Si determinations obtained from aqua regia solutions are usually biased low relative to those obtained from the sodium peroxide method. Therefore, the sodium peroxide fusion method is used to determine Si.

5.1.3 Equipment

Teflon® pressure vessels: These vessels are also used for the microwave oven dissolution method. They contain a pressure relief valve that prevents the internal pressure from exceeding 120 ± 10 psig. The manufacturer of the vessels is CEM. The vessels are marketed by:

CEM P. O. Box 200 Matthews, NC 28106

Capping station: Also marketed by CEM or manual capping tools (fabricated by SRNL) Certified, calibrated analytical balance: Certified laboratory analytical balance should be able to weigh to at least the nearest 0.0001 g. For shielded cell dissolutions, the remote balances currently used are capable of weighing to the nearest 0.001 g. These balances are acceptable for shielded cell dissolutions. Drying oven Calibrated temperature controller for oven 250 mL plastic volumetric flasks or as directed by task supervisor

250 mL plastic bottles or as directed by task supervisor


5

5.1.4 Reagents

Hydrochloric acid - (HCl)-Concentrated, 37%, ACS reagent grade Nitric acid - (HNO3)-Concentrated, 65%, ACS reagent grade

5.2 Sample Preparation

5.2.1 Verify that the oven controller is within calibration. Record balance M&TE information in Attachment 8.1.

5.2.2 Preheat a drying oven to 115 ± 5 °C. 5.2.3 Tare the Teflon pressure vessel bottom on an analytical

balance.

5.2.4 Transfer about 0.25 g of sample to the pressure vessel. Record the weight to the nearest 0.001 g or 0.0001 g (depending on the sensitivity of the balance) in the Data Sheet (see Attachment 8.1) or R&D direction for pasting in a laboratory notebook.

5.2.5 Add 9 mL of concentrated HCl and 3 mL concentrated HNO3

to the sample. 5.2.6 Cap the vessel using the CEM capping station or manual

capping tools. 5.2.7 Place the vessel in the drying oven and heat for 2 hours ± 10

minutes after the temperature equilibrates to 115 ± 5 °C. 5.2.8 Remove the vessel from the drying oven and let it cool for at

least 30 minutes.

Caution: Opening the vessels while still hot can result in the top popping off dangerously.


6

5.2.9 Use the CEM Capping Station or manual capping tools to loosen the vessel caps.

5.2.10 Place a plastic funnel in the mouth of a plastic 250 mL plastic

volumetric flask. If smaller dilutions are required, i.e., 50 or 100 mL, substitute the required volumetric flask to obtain the desired dilution factor.

5.2.11 Pour the dissolved sample into the volumetric flask. 5.2.12 Add about 20 mL of distilled, deionized water to the digestion

vessel. 5.2.13 Pour the solution from the digestion vessel into the volumetric

flask. 5.2.14 Repeat Steps 5.2.12 through 5.2.14 to quantitatively transfer

the sample to the volumetric flask. 5.2.15 Add de-ionized water to the mark on the flask. 5.2.16 Cap the flask and shake vigorously to mix. 5.2.17 Pour the solution from the flask into a labeled plastic bottle

and transfer this bottle to AD sample receiving. Supply AD sample receiving with the sample weights and volumes.

5.2.18 Ensure data table is completed and pasted in a notebook.

Record additional information on data sheet, if necessary.

6.0 RECORDS

Lab notebook 7.0 REFERENCE

C. J. Coleman, ADS 2502, "Alkali Fusion Dissolutions Of Sludge And Glass For Elemental And Anion Analysis," March 5, 1990.


7

8.0 ATTACHMENT Attachment 8:1: Data Table


8

ATTACHMENT 8.1 Balance M&TE Number: __________________ Calibrated: _______________________________ Expires: __________________________________

Data Table

LIMS Number

Customer I.D.

Sample wt. to be used as directed by

task supervisor

(g)

Actual sample

weight used (g)

Final Dilution

Volume (mL)

Did Task Supervisor visibly observe digested sample?_____ Is solution clear or cloudy?_____ Visible solids after digestion?_____


Analysis of Solutions by Ion Approved by: Chromatography (U) Approval on File AD Manager MAJOR REWRITE 1.0 PURPOSE This procedure covers anion and cation determinations using ion exchange

chromatography in ADS labs. 2.0 SCOPE This procedure covers Dionex Instrumentation currently used and the

associated types of eluent systems. The system configurations, column types, eluent identities and concentrations, standard values, etc. are those recommended by the cognizant technical function (the task supervisor). They can be modified as instructed and documented by the Task Supervisor.

Ion chromatography is used to separate and quantitate ions in solutions.

Anions such as F-, Cl-, NO2-, NO3

-, Br-, SO42-, PO4

3-, C2O42-, CHO4

- , and NH4+

are routinely determined by this method. Many other inorganic and organic anions and cations can readily be determined without instrument modification.

Requests for determinations of other ions need to be made through the Task

Supervisor. Section 5 of ADS-2306 (this procedure) describes the method for handling the determination of non-routine ions.

2.1 Responsibilities

Analyst must:

• Follow ADS safety procedures and any special safety procedures instituted by the Task Supervisor.

• Be able to change eluent, for anion and cation analysis. • Operate and program the computer data acquisition system. • Prepare standards, eluents, and calibration standards. • Have a basic understanding of Ion Chromatography (IC) such that

new procedures can easily be implemented, column degradation can be recognized and the need for basic maintenance can be identified.


• Maintain adequate supplies in the IC Laboratory.

The Task Supervisor must:

• Make sure all analysts adhere to SRNL and AD safety requirements.

• Verify and approve all determinations or assign approval to another person.

• Develop new procedures and revise existing procedures when necessary.

• Develop R&D Directions for non-routine samples (see Section 5). • Maintain and troubleshoot the IC Instrument. • Maintain adequate supplies in the IC Laboratory.


3.1 Safety

3.1.1 See Hazard Assesment Package # SRNL-ADD-2008-00163 for detailed hazard identification and mitigation.

Hazard Hazard Control

Working with Liquid Samples - Mixed radioactive/toxic/corrosive

materials

Handle materials in the appropriate containment unit with two pair

gloves, protective eyeware with side shields and laboratory coat (PPE). Use care to avoid splashing, use

limited quantites Glass Breaking Eyes on task

Lifting Use correct lifting technique Flammable cleaning material Handle limited quantities with no

local ignition source. Store material in a flammable cabinet

Sample injection Sample injection is performed in an auto-sampler, auto-sampler is self contained in a housing with cover

preventing contact during injection Pressure (IC systems) Use proper pressure relief systems

Pressure (purge and trap system) Use small volumes and gentle streams for purge


3.1.2 Additional Safety Considerations Follow all SRNL Laboratory radiation work practices (Manual

L1, 2.32). and chemical handling guidelines (L1, 3.14,3.15). Only authorized personnel may operate the ion chromatograph

instrument. Always add acid to water when working with acids.

4.0 PREREQUSITE ACTIONS None 5.0 PERFORMANCE



Ion chromatography is a liquid chromatographic technique. Separation of sample components (ions) result from unequal velocities of migration through a resin column because of differences in the equilibrium distribution between the mobile phase (eluent) and the stationary phase (ion-exchange resin). In 1975, the Dionex Corporation introduced suppressed ion conductivity to ion chromatography, enabling the routine use of sensitive ion conductivity as a universal detector for ion chromatography. In suppressed ion detection, a second ion exchange column is employed between the separator column, and conductivity cell (two column chromatography). This second column reduces the normal high conductivity of the eluent by converting the eluent to a lower conduction species, enhancing the sample signal to background ratio. The Dionex Ion Chromatograph (IC instrument) with an integrator or computer data acquisition system is a completely automatic ion analysis system. After the injection of sample, the instrument controls the pumps and valves to effect separation ending with the generation of a written analytical report. See the appropriate Dionex operating manuals for descriptive details of the system. (Reference #1)


5.1.2 General Limitations and Interferences

The nominal instrument detection limits are as follows when using a 100 µL sample loop: F-(0.2 µg/mL), Cl- (0.2 µg/mL), NO2

-

(1.0 µg/mL), NO3-(1.0 µg/mL), SO42- (0.5 µg/mL), PO43-(1.0

µg/mL), C2O4-2(1.0 µg/mL) and CHO2

- (1.0 µg/mL), Br- (1.0 µg/mL). If a sample needs to be diluted to prevent poisoning of the analytical columns, the sensitivity will decrease and the reporting limit will increase by that dilution factor. If a particular anion is not detected at the detection limit, the concentration value will be reported as “< (reporting limit).”The method precision is + 10% RSD (1σ) for clean water samples containing the ions listed within the calibration limits of the instrument. The precision for other samples may vary depending on the sample matrix and level of ions in solution. Only aqueous samples can be analyzed by this method. Samples should be filtered through a 0.22 µm filter prior to analysis to remove suspended particulate matter. Organic species in solution may interfere with this method. Hydroxide, carbonate and high acid concentrations will interfere with the determination of fluoride, chloride, and formate. High concentrations of any anion may prevent the determination of other anions. High sodium concentrations may interfere with the determination of ammonium.


The instrument is calibrated using at least a 3 point calibration curve. A linear curve fit is plotted through each calibration point (ignoring the origin). Linearity is demonstrated over the entire linear dynamic range of the curve when the r2 standard deviation of the calibration factors is 0.990 or better. Samples having ion concentrations which do not fall within the range of the linear calibration or check standard range must be diluted. • Initial Calibration

All standards prepared should be labeled with an AD identification number denoting the notebook number and


page number on which the preparation data is recorded. All prep standards must be labeled with the date of preparation, concentration, initials of preparer, and the solvent used to make the dilution. Standards prepared from NIST traceable standards can be diluted and the dilutions, pipette information, and lot # recorded on the software schedule.

The eluent and anion/cation standards must be prepared using milli-Q water at 18 Megaohm resistance. For each analyte of interest, prepare calibration standards at a minimum of three concentrations by adding volumes of one or more stock standards to a volumetric flask and diluting to volume with an appropriate eluent/solvent. The other concentrations should correspond to the expected range of concentrations found in real samples or should define the working range of the detector.

Anion/Cation Standard Preparation for Three-Point Calibration Preparation

Standard

Name Original

Conc. (µg/mL)

Amount Added

SolventUsed

Final Vol. (mL)

Final Conc.

(µg/mL)

Level

STD 10 1000 500 µL Eluent 50.0 10 1 STD 25 1000 1250 µL Eluent 50.0 25 2 STD 50 1000 2500 µL Eluent 50.0 50 3

NOTE: Stock standards for anions and cations are ordered at 1000 µg/mL from the vendor.

• Daily Calibration

At the beginning of each day a new calibration curve is prepared at all three levels of calibration. The daily calibration sequence is analyzed in the following order: blank, STD10, Autocal1, Autocal2, Autocal3, using a linear fit ignoring the origin. The STD10 standard is used to update analyte retention time. The STD25 or any other standards run afterwards are used as a calibration verification


standard. The continuing calibration verification standard may be any point on the calibration curve, but in most circumstances this procedure will use level 1 or level 2 (10 µg/mL and 25 µg/mL, respectively). If the response for any analyte in the continuing calibration standard varies from the average response by more than ±10 % (1σ), repeat the injection. If the response or analytical result still varies by more than ±10 %(1σ), a new calibration curve must be prepared and analyzed for that analyte and the associated samples must be reanalyzed. The Task Supervisor should be contacted for instructions. Calibration verification standards should be run after every twelve to eighteen sample injections and at the end of the analytical sequence. Calibration Standards and Check Standards should be from different manufacturer lots for more rigorous Quality Assurance.

• Spikes

At the discretion of the Task Supervisor, each sample may be spiked with a surrogate solution or matrix spike solution to monitor the overall efficiency of the procedure, thus insuring the quality of the data. Surrogate recoveries must be within two standard deviations of historical recoveries. Surrogate recoveries greater than three standard deviations will warrant a reanalysis of the sample. Matrix Spike and Matrix Spike Duplicate samples should be analyzed at the discretion of the customer or the Task Supervisor or at least once per every 20 samples for each matrix type or once per sample delivery group, whichever is most frequent.

• Sample Analysis/Sequence

Data should be stored in correlation to the date (Mo, Day, Yr) on which it was generated. Each Data Sub-directory generated on the IC system should be generated such that the system ID and date are reflected. (e.g., SYS4-072008).


Each sequence or analytical batch must be preceded by an acceptable Continuing Calibration Verification standard.

NOTE: All standard solutions should be checked at least monthly for stability. These solutions must be replaced prior to expiration date or sooner if comparison with independent standards and historical data indicates the standard has concentrated or degraded.

• Calibration Frequency

A QC check standard is run after startup, after every 12 to 18 sample injections and at the end of the day. If the result is not within ±10% (1σ), of the standard value, consult the Task Supervisor before continuing

5.1.4 Manufacturer

Manufacturer(s) - Dionex Corporation

P.O. Box 3603 Sunnyvale, CA 94088-3603

1-800-346-6390

5.1.5 Equipment

• DX-120 or equivalent • Dionex Gradient pump (GP-40) • Dionex Conductivity Cell (DS-3 or DS-4) • Dionex Conductivity Detector (CD-20) • Printer • 4L Polyethylene bottles • 486 or greater IBM Computer or equivalent clone • Dionex Peaknet 5.1 Software • 22 mL Glass vials w/ Teflon™ liners • Transfer Pipettes • Pipette Tips • Calibrated Pipettes. 50 µL, 100 µL, 250 µL, 500 µL, 1.0 mL,

5.0 mL. • AG 14 Guard Column; 4x50 mm • AS 14 Analytical Column; 4x250 mm • Regenerant System: Self regenerating suppressor


• 2-4 L polyethylene eluent containers

Anion Analysis: IonPac AG14 Guard Column or equivalent IonPac AS14 Separator column or equivalent Anion Supressor ASRS II or equivalent

Cation Analysis: IonPac CG16 Guard Column or equivalent IonPac CS16 Separator Column or

equivalent Cation Suppressor CSRS II or equivalent

5.1.6 Reagents

• Purity of reagents - Unless otherwise stated, ACS reagent grade chemicals shall be used.

• Purity of water - Unless otherwise indicated, reference to

water shall be understood to mean deionized water, which meets the ACS requirements for reagent water. (Greater than 16 MΩ resistivity)

• Concentrations of eluents may be varied to accommodate

better peak separation. The concentrations listed in this procedure should be used unless otherwise instructed by the Task Supervisor.

Solvents

• ASTM Type II Water - Organic Free, Milli-Q (18 MegaOhm)

Eluent

• 1.0 mM NaHCO3 in water • 3.5 mM Na2CO3 in water

Standards • Anions Stock Standard Mix (1000 µg/mL) • Cation Stock Standard (1000 µg/mL)


5.2 Startup

NOTE: For Operating instructions on specific IC Instrument configurations, consult Attachment 3.

5.2.1 Check eluent. There should be at least one liter of eluent for

eight hours of operation, two liters of eluent if sample load will run beyond 8 hours.

NOTE: The nominal eluent flow rate should be 1.2 mL per minute for anions and 1.2 mL per minute for cations unless otherwise instructed by the Task Supervisor.

5.2.2 Turn the eluent pump on and wait until a steady pressure reading is observed (any reading between 600 and 1600 psi is acceptable). It is recommended to allow pressure and flow for 30 minutes for column stabilization.

NOTE: If the pressure fluctuates more than +/-25 psi, if the error light comes on, or if the pressure drops to below 600 psi, the pump needs to be primed. Consult lab notebook for instructions.

NOTE: The analytical pump uses a constant eluent concentration. The gradient pump varies the eluent concentration and must be programmed.

5.2.3 Observe the conductivity reading on the Detector Module.

NOTE: When a low steady reading (background) is observed, the instrument is ready for sample analysis, approximately 30 minutes of steady eluent flow. Consult Task Supervisor for acceptable background values for the system being used.

5.3 Calibration & Sample Analysis

There are several different instrument configurations in the IC labs and the analysis protocol varies slightly among them. The following protocol is for an autosampler injection on a DX120. Specific steps for the various instrument configurations are listed in attachments at the end of the document. Any change made to any system (i.e.: when fresh


eluents or standards are made, columns changed, new modules installed) must be documented in the appropriate laboratory notebook.

5.3.1 Ensure that the instrument is running as instructed in section

5.2 of this procedure. 5.3.2 Sample preparation: Prepare samples per the required dilutions

in 5 ml Dionex vials. Non-radiological samples may be prepared on the benchtop. Cap vials flush to top of cassette with Dionex 5 ml vial caps. For Anion samples dilute with eluent, for cations dilute with 18 mΩ water.

5.3.3 Edit the schedule per attachment 3. Samples should be loaded

onto the autosampler as stated in 5.1.3 and in the table below in the following order unless otherwise indicated by the Task Supervisor:

Sample order

Sample

1 Blank 2 STD 10 3 CAL 1 4 CAL 2 5 CAL 3

6-9 STD Checks Samples

5.3.4 Enter all subsequent samples with at-least one “Check

Standard” for every twelve to eighteen samples. 5.3.5 Load vials into cassettes into the Autosampler (AS40). Six vials

can be loaded into each cassette. Ensure that the black dot of the cassette is facing the injector. Ensure that the “waste” side of the autosampler is free of cassettes.

5.3.6 When analysis is complete, review the report. If the results are

not within the calibration value for the ion, notify the Task Supervisor. Results are acceptable if they are within 10% (1σ) of the targeted standard.


5.4 Non-Routine Samples

Non-routine ions are determined if the customer makes a formal request of the Task Supervisor (See Section 2.0 for list of routine ions). The Task Supervisor determines if the analysis is feasible. It is the Task Supervisor's responsibility to determine any changes to the instrument configuration, eluent and regenerate solutions. These changes are to be recorded in the appropriate lab notebook. The customer and Task Supervisor are to agree on the source of the stock standard solutions. The source of the stock standard solution is to be recorded in the appropriate lab notebook.

5.5 Calculations

Normal liquid samples have the calculations performed by the integrator or computer using information supplied by the analyst during the sample dialogue phase of the procedure. Results from solid samples which have been dissolved must be multiplied by the dissolution factor (total volume liquid in mL divided by the weight of the sample in grams). Other samples may require unusual calculations. The Task Supervisor should be consulted. Any calculations made should be recorded in the appropriate laboratory notebook.

5.6 Shutdown

5.6.1 Shut down the IC system by loading a Shutdown method, as detailed in Attachment 3 C.

5.6.2. Ensure that the work space is left clean and orderly. Remove

any waste that has accumulated per applicable laboratory procedures. Wipe any spills and remove samples from the laboratory when analysis is complete.

6.0 RECORDS The data generated shall be recorded in a controlled, approved, numbered

SRNS (or existing WSRC) Laboratory notebook. Completed laboratory notebooks shall be returned to the Task Supervisor.


7.0 REFERENCES

7.1 Dionex Corporation, System DX120 Operating Manual (located lab module B134).

7.2 SRNL Procedure Manual L1, 2.32 & L15.17 - Radiological Chemistry

Procedures and Work Instructions.” 7.3 SRNL Procedure Manuals L1, 3.14 & L1, 3.15 & L15.1 - NTS General

Laboratory Procedures and Work Instructions

8.0 ATTACHMENTS

Attachment 1 - Terminology and Acronyms

Attachment 2 - Dilution Factor Calculations

Attachment 3 - Operation of Ion Chromatograph Using Dionex Peaknet Software


ATTACHMENT 1

Terminology and Acronyms ACS American Chemical Society AD Analytical Development Calibration Standards Solutions with known concentrations of ions or working standard obtain used to calibrate instrument. Eluent Solution which causes the analytical species to desorb from the ion exchange material. IC Ion Chromatography QC Standards Solutions with known concentrations analyzed same in the manner as the customer samples (See Section 5.1.3) and plotted on QC chart. Regenerate Solutions used to replace H+ (anion) or OH- (cations) species in the supressor column Regularly assigned The analyst that maintains and operates the Analyst instrument on a regular assigned basis (See Section 2.1). Stock Standard Standards that are obtained and verified by an Solutions outside agency or made in B-134. Stock Solutions Solutions used in preparing the eluent or

regenerate. Task Supervisor Chemist in charge of the method and equipment

(See Section 2.1). SRS Self Regenerating Suppressor


ATTACHMENT 2

Dilution Factor Calculations To calculate sample volume for dilution:

Sample volume = Final Solution Volume Desired dilution factor

Example: To perform a 100 fold dilution with a final solution volume of 5 mL, bring 0.05 µl of sample (50µl) up to 5 mL. Sample volume = 5 mL : 0.05 mL = 50 µl 100 For larger dilution factors, do smaller, multiple dilutions: Example: To perform a 10,000 fold dilution, do two consecutive 100 fold dilutions: 50µl sample up to 5 ml; then take 50µl of this 100 fold dilution and dilute to 5 mL. 100 x 100 = 10,000 fold dilution

To calculate the volume of stock standard to use to prepare a working standard. (Stock Standard Vol) =

Calibration working standard concentration

stock standard concentration x (Working standard volume)

Example: To prepare 100 mL of a 10 ppm standard using a 1000 ppm stock standard, use 1 mL of stock standard.

10 ppm 1000 ppm x (100 mL) = 1 mL stock standard


ATTACHMENT 3 Page 1 of 3

Operation of Ion Chromatograph Using Dionex Peaknet Software

A. Accessing Dionex Peaknet Software

1. Press the remote button on the pump module and the detector module to place them in the remote mode.

2. Using the computer mouse, move the arrow cursor the Dionex Peaknet Icon on the Windows 95 program menu screen and click the left mouse button.

B. Editing Retention Times

NOTE: Before re-calibration or an auto calibration can take place, the method must have the correct component/analyte retention times entered in the components file. Therefore, it is necessary to first analyze a check standard in the appropriate schedule to know the retention times.

1. Click on the “Method” button from the Peaknet main menu. 2. Click the “File” option from the “Method program menu and select “Open.” 3. Scroll the method files and double click on the desired method to edit it. 4. In the Data Processing Parameters section, select the “Detector” button. 5. Select the “Components” button. 6. Enter the new retention times for each component/analyte. 7. Click the “O.K.” or “Apply” buttons to update the retention times into the

method.

8. Save the newly edited method. C. Loading Method

1. Press the remote button on the pump module and the detector module to place them in the remote mode.



2. Using the computer mouse, move the arrow cursor to the Dionex Peaknet

Icon on the Windows 95 program menu screen and click the left mouse button.

3. Click on the “Run” button from the Peaknet main menu.

4. Select the “Load” option from the “Run” program menu.

5. Scroll the method files and double click on the desired method to load it. D. Editing Schedule

NOTE: Auto Calibration is to be performed at the beginning of the day only. However, the Task Supervisor (at his discretion) man re-calibrate on a subsequent check standard if detector response changes.

1. Click on the “Schedule” button from the Peaknet main menu.

2. Scroll the schedule files and double click on the desired schedule to edit.

3. Start the schedule with “Check Standard” to be run by the appropriate

method.

4. Enter an “AutoCal1, AutoCal2, AutoCal3,” standards in the second, third, and fourth position, respectively.

5. Enter “Check Standards” after the fourth position as outlined by the Task Supervisor.

6. Enter all subsequent samples with at-least one “Check Standard” for every twelve to eighteen samples.

7. Enter a “Check Standard” after the last sample.

8. Enter the “Shutdown” method at the end of the schedule if no more samples or standards are to be analyzed.

9. Save the newly edited schedule appropriately as Anion.sch or Cation.sch.



E. Loading the Schedule

1. Click on the “Run” button from the Peaknet main menu.

2. Select the “Load” option from the “Run” program. 3. Scroll the schedule files and double click on the desired schedule to load it. 4. Enter the appropriate number in the second box from which to start

analyses. 5. Select the “Automatic” option if injections will be done by an autosampler.

6. Select the “Signal At Interface” option if injections will be made manually.

7. Select “Store Data In Directory.”

8. Type in the correct directory in which the data is to be stored.

NOTE: Data should be stored in correlation to the date (Mo, Day, Yr) on which it was generated. Data directories should be entered such that the run date is the sub-directory for the data. Sub-directories created on the same day should be distinguished by a letter in the alphabet positioned at the end of the sub-directory name denoting which sub-directory was created first. (Ex. 080507A, 080597B).

F. Running Method and Schedule

1. Select “Start” from the “Run” program menu.

2. Select the “O.K.” button to start the system. NOTE: Data acquisition has now begun. Make sure sufficient paper is in the printer tray.


Analysis of Ions in Solutions Using Approved by: a Dionex ICS3000 Ion Chromatography System (U) Approval on File AD Manager _____________________________________________________________________________________________ 1. 1. PURPOSE

This procedure provides requirements by Analytical Development for using a Dionex ICS3000 Reagent-Free (RFIC) Ion Chromatography System for Anion and Cation analysis.

2. SCOPE

This procedure describes the requirements for the use of the Dionex ICS3000 Ion Chromatography System to separate and quantitate ions in solution. Anions such as F-, Cl-, NO2-, NO3-, Br-, SO42-, PO43-, C2O42-, CHO2- , and NH4+ are routinely determined by this method. System settings, method protocol, sample preparation instructions, procedures for data acquisition and report generation using the Chromeleon ® Chromatography Management Software for Windows, and quality assurance procedures are included. Use of the Dionex ICS3000 outside of the processes outlined in this document must be performed under direct supervision of the Task Supervisor.


2.1.1 Technical Analyst is responsible for:

2.1.1.1 Preparing sample(s)/standard(s) as instructed by the Task supervisor.

2.1.1.2 Running the sample(s)/standard(s).

2.1.1.3 Obtaining results.

2.1.1.4 Maintaining the maintenance logbook, and all other general documentation required for laboratory operations.

2.1.1.1 Maintaining lab RBA & Radiological Containment Unit (RCU) cleanliness and order.

2.1.1.2 Maintaining adequate supplies for routine analysis.

2.1.2 Task Supervisor is responsible for:

2.1.2.1 Configuring the sample/standard parameters.


2.1.2.2 Reviewing the results generated by the Analyst.

2.1.2.3 Entering the results into the AD Laboratory Information Management System.

2.1.2.4 System troubleshooting.

3 PRECAUTIONS/LIMITATIONS

3.0 Safety

3.0.1 See Hazard Assessment Package # SRNL-ADD-2008-00163 for detailed hazard identification and mitigation.

Table 1: HAP reference table

Hazard Hazard Control

Samples - Mixed radioactive/toxic/corrosive materials

Handle materials in the appropriate containment unit with two pair gloves, protective eyewear with side shields and laboratory coat (PPE). Use care to avoid splashing, use limited quantities.

Glass Breaking Eyes on task

Lifting Use correct lifting technique

Flammable cleaning material Handle limited quantities with no local ignition source. Store material in a flammable cabinet, amount typically ≤ 20 mL

Sample injection Sample injection is performed in an auto-sampler, auto-sampler is self contained in a housing with cover preventing contact during injection

Pressure (IC systems) Use proper pressure relief systems

Pressure (purge and trap system) Use small volumes and gentle streams for purge

Heat (hot plate) Use UL listed hot plate, use hot signs, do not use flammable substances near hot surface

3.0.2 Additional Safety Considerations

3.0.2.1 Follow all ADS Laboratory radiation (L1, 2.32) and chemical handling guidelines (L1, 3.14, 3.15).

4 PREREQUISITE ACTIONS

4.0 To perform Ion Chromatography analysis it is required to be qualified on the Ion Chromatography Methods.


5 PERFORMANCE


5.1.1 Principles of Operation

Ion chromatography refers to the chromatographic separation of ions. Aqueous samples containing a mixture of ions are injected onto a column filled with ion-exchange resin. Buffered, acidic or basic eluent (mobile phase) carries the ions through the packed resin bed. The resin retains ionic species based on coulombic (ionic) interactions and an equilibrium (KD) is established between the resin (stationary phase) and eluent (mobile phase). Separation of the ions occurs by way of different distribution rates between the stationary phase and the mobile phase. The equilibrium constant (KD) depends on the ion size, its charge and its polarizability. A highly charged, highly polarizable, small ion will have the highest affinity for the ion exchanger (stationary phase) and will elute out of the ion chromatography column with the mobile phase after ions exhibiting less affinity for the column resin. The retention time of an ion on an ion chromatography column can be adjusted by changes in the ionic strength or pH of the mobile phase. The elution strength of the mobile phase is increased by raising the ionic strength of the mobile phase.

Once bands emerge from the IC column the background conductivity of eluent is reduced and the ions conductivity is enhanced by electrolytic suppression. For anion analysis, highly conductive sodium ions are exchanged electrolytically through a membrane for weakly conductive hydronium ions. The anion band is then analyzed by a conductivity detector. Suppression is also used in cation analysis to exchange the anion.

5.1.2 Instrument Configuration

5.1.2.1 Basic Configuration

The Dionex ICS3000, data acquisition workstation, and Chromeleon ® Chromatography Management Software is a completely automatic ion analysis system. Eluent and sample flow path are shown in Figure 1 below. Eluent moves either from a bench prepared eluent bottle or self generated in the instrument with eluent generation coupled with supplied Deionized (DI) water to an inject/load valve. The inject/load valve is connected to an autosampler to load the sample into the eluent flow. Flow continues through a column for separation, then a suppressor and conductivity detector cell. Eluent and


sample waste is collected for disposal. Upon completion of the analysis, the Dionex ICS 3000 generates a report containing the chromatogram, and various instrument parameters. See the appropriate Dionex operating manuals for descriptive details of the system.

5.1.2.2 Suppressed Ion Detection

In suppressed ion detection, an electrolytic self-regenerating suppressor is employed between the ion exchange column and conductivity cell. This suppressor greatly increases ion sensitivity and improves linearity for ion analysis.

5.1.2.3 Eluent Generation

Dionex eluent generators use electrolysis to convert pure water into potassium hydroxide eluent for anion separations or methanesulfonic acid (MSA) eluent for cation separations. The eluent's counter ion (potassium or methanesulfonate) comes from the EluGen® cartridge reservoir; it diffuses across a membrane into the cartridge's high-pressure chamber during electrolysis. The dual membrane system of the EluGen K2CO3 allows electrolytic production of carbonate eluents. A degasser built into the cartridge outlet removes by-product gas (hydrogen or oxygen) from the eluent stream. This system can be run using either eluent generation and/or operator supplied eluent.

5.1.3. Instrumentation

5.1.3.1 MS&E - The MS&E program controls:


5.1.3.1.1 ICS SYSTEM 1

Model Number: Dionex ICS3000 (dual channel RFIC)

Serial Number: 08100105

ELI Number: 0000414957

5.1.3.1.2 Auxiliary Pipettes (non-M&TE)

5.1.3.2. M&TE - The M&TE program controls:

5.1.3.2.1. Analytical balance(s)

5.1.3.2.2. Pipette(s)

5.1.4. Manufacturer

North American Headquarters

3000 Lakeside Drive, Suite 116N

Bannockburn, IL 60015

Phone: (847) 295-7500 / Fax: (847) 283-0722

5.2 Calibration and Measurement Control Program

5.2.1 ICS3000 Systems Calibration and Quality Checks

5.2.1.1 Calibrations shall be performed prior to running samples.

5.2.1.2 Calibrations can be performed weekly; however, a daily calibration is preferred.

5.2.1.3 Calibrations shall have a minimum of 3 points and generally covers a concentration range of 10 mg/L to 100 mg/L.

5.2.1.4 Calibrations shall fit a linear or polynomial curve fit to 99.5% or better (r2 = 0.995).

5.2.1.5 Quality Control (QC) checks will be performed after calibration, periodically throughout a sample batch, and at closing of a batch. (for example: every 12-18 injections). Quality control checks shall be in amounts within the range of the calibration curve. Additional quality control checks can be made for amounts less than the calibration curve to observe performance below the calibration curve.


5.2.2 Auxiliary Pipettes (non-M&TE)

5.2.2.1 If auxiliary pipettes are to be used, a weight check shall be performed prior to use on samples or standards. Perform weight check on the volumes intended for use by measuring a known amount of DI water. Amount should be within +/- 1% of target weight. For example see figure 2:

Figure 2: Pipette acceptance table for weight checks

Low (g)

Target (ml)

High (g)

0.0495 0.05 0.05050.099 0.1 0.1010.99 1 1.014.95 5 5.059.9 10 10.1

5.2.3 Standards and Chemicals

5.2.3.1 Reference Standards: Quality control checks and calibration standards shall be dilutions of NIST traceable standards that are within the expiration date and from independent lot #s.

5.2.3.2 American Chemical Society (ACS) reagent grade chemicals should be used unless otherwise specifies.

5.2.3.3 Deionized (DI) water shall be 18.0 ΜΩ or better resistivity.

5.2.3.4 Bench prepared eluent or instrument Eluent Generation can be used. Methane Sulfonic Acid (MSA) when used should be diluted from a filtered concentrated solution.

5.3 Non-Routine

5.3.1 Non Conforming Conditions

5.3.1.1 If the standard is out of specifications, see the Task Supervisor. It maybe necessary to generate a Non-Conformance (NCR) for any data generated since the last acceptable calibration check.

5.3.2 Non-Routine Samples

5.3.2.1 Non-routine ions are determined if the customer makes a formal request of the Task Supervisor. The


Task Supervisor determines if the analysis is feasible. It is the Task Supervisor's responsibility to determine any changes to the instrument configuration, eluent and regenerate solutions. These changes are to be recorded in the appropriate lab notebook and carried out through written laboratory R&D directions.

5.3.2.2 The customer and Task Supervisor are to agree on the source of the stock standard solutions. The source of the stock standard solution is to be recorded in the appropriate lab notebook.

5.4 Operating procedure

5.4.1 Ensure the computer, IC instrument and printer are powered on.

5.4.2 Load Chromeleon ® Chromatography Management Software by selecting the desktop icon on the computer.

5.4.3 Prepare Eluent

5.4.3.1 For Reagent-Free (RFIC) Ion Chromatography the eluent is generated by the instrument. Ensure the eluent concentrate cartridge has adequate supply, and the DI Water supply bottle is full. (An eluent concentrate cartridge has an estimated 6 month supply at typical rate of consumption).

5.4.3.2 Eluent can be prepared from American Chemical Society (ACS) reagent grade chemicals.

5.4.3.2.1 For anion analysis, eluent is prepared as a mixture 1.0 mM NaHCO3 in DI water / 3.5 mM Na2CO3 in DI water.

5.4.3.2.2 For cation analysis, eluent is prepared as 20.0 mM Methane Sulfonic Acid in DI Water.

5.4.3.2.3 Other eluent solutions may be specified by the task supervisor.

5.4.4 Prime pump

5.4.4.1 Open bypass valve for the pump you are attempting to prime.


Figure 3: Instrument control workspace screen.

5.4.4.1.1 From the instrument control workspace screen, select the Gradient Pump or Isocratic Pump tab followed by the Prime Control button. The software will alert you to ensure you have opened the bypass valve. Click OK. Leave the prime pump on until no bubbles can be seen through the pump line. Thirty seconds is usually sufficient. (see figure 3)

5.4.4.2 Close bypass valve.

5.4.5 Ensure mobile phase collection bottles are empty and ready to receive eluent.

5.4.6 Startup Pump

5.4.6.1 From the instrument control workspace screen select the Home tab followed by the Start up button. Allow the system to stabilize for about 30 minutes. Stabilized pressure is dependant upon specific method conditions.


5.4.6.2 Verify that cell heater, suppressor, eluent generation (if configured), and pump are on green, (if not press Start up button and second time.) (see figure 4)

Figure 4: Instrument control workspace screen.

5.4.7 Quality assurance test pipettes and balances to be used and record in MT&E notebook. Ensure the calibration certifications are within the expiration date. (See Figure 2: Pipette acceptance table)

5.4.8 Prepare Calibration standards and Quality Control check standards.

5.4.9 Prepare Batch Sequence

5.4.9.1 Open the browser workspace screen. (see figure 5)

5.4.9.1.1 Select the Anions or Cations folder.

5.4.9.1.2 Select a sequence to copy (usually the most recent).

5.4.9.1.3 Select Save As from the file menu and rename the sequence using the yyyymmdd method, eg. 20090302 Anions.


5.4.9.1.4 Populate the batch sequence with QC standards, Calibration standards, and sample numbers.

5.4.9.1.5 Ensure that the last sample line ends with the “Shutdown” method.

Figure 5: Bowser workspace screen

5.4.10 Quality assurance tests of radiological pipettes and balance (record in MT&E notebook) if used. (See Figure 2: Pipette acceptance table)

5.4.11 Prepare sample dilutions (observe laboratory and radiological best practices)

5.4.12 Load autosampler with standards and samples. Ensure that the run light is selected, cassettes are loaded with the black dot facing the injection port and the first cassette loads to the injection port.


5.4.13 Press Run/Hold.

5.4.14 Verify batch schedule and check the autosampler to ensure that the # of samples match the sequence.

5.4.15 Start the batch on Chromeleon ® Chromatography Management Software.

5.4.16 From either the Browser or Dual workspace screen, Select Batch followed by Start. (see figure 6)

Figure 6: Start batch screenshot

5.4.17 A start menu will appear. Verify the sequence is loaded and reporting is turned on. Press OK.

5.4.18 Print Batch Sequence and update the Machine Logbook.

5.4.19 Select Print Sequence from the file menu on the browser workspace screen. Modify print parameters as needed to fit to a page that can be attached to the Machine Logbook. (see figure 7)


Figure 7: Print sequence screenshot

5.4.20 Clean and prepare work areas for the next analyst.

6.0 RECORDS

6.1 The Ion chomatography results Logbook shall be maintained by the task supervisor and handled in accordance with Records Management procedures. Results for all routine analytical samples will be entered into the AD Laboratory Information System (LIMS) using the AD LIMS numbers.

6.2 An electronic copy of all the Ion Chromatography data shall be stored for five years on the AD file server.

6.3 An Ion chromatography Maintenance logbook shall be maintained. This logbook is instrument specific and will be kept near the instrument in the laboratory. A copy of the sample schedule and maintenance or instrument configuration changes shall be entered into the notebook.

7.0 REFERENCES

Dionex ICS300 Ion Chromatography System Operations Manual


8.0 ATTACHMENTS

Attachment 1 Quick Guide for start up of ISC3000 sample batch

Attachment 2 Standard and Dilution Table

Attachment 3 Method Parameters for Anions

Attachment 4 Method Parameters for Cations


Attachment 1: Quick Guide for start up of ISC3000 sample batch

Anion Cation

Power instrument on, computer on, printer on

Load Chromeleon software

Prepare eluent

Prime pump (15 seconds)

Ensure waste bottles are empty and ready for the batch

Startup Pump (30 minutes of eluent flow needed prior to 1st sample injection)

Quality assurance tests of pipettes and balance (record in MT&E notebook)

Prepare Calibration standards and Quality Control check standards

Prepare batch schedule

Quality assurance tests of radiological pipettes and balance (record in MT&E notebook)

Prepare sample dilutions (observe laboratory and radiological best practices)

Load autosampler with standards and samples & press "Run/Hold" (ensure that the run light is selected, cassettes are loaded with the black dot facing the injection port & the first

cassette loads to the injection port)

Verify Batch Schedule

Start the batch on Chromeleon software

Print Batch Schedule and update Machine Logbook

Clean and prepare work areas for the next analyst

Quick Guide for start up of sample batch

Not required if using eluent generation


Attachment 2: Sample Dilutions

1. PI: Boyd Wiedenman 2. Task Title: Analysis Anions by IC 3. Date: __________________ Customer Name: ___________________ Analyst: __________________ 4. Work Group and Location: Analytical Development, Bldg. 773A, Lab B134 5. Applicable Reference Documents: L1 Manual, AD Procedure 2306 Analysis of Solutions by Ion Chromatography 6. Directions (Provide activity-specific directions):

Sample

Dilutions

Bottle A Bottle B

100 mg/L 4.0 mL 0.5 mL 0.5 mL N/A N/A

50 mg/L 2.5 mL N/A N/A 2.5 mL N/A

25 mg/L 3.75 mL N/A N/A 1.25 mL N/A

10 mg/L 4.5 mL N/A N/A 0.5 mL N/A

5 mg/L 2.5 mL N/A N/A N/A 2.5 mL

2.5 mg/L 3.75 mL N/A N/A N/A 1.25 mL

1 mg/L 4.5 mL N/A N/A N/A 0.5 mL

Bottle A

100 mg/L 4.5 mL 0.5 mL N/A N/A

50 mg/L 2.5 mL N/A 2.5 mL N/A

25 mg/L 3.75 mL N/A 1.25 mL N/A

10 mg/L 4.5 mL N/A 0.5 mL N/A

5 mg/L 2.5 mL N/A N/A 2.5 mL

2.5 mg/L 3.75 mL N/A N/A 1.25 mL

1 mg/L 4.5 mL N/A N/A 0.5 mL

100 mg/L Standard 10 mg/L Standard

ANION (1000 mg/L) Stock

Standards and Dilution Table

CATION (1000 mg/L) Stock

Target Concentration Eluent100 mg/L (A+B)

Standard10 mg/L (A+B)

Standard

Target Concentration Eluent

Target Dilution Eluent Sample

10,000 4.95 mL 0.05 mL

followed by 4.5 mL 0.5 mL


5,000 4.9 mL 0.1 mL


1,000 4.95 mL 0.05 mL


500 4.9 mL 0.1 mL


100 4.95 mL 0.05 mL

50 4.9 mL 0.1 mL

25 4.75 mL 0.25 mL

10 4.5 mL 0.5 mL

5 4 mL 1 mL

2 2.5 mL 2.5 mL

1 N/A 5 mL


Attachment 3: Method Parameters for Anions

Anion Method

Injection 50 µL

Flow rate 1.3 mL/min

Stop Time 17.5 min

Guard Column IonPac AG-14 4x50 mm

Analytical Column IonPac AS-14 4x250 mm

Mobile Phase 1.0 mM NaHCO3 / 3.5 mM Na2CO3 (self generated)

Self-Regenerating Suppressor (ASRS) 300

Calibration Curve (Linear) 5 mg/L to 100 mg/L, r2 = 0.995 +

Retention Time of Fluoride 2.9 min

Retention Time of Formate 3.4 min

Retention Time of Chloride 4.3 min

Retention Time of Nitrite 5.1 min

Retention Time of Bromide 6.6 min

Retention Time of Nitrate 7.7 min

Retention Time of Phosphate 10.1 min

Retention Time of Sulfate 11.9 min

Retention Time of Oxalate 14.0 min

Detector cell power Software auto select


Attachment 4: Method Parameters for Cations

Cation Method

Injection 25 µL

Flow rate 1.2 mL/min

Stop Time 17.5 min

Guard Column IonPac CG-16 5x50 mm

Analytical Column IonPac CS-16 5x250 mm

Mobile Phase 30 mM Methanesulfonic acid

Self-Regenerating Suppressor (CSRS) 300

Calibration Curve (Quadratic) 5 mg/L to 100 mg/L, r2 = 0.995 +

Retention Time of Ammonium 8.0 min

Detector cell power Software auto select

Analytical Development SectionAnalytical Operating ProceduresVolume 2


Revision: 5Alpha Pulse Height Analysis

Major Revision



Author ________________________________C. C. DiPrete

Peer Reviewer ________________________________D. P. DiPrete

AD Materials Characterization &Nuclear Measurements Group Manager ________________________________

R. H. Young

AD Procedure Coordinator ________________________________M. S. Hanks

Procedure: ADS-2402Alpha Pulse Height Analysis Revision: 5

Page: 2 of 8

1.0 INTRODUCTION

1.1 Purpose

This procedure describes a method for analyzing material prepared for analysis of alpha-emitting nuclides. A wide variety of sample matrices can be measured using this technique.

This procedure will outline the requirements for routine use of alpha detectors for sample analysis.

1.2 Scope

This procedure applies to alpha pulse height analysis (PHA) using a solid state detector system coupled with a Multichannel Analyzer (MCA), using Genie 2000 Alpha Analyst software for data processing.

Samples can be chemically separated prior to analysis to isolate the analyte of interest. In order to account for inevitable sample loss during separation, a tracer, an isotope of the element of interest (i.e., 236Pu for plutonium analysis), is often added to the sample prior to separation. Assuming that homogeneity and chemical equilibrium have been achieved, the percent of tracer lost during separation is equal to the percent of sample analyte lost.

The batch preparation and associated quality control samples are addressed in the applicable preparation procedures.

Alpha PHA is also used as needed for absolute measurements of unknowns for quantification purposes (i.e., contamination samples).



1. Analysts are responsible for:

Reading, understanding, and following this procedure. Calling to the attention of the Task Supervisor any part of the

procedure that requires revision or that they believe to be unsafe.

2. Task Supervisor is responsible for:

Maintaining this procedure. Providing technical guidance.


Page: 3 of 8


1. Alpha particles readily interact with other atoms because of their high positive charge. Hence, an alpha particle can easily be stopped or significantly slowed by even the thinnest layer of any material present. It is therefore vitally important that alpha samples be as thin as possible. Alpha spectra of samples that are not “massless” display broad peaks and decreased count rates. Correction for self-absorption can be accomplished by the preparation of spiked matrix samples at the discretion of the Task Supervisor.

2. Alpha-emitting nuclides decay with characteristic energies and half-lives. If a sample contains nuclides which decay with similar energies,unambiguous nuclide identification might not be possible. In many instances, however, interfering nuclides can be removed by simple radiochemical procedures.

3. Variations in sample geometry and the low detection efficiencies of solid state detectors make the determination of absolute count rates difficult. To overcome this problem, the gross alpha decay rate may be determined by gas-flow proportional counters with relatively high efficiencies. Once the absolute count rate has been determined, alpha PHA is used to determine the relative count rates of the nuclides present. From these two pieces of information, the absolute quantities of the various nuclides present can be determined.

3.1 Safety

1. Follow L1 2.32 Radiological Work Practices and 8Q Laboratory Safety Guidelines.

2. Yellow (RAD) gloves shall be worn to handle the plastic plate holders in the count room.

3. Read, understand and follow applicable Job Hazard Analyses (JHAs) in the Conduct of R&D packet.

4.0 PREREQUISITES

Read, understand and comply with details in applicable JHA packets.

5.0 PROCEDURE


This procedure is utilized to determine the energies of alpha particles contained in analyte material. This is done using any of the alpha pulse height analysis


Page: 4 of 8

(PHA) systems. The systems consist of vacuum chambers, alpha particle detectors, analog-to-digital converters, mixer-routers, and multi-channel analyzers (MCAs). Several sets of vacuum chamber/detector combinations are available, to be used at the discretion of the Task Supervisor. Results from the alpha analysis provide peak energy and peak area, which can be used to quantify numerous alpha-emitting isotopes in a variety of approaches.

Each alpha PHA detector is calibrated for energy and efficiency using NIST-traceable alpha sources. It should be noted that energy calibrations are required for system use, while efficiency calibrations are not always necessary.

Often, alpha samples are mounted and assayed for gross alpha activity prior to alpha pulse height analysis. Sample preparation and analysis using gas-flow proportional counters are addressed in L16.1, ADS-2405.

5.2 Data Quality

The detector data quality indicators are addressed in the Quality Control section.

The quality assurance and quality control protocols applicable to alpha PHA are dependent upon the Data Quality Objectives (DQOs), when supplied. In the absence of specific DQOs, preparation QC is addressed in the R&D Directions:blanks, laboratory duplicates, blank spikes, and matrix spikes are several examples of quality indicators which can be utilized for this procedure. The blank contribution should be less than 10% of the sample result, and the measured activities for duplicates should overlap within 3 sigma. If QC indicators fall outside of these ranges, the Task Supervisor must determine whether the data is fit for release with additional scrutiny and/or qualifiers.

If a tracer with known alpha activity is utilized during sample preparation, detector efficiency does not need to be known. Quantification depends upon accurately knowing the activity of the tracer, coupled with acceptable peak shape and area.

All of the detectors are Measurement Systems and Equipment (MS&E) and, as such, comply with the requirements set forth by Manual 1Q, 2-7.


Page: 5 of 8

5.3 Quality Control

1. Background

A. An instrument background shall be obtained at least monthly for each spectrometer in use. At the direction of the Task Supervisor, detector backgrounds may be required more frequently.

B. Background spectra are used for background subtraction of analyte spectra.

C. There are no pass/fail limits for background peak areas. However; as the area of a background peak for a given region of interest increases due to contamination, the minimum detectable activity (MDA) increases and the measurement uncertainty increases. If the background area negatively impacts the data quality and the ability to meet DQOs, the detectors and chambers are cleaned.

2. Calibration

A. Energy Calibration

An energy calibration over the energy range of interest must be performed upon detector set up. The energy calibration isperformed with NIST-traceable sources, or equivalent. The measured alpha peak energies at the high-energy edge of the peaks must differ by 0.1 MeV or less from the known peak energies for each alpha peak in the calibration spectrum.

B. Efficiency Calibration

An efficiency calibration may be performed on the alpha spectrometers system(s) at the direction of the Task Supervisor. Note that the efficiency calibration is not always necessary; for example, if the analysis is being performed with spikes of known alpha activity. The efficiency calibration must be performed with NIST-traceable sources, or equivalent. The calculated activities from the calibration must agree within three standard deviations (3 sigma) of the accepted average decay-corrected values for the standards used. Any values outside of two standard deviation limits may be investigated to determine the cause. Corrective action shall be taken for any values outside of three standard deviation limits. The investigation and/or action shall be documented in the instrument logbook.


Page: 6 of 8

3. Calibration Verification

The energy calibration and efficiency of the alpha spectrometer system(s) are checked weekly using standard sources independent from the sources used to establish the energy calibration and efficiency. The energy calibration check peaks must be within 0.1 MeV of the acceptedpeak energy. The efficiency must be within 3 sigma of the average established for the detector. The peak energy and efficiency will be recorded on the instrument control charts or in the instrument logbook. The analyst’s initials and corrective action taken (if any) will also be noted in the logbook. Deviations exceeding the tolerances specified in this procedure shall result in a recalibration of the system, unless specifically allowed by the Task Supervisor.

4. Documentation

A logbook is utilized to record spectra obtained on the alpha PHA systems. Every spectrum that is obtained is documented in the logbook with the analyst’s identity, date of analysis, detector identity, file name, and any other pertinent information (customer identity, purpose for count, etc.).

5.4 Equipment

The following list is indicative of the type of detectors and software used. Additional equipment may be used at the direction of the Task Supervisor.

1. Canberra Quad Alpha Spectrometer

2. Passivated Ion-Implanted Planar Silicon detectors

3. Canberra Model 8224 Mixer/Router

4. Canberra Alpha Analyst

5. Canberra Model 8701 ADC

6. Canberra Genie 2K Alpha Software

7. PC

8. Vacuum pumps

9. Acquisition Interface Module (AIM 556)


Page: 7 of 8

5.5 Reagents

The only reagents needed are those required for the preparation of alpha counting plates as described in ADS-2405 or other applicable separation and alpha analysis procedures.

5.6 Analysis

1. Gross Alpha Determination

Follow the methods described in Procedure L16.1, ADS-2405.

2. Alpha PHA Counting

A. Select the alpha spectrometer(s) to be used: either the Canberra Quad Alpha Spectrometer or the Alpha Analyst.

B. Prior to loading each planchet, monitor it using the beta/gamma count rate meter. The counts should not exceed 10,000 cpm. If a planchet exceeds this limit, do not proceed with counting andconsult the Task Supervisor.

C. Load planchet into the appropriate detector chamber. The samples should be handled at the edge using tweezers. Care should be taken to only touch the planchet at the edge, since the alpha-containing material is mounted at the center of the planchet.

D. Using count rate meters, ensure tweezers are free of contamination after utilizing them to handle alpha planchets.

E. Acquire spectrum and save data as directed by Task Supervisor or designee. Record initials, date, spectrum name, customer, count time and additional comments in the laboratory logbook.

F. Remove sample from detector chamber.

5.7 Calculations

Data Control:

Sample preparation data are recorded on the preparation data sheet and recorded in the Radiochemistry Laboratory logbook.

The final data packet, containing the prep sheet, computer printouts, and calculations are stored in the counting room data notebook and associated binders. The Laboratory Information Management System (LIMS) contains a pointer to the raw data packet.


Page: 8 of 8

All calculations are completed by the task supervisor or a trained designee.

6.0 REFERENCES

1. Canberra Nuclear Products Group Catalog, Eighth Edition, 1990. Chart of the Nuclides, Thirteenth Edition, General Electric Company,

1984.

2. Table of Isotopes, Seventh Edition, John Wiley and Sons, 1978.

3. Canberra Genie-2000 Spectroscopy System, Canberra Industries, Inc., 1997.

4. Manual L16.1, ADS-2405, “Alpha and Beta Plate Making, Direct Mount and Count .”

5. Canberra Model S570 Genie-2000 Alpha Analyst Users Manual, 2000.

7.0 RECORDS Data are recorded and maintained as described in Data Control above.

The ADS LIMS is used as the primary data storage location.

8.0 ATTACHMENTS

None

Manual: L16.1Analytical Development Section Analytical Operating Procedures Procedure: ADS-2405Volume 2 Revision: 6

Effective Date: 03/10/10Type-Category: TechnicalAlpha and Beta Plate Making

Direct Mount and Count (U) Page: 1 of 9

Author/Analytical Task Supervisor: SIGNED COPY ON FILE C.C. DiPrete

Peer Reviewer: SIGNED COPY ON FILE D.P. DiPrete

AD Materials Characterization andNuclear Measurements SIGNED COPY ON FILEGroup Manager R. Young

AD Procedures Coordinator SIGNED COPY ON FILE Mary Sue Hanks

Procedure: ADS-2405Revision: 6Alpha and Beta Plate Making


1.0 INTRODUCTION

1.1 Purpose

This procedure describes the preparation of “direct mount” plates for gross alpha and gross beta determination. In addition, alpha pulse height analysis (PHA) can be performed on these same plates. Alpha PHA is performed using ADS Procedure ADS-2402.

1.2 Scope

This procedure applies to the direct mount preparation and the gross alpha and/or gross beta counting of liquid samples. Solid samples may be analyzed by first leaching or dissolving to generate a liquid. In addition, particulates or other solids may be directly mounted to a sample plate. The plates may also be analyzed according to the alpha PHA procedure (ADS-2402).



Analysts are responsible for reading, understanding and following this procedure, and calling to the attention of the Analytical Task Supervisor any part of the procedure that requires revision or that they believe to be unsafe.

The Analytical Task Supervisor is responsible for maintaining this procedure, providing analysts with otherwise difficult-to-obtain spikes and reagents, and providing technical guidance.


3.1 Safety

1. Follow L1, 2.32, Radiological Work Practices, and 8Q laboratory safety guidelines.

2 Make sure that collodion completely covers the plate or dish.

3. Yellow (Rad) gloves shall be worn to handle the plastic plate holders in the Counting Room.

4. Always: • Add acid to water • Wear plastic gloves when handling chemicals. • Avoid contact with skin and breathing of vapors. • Do not exceed hood and radiobench activity limits (SRNL L1, 2.32,

Radiological Work Practices)



5. Ensure there are no open flames or spark sources when using collodion.

4.0 PREREQUISITES

Read, understand and comply with details in JHA.

5.0 PROCEDURE


1. Alpha and beta plates are prepared by pipetting a small sample aliquot (typically 25-200 uL) directly onto a stainless steel plate. The liquid is evaporated (typically under a heat lamp). The plate is then heated to red heat to further evaporate residual material. A solution containing collodion in ethanol is then evaporated onto the plate to hold the dried material on the plate. The gross alpha activity on the plate is measured with a gas flow proportional counter. The gross beta activity may be measured with a gas flow proportional counter adjusted to provide beta sensitivity. These same plates may be analyzed directly by alpha PHA with no additional preparation (per Procedure ADS-2402).

2. Dishes are used to mount larger sample aliquots of low activity samples.

5.2 Data Quality

1. General Limitations:

Solid material on a plate can absorb some of the alpha particles emitted, thus preventing their detection and causing results to be biased low. If solids are visible, their presence must be recorded at all levels as part of the analytical data. Solids resulting from the corrosive effects of HCl, HF, or other chemicals on stainless steel can usually be avoided by use of Hastelloy or platinum plates. Solids from the sample itself can be minimized somewhat by dilution and mounting a smaller aliquot of the sample.

2. Interferences:

The gas flow proportional counters show approximately equal response for all alpha particle energies. Thus, the count yields total alpha content on the plate with no isotopic information determinable. The gas flow proportional counters’ alpha channels exhibit some sensitivity to beta particles as well as alpha. Typical beta response is less than about 0.5% (compared to about 50% for alpha particles).Alpha samples with high levels of beta activity and low levels of alpha may require chemical separation. Contact the Task Supervisor.



3. Detection Range Limits:

The low limit of activity determinable is the minimum detectable activity (MDA).The MDA is dependent on sample size, count time, counting statistics and the background levels associated with the counters.

The maximum activity determinable is constrained only by making dilutions so that the activity on a plate is on the order of 105 dpm or less. Solutions with high levels of activity may be determined by making an appropriate dilution. Contact the Task Supervisor.

The precision of the method is primarily dependent on counting statistics. For example, a precision of about 1% is obtained on duplicate plates containing ~104

cpm counted for 1 minute using the gas flow proportional counter. Samples with solids or volatile components may exhibit degraded counting efficiency and reduced precision.

For samples where solid deposits are unavoidable, an approximate correction factor may be applied by the use of an internal standard. A known alpha spike is added to one of the samples and the samples are then processed in the usual manner. The correction factor (Cf) is calculated and used to adjust final results.

5.3 Quality Control

1. Method Validation:

The calibration and background data for the counters in use are verified daily or, at a minimum for each day used, per this procedure. If the data are not within the limits as given by the Task Supervisor, the Task Supervisor is contacted. The data is plotted on a QC chart.

When necessary, a spiked plate shall be prepared to correct for sample self absorption.

2. Calibration Frequency:

• Instrument background for the detectors in use is determined daily, or at a minimum on days used for sample analysis.

• Instrument efficiency for detectors in use is verified daily using National Institute of Standards and Technology (NIST)-traceable sources kept by the technician in the Counting Room, or at a minimum on days used for sample analysis.

• All calibration results are recorded in the appropriate logbook or radiometric

laboratory notebook.



3. Calibration and Standardization

Known standards are counted. This establishes an efficiency factor for the counters as follows:

Efficiency = cpm/dpm.

Where: cpm = counts per minute dpm = disintegrations per minute

For the standard, the dpm is known and the cpm is determined by the counting. This efficiency factor determines only the counter efficiency. It does not correct for self shielding and sample ablation.

5.4 Equipment

See APPENDIX A

5.5 Reagents

• Purity of reagents - Unless otherwise stated, American Chemical Society (ACS) reagent grade chemicals shall be used.

• Purity of water - Unless otherwise indicated, reference to water shall be understood to mean distilled or demineralized (deionized) water, [which meets the ACS requirements for Reagent water] as delivered through building systems.

• Collodion solution – (Prior to opening bottle, ensure peroxide testing has been performed within the past 6 months and ensure no open flames or spark sources are present). To prepare collodion solution, add 1 mL of collodion to 100 mL of isopropanol. Mix well. Apply a “Flammable” label. Properly label, date and initial the bottle. Remove small quantities as needed.

• Nitric acid solution - (HNO3) 1M - Prepare by carefully pouring 63 mL of concentrated HNO3 into 700 mL of water contained in a one liter volumetric flask. Dilute to one liter with water. Mix, then transfer to a one liter polyethylene bottle. Label, initial, and date the bottle.

5.6 Aqueous Sample Analysis

1. Accurately prepare the necessary sample dilution in dilution bottles containing 1 M HNO3 unless directed otherwise. Final dilution should contain less than 610 dpm.

2. Add a sample aliquot as directed by task supervisor to the center portions of a plate on a fiberboard. Place the board under a heat lamp. Make duplicate mounts on each sample. If the sample shows a large amount of solids, contact the Task Supervisor.



NOTE: Add sample aliquot to center of plate. The objective is to make a plate with the sample centered like the standard plates used to calibrate the counting instruments.

3. Turn on lamp and allow the sample to dry completely.

4. Using forceps, grasp edge of plate and hold over the flame of meeker burner until plate reaches a dull red color. Place plate on a clean fiberboard to cool (5 min.).

NOTE: Plate should reach a dull red color all over, except near the forceps.

5. Ensure no open flames or spark sources prior to opening collodion.

6. Once burner has been turned off, add 2 drops of collodion solution to the plate and tilt, if necessary, to spread over entire surface. Let dry.

7. Record sample number on a plastic planchet holder. Place sample plate in the planchet holder. Put the planchet holder in a plastic carrier. Plastic carrier is placed in CA for RCO to clear. Once carrier is cleared by RCO, ensure RCO dose rates are acceptable for transport, and place the carrier in a 5-gallon DOT-approved bucket for delivery to the AD Counting Room for assay.

8. Use radiological gloves to hold the gray sample holder. Use the 110 probe to determine the activity on each plate. If the response is >104 cpm for flamed plates or >102 cpm for non-flamed plates, do not proceed without further evaluation of the safety of transferring the plate to the counter. If the response is <104 dpm for flamed plates or <102 cpm for non-flamed plates, load plate into appropriate counter as directed by the task supervisor.

9. Should results on duplicate mounts differ by more than 10% or 3 sigma counting uncertainty on proportional counters, consult the Analytical Task Supervisor.

5.7 Calculations

All calculations are completed by the Task Supervisor or a trained designee.

5.8 Data Control

Plate preparation data are recorded on the preparation data sheet and recorded in the Radiometric Laboratory notebook.

The final data packet, containing the prep sheet, computer printouts, and calculations are stored in the counting room data notebook and associated binders.



6.0 REFERENCES

1. Rider, B.F., Radiochemical Analysis, AECU-1046, 1952.

2. Prohaska, C. A., The SRP Standard Windowless Flow Counter, DP - 451, 1954.

3. Conner, J. E., ADS Procedure, Gross Alpha Activity (Direct Mount), May 1984.

4. Manual L16.1, Procedure ADS-2402.

7.0 RECORDS

Data are recorded and maintained as described in Data Control above. The ADS LIMS is used as the primary data storage location.

8.0 ATTACHMENTS

Appendix A Radiometric Laboratory Equipment Description.

Appendix B Detailed Calculations



APPENDIX A Page 1 of 1

Radiometric Laboratory Equipment Description (example)

Stainless Steel Plate (1 7/16"dia. x 0.020" thick) Meeker or Fisher-type Burner MicropipetsDilution bottles Plastic planchet holders Forceps, 6" or 8" size Cold spot heater and heat lamp Fiberboards

COUNTING SYSTEMS: (not necessarily inclusive of all instruments) Component Model Information Gross Alpha Detector (P-10 gas flow proportional counter)

Gamma Products, G542M QUAD

Gross Alpha Detector (ZnS counter) Gamma Products, Mini-T, G6020/30 Gross Alpha/Beta Detector (P-10 gas flow proportional counter)

Gamma Products, Traveler, G5020



APPENDIX B Page 1 of 1

Detailed Calculations

All alpha calculations are performed by the Task Supervisor or a trained designee.

Analytical Development Section Analytical Operating Procedures


Volume 2 Revision: 8

Californium Neutron Activation Analysis Major Revision


Electronic Approval on File

Author/Task Supervisor: ______________________ C. C. DiPrete

Peer Reviewer ______________________ D. P. DiPrete

AD Materials Characterization and Nuclear Measurements Group Manager: ______________________ R. H. Young

AD Procedure Coordinator: ______________________ M. S. Hanks

Procedure: ADS-2407Californium Neutron Activation Analysis Revision: 8

Page: 2 of 10

1.0 INTRODUCTION

1.1 Purpose

This procedure describes the californium neutron activation analysis method.

1.2 Scope

A 252Cf source (Half life t1/2 =2.646 years), contained in a water-filled pool in B-003, is used to provide a flux of neutrons for activation analysis (NAA). At this facility, practically any liquid or solid sample, contained in a sealed capsule called a "rabbit," can be irradiated with neutrons to induce radioactivity. Sample size is limited to 10 mL or 5.7 cm long x 1.5 cm diameter. The induced activity is measured and the components of interest are determined by ratio to a standard.Usually the activity is measured by -Pulse Height Analysis (PHA); however, delayed neutrons are used for

235U.

Tracers can also be produced by irradiating large amounts of an element. This has been done for

99mTc,

239Np, and

103Ru. Consult the Task Supervisor for

candidate elements and uses. This facility does not compete with commercial sources for long-lived (half life > 1 week) nuclides.


None


3.1 Safety

1. Follow L1 2.32 Radiological Work Practices and 8Q Laboratory Safety Guidelines.

2. Rabbits are sealed prior to activation.

3. Read, understand, and follow applicable JHAs in Conduct of R&D packet.

4. Maintenance activities required for B-003 are contained in L16.1, ADS-1402. In addition to requirements outlined in ADS-1402, a monthly well water sample is analyzed for gross alpha, gross beta, and tritium activities.

5. The Cf-252 source is locked under the lock control program implemented by the SRNL Control Room.


Page: 3 of 10

4.0 PREREQUISITES

Read, understand, and follow applicable JHAs in Conduct of R&D packet.

5.0 PROCEDURE


1. General Limitations and Interferences

Because various product nuclides differ widely in cross-sections, half-lives, and decay schemes, each run must be planned in advance with the aid of a radiochemist. Some generic materials have standard plans for a specific element (For example, plastics and rubbers for chlorine content).

2. Quality of Data/Data Validation

A calibration standard (that has the same volume and shape as the sample) and a blank (aqueous, air, matrix) are run with each sample. This greatly simplifies the computations involved, such as corrections for flux density and sample geometry. Even so, accurate results require careful planning, involving radiochemical growth and decay calculations. A well-planned and well-executed test can produce accuracies approaching the statistical precision of the data acquired on the multi-channel analyzer (MCA) used for the -PHA (pulse height analyzer).

An additional QA standard may be run along with the samples having sufficiently short irradiation times.

3. Description

All samples, including calibration standards and matrix blanks, must be encapsulated in containers (rabbits) provided by the NAA facility. Solid samples are weighed and liquid samples are pipetted or weighed. All radioactive liquid samples must be doubly encapsulated prior to irradiation. This is accomplished by adding and capping the liquid sample to a 6 mL "Pony Vial" (Packard No. 6000292 or equivalent) which is then sealed in a rabbit.

4. Equipment

See APPENDIX A

5. Reagents

Purity of reagents - Unless otherwise stated, reagent grade chemicals shall be used, where available. All reagents shall conform to the specifications of the Committee on Analytical Reagents of the American


Page: 4 of 10

Chemical Society (ACS), where such specifications are available.

Purity of water - Unless otherwise indicated, reference to water shall be understood to mean distilled, as delivered through the Building 773-A distilled water system.

Except on rare occasions, the only chemical manipulations involved in NAA are in the preparation of standards and blanks. Since these are always tailored to fit a specific test, the analyst should consult with the Task Supervisor for recommended procedures for the appropriate standards and blanks. Should the need arise for a chemical separation due to masking or interference, consult with the Task Supervisor.

6. Calibration Frequency

Prior to use, detectors must be calibrated as described in L16.1, ADS-2420. Since the application of NAA involves the comparator method, energy calibration is required while efficiency calibration is optional.

As a general rule, method calibration (with standards and blanks) occurs each time a sample is analyzed.

Pipettes and balances are part of the M&TE program and are verified prior to their use.

7. Calibration Standardization

Calibration standards, containing known quantities of the element being analyzed, are prepared and irradiated in an identical fashion as the samples. By comparing the measured activity in a sample to that in the standard, a ratio can be used to compute the concentration in the sample.

5.2 Analysis

The various procedural aspects of Neutron Activation are covered here. They are grouped as follows:

Loading the rabbit Heat-sealing the rabbit with pneumatic sealer Manual irradiation, including tracer production Automated Irradiation

1. Loading the Rabbit

A. Solid samples are sealed into a capsule called a rabbit. Solid samples are quantified by weight. Unless otherwise noted, liquid samples submitted for NAA should be placed in 6 mL "Pony Vials."


Page: 5 of 10

After being tightly capped, they are loaded into rabbits. Liquid samples are quantified by volume using pipettes or by mass using balances.

(1) After loading the sample into the rabbit, insert snap cap using the plunger.

2. Heat-Sealing the Rabbits with Pneumatic Sealer.

NOTE: Training from Task Supervisor or qualified designee is required for this operation.

A. Approximately three (3) minutes before use, turn on sealer heater coil at the Variac.

B. Turn on pneumatic air.

C. Place rabbit in sealer and adjust to sealing position.

D. Push the coil switch to position the heater over the rabbit and heat the rabbit top until it just starts to melt (~20 sec.).

E. Reverse the coil switch to remove the heater.

F. Immediately push the sealer press switch.

G. Wait several seconds and reverse sealer press switch.

H. Remove the sealed rabbit and visually inspect to confirm a good seal.

3. Manual Irradiation

A. Decide on irradiation-cool-count times and detector geometry. (Discuss with Task Supervisor as necessary.) Record irradiation cool-count times in Logbook.

B. Initiate QA protocol for the NAA detector per ADS-2420 procedure.If the results of the QA report are out of specifications, notify Task Supervisor.


Page: 6 of 10

C. Begin sample irradiation.

(1) Have stopwatch on hand.

(2) Turn survey instrument on and set to x1000 scale.

(3) Rapidly lower capsule to bottom of tube and start stopwatch.

(4) For a given set of samples, all samples and standards must be irradiated in the same tube using the same irradiation duration.

D. End of irradiation.

(1) Rapidly remove sample from irradiation tube exactly at the end of the irradiation duration. Start stopwatch to monitor cool time as soon as rabbit is removed from neutron flux.

(2) Place the sample two (2) or three (3) inches from the survey instrument.

If count-rate is greater than 300,000 CPM, the sample will be too hot to count. Lower the sample to just below the water level in an irradiation tube to further cool.Periodically check the count rate, and if additional cooling time is necessary, document the change in the cooling time on the log sheet that accompanies the samples.

If the sample has <300,000 CPM, it can be counted at the end of the cool time.

E. Begin preparation for sample counting near the end of the cooling time. For a given batch, all samples and standards must be counted on the same detector. ADS-2420 and ADS-1401 cover necessary information on gamma analysis and liquid nitrogen dispensing.

(1) Place sample in rabbit holder designed for the detector.

(2) Initiate data collection for the pre-defined count time at the end of the pre-defined cool time.


Page: 7 of 10

(3) Record the following in logbook and/or in software:

sample file name, time and date of count, detector’s ID any deviations to the predefined irradiation, cool, and

counting time, dead time (if >10%, notify Task Supervisor for

additional instructions and clearly document in the notebook)

irradiation tube.

(4) Continue steps 3C-3E in this section, for all samples.

NOTE: Samples can be irradiated while other samples are being counted.

4. Automated Irradiation

A. The Neutron Activation System (ANAS-34) automatically processes multiple rabbits by sequentially moving the rabbits to the neutron activation wells, then to a gamma detector for counting with cooling time in between, and back again as needed for a series of predetermined cycles. This is done via a pneumatic system of plastic tubes that carry the rabbits with air pushing them through.The system can process 12 rabbits per hopper, and there are 2 hoppers. All aspects of the automated neutron activation system are controlled and monitored via a computer control system.

Detailed operating instructions are contained in the vendor’s supplied manual (Section 6, Reference 6).

Consult with the Task Supervisor if you have any questions.

B. As with manual irradiation, record all necessary information in logbook and/or in software, as described in section 5.2, 3E (3).

5.3 Directions for Use of Electric Rabbit Cutter

1. Turn on unit by pressing orange switch; the orange light will turn on when the unit is powered up.


Page: 8 of 10

2. Place the rabbit in the rabbit hole. It is critical the rabbit is placed in the hole upright. The top surface should have a circular depression in it, the bottom surface is flat. Contact the Task Supervisor if you are unsure.

3. Close the cover on the unit to protect from possible projectiles.

4. Press white switch and hold down, extending cutter until rabbit is cut clean through and the cutting arm is fully extended.

5. Release the white switch. 6. Remove the top of the rabbit; discard into the appropriate waste stream.

7. Press the white button again and hold down, retracting the cutting arm back into its protective assembly.

8. Remove rabbit; discard the rabbit and its solid contents into the appropriate waste stream. If the rabbit contains a pony vial, decant the contents of the pony vial into the appropriate waste stream.

9. For additional rabbits return to step 2 in this section.

10. Once all rabbits have been opened, turn off the unit by pressing the orange button.

5.4 Calculations

Calculations are based on a comparison of the activity of the element of interest in a standard to the activity of the element of interest in a sample. The results are background subtracted. Calculations for neutron activation are carried out under the Task Supervisor’s directions. They require a blank or background, a standard, and a sample.

5.5 Data Control

Sample preparation data are recorded on the preparation data sheet and recorded in the Radiochemistry Laboratory notebook.



Page: 9 of 10

6.0 REFERENCES

1. Instrument Manual for Canberra Genie-PC.

2. William S. Lyon, Jr., Guide to Activation Analysis, Van Nostrand (1964).

3. L16.1, ADS-1401

4. L16.1, ADS-2420

5. L16.1, ADS-1402

6. System Manual for the Model ANAS-34 Automated Neutron Activation System.

7.0 RECORDS

Data are recorded and maintained as described in Data Control above. The ADS LIMS (Laboratory Information Management System) is used as the primary data storage location.

8.0 ATTACHMENTS

Appendix A Title: “Equipment”


Page: 10 of 10

APPENDIX A

EQUIPMENT

Containers (rabbits, vials) are provided by the NAA facility

Pipettes (various sizes)

Tips (various sizes)

Analytical Balance

Heat Sealer

Stopwatch

Gloves

Various Gamma Detectors

Electric Rabbit Cutter

Neutron Activation System (ANAS-34)

Analytical Development Section Analytical Operating Procedures


Volume 2 Revision: 6High Purity Germanium Detector Gamma Pulse Height Analysis Major Rewrite


1.0 INTRODUCTION

1.1 Purpose

This procedure covers the application of high-purity, high resolution germanium detectors to the detection, identification and quantification of gamma rays from a variety of low- to moderate-density sample matrices.

This procedure will outline the requirements for routine use of high purity germanium detectors for sample analysis. Portions of this procedure are applicable to the use of gamma pulse height analysis for accountability measurements.

1.2 Scope

This procedure applies to gamma pulse height analysis (PHA) using high purity germanium detectors of different types (coaxial, semi-planar, well, and planar) coupled with Genie 2000 Acquisition and Analysis Software (or similar industry software). The analysis software applies known gamma ray energies and calibrated detection efficiencies to spectral data to determine nuclide content of samples.

Gamma pulse height analysis is used by Analytical Development in a variety of different ways to quantify material: it is used for the measurement of relative amounts of known nuclides for comparative purposes (i.e., tracing or trending), it is used for absolute measurements of samples containing unknown concentrations of unknown nuclides for the purpose of quantification, and it is used for Material Control and Accountability (MC&A) measurements.

The quality assurance and quality control process varies with each different application. For example, comparative measurements require only that the detector can be used to accurately determine the relative peak areas of a given peak of known energy. Therefore, only energy calibration and verification is needed to provide data of sufficient quality. In comparison, MC&A measurements require very detailed studies of the detector behavior over time, control charts of the energies and inferred efficiencies of defined peaks within the expected energy range, verification of the quality assurance parameters each day the detector is used, and extensive evaluation if the quality assurance parameters fail defined acceptance criteria. It is the approach of this laboratory to maintain MC&A quality assurance (QA) on several characterized detectors, while maintaining less stringent QA on detectors that are not utilized for MC&A.The required QA for each type of application will be addressed.

Procedure: ADS-2420High Purity Germanium Detector Gamma Pulse Height Analysis



2.1 Background Information

Liquid and low- to moderate-density solid samples can be analyzed by gamma-PHA. The detector systems quantify gamma-emitting nuclides using pre-defined, calibrated, and validated counting geometries. Determinations of sample activity and supporting calculations are performed by vendor-qualified software (Section 6.0 References 3 and 4).

Although gamma pulse height analysis is relatively simple, specific and rapid, there are limitations that must be taken into account.

1. Detectors must be energy calibrated with known standards.

2. Detection efficiencies for gamma-rays vary with energy and must be obtained during the calibration process if the detector is being used for absolute quantification of unknown material.

3. The counting geometry (configuration of prepared sample and position of prepared sample relative to the detector) is established during calibration and must be carefully duplicated for accurate work.

4. The amount of activity in the counting vessel must be within an optimum range for accurate work. The Multichannel Analyzer (MCA) displays a "dead time” on the screen as the sample counts. During this "dead time", the MCA does not accept additional events. If the "dead time" is >10%, the sample should be analyzed in a different manner (diluted, moved away from the detector, etc.) for accurate measurements.

5. The relative abundance of the various gamma nuclides in the samples has an effect on the method sensitivity. Higher energy gammas can interfere with, or even mask, lower energy gamma rays.

The quality assurance and quality control protocols applicable to gamma PHA are dependent upon the Data Quality Objectives. If the data will be used for MC&A determinations, a higher level of QC must be maintained than if the data will be used for a trending study using a known standard. These different QC approaches are described in more detail throughout this procedure.

All of the detectors are measurement systems and equipment (MS&E) and, as such, comply with the requirements set forth by Manual 1Q, 2-7.

Only a subset of the detectors is maintained for MC&A analyses.





Reading, understanding and following this procedure. Calling to the attention of the Task Supervisor any part of the procedure

that requires revision or that they believe to be unsafe.


Maintaining this procedure. Providing technical guidance.


3.1 Safety

1. Follow L1 2.32 Radiological Work Practices and 8Q Laboratory Safety guidelines.

2. Read, understand, and follow applicable Job Hazard Analyses (JHAs) in the Conduct of R&D packet.

3. Per JHA, be cautious of moving parts, lead, and pinch points.

4. Carefully examine all packaging for evidence of leaks prior to handling radioactive samples.

4.0 PREREQUISITES

None

5.0 PROCEDURE

5.1 Equipment

High purity germanium detectors, and associated gamma spectroscopy electronics

Canberra Genie 2K gamma spectroscopy software (or similar industry product)

Changer Labs sample changers Calibrated M&TE pipettes Calibrated M&TE analytical balances If necessary, additional items are maintained in the MS&E file for the

method.



5.2 Reagents

Purity of reagents - Unless otherwise stated, ACS reagent grade chemicals shall be used.

5.3 Standards

Standards utilized for establishing and validating energy and efficiency calibrations are NIST-traceable mixed gamma ray standards. The mixed gamma ray standards typically contain the following radionuclides: Am-241 (59.5 keV), Cd-109 (88.0 keV), Co-57 (122.1 keV), Ce-139 (165.9 keV), Hg-203 (279.2 keV), Sn-113 (391.7 keV), Sr-85 (514.0 keV), Cs-137 (661.6 keV), Mn-54 (834.8 keV), Y-88 (898.0 keV and 1836 keV), Zn-65 (1116 keV), and Co-60 (1173keV and 1333 keV). Single-nuclide NIST-traceable standards can also be used, if necessary, to augment the energy range for example.

Standards are diluted gravimetrically utilizing standard industry practice.Balances utilized for the preparation are M&TE (measuring and test equipment) and, as such, comply with the requirements set forth by Manual 1Q, 12-1.Documentation of standard preparation, including M&TE identification, is maintained in a logbook and is referenced in the dilution calculation spreadsheet.

Quality control standards are often prepared from the same source as the calibration standards. These standards are validated using previously validated standards from an independent lot.

5.4 Energy Calibration

Energy calibrations are performed during detector set-up using a known, validated standard in conjunction with the Genie 2000 data acquisition system.Algorithms for the peak search, peak fitting and energy calibration are described in Section 6.0 Reference 4. The calibration peaks should span the entire range of energies to be reported.

5.5 Efficiency Calibration

Detection efficiencies for gamma-rays vary with energy and must be determined during the calibration process if the detector is being used for absolute quantification of unknown material. Efficiency calibrations are performed during detector set-up, and on an as-needed basis, utilizing a mixed gamma ray standard.

The standard for a given geometry, prepared and validated as previously described in Section 5.3, is analyzed using the Genie 2000 data acquisition procedure to determine detection efficiencies throughout the energy range of



interest. After the detection efficiency has been determined for each calibration peak in the standard, a weighted least mean squares fit is applied to a polynomial. The resultant polynomial is used to determine detector efficiencies for gamma rays within the span of the peak energies in the mixed gamma ray standard (typically, 59.5 keV from Am-241 through 1836 keV from Y-88).Periodically, the energy range of the calibration is extended using lower- or higher-energy emissions from additional NIST-traceable gamma standards.Newly established efficiencies are validated using previously validated efficiencies from an independent standard. Algorithms for the efficiency calibration are described in Section 6.0 References 3 and 4.

Efficiency calibrations are evaluated at least annually. Radionuclide activities determined during the efficiency calibration should overlap the expected radionuclide activities for the standard within 3-sigma or have a deviation of less than 10%. The efficiency calibrations are documented in the systems’ measurement systems and equipment (MS&E) history files.

5.6 Quality Control Check Standard

1. Energy

A check-source, prepared using the NIST-traceable standard, is counted each day that samples are analyzed. Three peaks with well-established energies (typically; 59.5 keV from Am-241, 661.6 keV from Cs-137, and 1333 keV from Co-60) are used to validate detector performance. It should be noted that the low-energy gamma detectors use different peaks to allow evaluation of the lower range of the energy spectrum (typically; 59.5keV from Am-241, 88.0 keV from Cd-109, and 122.1 keV from Co-57).Results from the daily check source are evaluated each day samples are analyzed. Gamma energies for the check standard should be within ± 0.5 keV of the true emission energy (investigate warning), and are required to be within ±1.0 keV of the true emission energy (action warning).

Detectors are monitored with respect to the investigate warning, and controlled to the action warning. Any action warning requires immediate attention; no further analytical analyses can be performed until the event causing the action warning has been remedied. Any investigate warning requires attention; however, analytical analyses can be performed with an investigate warning.



A. Additional MC&A protocol:

(1) Any investigate warning shall be thoroughly evaluated to ensure there has not been an additional investigate warning within the past 2 evaluations. Violation of the 2-out-of-3 rule requires immediate action; no further analytical analyses can be performed until the event causing the 2-out-of-3 rule violation has been remedied. The system is validated following any corrective actions with three subsequent QA measurements which fall within the warning limits.

(2) If the detector has been deemed “out of control”, and the MC&A capability within AD is unavailable (i.e., no other detectors are working that can be used for MC&A determinations), the MBA custodian will be notified.

(3) Results from the energy calibration check standard are entered into control charts which are reviewed weekly.

(4) The result of the evaluations initiated by the QA protocol, and the subsequent corrective actions, will be documented in the logbook and in the MS&E history file.

2. Efficiency

A check-source, prepared using the NIST-traceable standard, is counted each day that samples are analyzed, and three peaks with acceptable counting statistics and statistical uncertainties (typically; Am-241, Cs-137, and Co-60) are used to validate detector performance. It should be noted that the low-energy gamma detectors use different peaks to allow evaluation of the working range of the detector (typically; Am-241, Cd-109, and Co-57).

Historically, the activity/efficiency control limits have been set by a combination of the gamma-ray standard uncertainties from the NIST certificate, the uncertainties from the polynomial fit for a gamma ray of the energy in question, the uncertainties of the gamma branching ratio for the isotope generating the tracked gamma ray, as well as the counting statistics for the gamma ray in the ~15 minute count of the check standard. This approach is still applicable for detectors not carrying an MC&A pedigree.

As a result of an effort to update the Material Control & Accountability (MC&A) qualifications of the SRNL Analytical Development gamma method, SRNL’s Statistical Consulting Section was contracted to analyze the performance of 6 of SRNL AD gamma spectrometers’ historical check standard results. The results of this analysis are available in Reference 8.



Control limits for MC&A approved detectors are established using the total uncertainties as determined by the statistical analysis. The control limits are centered on the values of the check standards adjusted for any measured deviations in the efficiency calibration polynomial fit’s calculated efficiency versus its measured efficiency.

Results from the daily check-source standard are evaluated each day prior to detector use. Detectors are monitored with respect to the investigatewarning, and controlled to the action warning. Any action warning requires immediate attention; no further analytical analyses can be performed until the event causing the action warning has been remedied.Any investigate warning requires attention; however, analytical analyses can be performed with an investigate warning.

A. Additional MC&A protocol:

(1) Any investigate warning shall be thoroughly evaluated to ensure there has not been an additional investigate warning within the past 2 evaluations. Violation of the 2-out-of-3 rule requires immediate action; no further analytical analyses can be performed until the event causing the 2-out-of-3 rule violation has been remedied. The system is validated following any corrective actions with three subsequent QA measurements which fall within the warning limits.

(2) If the detector has been deemed “out of control”, and the MC&A capability within AD is unavailable (i.e., no other detectors are working that can be used for MC&A determinations), the MBA custodian will be notified.

(3) Results from the check standard are entered into control charts which are reviewed weekly.

(4) The result of the evaluations initiated by the QA protocol, and the subsequent corrective actions, will be documented in the logbook or in the MS&E history file.

3. Full Width at Half-Maximum

As a further control of detector stability, the resolution of the detector is also monitored daily for any sudden changes. The full-width at half maximum (FWHM) of one of the peaks utilized in the daily system verification is measured with each check standard count. The FWHM shall be within 0.3 keV of the average value for that peak.

Results from the daily check-source standard are evaluated each day prior to detector use. Detectors are monitored with respect to the investigatewarning, and controlled to the action warning. Any action warning requires immediate attention; no further analytical analyses can be



performed until the event causing the action warning has been remedied.Any investigate warning requires attention; however, analytical analyses can be performed with an investigate warning. The result of the evaluations initiated by the QA protocol, and the subsequent corrective actions, will be documented in the logbook or in the MS&E history file.

5.7 Quality Control Background

A background spectrum will be collected for each detector as determined by the Analytical Task Supervisor, but at least monthly.

In the absence of any material, the spectrum should be accumulated over a period of time sufficient to properly determine a true background spectrum for the energy region normally used for sample analyses. Preferably the spectrum will be acquired for 200,000 seconds. The minimum acquisition time is 50,000 seconds, unless otherwise directed by the Analytical Task Supervisor.

5.8 Analysis

1. Daily QA Check

A. See previous sections for a detailed discussion of the daily QA check protocol.

2. Liquid Samples

A. Prepare sample in geometry and dilution as directed by Analytical Task Supervisor. Samples requiring extensive manipulation in a radiological containment unit will have batch blanks prepared along with the sample. However, samples undergoing simple dilution or transfer may not require batch blanks.

B. Record preparation information.

C. Have samples cleared to be transported to final counting facility.



D. Count sample on detector as directed by Analytical Task Supervisor. Ensure detector has had QA successfully completed prior to counting the sample.

E. Record file ID, date, time, detector, geometry, and initials in log book.

F. After data has been reviewed, enter results into LIMS as directed by Analytical Task Supervisor

3. Solid Samples

A. Prepare sample in geometry as directed by Analytical Task Supervisor. Samples requiring extensive manipulation in a radiological containment unit will have batch blanks prepared along with the sample. However, samples undergoing simple transfer may not require batch blanks.

B. Record preparation information.

C. Have samples cleared to be transported to final counting facility.

D. Count sample on detector as directed by Analytical Task Supervisor. Ensure detector has had QA successfully completed prior to counting the sample.

E. Record file ID, date, time, detector, geometry, and initials in log book.

F. After data has been reviewed, enter results into LIMS as directed by Analytical Task Supervisor.

4. Data Control

Preparation data are recorded on the preparation data sheet and recorded in the Radiochemistry Laboratory notebook.

The final data packet, containing the preparation sheet, computer printouts, and calculations are stored in the counting room data notebook and associated binders.



6.0 REFERENCES

1. Nuclear and Radiochemistry, G. Friedlander, J.W. Kennedy, E.S. Macias, J.M. Miller, 3rd Ed., pp. 243-286.

2. ANSI N42.14-1999. American National Standard Calibration and Use of Germanium Spectrometers for Measurement of Gamma-Ray Emission Rates of Radionuclides.

3. Genie 2000 Operations Manual, Canberra Industries, Inc., 2002.

4. Genie 2000 Customization Tools Manual, Canberra Industries, Inc., 2002.

5. Changer Labs Operations and Set-up manual, Westinghouse Savannah River Technical Center, Changer Labs 1996.

6. Manual 1Q, 12-1, Control of Measuring and Testing Equipment.

7. Manual 1Q, 2-7, QA Program Requirements for Analytical Measurement Systems.

8. SRNL-ACS-2007-00002, Statistical Uncertainty of SRNL’s Gamma Detectors.

9. SRNL-ADD-2007-00216, Recommendation for Update of SRNL’s Analytical Development Gamma Pulse Height Analysis 14Q302 Qualification

7.0 RECORDS

Data are recorded and maintained as described in Data Control section above.

The AD LIMS is used as the primary data storage location.

8.0 ATTACHMENTS

None

SAVANNAH RIVER NATIONAL LABORATORY Manual: L16.1 ANALYTICAL DEVELOPMENT Procedure: ADS-2424 ANALYTICAL OPERATING PROCEDURES Revision: 7 Page: 1 of 10 TECHNICAL REFERENCE Effective Date: 8/20/2008 Gross Alpha/Beta Determination Approved by: by Liquid Scintillation Counting (U) Approval on File ADS Manager MAJOR REWRITE 1.0 PURPOSE

This method is used to screen a variety of sample matrices for both alpha and beta activities by liquid scintillation counting. This procedure is an approved method for determining Measurement Control and Accountability (MC&A) values for SRNL. All required QA/QC are performed whether the sample is used for accountability purposes or not.

2.0 SCOPE

2.1 Applications of this method may include initial screening of:

Environmental samples (soils, etc.). “Clean” samples which have never been in a Radiological

Controlled Area (RCA).

Samples which have been in RCAs, but which are not expected to be contaminated.

Samples which may contain small quantities of radionuclides,

such as the Low Level Residue Tanks at 773-A.

High activity samples which may or may not contain fission products.

2.2 The data produced by the method may be used for a variety of

applications such as:

Providing adequate information concerning the activity within samples, and thus determine if further, more detailed analyses are required.


Ensuring that the Department of Transportation regulations concerning the transport of radioactive materials are not exceeded.

Accountability measurements for gross alpha activity

2.3 Gross screening analyses are not expected to be as accurate nor as

precise as more detailed radiochemical separations. Rather, they are intended to provide rapid information associated with a particular action level with minimal chemical preparation. Additionally, these types of analyses are intended to give estimates rather than absolute activity measurements unless they are implemented with the use of NIST-traceable standards.

2.4 If a sample is analyzed by this method and is found to contain

significant quantities of alpha and/or beta-gamma activity, then the sample may be analyzed by additional ADS procedures. “Significant” will usually be determined by the customer, depending on how the data are to be used.


2.5.1 Analysts are responsible for: Reading, understanding and following this procedure. Calling to the attention of the Task Supervisor any part of

the procedure that requires revision or that they believe to be unsafe.

2.5.2 Task Supervisor/Cognizant Technical Function is responsible

for: Maintaining this procedure. Providing technical guidance. Providing additional directions, when needed, through the

use of R&D directions.

SAVANNAH RIVER NATIONAL LABORATORY Manual: L16.1 ANALYTICAL DEVELOPMENT Procedure: ADS-2424 ANALYTICAL OPERATING PROCEDURES Revision: 7 Page: 3 of 10 TECHNICAL REFERENCE Effective Date: 8/20/2008 3.0 PRECAUTIONS/LIMITATIONS

3.1 Safety

3.1.1 Follow L1, 2.32 Radiological Work Practices and 8Q Laboratory Safety guidelines

3.1.2 Read understand, and follow applicable Job Hazard Analyses

(JHAs) in Conduct of R&D packet. 3.1.3 The instrument contains a small sealed Ba-133 source

3.2 General Limitations

3.2.1 Chemical quenching and/or color quenching of the light output

can reduce detection efficiency. This can be prevented with the sample preparation or accounted for using a quench curve.

3.2.2 The presence of static electricity within the system can cause

erroneous results. This is monitored via duplicate counts. 3.2.3 High-energy beta emissions can be misidentified as alpha

emissions, biasing alpha results high and beta results low. An added standard is used to determine the degree of spill-over when quantification is needed.

3.2.4 High activity samples can cause pulse pile-up and high dead

time on the instrument, which would bias reported results low.

3.2.5 A large beta/alpha activity ratio can lead to erroneously high alpha results (due to spillover). Results are reported as upper limits in this case.


N/A

5.0 PERFORMANCE


5.1 Description

The method may be used for nearly all aqueous and organic solutions, provided they do not react with and are miscible with the cocktail used for analysis. Generally, Ultima Gold AB is used since it is specifically formulated for alpha/beta discrimination, and it is the best choice for samples dissolved in mineral acids. Other cocktails may be used at the discretion of the Task Supervisor/CTF. Packard instruments automatically correct for quenching and many other interference problems commonly associated with liquid scintillation counting. The Gross Alpha/Beta counting protocol, as utilized in this laboratory, is designed to provide a conservative screening for gross beta (including tritium) and gross alpha activities.

5.2 Equipment

5.2.1 Packard Instruments 2550AB, 2750AB and 3150AB TriCarb Liquid Scintillation Counters are presently being used. These instruments electronically separate alpha and beta counts into two separate energy spectra based on differences in pulse shapes.

5.2.2 Calibrated pipets and balances 5.2.3 20 mL polyethylene liquid scintillation vials, Packard No.

6008117 or equivalent. 5.2.4 6 mL polyethylene liquid scintillation (“pony”) vials, Packard

No. 6000292 or equivalent.

5.3 Reagents

5.3.1 Ultima Gold AB - used as delivered from the manufacturer. 5.3.2 Distilled Water - as delivered through the Building 773-A

distilled water system. 5.3.3 Nitric Acid

5.4 Standards


5.4.1 Standards utilized for establishing and validating efficiency

calibrations, for determining the optimum discriminator setting, and for generating quench curves, are NIST-traceable.

5.4.2 The Packard Tri-Carb Liquid Scintillation Counters use three

vendor-supplied sealed sources in glass counting vials for routine calibrations and diagnostics. These include 3H, 14C, and a background standard, which are counted every day that samples are analyzed.

5.4.3 Standards are diluted gravimetrically utilizing standard

industry practice. Balances utilized for the preparation are M&TE (measuring and test equipment) and, as such, comply with the requirements set forth by Manual 1Q, 12-1.

5.4.4 Documentation of standard preparation, including M&TE

identification, is maintained in a logbook and is referenced in the calibration spreadsheet.

5.5 Efficiency Calibrations

5.5.1 The alpha detection efficiencies for the liquid scintillation counters were determined using NIST (National Institute of Standards and Technology) -traceable Pu-238 standard and later validated using an independent source of Pu.

5.5.2 A 70% beta detection efficiency is utilized for beta activity

outside the tritium region for gross screening analyses. This is an average of the experimental efficiencies typically observed for medium- to high-energy beta emissions.

5.5.3 A quench curve is utilized for tritium detection efficiency due to

its low energy, and thus, susceptibility to quench. This quench curve is validated yearly.

5.6 Routine System Verification


5.6.1 As previously mentioned, the Packard Tri-Carb Liquid

Scintillation Counters use three sealed sources in glass counting vials for routine calibrations and diagnostics. These are counted every day that samples are analyzed.

5.6.2 For the 3H and 14C efficiency protocols, the instrument

establishes baseline efficiencies from the mean of the first 5 measurements stored for that parameter. If a change in the efficiency for that parameter is greater than 3% of the mean observed, the software will generate a warning flag.

5.6.3 Background baselines for 3H and 14C are also established from

the first 5 measurements. If the background increases to a value greater than 4 standard deviations above the baseline, a warning flag is generated.

5.6.4 Any flags that arise from these routine verifications are

investigated prior to further sample analysis.

5.7 Alpha Efficiency Validation and Control Charting

5.7.1 Due to site Material Control and Accountability (MC&A) requirements, additional Quality Control measures are performed daily.

5.7.2 A NIST-traceable 238Pu standard is counted daily as a check

source to validate the efficiency calibration. The results of this daily check standard are control charted weekly.

5.7.3 The counters are monitored with respect to the warning limit

(2) and controlled to the action limit (3). The uncertainties were determined by the Statistical Consulting Section as described in Reference 7.8.

5.7.4 Any action limit requires immediate attention; no further

analyses can be performed until the event causing the action limit has been remedied.


5.7.5 Any warning limit requires attention; however, analyses can be performed with a single warning limit. It should be noted that any warning limit shall be thoroughly evaluated to ensure there has not been an additional warning limit within the past 3 evaluations. Violation of the 2-out-of-3 rule requires immediate action; no further analytical analyses can be performed until the event causing the 2-out-of-3 rule has been remedied.

5.7.6 The system is validated following any corrective actions with

three subsequent QC measurements which fall within the warning limits using the daily check-source standard. The counter is considered back in control if one of the three responses falls on the opposite side of the centerline from the other two or at least equals the target centerline value. The counter will be recalibrated if the results of the three measurements do not indicate the counter is back in control. The result of the evaluation and the recalibration (if necessary) will be documented in the logbook and in the MS&E history file.

5.7.7 The system is reviewed for any non-random pattern in the data.

Specifically, it is controlled to the eight runs rule using the 238Pu standard results. The counter is considered to be in an adverse condition if a pattern of eight consecutive points for the 238Pu standard lie on the same side of the control chart center line.

5.8 Accuracy

In order to evaluate the accuracy of the liquid scintillation counters, a dilution of the Analytical Laboratory Department (ALD)’s Coulometry Lab plutonium standard solution was analyzed 15 times on each counter. Results for both counters overlapped the value of the ALD standard within the 95% confidence interval.

5.9 Sample Preparation

Due to the variety of sample types (soil leachates, filters, and residue tank solutions) that may be analyzed using gross alpha-beta, sample preparation details will vary with sample type at the discretion of the Task Supervisor.


5.9.1 Using the recommendations of the CTF, add cocktail to the appropriate LS vial.

5.9.2 Place vial(s) on a clean surface in the hood or radiobench to

avoid contamination on the outside of the vial. 5.9.3 Pipette the volume of sample recommended by the CTF into the

LS vial. If the sample is too dark, reduce the aliquot size to one-half of the initially recommended volume. Cap the vial tightly.

5.9.4 If a pony vial is used, insert the sealed pony vial inside the large

scintillation vial. Keep the outer vial clean. Cap the outer vial tightly.

5.9.5 Label the outer lid with sample ID. Do not write on the sides of

the vials. Shake the sealed vials thoroughly to ensure that the sample and cocktail are mixed well.

NOTE: Change plastic gloves to avoid contaminating the outside of vial(s) when capping.

5.9.6 Submit the vial(s) to the ADS Counting Room (773-A, B-145

after having them cleared by RCO) for analysis on the Packard instruments.

5.10 Counting

5.10.1Load the samples into a sample cassette, with the appropriate

blank in the first position. The counting protocol to be selected depends on which counter is to be used, and on how the sample was prepared. Select the protocol number as instructed by the CTF.

5.10.2The counting protocols may be edited to change the counting

parameters (i.e. counting time) only under direct supervision of the CTF. See the operation manuals for details.

5.10.3Push the slide tab (on the left side of the cassette) to the left and

place the cassette(s) in the sample changer magazine. Start the instrument.


5.10.4After the samples have been analyzed and the results approved, all vials except those marked with special hazard dots should be emptied down the high activity drain. The vials themselves should be put in the solid radioactive waste. Vials marked with special hazard dots are treated according to specified guidelines.

5.11 Background

Check the count rate of the batch blank and ensure that levels are acceptable to the CTF. Large changes in blank counts could be a sign that further investigation or additional counting is required.

5.12 DPM Calculations The gross alpha and gross beta dpm values are listed on the printout. Multiply the dpm value by the appropriate dilution factor to obtain the dpm/unit of interest (ml, g, smear, etc.) value for the sample.

DPM/Unit of Interest = (DPM) (DF)

5.13 LLD Calculation

If net activity is not detected, then Lower Limits of Detection (LLD’s) must be calculated for the gross alpha and/or gross beta activities. The total background counts for any given region of interest are used in the following equation to calculate an LLD value:

.

LLD (DPM) = )count time)(efficiency(

regionincountsbackgroundtotal65.471.2

The LLD value is then adjusted for the dilution factor per the equation in 5.12

SAVANNAH RIVER NATIONAL LABORATORY Manual: L16.1 ANALYTICAL DEVELOPMENT Procedure: ADS-2424 ANALYTICAL OPERATING PROCEDURES Revision: 7 Page: 10 of 10 TECHNICAL REFERENCE Effective Date: 8/20/2008 6.0 RECORDS

All prep and analysis data is recorded and maintained in the laboratory notebooks. The final data packet, containing the prep sheet, computer printouts, and calculations are stored in the counting room data notebook and associated binders. The ADS LIM’s is used as the primary data storage location.

7.0 REFERENCES

7.1 "Liquid Scintillation Analysis -Science and Technology," Publication No. 169-3052, Packard Instrument Co., Inc. 1987.

7.2 Tri-Carb Series Liquid Scintillation Analyzers, Model 2250CA Operation Manual, Publication No. 169-3094, Packard Instrument Co., Inc. 1987.

7.3 Tri-Carb Series Liquid Scintillation Analyzers, Model 2550TR Operation Manual, Publication No. 169-4044, Packard Instrument Co., Inc. 1990

7.4 SRNLProcedure Manual L1, 2.32 “Radiological Work Practices.” 7.5 SRNL-ADD-2007-00584, Recommendation for Update of SRNL’s

Analytical Developments Liquid Scintillation Analysis 14Q302 Qualification, December 20, 2007.

7.6 Manual 1Q, 2-7, Revision 6, QA Program Requirements for Analytical Measurement Systems.

7.7 Manual 1Q, 12-1, Revision 11, Control of Measuring and Test Equipment.

7.8 SRNL-SCS-2008-00004, Statistical Uncertainty of SRNL’s LSC Counters, January 14, 2008.


SAVANNAH RIVER TECHNOLOGY CENTER Manual: L16.1 ANALYTICAL DEVELOPMENT SECTION Procedure: ADS-2444 ADS ANALYTICAL OPERATING PROCEDURES Revision: 5 Page: 1 of 8 TECHNICAL REFERENCE Effective Date: 05/18/2006

Tritium In Environmental Samples -

A Distillation Procedure Signatures Author/ Task Supervisor: C. C. DiPrete Peer Reviewer R. A. Sigg Analytical and Radiochemistry Research Group Manager: P. E. Filpus-Luyckx ADS Procedures Coordinator: L. Hillary

SAVANNAH RIVER TECHNOLOGY CENTER Manual: L16.1 ANALYTICAL DEVELOPMENT SECTION Procedure: ADS-2444 ADS ANALYTICAL OPERATING PROCEDURES Revision: 5 Page: 2 of 8 TECHNICAL REFERENCE Effective Date: 05/18/2006 1.0 PURPOSE This procedure describes preparation of samples for Tritium analysis. 2.0 SCOPE

The distillation method may be used to separate water containing tritium activity from matrices and from most interfering radionuclides. The method may be applied to a number of matrices, including soil, vegetation, tissue and water samples.


Analysts are responsible for:

Reading, understanding and following this procedure. Calling to the attention of the Task Supervisor any part of the

procedure that requires revision or that they believe to be unsafe.

Task Supervisor is responsible for:

Maintaining this procedure, providing analysts with otherwise difficult to obtain spikes and low-

tritium water, and providing technical guidance.


3.1 Safety

3.1.1 Follow L1 2.32 Radiological Work Practices and 8Q Laboratory Safety Guidelines. 3.1.2 Read, understand and follow applicable JHAs in Conduct of

R&D packet.



Read, understand and follow applicable JHAs in Conduct of R&D packet.

5.0 PERFORMANCE


5.1.1 Overview

Tritiated water is: separated from the sample matrix by distillation, pipetted into a liquid scintillation vial, mixed with scintillation cocktail, and analyzed for tritium by liquid scintillation spectrometry

(Ref. 1)


The method may be applied to a variety of matrices, including soil, vegetation, tissue and water samples. Since distillation separates water from the matrix and does not oxidize the sample, the method does not yield results for organically-bound tritium unless a separate oxidation procedure, such as wet ashing, is also applied. Volatile organic compounds may not be totally removed by this distillation procedure. While such compounds may cause chemical quenching, the Packard Liquid Scintillation Counting (LSC) instrument automatically determine quenching and its effects on counting efficiency for every sample.

If other volatile radionuclides are present, they may also interfere. The presence of such radionuclides may be determined from the beta spectra collected by the Packard LSC instruments. If significant interferences are present, the Task Supervisor may suggest additional sample purification steps.


Luminescence effects can increase count rates in the tritium window. The LSC instruments automatically correct for luminescence effects; however, if luminescence corrections are large, uncertainty in low-level tritium values can be significant. Rerunning the sample may not be necessary because luminescence generally decreases with time. Recount the sample after several hours to see if luminescence decreased. Repetitive counting of samples to determine the half-life for "long-lived" luminescence and calculation of a correction factor is a second method. Consult the Task Supervisor for guidance.

Simple redistillation is probably not effective for previously distilled samples. Redistillation using an oxidizing agent may eliminate volatile organic codistillates.

5.1.3 Detection Limit Ranges

Minimum Detectable Activities (MDAs, Ref. 2) depend on the length of count, counter background, detector efficiencies and the volume of water added to the cocktail. As an example, for an LSC instrument having nominal backgrounds and efficiencies of 21 CPM and 50%, respectively, MDAs are 10-minute count: 6.5 pCi/sample 60-min count: 2.5 pCi/sample Two (2) Sigma counting uncertainties are provided by the LSC instruments. Additional uncertainties may result from determination of weight percent water in the sample and in efficiency calibration.

5.1.4 Method Validation

Standard addition of known quantities of tritium (spikes) to duplicate samples or blanks may be conducted in each sample preparation batch if specified by the Task Supervisor.


5.1.5 Equipment

Distillation Apparatus Scintillation counting vials: 20-mL (nominal) polyethylene

with plastic caps Pipette with disposable tips Hot plates Liquid scintillation counter. Packard Model 2550 AB or

Packard Model 2250, or equivalent. Kimwipes

5.1.6 Reagents

Liquid scintillation cocktail: Packard Instrument Co. Ultima Gold AB


Be sure to run the instrument Self-Normalization and Calibration (SNC) protocol each day that samples are counted (Ref. 1). This protocol provides data to QC chart detector backgrounds, and tritium and C-14 efficiencies.

5.1.8 Calibration and Standardization

Determine a tritium quench curve for each instrument as required by the LSC procedure (Ref. 1). Alternatively, tritium counting efficiency can be determined for each sample by:

first counting each sample, adding a small volume (e.g. 100 microLiters) of tritium spike to the sample, and recounting the spiked samples.


NOTE: the low volume of spike does not significantly change quenching.

5.2 Procedure details

5.2.1 Solid Samples

S1. Fill an appropriate vessel with the sample to be distilled. Weigh and record the sample weight (vessel may be weighed or tared prior to obtaining sample weight). Add a sufficient volume of appropriate solvent (D.I. Water, dilute nitric acid, etc.) and allow to set while closed at least 4 hours. Task Supervisor will provide specific guidance.

Leachate solutions from solid samples can also be

analyzed for tritium following the procedure for solutions provided below.

If a sample is to be spiked, follow Task Supervisor’s

guidance.

S2. Set up the distillation apparatus as per the Task Supervisor’s instructions.

S3. Gradually raise the temperature on the hot plate, until

the solution begins to boil. S4. Once a sufficient quantity of water has been collected,

turn off heat and allow to cool. Collect at least 2 mL of distillate, if possible.

S5. Pipette an aliquot of sample from the collection flask into

a 20-mL polyethylene counting vial. A volume of 2 mL is preferable but less may be used. Add enough Ultma Gold AB cocktail to the vial to bring the total volume to 19-20


mL. Record the volume of distillate added to the scintillation vial. Cap the vial tightly and shake.

S6. Label the cap of the scintillation vial with the sample

number and submit to the counting facility for liquid scintillation counting.

5.2.2 Liquid Samples:

W1. Add an appropriate amount of liquid (approximately 10

mL) to the distillation apparatus. Record the volume of sample added.

Volumes used may be altered at discretion of Task

Supervisor. If a sample is to be spiked, follow Task Supervisor’s

guidance. W2. Proceed with steps S2 to S6.

5.3 Calculations

Manual L16.1, Procedure ADS-2424, describes calculations for LSC counting. Calculations for sample requests are done using in-house software under the guidance of the Task Supervisor. All calculations are completed by the Task Supervisor or a trained designee. 5.3.1 Data Control

Preparation data are recorded on the preparation data sheet and recorded in the Radiometric Laboratory notebook.



6.0 RECORDS

Data are recorded and maintained as described in Data Control section above. The ADS LIMS is used as the primary data storage location.

7.0 REFERENCES

1. ADS Manual L16.1, Procedure ADS-2424,”Gross Alpha/Beta Determination by Liquid Scintillation Counting.”

2. Currie, L. A., Limits for Qualitative Detection and Quantitative

Determination, Analytical Chemistry 40, 586 (1968). 3. Peters, R.J. and G.H. Brooks, Tritium in Environmental Matrices -

Distillation Procedure, LANL Method # ER210. 4. EG&G Mound, Sample Preparation for Analysis of Tritium by Liquid

Scintillation Counting, Method # 1162. 5. SRTC Procedure Manual L1, 2.32, Radiological Work Practices.

8.0 ATTACHMENTS None.


Technetium-99 by Extraction Approved by: Chromatography

APPROVAL ON FILE AD Manager

MAJOR REVISION 1.0 PURPOSE This procedure describes a method to separate technetium-99 (Tc-99) by

extraction chromatography and subsequent activity measurements by gamma-ray spectrometry and liquid scintillation counting.

2.0 SCOPE

The procedure describes the general method for separating Tc-99 from interfering nuclides, and analyzing the separated sample for Tc-99 content. Tc-99m is added to each sample as a tracer. Samples spiked with National Institute of Standards and Technology (NIST) traceable Tc-99 are also processed and counted. Gamma-PHA (Pulse Height Analysis) is used for tracer yield determination and liquid scintillation counting (LSC) is used for Tc-99 determinations. 2.1 Definitions and Abbreviations

JHA Job Hazards Analysis HAP Hazards Assessment Package LSC Liquid Scintillation Counting RWP Radiological Work Permit


Analysts are responsible for: Reading, understanding and following this procedure, Calling to the attention of the Task Supervisor any part of the

procedure that requires revision or that they believe to be unsafe, Reading, understanding, and signing applicable RWPs, JHAs, and

HAPs (or equivalent) prior to independent work.


Task Supervisor is responsible for: Maintaining this procedure, Providing technical guidance as needed, Providing additional directions, when needed, through the use of

R&D directions. 3.0 PRECAUTIONS/LIMITATIONS

3.1 Safety

3.1.1 Follow L1, 2.32 Radiological Work Practices and 8Q Laboratory Safety Guidelines

3.1.2 Read, understand, and follow applicable Job Hazard Analyses

(JHAs) in Conduct of R&D packet. Specifically, be aware for the additional precautions when working with flammable solvents.


None 5.0 PERFORMANCE


5.1.1 Description

Tc-99 is separated from samples using a variety of different approaches dependent upon the sample type and customer needs. Ultimately, the sample is separated using Eichrom TEVA resin and or TEVA disks (or equivalent) prior to liquid scintillation counting. After removal of the pertechnetate ion (TcO4

-), Tc-99 is measured by liquid scintillation counting after adding the resin or filter disk directly to liquid scintillation cocktail. Each sample is analyzed with the short-lived gamma emitter, Tc-99m, as a tracer.

This method is a rapid, reliable method for measurement of Tc-

99 in a variety of samples that is more cost-effective and efficient than traditional anion exchange, solvent extraction or precipitation techniques.



Due to the relatively short half-life of Tc-99m (6.01 hr), the method requires closer attention to measurement times than most other samples measured at ADS. Also due to the relatively short Tc-99m half-life, good communication and close coordination are needed between analysts performing the separations and Counting Room personnel. The method used separates Tc in the pertechnetate form (TcO4-). If total Tc-99 measurement is desired, steps must be taken to ensure all available Tc-99 is converted to TcO4-.

5.1.3 Interferences

Organic matter present in the sample can interfere by quenching during liquid scintillation counting. While the Packard liquid scintillation counters automatically correct for most quenching, it may be desirable to minimize quenching by using a prefilter column (such as Eichrom Prefilter or XAD-7 resin) to remove organics from the sample.

Some samples having high initial actinide concentrations have shown retention of some alpha activity on the TEVA columns. Therefore, care must be used when evaluating the analysis protocol and associated data.

Most radionuclides that undergo beta emission (including C-14,

P-32, S-35, and Sr-90) and materials that quench scintillation counting are effectively removed using Eichrom TEVA resin. Tritium may sometimes follow the technetium due to exchange of tritium with the resin or due to extraction of tritiated compounds. Possible interference by tritium is eliminated by setting the Tc-99 counting window above the maximum energy for tritium beta particles.

5.1.4 Detection Limit/Ranges

Minimum Detectable Activities (MDAs, Ref. 1) depend on the length of count, counter background, detector efficiencies, separation efficiencies, and the volume of sample added to the cocktail. As an example, for an LSC instrument having nominal


background and counting efficiency of 30 CPM and 85%, respectively, in the Tc-99 25 keV to 290 keV window, MDAs are

30 minute count: 2.5 pCi/sample 60 min count: 1.8 pCi/sample

2 Sigma counting uncertainties are provided by the LSC instruments.

5.1.5 Method Validation

For tracer determination (yield) the method requires direct comparison of samples spiked with Tc-99m tracer and Tc-99 standard to samples spiked with Tc-99m tracer only. Gamma-ray spectrometer calibration is not required for this application since only ratio data are required for yield determination.

5.1.6 Equipment

Equipment will vary dependent upon preparation method provided by the Task supervisor. Some general equipment needs are: Glass beakers and vials Liquid scintillation counters, with beta spectrometer

capabilities (such as Packard Models 2750 Series instruments).

Liquid scintillation vials, 20 mL polyethylene Calibrated pipets Calibrated balances Heat lamp or hot plate Vacuum manifold Gamma detector for Tc-99m determination

5.1.7 Reagents

Reagents are subject to change based on specific preparation methods provided by the Task Supervisor. Tc-99m tracer Tc-99 Spike Deionized distilled water (DI water)


Ammonium hydroxide 4M - Add 135 mL of concentrated NH4OH (14.8M) to 200 mL of water and dilute to 500 mL with water.

Methyl Isobutyl Ketone (MIK) Methyl Alcohol Hydrogen peroxide (30 wt %) Liquid scintillation cocktail - Packard Ultima Gold-AB Nitric acid solution (0.1M) - Add 6.4 mL of concentrated

nitric acid (sp gr 1.42) to 950 mL of water and dilute to 1 liter with water.

Nitric acid solution (1M) - Add 64 mL of concentrated nitric acid (sp gr 1.42) to 900 mL of water and dilute to 1 liter with water.

Nitric acid solution (12M) - Add 764 mL of concentrated nitric acid (sp gr 1.42) to 150 mL of water and dilute to 1 liter with water.

Prefilter column (Eichrom sodium vanadate (20 g/L) - Dissolve 1 g NaVO3 in 50 mL of water, warming as necessary.

Eichrom TEVA resin- prepacked columns Eichrom TEVA filter disks


Liquid scintillation counters (LSC) must be checked, using the self-normalization and calibration (SNC) protocol, each day that samples are run. LSC efficiencies shall be determined using NIST-traceable Tc-99 solutions. Since the Tc-99m recovery is determined by comparison, no routine QA is necessary for the detector used, as long as the Tc-99m peak is observed.

5.2 Procedure Details

5.2.1 Separation and Analysis

Follow written instructions (R&D Directions) provided by the Task Supervisor.


The final LSC vials are counted by gamma analysis first and then by liquid scintillation analysis to quantify Tc-99m and Tc-99, respectively.

5.3 Calculations

All calculations are done by the Task Supervisor or trained designee.

6.0 RECORDS

All prep and analysis data is recorded and maintained in the laboratory notebooks. The final data packet, containing the prep sheet, computer printouts, and calculations are stored in the counting room data notebook and associated binders. The ADS LIMS (Laboratory Information Management System) is used as the primary data storage location.

7.0 REFERENCES

7.1 Currie, L.A., Limits for Qualitative Detection and Quantitative Determination, Analytical Chemistry 40, 586 (1968).

7.2 Manual L16.1, Procedure ADS-2420, Gamma-Sample Preparation and Analysis (Gamma-PHA). 7.3 Manual L16.1, Procedure ADS-2401, Liquid Scintillation Counting. 7.4 Eichrom Industries, Inc., Procedure TCS01, Technetium-99 in Soil. 7.5 Sullivan, T., Nelson, D., and Thompson, E., "Determination of

Technetium-99 in Borehole Waters using an Extraction Chromatographic Resin," presented at the 37th Annual Conference on Bioassay, Analytical and Environmental Radiochemistry, Ottawa, Canada, 1991.

7.6 RP550, "Technetium-99 Analysis Using Extraction Chromatography," DOE

Methods Compendium. 7.7 Manual L1, Procedure 2.32, Radiological Work Practices.


SAVANNAH RIVER NATIONAL LABORATORY Manual: L16.1 ANALYTICAL DEVEOPMENT SECTION Procedure: ADS-2447 AD ANALYTICAL OPERATING PROCEDURES Revision: 4 Page: 1 of 8 TECHNICAL REFERENCE Effective Date: 3/18/09

Strontium-90 In Environmental Approved by: Samples APPROVAL ON FILE AD Manager MAJOR REWRITE 1.0 PURPOSE This procedure describes a method for separation of Strontium-90 in

samples using Eichrom Sr Resin, followed by the measurement of the purified Sr-90 using liquid scintillation counting.

2.0 SCOPE

This method is intended to permit measurement of Sr-90 in a variety of matrices. Radioactive strontium is separated from the remainder of the sample matrix using Eichrom Sr resin. Following the radiochemical separation, the Sr-90 content is determined by liquid scintillation counting (LSC) utilizing a Packard LSC System.

Samples are separated using a strontium-selective resin that removes Sr from other nuclides. Sample pretreatment should place the sample in a nitric acid medium for the subsequent loading into the strontium-selective resin. The purified Sr is then eluted from the resin and analyzed by liquid scintillation counting. The high energy -emission from Y-90 is generally used for quantification since it is relatively free of interferences. Strontium carrier is utilized to monitor method yields and trace separation recovery. Carrier yields can be measured using Neutron Activation Analysis (NAA), Inductively-Coupled Plasma Emission Spectroscopy (ICPES), or other methods as determined by the Task Supervisor.


JHA-Job Hazards Analysis HAP-Hazards Assessment Package LSC-Liquid Scintillation Counting


NAA-Neutron Activation Analysis ICPES-Inductively Coupled Plasma Emission Spectroscopy


Analysts are responsible for Reading, understanding and following this procedure. Calling to the attention of the Task Supervisor any part of

the procedure that requires revision or that they believe to be unsafe.

Reading, understanding, and signing applicable RWPs, JHAs and HAPs (or equivalent) prior to independent work.

Analytical Task Supervisor is responsible for Maintaining this procedure. Providing technical guidance as needed. Providing additional directions, when needed, through the

use of R&D directions.


3.1 Safety

3.1.1 Follow L1, 2.32 Radiological Work Practices and 8Q Laboratory Safety guidelines

3.1.2 Read, understand, and follow applicable Job Hazards

Analyses (JHAs) in Conduct of R&D packet. Specifically, be aware of the need for splash protection. Since the configuration of the sample changes throughout this method, pay careful attention to dose rates.

3.1.3 Before beginning this procedure, read all of the Material

Safety Data Sheets (MSDS) for the chemicals listed in Reagents.


None


5.0 PERFORMANCE 5.1 Description

This procedure uses Eichrom Sr Resin (Ref. 1 to 5) to separate strontium from a variety of sample matrices. Aliquots of the separated fraction are analyzed by liquid scintillation counting to quantify Sr-90, typically from the Y-90 tail. Yields are generally determined by NAA or ICPES analyses. The Task Supervisor may specify other methods to determine yields. This method provides a rapid, reliable method for measurement of Sr-90 in a variety of samples that is more cost-effective and efficient than traditional anion exchange or precipitation techniques.

5.2 Equipment

Liquid Scintillation Counter - Packard Model 2550 TR/AB or equivalent for Sr-90/Y-90 beta radiation

Liquid Scintillation Vials - 20 mL polyethylene

Fume Hood, Hot Plate

Gamma Pulse Height Detector - For Sr carrier determined by NAA

Calibrated pipets and balances

5.3 Reagents

Liquid Scintillation Cocktail - Ultima Gold AB

Nitric acid (15.7 M) - concentrated nitric acid. Nitric acid (3 M) - Add 191 mL of concentrated HNO3 to

800 mL of water and dilute to 1 liter with water.


Nitric acid (3 M) - oxalic acid solution (0.05 M) - Add 191 mL of concentrated HNO3 and add 6.3 grams of oxalic acid dihydrate to 800 mL of water and dilute to 1 liter with water.

Nitric acid Solution (0.05 M) - Add 3.2 mL of concentrated

nitric acid to 900 mL of water and dilute to 1 liter with water.

Nitric acid solution (0.1 M) - Add 6.4 mL of concentrated


Nitric acid solution (8 M) - Add 510 mL of concentrated


Nitric acid solution (0.0001 M) - Add 2 mL of 0.05 M nitric

acid solution to 800 mL H2O and dilute to 1L with H2O. Eichrom Sr Resin – pre-packed columns, 0.7 grams resin

of small particle size (50 to 100 um) in appropriate size column or alternate as specified by Task Supervisor.

Sr Carrier - (about 5000 ppm)-as designated by the task

supervisor. The mass of Sr added to each sample should be less than 5 mg to prevent overloading the Sr Resin column.

Sr-90 spike - as designated by the Task Supervisor. Ce carrier - as designated by the Task Supervisor.

5.4 Data Quality

5.4.1 Method Validation 5.4.1.1 Yield determination

A small amount of non-radioactive Sr is added to the sample before the radiochemical separation begins. Yields are determined by measuring the amount of carrier that is recovered relative to the amount added.


Normally the carrier is determined by neutron activation analysis (NAA, Ref. 9), but other methods such as ICPES can be used as well.

NIST-traceable (National Institute of Standards and Technology) Sr-90 solution is used for spiked sample preparation and for preparing and testing the liquid scintillation counting efficiency (Ref. 5).

Alternatively, an LSC counter that does not have a Sr-90 quench efficiency curve may be used by first counting un-spiked samples, and recounting after adding NIST-traceable Sr-90 (with Y-90 at equilibrium) solution to each sample (standard addition method).

5.4.1.2 Precision and Bias

Relative standard deviations of 8% at the 500 DPM level (Sr-90) and mean tracer recoveries, corrected for chemical yield, of 104% ± 8% (Sr-90), have been reported (Ref. 1-5).

5.4.1.3 Interferences

Since the Sr carrier is non-radioactive, it will not interfere with LSC counting of Sr-90/Y-90. The determination of yield by carrier additions will be uncertain if the sample contains relatively large amounts of stable Sr in addition to the Sr added as carrier.

If present, Sr-89 will interfere with LSC results. Strontium is separated from interfering radio elements by Eichrom Sr Resin to enable measurement by liquid scintillation counting.

Eluting Eichrom Sr Resin with 8 M HNO3 effectively removes barium and potassium isotopes as well as other matrix interferences. Tetravalent plutonium, neptunium, cerium and ruthenium, however, are not removed using


nitric acid. If necessary, these isotopes can be effectively removed by including an additional rinse of approximately four free column volumes of 3 M HNO3-0.05 M oxalic acid. If necessary, actinides can be removed in Diphonex resin or Actinide Resin clean-up steps.

5.5 Quality Control


Calibration of the gamma-ray spectrometer is validated per Procedure ADS-2420 (Ref. 7).

Calibration of the liquid scintillation counters are validated per Procedure ADS-2424 (Ref. 8).

5.5.2 Calibration and Standardization

If yields are determined by NAA, no efficiency determination is required for the gamma instrumentation since yields are determined by a simple ratio of the counts obtained in the activated unknown and the counts obtained in the stable Sr carrier samples.

LSC efficiencies shall be determined using NIST-traceable Sr-90/Y-90 solutions.

5.6 Analysis

5.6.1 Samples are to be analyzed as directed by the Task

Supervisor in R&D directions.

5.6.2 In general, samples are spiked with Ce carrier (to help flush residual Y) and Sr carrier (for yielding purposes).

5.6.3 The spiked samples are acidified using 8 M HNO3 to

convert all available Sr to the nitrate form.

5.6.4 The Eichrom Sr columns are conditioned using 8 M HNO3 and the samples are loaded.


5.6.5 The interferences are then eluted from the columns using 8 M HNO3 (and possibly other reagents).

5.6.6 The purified Sr is then eluted from the columns using

0.0001 M HNO3.

5.6.7 Aliquots of the purified Sr elute are analyzed for Sr 90 content (by liquid scintillation analysis) and stable Sr (by NAA, ICPES or alternate method per Task Supervisor).

5.7 Calculations

Calculations and data review are done by the Task supervisor or trained designee.

6.0 RECORDS

All prep and analysis data is recorded and maintained in the laboratory notebooks. The final data packet, containing the prep sheet, computer printouts, and calculations are stored in the counting room data notebook and associated binders. The ADS LIMS (Laboratory Information Management System) is used as the primary data storage location.

7.0 REFERENCES

7.1 Eichrom Industries, Inc., Procedure SRW01, Strontium 89/90 in Water.

7.2 Horwitz, E.P., Dietz, M.L., Chiarizia, R., 1992. "A Novel

Strontium Selective Extraction Selective Chromatographic Resin," Solvent Extraction and Ion Exchange, 10(2) 1, pp 313-336.

7.3 Nelson, D.M., "Purification of Strontium in Water before

Strontium-89/Strontium-90 Measurement," DOE Methods Compendium, RP500.

7.4 Maxwell, III S.L., Nelson, M.R., and Mahannah, R.N. "High

Speed Separations to Measure Impurities in Plutonium-238 Oxide and Trace Radionuclides in Waste," presented at 34th


ORNL-DOE Conference on Analytical Chemistry in Energy Technology, Gatlinburg, TN, October 5-7, 1993.

7.5 Banavali A.D., Moreno, E.M., and McCurdy, D.E., "Strontium-

89/90 Analysis by Eichrom Column Chemistry and Cerenkov Counting," presented at the 38th Annual Conference on Bioassay, Analytical and Environmental Radiochemistry, Santa Fe, NM, November 2-6, 1992.

7.6 Currie, L.A., Limits for Qualitative and Quantitative

Determination, Analytical Chemistry 40, 586 (1968). 7.7 Manual L16.1, Procedure ADS-2420, Gamma Sample

Preparation and Analysis. 7.8 Manual L16.1, Procedure ADS-2424, Gross Alpha/Beta

Determination by Liquid Scintillation Counting. 7.9 Manual L16.1, Procedure ADS-2407, Californium Neutron

Activation Analysis. 7.10 Manual L1, 2.32, Radiological Work Practices.

7.11. Manual L1, 2.39, Use of ARW Instruments.

8.0 ATTACHMENTS

None

Analytical Development SectionAnalytical Operating Procedures


Volume 2 Revision: 4Actinides in Environmental Samples

Major Revision



Author/ Task Supervisor:C. C. DiPrete

Peer Reviewer:D. P. DiPrete

AD Materials Characterization and NuclearMeasurement Research Group Manager: R. H. Young

AD Procedures Coordinator:M. S. Hanks

Procedure: ADS-2449Actinides in Environmental Samples Revision: 4

Page: 2 of 15

1.0 INTRODUCTION

1.1 Purpose

This procedure provides a generic description of methods utilizing resins for the separation of actinides from a wide variety of matrices. The separated material contains the actinides originally present in the matrix without many of the interfering radionuclides. The separated material is quantified utilizing alpha pulse height analysis, gamma spectrometry, mass spectrometry, or a combination of these.

1.2 Scope

The material in this procedure provides separation techniques to efficiently separate individual actinides from a variety of matrices for eventual quantification. Actinides are separated using Eichrom TEVA, UTEVA, RE and/or TRU resins prior to measurement by alpha, gamma, and/or mass spectrometry.

This procedure is designed to be generic due to the wide variety of matrices and analytes for which it is used. Sample matrix materials vary widely and include, but are not limited to, high-and low-activity tank liquids, high- and low-activity tank solids, environmental solids, environmental liquids, and process material.

This procedure, along with R&D Directions written for each batch of samples, describes the separation and preparation steps of the analysis. The counting and quantification steps are described in procedures L16.1 ADS-2405, ADS-2402, ADS-2420, and ADS-1543.


2.1 Background

This procedure is based on methods discussed in references 1 to 5; however, research and experimentation are routinely utilized to provide additional robustness, sensitivity, or capability to the procedure. The R&D directions in addition to this procedure provide the level of detail needed for an experienced analyst to reproduce analyses.

Appropriate tracers and standards are used, when possible and practical, to monitor chemical recoveries and yields. There are no lower limits applicable for the tracer recovery; many of the separations require aggressive decontamination of interfering nuclides which, in turn, reduces tracer recovery. Provided the tracer recovery is high enough to allow quantification of the isotope of interest with the criteria set forth by the customer’s data quality objectives, the recovery is considered acceptable.

The quality assurance and quality control samples (blanks, lab control spikes, etc.) utilized vary depending upon the customer’s data quality objectives. Blanksand laboratory spiked blanks are generally part of each batch. The recovery of


Page: 3 of 15

the blank spike should be between 75-125% and the blank should be less than 10% of the sample result. If QC indicators fall outside of these ranges, the Task Supervisor must determine whether the data is fit for release with additional scrutiny, qualifiers, or alternate calculations.



A. Reading, understanding and following this procedure, and

B. Calling to the attention of the Task Supervisor any part of the procedure that requires revision or that they believe to be unsafe.

2. The Analytical Task Supervisor is responsible for:

A. Maintaining this procedure, and

B. Providing technical guidance.


3.1 Safety

1. Follow:

A. L1 2.32; Radiological Work Practices

B. 8Q; Laboratory Safety guidelines

C. L1 3.20; Handling HF Acid Solutions

D. ADS-WI-00021; Analytical Development Safety Practices

2. Read, understand, and follow applicable Job Hazard Analyses (JHAs) in the Conduct of R&D packet.

4.0 PREREQUISITES

None

5.0 PROCEDURE


1. Actinides are separated from interfering radionuclides using Eichrom TEVA, UTEVA, RE and/or TRU resins prior to measurement by alpha, gamma, and/or mass spectrometry. This procedure is designed to be generic due to the wide variety of matrices and analytes for which it is used. This procedure, along with R&D Directions written for each batch of samples, describes the separation and preparation steps of the analysis.


Page: 4 of 15

The counting steps are described in procedures L16.1 ADS-2405, ADS-2402, ADS-2420, and ADS-1543.

5.2 Data Quality

1. Interferences

Actinides with non-resolvable alpha energies such as 241Am and 238Pu, or 237Np and 234U, must be chemically separated prior to measurement. The methods described in this procedure, or derivations of these methods, are utilized to strategically separate radionuclides prior to analysis.

Complementary methods (gamma pulse height analysis or ICP-MS, for example) are often utilized to further decouple interferences, or check for unexpected interferences.

Incomplete removal of interfering radionuclides can impact the data quality in numerous ways, including increasing the minimum detectable activity (MDA) of the isotope of interest, or effecting a high bias in the measured radionuclide.

2. Detection Limit Ranges

Minimum detectable activities (Ref. 7) depend on the aliquot size, separation yield, count duration, counter background, and detector efficiencies.

Analyses are customized to meet the target MDAs prescribed by the customer’s data quality objectives. Some factors, such as limited sample size, sample dose rate, activity levels of the sample, and decontamination factors required to isolate the isotope of interest can impact the ability of the laboratory to meet requested detection limits.

3. Energy Calibration

Energy calibration of the alpha pulse height analysis detector, as described in L16.1, ADS-2402, is necessary for alpha isotope identification.

4. Efficiency Calibration

Efficiency calibration of the alpha pulse height analysis detector, as described in L16.1, ADS-2402, is not always a necessary part of this procedure.

A. Yield determination of the tracer is often calculated using a direct comparison of the peak areas of the tracer isotope to the sample isotopes from a single alpha count. This application of alpha spectroscopy, when applied with a quantified standard or known


Page: 5 of 15

amount of one of the isotopes, does not require knowledge of detector efficiencies.

B. Quantification can be performed using complementary methods such as gamma pulse height analysis of as-received (non-separated) sample, ICP-MS of as received (non-separated) sample, and numerous other methodologies deemed necessary on a sample-by-sample basis. Quantification via these methods does not require knowledge of alpha detector efficiencies.

5. Yield Determination

When possible, NIST-traceable solutions are used for spiked sample preparation. There are numerous approaches to monitor separation yield and provide quantitative, yield-corrected actinide results. The R&D directions and the raw data packet, as well as the calculation spreadsheets, provide the information needed for an experienced analyst to re-create the yield determination.

6. Various quality control (QC) plates are prepared with sample batches, dependent upon the customer’s data quality objectives.

A. Possible QC plates are:

(1) A batch blank

(a) The activity of the blank relative to the sample should be less than 10% for un-qualified release. In some instances, dependent upon DQOs, sample availability, or other factors, data can be released as upper limits if the blank exceeds 10%.

(2) Spiked blanks

(a) Results should indicate recovery of 75-125% for unqualified data release.


Page: 6 of 15

5.3 Equipment

NOTE: This is a list of many types of equipment used. It will not be exhaustive since the separation is fined-tuned for each batch of samples analyzed.

1. Calibrated M&TE pipettes

2. Calibrated M&TE balances

3. Column racks

4. Drying oven - capable of 120°C

5. Filter apparatus

6. Hot plate - capable of 100°C

7. Various Eichrom columns, cartridges, and associated hardware

8. Teflon Beakers - small

9. Filter Apparatus - 25 mm diameter.

10. Filters - 25 mm diameter polypropylene, 0.1 micron.

11. Filters – 50 mm diameter cellulose nitrate, 0.45 micron, contained in disposable filter apparatus

12. Vacuum Filter Flasks

13. Vacuum Filter Manifold

14. Stainless steel planchets-1 inch diameter

15. Alpha detectors-see L16.1, Procedure ADS-2402

16. Low energy gamma detectors-see L16.1, Procedure ADS-2420

5.4 Reagents

NOTE: This a list of many of the reagents used. It will not be exhaustive since the separation is fined-tuned for each batch of samples analyzed.

NOTE: All references to water refer to de-ionized or distilled water.


Page: 7 of 15

1. Sodium Nitrite solution (NaNO2) 4M - Dissolve 6.9g of NaNO2 in 15mL of water. Dilute to 25mL with water. Make fresh daily.

2. Nitric Acid 2.5M – sodium nitrite (0.1M) solution - Add 32mL of concentrated HNO3 to 100mL of water, dissolve 1.38 grams of sodium nitrite in the solution and dilute to 200mL with water. Make fresh daily

3. Oxalic Acid 0.1M - Dissolve 12.6 g of oxalic acid dihydrate in 800mL of water. Dilute to 1000mL with water.

4. Aluminum Nitrate (1M) - Add 106 grams of anhydrous nitrate to 400mL of water. Dissolve and then dilute to 500mL with water.

5. Ammonium bioxalate (0.1M) - Dissolve 6.31 grams of oxalic acid dihydrate (H2C2O4•2H2O) and 7.11 grams of ammonium oxalate monohydrate (NH4) 2C2O4•H2O in 900mL of water, filter and dilute to 1 liter with water.

6. Ammonium hydroxide - concentrated (sp gr 0.9).

7. Ammonium Hydrogen Phosphate (3.2M) - Dissolve 106 grams of (NH4) 2 HPO4 in 200mL of water. Heat gently to dissolve, and dilute to 250mL with water.

8. Ammonium Hydrogen Phosphate [(NH4)2 HPO4] (3.2M) - Alternate preparation steps:

A. Slowly add 108mL of concentrated ammonium hydroxide to 40mL DI water.

B. Slowly add 54mL of concentrated phosphoric acid to 20mL of DI water.

C. Slowly add the ammonium hydroxide from step “A” to the phosphoric acid from step “B”.

D. Dilute to 250mL with DI water.

9. Ascorbic acid - solid

10. Calcium nitrate (1.25M) - Dissolve 51 grams of Ca (NO3)2 in 100mL of water and dilute to 250mL with water.

11. Hydrochloric acid (3M) - Add 250mL of concentrated HCl (sp gr 1.19) to 600mL of water and dilute to 1 liter with water.



Page: 8 of 15


14. Hydrogen peroxide (30 wt %)

15. Nitric acid (15.8M) - concentrated HNO3 (sp gr 1.42)

16. Nitric acid solution (3.0M) - Add 192mL of concentrated nitric acid (sp gr 1.42) to 600mL of water and dilute to 1 liter with water.

17. Nitric acid solution (2.5M) - Add 159mL of concentrated HNO3 (sp gr 1.42) to 800mL of water and dilute to 1 liter with water.

18. Nitric acid (2.5M) - oxalic acid solution (0.05M) - Add 159mL of concentrated HNO3 (sp gr 1.42) and add 6.3 grams oxalic acid dihydrate to 700mL of water and dilute to 1 liter with water.



21. Nitric acid solution (0.01M) - Add 10mL of 1N nitric acid to 800mL of water and dilute to 1 liter with water.

22. Ferrous Sulfamate - laboratory stock

23. EichromTEVA Resin

24. Eichrom TRU or RE Resin

25. Eichrom UTEVA Resin

26. Eichrom LN Resin

27. Cerium Carrier - Dissolve 0.155 g cerium (III) nitrate hexahydrate in 50mL water and dilute to 100mL in water

28. Titanium (III) Chloride - >10 wt % Titanium (III) chloride in 20 to 30 % hydrochloric acid. Used for uranium sample preparation only.

29. Hydrofluoric Acid - Concentrated

NOTE: In the event that high chloride residue is generated, the R&D directions provide guidance to neutralize the residue with NaOH, reduce the volume to dryness, and discard the resulting solid material in solid waste.


Page: 9 of 15

5.5 Analyses

Samples are prepared as instructed by the task supervisor in the R&D directions. The R&D directions must be used along with the procedure to understand the full analysis. A very generic procedure, indicating the types of activities performed during the actinide separation process, follows.

1. Actinide Separations

A. Np, Th Separation from Am, Pu, and U using TEVA Resin Columns

(1) For each sample (typically prepared in a 2.5M HNO3 load solution as directed by the Task Supervisor), place a TEVA column in the column rack.

(2) Place a centrifuge tube or other appropriate catch vessel below each column, remove the bottom plug from each column and allow it to drain.

(3) Pipet 5mL of 2.5M HNO3-0.05M ferrous sulfamate (made fresh weekly) into each column (to condition the resin) and allow it to drain. Discard the eluate.

(4) Place a clean, labeled centrifuge tube or other appropriate catch vessel below each column.

(5) Add 2.5mL of ferrous sulfamate to each sample as directed by the Task Supervisor. Swirl to mix.

(a) Transfer the solution to the appropriate labeled TEVA resin column and collect the eluate in labeled catch vessel.

(6) Add 5mL of 2.5M HNO3•0.05M ferrous sulfamate to rinse the original vessel and transfer each solution to the appropriate TEVA resin column. Collect eluate in the same catch vessel used for collection in step 5.5.1.A.5.a.

NOTE: Pu, U, and Am are removed with the load solution and 2.5M HNO3 - 0.05M ferrous sulfamate rinses.


Page: 10 of 15

(7) Add 5mL of 2.5M HNO3 - 0.05M ferrous sulfamate to each column and collect eluate in same catch vessel.

(8) Save this vessel for U, Pu, Am separation step 5.5.2.E. The TEVA column contains Th and Np. If these analyses are required, consult the Task Supervisor.

2. U Separation from Pu, Am Using UTEVA Resin

A. For each sample solution, place a UTEVA resin column in the column rack.

B. Place a centrifuge tube or other appropriate catch vessel below each column, remove the bottom plug from each column and allow the column to drain. Discard the eluate.

C. Add 5mL of 2.5M HNO3 - 0.05M ferrous sulfamate (prepared fresh each week) into each column to condition the resin and allow the column to drain. Discard the eluate.

D. Place a clean, labeled centrifuge tube or other appropriate catch vessel below each column.

E. Transfer each solution from step 5.5.1.A.8 or as generated per Task Supervisor direction into the appropriate UTEVA resin column by pouring or by using a plastic transfer pipet. Collect eluate in catch vessel.

F. Add 5mL of 2.5M HNO3 - 0.05M ferrous sulfamate to rinse the vessel from step 5.5.1.A.8 and transfer each solution into the appropriate UTEVA resin column. Collect the eluate in same vessel as used in steps 5.5.2.E.

G. Add 5mL of 2.5M HNO3 - 0.05M ferrous sulfamate into each column. Collect eluate in same vessel.

H. Set aside the labeled vessels with solutions collected in this section for Pu, Am separation described in the following section.

I. Place a clean, labeled centrifuge or other appropriate catch vessel below each column. Add 5mL of 2.5M HNO3 - 0.05M oxalic acid into each column and allow to drain. Discard this rinse.

NOTE: This rinse removes any trace amounts of neptunium that may have passed through the TEVA Resin and any residual ferrous ion.


Page: 11 of 15

J. Place a clean, labeled centrifuge tube or other appropriate catch vessel below each column.

K. Add 10mL of 0.1M ammonium bioxalate to each column to strip the uranium. Collect eluate.

L. Add 2mL of concentrated nitric acid to the eluate. Set aside for cerium fluoride precipitation of the uranium sample. (5.5.4 of this procedure)

3. Pu, Am Separation Using TRU Resin Columns:

A. For each sample, place a TRU resin column in the column rack.

B. Place a centrifuge tube or other appropriate catch vessel below each column.

C. Remove the bottom plug from each column and allow each column to drain. Discard eluate solution.

D. Just prior to sample loading, pipet 5mL of 2.5M HNO3 into each column to condition resin and allow to drain. Discard eluate solution.

E. Add solid ascorbic acid to each solution from step 5.5.2.H as instructed by the Task Supervisor.

F. Immediately

G. Allow the load solution to drain through column into a labeled centrifuge tube or other appropriate catch vessel.

transfer each solution from the previous step into the appropriate TRU Resin column by pouring or using a plastic transfer pipet.

H. Add 5mL of 2.5 M HNO3 into the sample vessel from step 5.5.3.Eand transfer this rinse to the appropriate column using the same plastic transfer pipet.

I. Allow the initial rinse solution to drain through each column.

J. Add 5mL of 2.5 M nitric acid - 0.1 M sodium nitrite (prepare fresh each week) directly into each column.

NOTE: Sodium nitrite is used to oxidize Pu+3 to Pu+4 and enhance the Pu/Am separation.

K. Allow the rinse solution to drain through each column.

L. Add 1mL of 0.5M HNO3 to each column and allow to drain.


Page: 12 of 15

NOTE: 0.5M HNO3 is used to lower the nitrate concentration priorto conversion to the chloride system.

M. Place clean, labeled vessels below each column.

N. Add 3mL of 9M HCl to each column to convert to chloride system.

O. Add 12mL of 4M HCl to the column to elute americium.

P. Add 2 drops of 30 wt% H2O2, and 1mL of concentrated nitric acid to the americium solution from the previous step. Set aside for cerium fluoride precipitation of the americium sample (Section 5.5.4).

NOTE: This step destroys any extractant that may have been stripped from the column that may interfere with the counting technique. If a prefilter is used on each column tip to prevent stripping of small amounts of extractant, addition of the H2O2 andconcentrated nitric acid is not necessary.

Q. Ensure that clean, labeled vessels are below each column.

R. Add 10mL of 0.1M ammonium bioxalate to elute plutonium from each column.

S. Add 2mL of concentrated nitric acid to each vessel from the previous step and set aside for counting preparation (Section 5.5.4).

4. Cerium Fluoride Preparation Method for Alpha Spectrometry

A. Evaporate the samples prepared in the previous sections, as directed by the Task Supervisor, to dryness.

B. Dissolve the residue in 2 to 10 mL of 9M HCl and transfer the solution to a plastic or Teflon container. Rinse the beaker with 2mL of 9M HCl and transfer this rinse solution to the plastic or Teflon container.

C. Add 0.2 ml of cerium carrier to each sample.


Page: 13 of 15

D. To uranium

E. Add 1.0 mL of concentrated HF to each beaker. Swirl to mix. Let the beakers sit for at least 30 minutes before filtering.

samples only, add 0.5mL of titanium chloride solution.

Caution: Concentrated HF requires additional care. Review L1, 3.20 Handling HF Solutions when using HF.

F. Label each stainless steel planchet as directed by the Task Supervisor.

G. Set up a 0.1 micron 25 mm filter, with glassy side down on a Gelman filter apparatus or a vacuum filtering manifold.

H. Before adding the sample, add 2 to 3 mL water to each filter, apply vacuum and assure there are no leaks around the sides of the filter.

I. Filter the sample and rinse the beaker with ~ 2mL water, transferring the rinse to the filter apparatus.

J. Draw air through the filter until dry.

K. Mount filters on stainless planchets using a glue stick or double-sided tape.

L. Count each according to the ADS Alpha Spectrometry Procedure (Ref. 6)

5.6 Calculations

Sample preparation data are recorded on the preparation data sheet and recorded in the Radiochemistry Laboratory notebook.

The final data packet, containing the prep sheet, computer printouts, andcalculations are stored in the counting room data notebook and associated binders.

All calculations are completed by the Task Supervisor or a trained designee.

5.7 Data Control

Preparation data are recorded on the preparation data sheet and recorded in theRadiochemistry Laboratory notebook.

The final data packet, containing the preparation sheet, computer printouts, and calculations are stored in the counting room data notebook and associated binders.


Page: 14 of 15

6.0 REFERENCES

1. Maxwell, III S.L., Nelson, M. R., and Mahannah, R.N. "High Speed Separations to Measure Impurities in Plutonium-238 Oxide and Trace Radionuclides in Waste at SRS," presented at 34th ORNL-DOE Conference on Analytical Chemistry in Energy Technology, Gatlinburg, TN, October 5-7, 1993.

2. Nelson, D. "Improved Methods for the Analysis of Radioactive Elements in Bioassay and Environmental Samples," presented at the 38th Annual Conference on Bioassay, Analytical and Environmental Radiochemistry, Santa Fe, NM, November, 1992.

3. Horwitz, E.P., Chiarizia, R., Dietz, M. L., Diamond, H., Essling, A.M., and Gracyk, D.W. "Separation and Preconcentration of Uranium form Acidic Media by Extraction Chromatography,” Analytical Chimica Acta, 266 (1992) 25-37.

4. Horwitz, E.P., Chimica, R., Dietz, M.L., Diamond, H., and Nelson, D., "Separation and Preconcentration of Actinides from Acidic Media by Extraction Chromatography," Analytical Chimica Acta, 281 (1993) 361-372.

5. Eichrom Industries, Inc., “Americium, Curium, Plutonium and Uranium Determination in Water-Method Validation Report,” August 8, 1994.

6. Manual L16.1, V2, ADS-2402, “Alpha Pulse Height Analysis.”

7. Currie, L. A., “Limits for Qualitative and Quantitative Determination,” Analytical Chemistry 40, (1968) 586.

8. Manual L16.1, V2, ADS-2405 “Alpha & Beta Plate Making Direct Mount and Count.”

9. Manual L16.1, V2, ADS-2420 “High Purity Germanium Detector Gamma Pulse Height Analysis.”

10. Manual L16.1, V2, ADS-1543 “Inductively Coupled Plasma-Mass Spectrometer Elemental and Isotopic Analysis for Aqueous Liquid Samples Plasmaquad II.”

7.0 RECORDS

Data are recorded and maintained as described in the Data Control section. The ADS LIMS (Laboratory Information Management System) is used as the primary data storage location.


Page: 15 of 15

8.0 ATTACHMENTS

None

SAVANNAH RIVER NATIONAL LABORATORY Manual: L16.1 ANALYTICAL DEVEOPMENT Procedure: ADS-2452 ANALYTICAL OPERATING PROCEDURES Revision: 2 Page: 1 of 10 TECHNICAL REFERENCE Effective Date: 11/12/2007

Ni-59,63 In Environmental and High Approved by: Activity Samples APPROVAL ON FILE AD Manager 1.0 PURPOSE This procedure describes a method for separation and measurement of

Ni-59 and Ni-63 in solid and aqueous samples. The separation method is based on the DOE Methods Nickel-59 and Nickel-63 Determination in Aqueous Samples, Method #RP300 (Ref. 1).

2.0 SCOPE The method is intended to permit measurement of Ni-59 by X-ray

spectrometry and Ni-63 by liquid scintillation counting (LSC).

2.1 The method is acceptable for:

Solid samples prepared by a non-volatile digestion method, with nickel and cobalt carriers added prior to the digestion, or aqueous samples with nickel and cobalt carriers added.

ICP-ES results for nickel carrier levels to monitor method yields and to correct results.

2.2 The samples are analyzed for:

Ni-59 using a high purity germanium planar or semi-planar spectrometer (LEPS, LOAX) detector, with a Canberra Genie-2000 MCA interface, and

Ni-63 using a liquid scintillation counter and a quench curve.


2.3.1 Analysts are responsible for

reading, understanding and following this procedure,


calling to the attention of the Analytical Task Supervisor any part of the procedure that requires revision or that they believe to be unsafe.

2.3.2 Analytical Task Supervisor is responsible for

maintaining this procedure

providing technical guidance as needed. 3.0 PRECAUTIONS/LIMITATIONS

3.1 Safety

3.1.1 Follow L1 2.32 Radiological Work Practices and 8Q Laboratory Safety Guidelines.

3.1.2 Read, understand, and follow applicable JHAs in Conduct

of R&D packet.

3.1.3 Per JHA for oven use, be cautious of heat and electrical hazards. Ensure nothing flammable/combustible is within 6 inches of the oven when it is operating, ensure it is not on top of paper.

3.1.4 Per JHA for NI-59/63 analyses, be cautious when

handling plates which are taped.

3.1.5 Stop and contact Task Supervisor of loose material, if noticed.



5.0 PERFORMANCE

5.1 Description


This procedure uses dimethyl glyoxime (DMG) extractant on a solid substrate (Eichrom Ni columns). The method is a variation on classic DMG precipitations for separating radioactive nickel from other radioactive interferences. It provides a rapid, reliable separation of Ni-59 and Ni-63 from interferences in sample matrices ranging from high activity solids to aqueous environmental samples.

Solid samples which have been previously dissolved using a

digestion procedure in which the samples have been spiked with nickel and cobalt carriers prior to the digestion.

Aqueous samples having nickel and cobalt carriers added. High-activity samples may be determined without preconcentration. Aqueous environmental samples generally require evaporation to dryness and redissolution prior to separation.

Yields are ideally determined by ICP-ES.

5.2 General Limitations Some prior knowledge of sample activity is recommended to

determine to appropriate path forward for the sample preparation.

5.3 Detection Limit Ranges Minimum Detectable Activities (MDAs, Ref. 2) depend on the

length of count, counter background, and detector efficiencies. Ni-59 detection limits of 70 pCi/g (or per mL) are readily obtainable from 1 gram or 1 milliliter samples, and an overnight gamma analysis using current equipment (counting efficiency for cobalt x-rays ~ 5%). Ni-63 detection limits of ~2 pCi/g (or per mL) are readily obtainable from 1 gram or 1 milliliter samples, and a 1 hour LSC analysis using current equipment. Using larger amounts of sample or longer counting times, the detection limits can be scaled accordingly.


5.4 Method Validation

Yield determination: Several methods may be specified by the task supervisor.

Nickel Carrier: A small amount (~2.5 mg) of non-radioactive

nickel may be added to the sample before the radiochemical separation sample preparation begins. Normally the carrier recovery is determined by ICP-ES. (Ref. 4). Yields are determined by ratioing carrier results for the separated sample to an unseparated aliquot of carrier.

Radioactive nickel tracer: For analyses requiring only Ni-63 or Ni-59, the isotope not analyzed for may be used as a tracer. Yields are determined by ratioing tracer results for the separated sample to as unseparated aliquot of tracer.

Standard addition: If necessary the recovery of the spiked

blank is used to correct batch data for yield. NIST traceable Ni-59 solution is used for the determination of

the LEPS gamma spectrometry counting efficiency and NIST traceable Ni-63 is used for determination of the Ni-63 quench curve for the LSC counters which is then used to determine Ni-63 counting efficiencies.

5.5 Precision and Bias

The overall uncertainty is determined from uncertainties in: Counting: Counting statistics and quench correction uncertainties. Generally, the counting statistic will dominate. Yielding: Yields determined by ICP-ES include uncertainties determined from repeated scans, and uncertainties that may be due to interfering elements. The latter may be minimized by measuring solutions that are at least one order of magnitude above the detection limit. If large dilutions are needed to compare standards to samples, dilution errors may also be important.


5.6 Interferences

Since the nickel carrier is non-radioactive, it will not interfere with the counting of either Ni-63 or Ni-59. The determination of yield by carrier additions will be uncertain if the sample contains stable nickel in addition to the nickel added as carrier. Co-60 can interfere with this method; in samples high in Co-60 activity, addition of a small amount (< 1 mg) of cobalt carrier is a generally effective pretreatment in minimizing cobalt interference.

5.7 Equipment

Vacuum Filtration Apparatus Fume Hood General Laboratory Glassware Note: For accurate yielding, the use of metal containers or crucibles must be avoided in this procedure. Muffle Furnace Ceramic Crucibles Drying Oven Liquid Scintillation Counter Liquid Scintillation Cocktail (Ultima Gold AB)

High Purity Germanium Planar or Semi-Planar Detector and Associated Electronics. These include NIM bin power supply, high voltage power supply, spectroscopy-grade amplifier, and multichannel analyzer (MCA). The MCA may either be PC-based or external to the computer with a suitable interface.

5.8 Reagents

Eichrom Ni Columns or Cartridges - pre-packed.


Nickel Carrier ~ 25,000 ppm Ni. Add ~ 3.33g of NiSO46H20 to 25 mL DI water. Cobalt Carrier ( Add ~ 0.37g Co(NO3)26H2O to 10mL DI water. Add more DI water so that the total solution weight is ~15 grams) 1M Sodium Citrate (add 25.8 g of sodium citrate to 80 mL of DI water, adjust volume to 100 mL with addition of DI water) Sodium Citrate Wash Solution - 15mL 1M sodium citrate diluted to 100 mL, add 1 drop of NH4OH. Test pH with some pH paper to confirm pH is between 8-10, if the pH goes beyond 10, use drops of HNO3 nitric to lower it. Nitric acid solution (3M) - 19.1 mL of concentrated nitric acid to 80 mL of DI water, dilute up to 100mL Nitric acid solution (1M) Add 64 mL of concentrated nitric acid to 900 mL of water and dilute to 1 liter with water.

5.9 Calibration Frequency The gamma-ray spectrometer must be maintained in accordance

with Ref. 3. The efficiency calibrations may be determined by use of an efficiency curve using standards having gamma

rays with energies covering the Ni-59 regions of interest, or direct comparison to a traceable Ni-59 standard. The liquid scintillation counter must be calibrated with standard solutions over a range of quench levels in order to determine a quench correction curve.

5.10 Calibration and Standardization The gamma detector energy calibration and QA records must be

maintained in accordance with Ref. 3. The LSC counter and its QA records must be maintained in accordance with Ref. 7.

Yields are determined by a ratio of the concentrations obtained

in the sample and carrier (or tracer if specified by the Analytical Task Supervisor) samples.


5.11 Procedure Details Analyze a blank with each set of samples analyzed. The blank

shall contain the same aliquot size of carrier or tracer as the samples. General steps are provided below. In select cases as determined by the Task Supervisor, R&D directions will be provided for particular matrices. The customized directions shall be maintained in a Laboratory Notebook.

Solid Sample Preparation:

A1. Solid samples are spiked with 0.1 mL of nickel carrier prior to any sample digestion . A surrogate sample may be spiked with a nickel carrier instead of the actual samples to measure digestion recoveries if necessary.

A2. Using a small (about 50-mL) beaker, evaporate the sample dissolution (or the aliquot to be analyzed) to dryness in a drying oven at 100 C (Note: Do not exceed 105 C. The nickel nitrate complex will volatize at 130C).

A3. Redissolve the sample in 5 mL of sodium citrate wash

solution. A4. Add 0.1 mL of cobalt carrier to the solution from step A3. A5. Continue at step D1.

Aqueous High Activity Sample Preparation:

B1. Add 0.1 mL of nickel carrier to 1 mL of sample in a small

glass beaker. Use a calibrated pipette for the sample measurements.

B2. Evaporate the samples to dryness in a drying oven at

100C. B3. Add 0.1 mL of cobalt carrier to the sample from step B2.


B4. Redissolve the sample in 5 mL of the sodium citrate wash solution.

B5. Continue at step D1. Environmental Water Sample Preparation

C1. Add 0.1 mL nickel carrier to 1000 mL of sample in a 2-L

glass beaker. C2. Evaporate the sample down to dryness in a drying oven. C3. Add 0.1mL of cobalt carrier to the sample from step C2. C4. Redissolve the sample in 20 mL of the sodium citrate

wash solution. C5. Continue on with step D1.

Nickel Separation

D1. Check the pH of the solution with pH paper, the pH

should be between 8- 10, if not contact the task supervisor.

D2. Check the necessary number of Eichrom Ni columns to

assure that they are full of resin, and that they have no visible void spaces. Label the columns with the sample ID’s, and pre-condition with 5 mL sodium citrate wash solution.

D3. Add the samples to the columns using transfer pipettes. D4. Replace the vials beneath the columns. D5. Add 5 mL of sodium citrate wash solution to the sample

beakers. Add that rinse solution to the columns. D6. Add 5 mL of sodium citrate wash solution to the columns

for a rinse.


D7. Add 10 mL of sodium citrate wash solution to the columns for a rinse.

D8. Replace the vials beneath the columns with 50 mL

beakers labeled with the sample ID’s. D9. Elute the nickel from each column with 15 mL of 3M

HNO3. D10. Evaporate the samples to dryness at 100C in a drying

oven. D11. Redissolve each sample in 3 mL of HNO3 nitric acid. D12. The Analytical Task Supervisor may specify other aliquot

sizes for sample preparation in steps D13 to D16. This is likely to happen if only one of the nickel isotopes is to be reported. Record the aliquot sizes in the laboratory notebook.

D13. Pipette 1.0 mL of the 3 mL sample from D11 into 19 mL

Ultima Gold AB in a 20-mL LSC vial for liquid scintillation analysis of Ni-63.

D14. Evaporate 1.0 mL of sample solution onto a stainless steel

planchet by successive additions of 0.1 mL. Secure the activity onto the plate with one layer of tape. Submit to the ADS Counting Room for LEPS analysis of Ni-59.

D15. Pipette 0.1 mL into 10 mL 1.0N nitric acid, submit this

solution to ICP-ES for yielding information. The result will be the "Sample Nickel Concentration."

D16. Pipette 0.1 mL of the nickel carrier into 10 mL 1.0N nitric

acid, submit this solution to ICP-ES for yielding information. The result will be the "Carrier Nickel Concentration."

5.12 Calculations

All calculations are completed by the Task Supervisor or a designee.


5.12.1 Data Control

Preparation data are recorded on the preparation data sheet and recorded in the Radiochemistry Laboratory notebook. The final data packet, containing the prep sheet, computer printouts, and calculations are stored in the counting room data notebook and associated binders.

6.0 RECORDS

Data are recorded and maintained as described in Data Control section above. The AD LIMS is used as the primary data storage location.

7.0 REFERENCES

1. DOE Methods for Evaluating Environmental and Waste Management Samples, Nickel-59 and Nickel-63 Determination in Aqueous Samples, Method RP300 (October 1994).

2. Currie, L.A., Limits for Qualitative and Quantitative Determination, Analytical Chemistry 40, 586 (1968).

3. Manual L16.1, Procedure ADS-2420, Gamma Sample Preparation and Analysis.

4. Manual L16.1, Procedure ADS-1573, Radioactive and Non-Radioactive Sample Analysis on The Leeman Prodigy Inductively Coupled Plasma Emission Spectrometer.

5. Manual L16.1, Procedure ADS-2402, Gross Alpha and Beta Determinations by Liquid Scintillation Analyses.

6. Manual L16.1, Procedure ADS-2251, Dissolution of Radioactive and Non-radioactive Sludge, Soil and Biological Materials for Elemental Analysis by Microwave Acid Digestion.

8.0 ATTACHMENTS

None

SAVANNAH RIVER TECHNOLOGY CENTER Manual: L16.1 ANALYTICAL DEVELOPMENT Procedure: ADS-2453 ANALYTICAL OPERATING PROCEUDRES Revision: 2 Page: 1 of 8 Technical Reference Effective Date: 4/26/06

Plutonium TTA Extraction and Alpha Analysis

Signature Author/Analytical Task Supervisor: SIGNED COPY ON FILE C. C. DiPrete Peer Reviewer: SIGNED COPY ON FILE R. A. Sigg AD Materials Characterization and Nuclear Measurements SIGNED COPY ON FILE Group Manager: F. M. Pennebaker AD Procedure Coordinator: SIGNED COPY ON FILE D. L. Eubanks

SAVANNAH RIVER TECHNOLOGY CENTER Manual: L16.1 ANALYTICAL DEVELOPMENT Procedure: ADS-2453 ANALYTICAL OPERATING PROCEUDRES Revision: 2 Page: 2 of 8 Technical Reference Effective Date: 4/26/06 1.0 PURPOSE

This procedure is designed for analysis of a variety of sample types for the determination of isotopic plutonium by -analysis.

2.0 SCOPE

This analysis can be applied to a variety of different sample types to determine Pu-238, Pu-239/240, and Pu-241 content. This procedure couples an extractive separation with alpha pulse height analysis to determine Pu-238 and Pu-239/240. The procedure is coupled to liquid scintillation analysis for the determination of Pu-241.


Analysts are responsible for reading, understanding and following this procedure, and calling to the attention of the Analytical Task Supervisor any part of the procedure that requires revision or that they believe to be unsafe. The Analytical Task Supervisor is responsible for maintaining this procedure, providing analysts with otherwise difficult to obtain spikes and reagents, and providing technical guidance.


3.1 Safety

3.1.1 Follow L1 2.32 Radiological Work Practices and 8Q Laboratory Safety Guidelines.

3.1.2 Make sure that collodian completely covers the plate or dish. 3.1.3 Ethyl ether is flammable and may form peroxides. Ether

solutions are tested for peroxide formation on a regularly scheduled basis (every 6 months). Ensure last test was within 6 months prior to using bottle.

3.1.4 Yellow (Rad) gloves shall be worn to handle the plastic plate

holders in the Counting Room.


3.1.5 Ensure no open flames or spark sources when using collodion or ethyl ether (flammable substances).

3.1.6 Read, understand, and follow applicable JHAs in Conduct of

R&D packet.



5.0 PERFORMANCE



Plutonium is reduced to Pu+3 then oxidized by thenoyltrifluoroacetone (TTA) to the extractable Pu+4. An aliquot of the organic extract is -analyzed. Americium, curium, lanthanides, uranium, cesium, and strontium are not TTA-extractable under the acidic conditions of the plutonium extraction. Neptunium is oxidized to the non-extractable Np+5. Thorium is partially extracted, but is effectively removed with a 2 M acid scrub.

A standard Pu spike solution will be used to determine the recovery factor (RF).

5.1.2 Data Quality

Data are validated using the following control measures: A batch blank is generally analyzed with the samples.

Various Quality Control (QC) plates are prepared with

sample batches dependent upon customer need. Some


possible QC plates are serial dilutions, spiked samples, and spiked blanks.


Calibration by means of internal standards is an integral

part of each run. The instruments (counter and spectrometers) are calibrated

daily as described in procedures number ADS-2405 and ADS-2424.

The recovery factor is determined with the spike by

integrating the spectrum for each isotope.

5.1.4 Equipment

See Attachment 1

5.1.5 Reagents

NOTE: This is a list of many of the reagents used. It will not be exhaustive since the separation is fined-tuned for each batch of samples analyzed. Use “JHA for Reagent Preps in Radiological Containment Units Using CA Holding Areas for Reagent Bottles” when necessary for reagent prep. Purity of reagents – Unless otherwise stated, American Chemical Society (ACS) reagent grade chemicals shall be used. Purity of water – Unless otherwise indicated, reference to water shall be understood to mean water which meets ACS requirements. The distilled water which is on tap in 773-A meets these requirements for this procedure. Aluminum nitrate solution – (Al (N03)3) 2 M – Prepared by placing 190 g of A (N03)3•9H20 in a 250 mL volumetric flask and adding 150 mL of water. Stir and heat until dissolved, then


cool, dilute to 250 mL with water, and transfer to a 250 mL polyethylene bottle. Label, initial, and date the bottle. Collodion solution (ensure peroxide testing has been performed within the past 6 months prior to opening bottle, and ensure no open flames or spark sources prior to opening bottle in hood) – 0.4% - To prepare, add 1 mL of collodion to 50 mL of anhydrous ethyl ether. Mix well, then dilute to 250 mL with isopropyl alcohol Mix, then transfer to a 500 mL amber glass bottle with a ground glass stopper. Apply a “Flammable” label. Properly label, date and initial the bottle. Remove small quantities as needed. Ferric nitrate solution – (Fe (N03)3) 0.025 M – To prepare, dissolve 1.0 g of Fe (N03)3 •9 H2O in 100 mL of water. Mix well, then transfer to a 125 mL polyethylene bottle. Label, initial, and date the bottle. MAKE FRESH WEEKLY! Hydroxylamine hydrochloride solution – (NH2OH•HC) 5 M – To prepare, dissolve 17.4 g of NH2OH•HC1 in 35 mL of water contained in a 50 mL volumetric flask. Dilute to 50 mL with water, mix well then transfer to a 125 mL polyethylene bottle. Label, initial, and date the bottle. MAKE FRESH WEEKLY! Nitric Acid Solution – (HNO3) 2 M – To prepare, carefully pour 126 mL of concentrated nitric acid into 800 mL of water contained in a one liter volumetric flask. Mix well. Dilute to one liter with water, and mix again. Transfer to a one liter polyethylene bottle. Label, initial, and date the bottle. Nitric Acid Solution – (HNO3) 1 M – To prepare, carefully pour 63 mL of concentrated nitric acid into 800 mL of water contained in a one liter volumetric flask. Mix well. Dilute to one liter with water, and mix again. Transfer to a one liter polyethylene bottle. Label, initial, and date the bottle. Sodium nitrite solution – (NaNO2) 4 M – To prepare, dissolve 6.9 g of NaNO2 in 15 mL of water. Dilute to 25 mL with water, then


transfer to a 1-oz. polyethylene bottle. Label, initial, and date the bottle. MAKE FRESH DAILY! Thenoyltrifluoroacetone solution – (TTA) (ensure no open flames or spark sources prior to opening petroleum ether bottle) To prepare, dissolve 56 g of TTA in 400 mL of petroleum ether Dilute to 500 mL with, mix well, then transfer to a 500 mL amber glass bottle with a ground glass stopper. Apply a “Flammable” label. Properly label, date and initial the bottle.

5.2 Analysis

Prepare samples as instructed by the Task Supervisor. The final plates should be prepared as described in procedure ADS-2405. NOTE: The alpha plates are to be analyzed using alpha pulse height analysis instrumentation. Peaks corresponding to Pu isotopes are integrated and used for calculations. Pu-241 if needed is determined via liquid scintillation counting of an aliquot of the separated samples.

5.3 Calculations

All calculations are completed by the Task Supervisor or a trained designee. 5.3.1 Data Control

Sample preparation data are recorded on the preparation data sheet and recorded in the Radiometric Laboratory notebook. The final data packet, containing the prep sheet, computer printouts, and calculations are stored in the counting room data notebook and associated binders.

6.0 RECORDS

Data are recorded and maintained as described in Data Control above. The ADS LIMS (Laboratory Information Management System) is used as the primary data storage location.

SAVANNAH RIVER TECHNOLOGY CENTER Manual: L16.1 ANALYTICAL DEVELOPMENT Procedure: ADS-2453 ANALYTICAL OPERATING PROCEUDRES Revision: 2 Page: 7 of 8 Technical Reference Effective Date: 4/26/06 7.0 REFERENCES

1. Selected Measurement Methods for Plutonium and Uranium in the Nuclear Fueled Cycle, edited by C. J. Rodden, UACEC, p.392-398, 1972.

2. Solvent Extraction of Metals, A. K. De, S. M. Khopkar, R. A. Chalmers,

Van Nostrand Reinhold Co., London, p. 57-65, 1970. 3. The Chemistry of the Transuranium Elements, C. Keller, Verlag Chemie,

p.454, 1971. 4. Manual L16.1, Procedure ADS-2402, Alpha Pulse Height Analysis (U). 5. Manual L16.1, Procedure ADS-2405, Alpha and Beta Plate Making Direct

Mount and Count (U). 6. Manual L16.1, Procedure ADS-2424, Gross Alpha/Beta Determination by

Liquid Scintillation Counting (U).

8.0 ATTACHMENTS

Attachment 1 -Equipment


ATTACHMENT 1

Equipment (SRS stocked) Assorted Pyrex beakers Assorted polyethylene bottles Assorted automatic pipets, 1mL 10 mL Equipment associated with alpha mounting (ADS-2405) Disposable plastic droppers 4-dram vials with polyseal caps 500 mL amber glass bottles with ground glass stoppers Vortex mixer Hot plate NOTE: This is not an exhaustive list, equipment will change with each batch of samples.

Analytical Development Section Analytical Operating Procedures Volume 2


Revision: 0Gamma Sample and Tc-99m Analysis on Nal Well Detector


1.0 INTRODUCTION

1.1 Purpose

This procedure covers the application of the NaI (TI) gamma well detector to the detection, identification and quantification of gamma rays from a variety of low- to moderate-density sample matrices. The detector described in this procedure is typically used to quantify Tc-99m for yield determination after traced radiochemical separations.

1.2 Scope

This procedure applies to gamma pulse height analysis (PHA) using a NaI (Tl) detector. Typically, this type of detector is used in the AD radiochemical laboratory for gamma-PHA associated with tracer yield determination. This detector is most often used for Tc-99m traced separations.

Although gamma PHA is relatively simple, specific and rapid, there are limitations that must be taken into account. The detector must be carefully energy calibrated with known standards. Detection efficiencies for gamma-rays vary with energy and must be obtained during the calibration process. The relative amount of activity in the counting vial must be within an optimum range for accurate work. Also, the relative abundance of the various gamma nuclides in the samples has an effect on the quality of the data. Higher energy gammas can interfere with, or even mask, low energy gamma rays.




Reading, understanding and following this procedure.

Calling to the attention of the Task Supervisor any part of the procedure that requires revision or that they believe to be unsafe.

Reading, understanding and following applicable Job Hazards Analyses (JHAs) in Conduct of R&D packet.


Maintaining this procedure.

Procedure: ADS-2462Gamma Sample and Tc-99m Analysis on Nal Well Detector


Providing technical guidance.


CTF - Cognizant Technical Function

JHA - Job Hazards Analysis

R&D - Research and Development

FWHM - Full Width Half Maximum

PHA - Pulse Height Analysis

M&TE – Measuring and Test Equipment

MCP – Measurement Control Program

MS&E – Measurement Systems and Equipment


3.1 Safety

1. Follow L1, 2.32 Radiological Work Practices and 8Q Laboratory Safety Guidelines.

2. Read, understand, and follow applicable Job Hazards Analyses (JHAs) in Conduct of R&D packet.

3. Per JHA, be cautious of moving parts, lead, and pinch points.

4. Carefully examine all packaging prior to handling radioactive samples for evidence of leaks.

4.0 PREREQUISITES

None

5.0 PROCEDURE

5.1 Equipment

1. NaI (Tl) gamma detector, and associated gamma spectroscopy electronics

A. History file and MCP for individual detectors will contain manufacturer, model number, and serial number.

2. Canberra Genie 2K gamma spectroscopy software or equivalent gamma spectroscopy software.



5.2 Standards

1. The standard utilized for establishing and validating energy calibration is a NIST-traceable gamma ray standard.

2. If necessary, standards are diluted gravimetrically utilizing standard industry practice prior to use. Balances utilized for the preparation are M&TE (measuring and test equipment) and, as such, comply with the requirements set forth by Manual 1Q, 12-1.

3. Quality control standards are often prepared from the same source as the calibration standards. These standards are validated using previously validated standards from an independent lot. Documentation of standard preparation, including M&TE identification, is maintained in a logbook and is referenced in the calibration spreadsheet.

5.3 Energy Calibration

Energy calibration is performed using a NIST-traceable standard in conjunction with the Genie 2000 data acquisition system. The energies of Am-241 (59.5keV) and Cs-137 (661.6keV) are typically used to calibrate the energy of the detector.

5.4 Efficiency Calibration

Since the detector is being used for intra-batch comparison, the efficiency of the detector does not need to be determined. Only the relative area of the Tc-99m (or other tracer) peak in the separated samples to the area of the Tc-99m (or other tracer) peak in the standard is being determined.

5.5 Routine System Verification/QA Check

1. Energy

A check-source, prepared using the NIST-traceable standard, is counted each day that samples are analyzed. The Cs-137 peak energy at 661.6 keV will be controlled to 1.5 keV for warning limits and 2 keV for control limits. Should the energy validation of the Cs-137 peak fail the acceptance criteria, the system will be evaluated by the CTF. The result of the evaluations and the recalibration (if necessary) will be documented in the logbook and/or in the MS&E history file.

2. Full Width at Half-Maximum

As a further control of detector stability, the resolution of the detector is also monitored for any sudden changes. The full-width at half maximum (FWHM) of the Cs-137 peak in the check standard is measured with each check standard count. The FWHM will be controlled to 2.0 keV for warning limits and 3.0 keV for control limits of the average value for that peak. This is based on data, as well as logic. When the resolution of the HPGe



detectors are compared to the NaI detector, a multiple of 10 is logical for the QA parameters.

3. Response to Non-Conforming Conditions

The results from the Routine System Verification/QA Check are evaluated daily prior to detector use. Any checks outside of the control limits require immediate attention; no further analytical analyses can be performed until the event causing the failure has been resolved.

5.6 Sample Analysis

1. Ensure the detector has had QA successfully completed prior to counting the sample.

2. Count each sample vial for one minute twice. The first count is performed with a given orientation, and the second count is performed with the vial rotated 180 degrees from the first-count orientation.

3. For each count, record the file ID, start time, area, % uncertainty, date, and detector on the prep sheet.

4. Once all vials in the batch have been counted, photocopy the hand-written gamma data from the previous step, record the logbook ID on the photocopy, and insert the photocopied entry into the logbook.

5. Data and samples are given to Counting Room personnel. Samples are then measured by liquid scintillation counting.

6. Gamma analysis and liquid scintillation data are used to quantify Tc-99 in the samples being analyzed.

5.7 Data Control

1. Sample preparation data are recorded on the preparation data sheet and recorded in the Radiochemistry Laboratory notebook.

2. The final data packet, containing the prep sheet, computer printouts, data from gamma counting, and calculations are stored in the counting room data notebook and associated binders.

6.0 REFERENCES

1. Nuclear and Radiochemistry, G. Friedlander, J.W. Kennedy, E.S. Macias, J.M. Miller, 3rd Ed., pp. 243-286

2. Genie 2000 Operations Manual, Canberra Industries, Inc., 2002.

3. Genie 2000 Customization Tools Manual, Canberra Industries, Inc., 2002.



4. Manual 1Q, 12-1 (current revision), Control of Measuring and Test Equipment

5. Manual 1Q, 2-7 (current revision), QA Program Requirements for Analytical Measurement Systems

7.0 RECORDS

Data are recorded and maintained as described in the Data Control section above.

8.0 ATTACHMENTS

None

SAVANNAH RIVER NATIONAL LABORATORY Manual: L16.1 ANALYTICAL DEVELOPMENT Procedure: ADS - 2502 AD ANALYTICAL OPERATING PROCEDURES Revision: 6 Page: 1 of 11 TECHNICAL REFERENCE Effective Date: 03/20/08

Alkali Fusion Dissolutions of Sludge Approved by: and Glass for Elemental and Anion APPROVAL ON FILE Analysis (U) AD Manager ______________________________________________________________________________________________ 1.0 PURPOSE: This procedure describes fusion dissolution methods to prepare sludge and

glass for elemental and ion analyses. 2.0 SCOPE: This procedure describes a Na2,O2/NaOH fusion method for dissolving samples.

Other alkali hydroxides (NaOH, KOH, CsOH) and alkali carbonates (Li2CO3,Na2CO3, K2CO3, Cs2CO3) can be used with minimal changes to this procedure.

These dissolution methods are used to prepare sludge and glass, for elemental

and anion analysis. The dissolution method produces solutions for analysis by Inductively Coupled Plasma - Atomic Emission Spectroscopy (ICP-AES) and Ion Chromatography (IC). Except for the alkali metals and crucible material, all elements that are of interest in SRS waste and residue can be measured in the solution. However, elemental analysis can be optimized by using tandem dissolutions consisting of the fusion procedure described here and a sealed-vessel acid dissolution.


3.1 Safety

3.1.1 Sodium peroxide is a powerful oxidizing agent and can cause explosions when mixed with certain organic chemicals and materials. This material is an extremely corrosive chemical that must be handled with great care. CONTACT SUPERVISION. Keep the Na2O2 container tightly closed and in a dry place.

3.1.2 Alkali peroxides, hydroxides, and carbonates are extremely

corrosive chemicals that must be handled with great care. Always wear laboratory gloves, lab coat, and safety glass or goggles when weighing these materials or using them in the fusion dissolution procedure.


3.1.3 Concentrated hydrochloric acid and nitric acid are extremely corrosive and toxic chemicals. The acids will produce burns, ulcerations, scarring on the skin, and mucous membranes (mouth and respiratory tract).

3.1.4 Always wear protective gloves, safety glasses, and a laboratory

coat during all fusion and uptake operations. 3.1.5 Perform all fusion and uptake steps in a shielded cell or a fume

hood.

3.1.6 The temperature of the alkali fusion will result in air combustion of organic materials, which can be manifested by a brief flame in the crucible. If it is known that organic materials are in the sample. Sample sizes are limited to 0.1g unless approved by Task Supervisor. This reduces the amount of combustible material. A face shield and heavy leather or Kevlar gloves must be worn when either placing the crucible in the muffle furnace or when removing it from the furnace. A pair of tongs must be used when placing crucibles into a hot furnace or when removing the crucibles.

3.1.7 Make up all solutions in a fume hood, and always wear protective gloves when handling any chemicals to avoid skin contact.

3.1.8 Inspect all glassware before and after each use for cracks, chips,

or jagged edges. Remove from service and dispose of faulty glassware in waste glass containers.



A dried, powdered sample is fused with a mixture of sodium peroxide and sodium hydroxide at 675°C 10C for 10 minutes in a zirconium (Zr) crucible. A nickel (Ni) crucible can be used when directed by the Task Supervisor. After brief cooling, deionized water is added and the mixture is swirled until the melt is decomposed. This alkaline slurry of metal hydroxides is then acidified with concentrated hydrochloric acid or nitric acid. This solution is transferred to a 250-mL volumetric flask and diluted with deionized water to the mark. A ten-fold volumetric dilution of this solution is made for elemental analysis.


The carbonate fusions must be performed using Pt or Pt-Au crucibles. The carbonate fusions require temperatures of 875- 1100 C. The fusion decomposes the sample and converts the elements to metallic hydroxides or water-soluble sodium compounds. Addition of concentrated HCI or HNO3 dissolves the metal hydroxides. A similar method is used to dissolve samples for anion analysis, except that no acid is needed to keep the water-soluble anions in solution.

4.2 Data Quality

4.2.1 The quality of sludge and glass elemental analyses depends on both the qualities of the dissolution and the instrumental analysis. It is easy to assess the quality of glass analyses because glass standards are available for analysis. Sludge standards are not available, and the dissolution method is usually verified by analyzing a glass standard.

4.2.2 All reagents shall conform to specifications of the Committee on

Analytical Reagents of the American Chemical Society (ACS), where such specifications are available.

4.2.3 Analytical balances shall have a current QC calibration for the

balance/balance weight combination. 4.2.4 The Alkali fusion dissolution for elemental and anion analysis is

highly effective. It is one of the most rigorous dissolution techniques commonly used for sludge and glass matrices. Excellent results can be obtained when careful technique is used.

4.2.5 Most elements except the alkali used in the fusion and the

crucible material (Zr or Ni) can be analyzed with a sensitivity of about 0.25 wt. % in the original solid. Because of their volatility at 675°C, As, Cd, Cs, Hg, Os, P, Rb, Re, Ru, Te, and Se oxides are partially or completely lost during the fusion. Most of these oxides can be most reliably determined by using the sealed-vessel acid dissolution. However, the fusion dissolution should be used for Ru determination since the acid dissolution appears to result in incomplete dissolution of Ru.


4.3 Equipment

55 mL Zirconium or Nickel Crucibles (used for perioxide alkali hydroxide fusions)

Platinum or Platinum Gold crucibles (used for carbonate fusions) Muffle Furnace Tongs – stainless steel Heat Protective Gloves 250 mL Plastic Volumetric Flasks 250 mL Plastic Bottles 100 mL Plastic Bottles Plastic Funnel Analytical Balance-Capable of reading to at least 1 mg and preferably

0.1 mg Timer

4.4 Reagents

Concentrated Hydrochloric Acid (HCl) – reagent grade Concentrated Nitric Acid (HNO3) – reagent grade

Sodium Peroxide (Na2O2) - Lot analysis on container must be less than

0.001 wt. % in any cation to analyzed. Usually, reagent grade is sufficiently pure.

Cesium Hydroxide-CsOH – Aldrich product is recommended because of

its high purity.

Potassium Hydroxide – KOH – Aldrich product is recommended Sodium Hydroxide (NaOH) - Ultrapure. Lithium Carbonate, Sodium Carbonate, Potassium Carbonate, Cesium

Carbonate – Aldrich or Alfa product is recommended.


5.0 PERFORMANCE

5.1 Preparation of Alkali Fusion Blank

5.1.1 At least 1 hour before starting the fusion, pre-heat the muffle furnace to 675oC + 10oC. For carbonate fusions, see Task Supervisor.

5.1.2 Tare a clean, dry crucible. For the type of crucible, see Task

Supervisor.

5.1.3 Add the appropriate fusion material. a) Carefully add 1.5 g Na2O2 (± 0.1g) and 1.0 g of NaOH (± 0.1 g)

to the crucible. OR

b) Carefully add 2.5 g alkali hydroxide (CsOH or KOH or NaOH)

(± 0.1g) to the crucible. OR c) 2.5 g alkali carbonate (Li2CO3, Na2, CO3, K2CO3, CS2CO3.) 5.1.4 If instructed by the Task Supervisor, place the lid on the

crucible. Use of crucible lids are required only if specified by the Task Supervisor.

5.1.5 Open the furnace door and quickly place the crucible in the

furnace. Be sure to have heat-resistant gloves on and use the tongs to grasp the crucible. Immediately close the furnace door to minimize heat loss.

5.1.6 After heating the furnace temperature increases to 675 C

again, note the time and heat the crucible for 10 minutes, then remove it from the furnace and set it on a clean, dry surface.

5.1.7 Place a plastic funnel in the mouth of a plastic 250-mL

volumetric flask. Plastic funnels and flasks are used to avoid dissolving any glass, which could affect the results.


5.1.8 Let the crucible cool for 3 or 4 minutes, then squirt about 5 mL of deionized water into the crucible. The water will react with the residue and begin to dissolve some of the salts. It is important to add the water while the crucible is warm (but not extremely hot) so that the melt residue will break up readily. If the crucible gets too cool before the water is added, it requires more effort to break up the melt residue. If the water is added when the crucible is too hot, then splattering will cause loss of sample and low ICP-AES results.

5.1.9 Pour the contents in the crucible into the volumetric flask. 5.1.10 Rinse the crucible with several 15-20 mL portions of deionized

water. After the water is added, carefully swirl the crucible and then transfer the contents to the volumetric flask. After several rinses, there should be no solid residue in the crucible.

5.1.11 Add 25.0 mL of concentrated HCl or HNO3 to the crucible.

Swirl the crucible and pour the contents into the volumetric flask.

5.1.12 Add about 10 mL of deionized water to the crucible. Swirl the

crucible and pour the contents into the volumetric flask. 5.1.13 The volumetric flask should now contain about 200 mL of

solution from all the rinses. Cap the flask and shake it to mix the contents. The solids in the flask should now dissolve in the acid solution. If solids remain in the flask, notify the Task Supervisor.

5.1.14 Uncap the flask and add deionized water to the mark on the

flask. 5.1.15 Cap the flask and shake it to mix the contents. 5.1.16 Pour the solution into a 250-mL plastic bottle. Label the bottle

as Alkali Fusion Blank.


5.2 Fusion Dissolutions of Samples

NOTE: If glass is to be dissolved, it must be finely crushed glass the consistency of fine talcum powder. If the glass is not already finely crushed, either return the glass to the customer for crushing or use glass crushers (or grinders) in the laboratory to crush the glass. If there is any doubt as to whether the glass is fine enough for dissolution ask the Task Supervisor or use sieve pans to obtain -200 mesh powder.

NOTE: Radioactive samples must be dissolved in a radioactive hood or

shielded cells depending on the activity of the sample. Consult with the Task Supervisor on where radioactive samples should be dissolved.

NOTE: Non-radioactive samples can be dissolved in a non-radioactive

hood. 5.2.1 Pre-heat the muffle furnace to 675°C 10C. For carbonate

fusions see the Task Supervisor. 5.2.2 Tare a clean, dry Zr or Ni crucible on the analytical balance.

For carbonate fusions, see Task Supervisor. 5.2.3 Carefully add 0.25g (to either 3 or 4 places, depending on the

balance of finely crushed sample to the crucible. The sample weight can be modified as directed by the Task Supervisor.

NOTE: Slurry samples must be dried prior to dissolution. The sample

weight will then be either the original slurry weight for the dry weight which can be obtained by measuring the total solids. Reference: ADS Procedure ADS-2284 “Procedure for Measuring Weight % Total Solids, Soluble Solids, and Insoluble Solids, Rev. 0 5/15/2003.”

5.2.4 Record the sample weight in the dissolution lab notebook and

the Data Sheet.

5.2.5 Add the appropriate fusion material.


a) Carefully add 1.5 g Na2O2 (± 0.1 g) and 1.0 g of NaOH (± 0.1 g) to the crucible. Swirl the crucible to mix the solid contents well.

OR

b) Carefully add 2.5 g of alkali hydroxide (CsOH or KOH, or

NaOH) (± 0.1 g) to the crucible. Swirl the crucible to mix the solid contents well.

OR

c) 2.5 g alkali carbonate (Li2CO3, Na2CO3, K2CO3, CS2CO3

5.2.6 If instructed by the Task Supervisor place the lid on the crucible. Use a crucible lid only if specified by the Task Supervisor.

5.2.7 Open the furnace door and quickly place the crucible in the

furnace. Be sure to have heat-resistant gloves on and use tongs to grasp the crucible. Immediately close the furnace door to minimize heat loss.

5.2.8 Heat the crucible for 10 minutes, after the temperature

equilibrates to the specified temperature. 5.2.9 Remove the crucible from the furnace.

5.2.10 Place a plastic funnel in the mouth of a plastic 250-mL

volumetric flask. Plastic funnels and flasks are used to avoid dissolving any glass, which could affect the results.

5.2.11 Let the crucible cool for 3 or 4 minutes, then squirt about 5 mL

of deionized water into the crucible. The water will react with the residue and begin to dissolve some of the salts. It is important to add the water while the crucible is warm (but not extremely hot) so that the melt residue will break up readily. If the crucible gets too cool before the water is added, it requires more effort to break up the melt residue. If the water is added when the crucible is too hot, then splattering will cause loss of sample and low ICP-AES results.


5.2.12 Lift the lid off the crucible with the beaker tongs and hold it over the funnel in the volumetric flask. Use the squirt bottle to completely rinse solids off the lid into the volumetric flask.

5.2.13 Pour the contents in the crucible into the volumetric flask. The

contents will contain solids. The objective is to completely transfer the entire residue to the volumetric flask.

5.2.14 Rinse the crucible with several 15-20 mL portions of deionized

water. After the water is added, carefully swirl the crucible and then transfer the contents to the volumetric flask. After several rinses, there should be no solid residue in the crucible.

5.2.15 Add 25.0 mL of concentrated HCl or HNO3 to the crucible.

Swirl the crucible and pour the contents into the volumetric flask. The acid should dissolve the solids in the flask within one minute. If solids remain in the flask, notify the Task Supervisor.

5.2.16 Add about 10 mL of deionized water to the crucible. Swirl the

crucible and pour the contents into the volumetric flask. 5.2.17 The volumetric flask should now contain about 200 mL of

solution from all the rinses. Cap the flask and shake it to mix the contents.

5.2.18 Uncap the flask and add deionized water to the mark on the

flask.

5.2.19 Cap the flask and shake it to mix the contents. 5.2.20 Pour the solution into a 250-mL plastic bottle. Label the bottle

with the sample identification number and the weight of solid dissolved (from the data sheet), and the dissolution volume.

5.3. Alkali Fusion Dissolution for Anion Analysis

5.3.1 Perform steps 5.2.1 – 5.2.14 in the procedure for fusion

dissolution for elemental analysis.


5.3.2 Add deionized water to the mark on the 250-mL plastic volumetric flask.

5.3.3 Cap the flask and shake it to completely mix the contents.

There will be solids (insoluble metal oxides and hydroxides) in the flask.

5.3.4 Let the solids settle to the bottom of the flask. This may take

several hours to achieve a clarified top layer. If a clear solution is needed more quickly, the slurry can be filtered through a disposable Nalgene-type filter.

5.3.5 Carefully decant or pipette about 15 mL (or the volume directed

by the Task Supervisor) of the clear supernatant in the flask into a plastic bottle. The supernatant contains the soluble anions that are determined by ion chromatography and ion selective electrode analysis. The solids are to be avoided since they will clog chromatography columns and, for radioactive samples, increase the radioactivity of the analytical sample.

5.3.6 Label the plastic bottle with the sample identification number and the weight of the sample dissolved (from the data sheet) and submit for ion chromatography and/or ion selective electrode analysis.

6.0 RECORDS Data generated from this procedure will be recorded in Laboratory Notebooks. 7.0 REFERENCES

7.1 A. R. Jurgensen, "Sodium Peroxide Fusion of Sludges, Flyash, and Other Highly Refractory Materials in Preparation for Cation Analysis by ICP-AES," Analytical Development Division Procedure, March 1985.

7.2 L. W. Reynolds, "Sodium Peroxide Fusion of Waste Glass, Glass Frit,

and Sludges In Preparation For Anion Analysis By Ion Chromatography and Ion Selective Electrodes," Analytical Development Division Procedure, August 1980. Revised: A. R. Jurgensen, February 1985.

8.0 ATTACHMENTS

8.1 Data Sheet


Attachment 8.1 Data Sheet Page 1 of 1

Savannah River National Laboratory Instruction: ADS-WI00023 Analytical Development Section Revision: 1 ADS Analytical Operating Instructions Page: 1 of 3 Effective Date: 2/28/08 Expiration Date: 2/28/13 Spreadsheet Quality Control for Originator: C. C. DiPrete Analytical Development Section (ADS) Approved By: Signature Copy on File Manager/Owner Dated Copy on File Date

1.0 Purpose

This work instruction establishes the minimum requirements for quality control of spreadsheets used to generate final analytical results released to customers.

2.0 Scope

This work instruction is applicable to spreadsheets used to generate analytical results released to customers.

The following is excluded from this work instruction:

• Spreadsheets used for scoping activities as defined by the 1Q

manual 2-3 • Spreadsheets that are defined as part of a Measuring System and

Equipment (MS&E) and thus subject to periodic validation provided all aspects of the spreadsheet are validated.


The originator (CTF/Task Supervisor, etc.) of spreadsheets used to generate external AD analytical results (i.e., results that are reported to a customer outside of AD) shall ensure quality control documentation is complete.

4.0 Work Instruction

Savannah River National Laboratory Instruction: ADS-WI00023 Analytical Development Section Revision: 1 ADS Analytical Operating Instructions Page: 1 of 3 Effective Date: 2/28/08 Expiration Date: 2/28/13

4.1 Spreadsheet Quality Control - Repeatedly used spreadsheets that contain calculations that do not change are subject to the following guidelines:

4.1.1 The calculation cells shall be protected (locked) or results

shall be verified by an alternate calculation. 4.1.2 The spreadsheet shall be assigned a revision number.

4.1.3 The spreadsheet shall be validated at a minimum with

test data that is subjected to the spreadsheet’s calculation(s) to confirm the calculation(s) provide the correct result(s). This can be done by:

• Processing a standard and confirming the calculated

results are correct. • Utilizing dummy data and confirming the calculated

results are correct. • Hand calculating the results and validating the

calculated results are correct.

4.1.4 The spreadsheet, and the calculations it contains, shall be peer reviewed by cognizant technical function (CTF) familiar with the subject matter. This will be documented in writing.

4.1.5 Changes to the spreadsheet shall be performed by the

CTF or a designee and documented by the CTF or a designee including a new revision number. If calculations are modified, revalidation and peer review is required before use.

4.1.6 Spreadsheet documentation shall include as a minimum:

• An example of the spreadsheet • Description of the function of the spreadsheet • Calculations contained in the spreadsheet • The validation method • The verifier • The revision number

Savannah River National Laboratory Instruction: ADS-WI00023 Analytical Development Section Revision: 1 ADS Analytical Operating Instructions Page: 1 of 3 Effective Date: 2/28/08 Expiration Date: 2/28/13

4.1.7 Single-use spreadsheets used for calculations of reported analytical results are subject to the following guidelines:

• The CTF shall review and confirm as correct all

calculations and then record the spreadsheet in a notebook or logbook with a signature and date. If a final report is issued as part of the delivered product, this report will suffice instead of a notebook or logbook. It is understood that the report has been through the guidelines established in WSRC-IM-2002-00011, Technical Report Design Check for Guidelines.

• The spreadsheet, and the calculations it contains, shall

be peer reviewed by a subject matter expert. Dummy data may be utilized to replace the peer review in the event no subject matter expert is available.

5.0 Records

Spreadsheet quality control documentation for repeatedly used spreadsheets that contain calculations that do not change shall be maintained in the MS&E history file or AD memo that is referenced in the MS&E history file. Single-use spreadsheets used for calculations shall be documented in a notebook, logbook, or a formal written document.

6.0 References

• QAP 2-7 QA Program Requirements for Analytical Measurement Systems


Summary of Analytical Methods Used for Residuals Sample Analyses

Attachment 2 consists of analytical method descriptions and applicable AOPs listed in Table A7-1.

The individual analytical method descriptions provided below contain standard information on the application of the AOPs, DQIs, and MPCs provided in Table A7-1. The Sample Analysis Report will contain detailed case narratives reporting the specific analytical methods used, including, any analytical problems and resolution, the results for the QC protocols and comparison back to the DQIs, and MPCs in Table A7-1.

Gross Alpha/Gross Beta

Aliquots of dissolution are added to liquid scintillation cocktail and analyzed for gross alpha and gross beta activity using liquid scintillation analysis. Alpha/beta spillover is determined for each sample by preparing two separate aliquots of each sample for analysis, one spiked with plutonium (matrix spike) and one without the spike. The spillover value is determined using the matrix spike and is subsequently used for accurately determining alpha and beta activity. Results are reported as disintegrations per minute (dpm) by converting counts per minute (cpm) from the instrument to dpm using appropriate efficiencies as described in the AOP.

Each batch contains a method blank, a matrix spike for each sample, and ≤20 samples. Results are reported with 1-sigma uncertainty, which is determined for each sample based on counting statistics and other known sources of uncertainty (pipet, standard certificate value, etc). Calculations are carried out using a spreadsheet maintained in accordance with ADS-WI00023.

Ni-59/63

Aliquots of dissolution are spiked with an elemental nickel carrier which will be used to trace the separation efficiency on a sample-by-sample basis. The nickel species are extracted from the matrix using dimethylglyoxime (DMG)-based extractant. An aliquot of the extracted Ni-containing material is transferred to a stainless-steel plate (for Ni-59 analysis), and an aliquot is added to liquid scintillation cocktail (for Ni-63 analysis). An additional aliquot is sent to the inductively coupled plasma emission spectroscopy (ICP-ES) laboratory to determine the nickel content in the separated material, and thus the separation yield.

Ni-59 concentrations are measured using low energy photon/x-ray, thin-windowed, semi-planar high purity germanium spectrometers with an appropriate efficiency calibration to convert peak size and counting duration to dpm. Ni-63 concentrations are measured by liquid scintillation analysis with an appropriate quench curve/efficiency calibration to convert cpm to dpm.

Elemental nickel carrier yields are measured by ICP-ES, and are used to correct the radioactive nickel species’ analyses for any nickel losses from the radiochemical separations.

The quality of the tracing is indicated by the successful laboratory spikes containing Ni-59 and Ni-63.

Each batch contains a method blank, ≤20 samples, a traced Ni-59 laboratory spike, and a traced Ni-63 laboratory spike. Results are reported with 1-sigma uncertainty, which is determined for each sample based on counting statistics and other known dominant sources of uncertainty (pipet, standard certificate value, etc). The percent (%) recovery for the Ni-59

and the Ni-63 [(measured dpm/added dpm)*100] for the laboratory spikes are used as data quality indicators. Calculations are carried out using a spreadsheet maintained in accordance with ADS-WI00023.

Cs-137/Cs-134

Aliquots of dissolution are analyzed by coaxial high purity germanium gamma-ray spectrophotometers with an appropriate efficiency calibration to convert peak energy, peak size and counting duration to dpm.

Each batch contains a method blank and ≤20 samples. Results are reported with 1-sigma uncertainty, which is determined for each sample based on counting statistics and other known dominant sources of uncertainty (pipet, standard certificate value, etc), or a minimum of 5% uncertainty, as described in the AOP. Calculations are carried out using a spreadsheet maintained in accordance with ADS-WI00023.

Sr-90

Aliquots of dissolution are spiked with an elemental strontium carrier which will be used to trace the separation efficiency on a sample-by-sample basis. The strontium species are extracted from the matrix using a crown-ether-based solid phase extractant. Sr-90 concentrations are measured by liquid scintillation analysis and an appropriate efficiency to convert cpm to dpm. Elemental strontium carrier yields are measured by neutron activation analysis (NAA), and are used to correct the Sr-90 analyses for any strontium losses from the radiochemical separations. The quality of the tracing is indicated by the successful laboratory spike containing Sr-90.

Each batch contains a method blank, ≤20 samples, a traced Sr-90 laboratory spike which contains a known amount of Sr-90, and a serial dilution of one of the samples being analyzed. Results are reported with 1-sigma uncertainty, which is determined for each sample based on counting statistics and other known dominant sources of uncertainty (pipet, standard certificate value, etc). The % recovery for the Sr-90 [(measured dpm/added dpm)*100] for the laboratory spike is used as a data quality indicator. In addition, when comparing the serial dilution aliquot and its counterpart, the concentration for Sr-90 must overlap within the limit established by each sample’s 3-sigma range. Calculations are carried out using a spreadsheet maintained in accordance with ADS-WI00023.

Pm-147/Sm-151

Aliquots of dissolution are spiked with an elemental samarium carrier which will be used to trace the separation efficiency on a sample-by-sample basis. The promethium and samarium species are extracted from the matrix using a combination of Octylphenyl-N,N-di-isobutyl carbamoylphosphine oxide/tri-n-butyl phosphate (CMPO/TBP) and di(2-ethylhexyl) orthophosphoric acid (HDEHP). The separation is designed to extract both Sm and Pm together.

Sm-151 concentrations are measured by liquid scintillation analysis with an appropriate quench curve/efficiency calibration to convert cpm to dpm. Pm-147 concentrations are also measured by liquid scintillation analysis. Elemental samarium carrier yields are measured by NAA, and are used to correct the analyses for any samarium and promethium losses from the radiochemical separations. The quality of the tracing is indicated by the successful laboratory spike containing Sm-151.

Each batch contains a method blank, ≤20 samples, and a traced Sm-151 laboratory spike. Results are reported with 1-sigma uncertainty, which is determined for each sample based on counting statistics and other known dominant sources of uncertainty (pipet, standard certificate value, etc). The % recovery for the Sm-151 [(measured dpm/added dpm)*100] for the laboratory spike is used as a data quality indicator. Calculations are carried out using a spreadsheet maintained in accordance with ADS-WI00023.

Na-22, Al-26, Co-60, Nb-94, Rh-106, Ru-106, Sb-125, Sb-126, Sn-126, Sb-126m, Te-125m, Ce-144, Pr-144, Eu-152, Eu-154, Eu-155, Am-241, Ra-228, Ac-227 (Cs-removed Gamma Analysis)

Aliquots of dissolution are subjected to a cesium-removal process utilizing BioRad Ammonium Molybdophosphate (AMP) resin. Following the resin extraction (which selectively removes the cesium in the matrix yet does not impact the analytes of interest), the samples are analyzed by coaxial high purity germanium spectrophotometers with an appropriate efficiency and energy calibration to convert peak energy, peak size and counting duration to dpm.


Pu-238, 239/240, 241

Aliquots of dissolution are spiked with Pu-236 tracer which will be used to trace the separation efficiency on a sample-by-sample basis. The plutonium is extracted from the matrix using thenoyltrifluoroacetone (TTA) following a series of oxidation state adjustments. The TTA extracts are mounted on stainless steel counting plates and counted using passivated implanted planar silicon (PIPS) detectors (alpha PHA chambers) to determine peak areas for the Pu-238, Pu-239+Pu-240, and Pu-236 peaks. Peak areas, coupled with the known amount of Pu-236 added to each sample, are used to provide traced results for Pu-238 and Pu-239+240.

Each batch contains a method blank, a traced Pu-238 laboratory spike, a serial dilution of one of the samples being analyzed, and ≤20 samples. Results are reported with 1-sigma uncertainty, which is determined for each sample based on counting statistics and other known dominant sources of uncertainty (pipet, standard certificate value, etc). Calculations are carried out using a spreadsheet maintained in accordance with ADS-WI00023.

Each separation is traced based on the Pu-236 recovery. The quality of the tracing is indicated by the successful laboratory spike containing Pu-238. The % recovery for the Pu-238 [(measured dpm/added dpm)*100] for the Pu-238 laboratory spike is used as a data quality indicator. In addition, when comparing the serial dilution aliquot and its counterpart, the concentration for the major Pu isotope must overlap within the limit established by each sample’s 3-sigma range.

In order to quantify the Pu-241, aliquots of each sample are subjected to Cs-removal with BioRad Ammonium Molybdophosphate (AMP) resin and extracted using Eichrom TEVA resin columns. The Pu-containing extracts are then measured by liquid scintillation analysis

to determine Pu-241 concentration. The region of interest for Pu-241 is equivalent to that of tritium due to similar beta-energies. The tritium quench-curve is used to convert from counts per minute to dpm. The Pu-241 value is obtained by applying the ratio of Pu-241 (dpm) to Pu-alpha (dpm) from the LSC analysis to the total Pu-alpha (dpm) from the alpha analysis. This provides a traced (and yield corrected) value for Pu-241.

Am-241, 242m, 243; Cm-242, 243, 244, 245, 247, 248; Cf-249, 251, 252

Paired aliquots of dissolved material are extracted using a CMPO/TBP-based solid phase extractant, and are further purified with an HDEHP-based solid phase extractant. One aliquot of the pair is analyzed without a spike, and one aliquot of the pair is spiked with a known quantity of Am-243 to determine separation yield. Aliquots of the extracted material are mounted on a stainless-steel plate and counted using PIPS detectors (for Am-242m, Cm-242, Cm-244, Cm-248, and Cf-252) as well as low energy photon/x-ray, thin-windowed, semi-planar high purity germanium spectrometers (for Am-241, Am-243, Cm-243, Cm-245, Cm-247, Cf-249 and Cf-251) with an appropriate efficiency calibration to convert peak size and counting duration to dpm. Some of the Am, Cm and Cf isotopes are also measured using inductively coupled plasma mass spectrometry (ICP-MS).

For simplicity, Am-241 quantities measured from the cesium-removed gamma analyses are used, when possible, instead of the matrix spikes to trace the separation yields for this method. This is accomplished by determining a multiplier for the Am-241 value from the extracted aliquot to the Am-241 value from the straight-forward Cs-removed gamma analysis. In turn, all Am, Cm, and Cf results are traced back to the Am-241 concentration present in the sample matrix. If the Am-241 from non-extracted sample can not be used as a yield monitor, the yield of the Am-243 from the matrix spike for each sample (in paired analyses) is used to correct for losses during the separation process.

Each batch contains a method blank, a matrix spike for each sample analyzed (for sample-specific tracing), and ≤20 samples. Results are reported with 1-sigma uncertainty, which is determined for each sample based on counting statistics and other known dominant sources of uncertainty (pipet, standard certificate value, etc). Calculations are carried out using a spreadsheet maintained in accordance with ADS-WI00023.

U-232

Paired aliquots of dissolved material for each sample undergo radiochemical separations and analyses. One aliquot of the pair is analyzed without a spike, and one aliquot of the pair is spiked with a known quantity of U-233 to determine separation yield. Uranium is extracted from the matrix using two stages of a diamyl, amylphosphonate-based (DAAP) solid phase extraction and purified further via co-precipitation with cerium. The uranium-containing precipitates are analyzed using PIPS alpha spectrometers (alpha PHA chambers) with known efficiencies to quantify U-232, U-233, and U-238. [dpm=((peak area-background peak area)/efficiency/count duration in minutes)/yield]

Each batch contains a method blank, ≤20 samples, and matrix spike for each sample. Results are reported with 1-sigma uncertainty, which is determined for each sample based on counting statistics and other known dominant sources of uncertainty (pipet, standard certificate value, etc). Calculations are carried out using a spreadsheet maintained in accordance with ADS-WI00023.

Often, the U-233 matrix spike can not be used for yield corrections because the U-234 inherent in the sample swamps out the U-233 signal. U-233 and U-234 have the same characteristic alpha energy. In this case, the U-232/U-238 activity ratios are determined from the alpha analysis, and are multiplied by the U-238 activities measured by the ICP-MS to determine U-232 activities in the samples.

Cs-135

Aliquots of dissolved material are purified using a solvent-solvent caustic side solvent extraction-based (CSSX) extraction system. The purified Cs-containing aliquots are analyzed using ICP-MS to measure Cs-135/Cs-137 mass ratios. These ratios are then converted to activity ratios using the specific activities. The Cs-135/Cs-137 activity ratio for each sample is then multiplied by the Cs-137 activity of the dissolved, non-purified sample which was obtained by simple coaxial high purity germanium gamma-ray spectrometry as previously described in the Cs-137/Cs-134 section.

Each batch contains a method blank and ≤20 samples. Results are reported with 1-sigma uncertainty, which is determined for each sample based on counting statistics and other known dominant sources of uncertainty (pipet, standard certificate value, etc). Calculations are carried out using a spreadsheet maintained in accordance with ADS-WI00023.

Np-237

Quantification of Np-237 can be carried out in a number of ways. The simplest process utilizes ICP-MS or gamma pulse height analysis using coaxial high purity germanium gamma-ray spectrophotometers on dissolved material to provide a Np-237 concentration.

In the event that the uranium content of the matrix is high enough to cause possible biases in the Np-237 peak, aliquots of the material are purified using a radiochemical separation scheme prior to ICP-MS and/or gamma pulse height analysis. Aliquots of dissolved material are spiked with Np-239 tracer (in the form of Am-243, which decays to Np-239) and then extracted with a quaternary amine-based solid phase extraction. If the matrix contains sufficient quantities of Am-243 (and thus Np-239) then the addition of a radiochemical tracer is not necessary since the yield of the separated fraction can be determined using the inherent Np-239. The purified Np-containing aliquots are analyzed either 1)using a low energy photon/x-ray, thin-windowed, semi-planar high purity germanium spectrometer with an appropriate efficiency calibration to convert peak size and counting duration to dpm or 2) with ICP-MS, or 3) with a combination of the two. Np-239 yields are calculated [dpm in final separated material divided by dpm added to material], and are used to correct the Np-237 result for each sample for any losses from the radiochemical separations.

Each batch contains a method blank, ≤20 samples, and, when necessary, a Np-237 laboratory standard. Results are reported with 1-sigma uncertainty, which is determined for each sample based on counting statistics and other known dominant sources of uncertainty (pipet, standard certificate value, etc). The % recovery for the Np-237 [(measured dpm/added dpm)*100] for the laboratory spike is used as a data quality indicator. Calculations are carried out using a spreadsheet maintained in accordance with ADS-WI00023.

Tritium

Aliquots of dissolved material are subjected to tritium separations via steam distillation. The distillation separates the tritium from non-volatile radionuclides. Aliquots of the tritium-

containing distillates are added to liquid scintillation cocktail and analyzed by liquid scintillation analysis with an appropriate quench curve/efficiency calibration to convert cpm to dpm.


Se-79

Aliquots of material are spiked with an elemental selenium carrier, which is used to trace the separation efficiency on a sample-by-sample basis, and dissolved. The selenium species are extracted from the matrix using a combination of resin decontamination, selenium metal precipitation, and TBP-based liquid-liquid extractions.

Aliquots of the purified selenium-containing extracts are analyzed by liquid scintillation counting (to measure Se-79), as well as by NAA (to measure elemental selenium carrier yields). The region of interest for Se-79 is equivalent to that of C-14 due to their similar beta-energies. The C-14 quench-curve is used to convert from cpm to dpm. The selenium carrier yields for each individual sample are used to correct for selenium losses from the radiochemical separations. The quality of the tracing is indicated by the successful quantification of the activated tracer (tracer activity is greater than the minimum detectable activity (MDA) for each individual count) as well as sufficient recovery to provide the customer-requested sensitivity. For instance, if the separation yield is low, and the Se-79 concentration is less than the minimum detectable activity, then the low yield could elevate the MDA to a value above the customer-requested detection limit.


Tc-99

Aliquots of material are spiked with Tc-99m (which is produced in-house using the NAA facility) to trace the separation efficiency on a sample-by-sample basis, and dissolved. The technetium species are extracted from the matrix using an Aliquat-336-based solid phase extractant. Aliquots of the purified Tc-containing extracts are added to liquid scintillation cocktail for quantification. Tc-99m yields for each individual sample are measured with a NaI gamma spectrometer, and are used to correct the Tc-99 analyses for any technetium losses from the radiochemical separations. Following a sufficient delay to allow the Tc-99m to decay, the Tc-99 concentrations are then measured by liquid scintillation analysis. NIST-traceable-standard-based efficiencies are used to convert from cpm to dpm. The LSC results are corrected for losses using the Tc-99m yield monitor. The quality of the tracing is indicated by the successful laboratory spikes containing Tc-99. The % recovery for the Tc-99 [(measured dpm/added dpm)*100] for the laboratory spike is used as data quality indicator.

Each batch contains a method blank, a traced laboratory spike, and ≤20 samples. Results are reported with 1-sigma uncertainty, which is determined for each sample based on counting statistics and other known dominant sources of uncertainty (pipet, standard certificate value,

etc). Calculations are carried out using a spreadsheet maintained in accordance with ADS-WI00023.

Ra-226

Paired aliquots of material for each sample undergo radiochemical separations and analyses. One aliquot of the pair is analyzed without a spike, and one aliquot of the pair is spiked with a known quantity of Ra-224 (from Th-228) to determine separation yield. The radium is extracted from the matrix using a combination of resin decontamination and ion exchange. The purified material containing Ra-226 is sealed in a polypropylene tube and rapidly analyzed for Ra-224 using a high purity germanium well gamma-ray detector and an appropriate efficiency calibration to convert peak energy, peak size and counting duration to dpm. The sealed tubes are then stored for at least several Rn-222 half-lives (Rn-222 is a daughter of Ra-226 which then decays to Pb-214). The Ra-226 progeny daughter isotope Pb-214 is then quantified using a high purity germanium well gamma ray detector. Ra-226 results are corrected for the tracer Ra-224 recoveries.

Each batch contains a method blank, a traced laboratory spike, and ≤20 samples. Results are reported with 1-sigma uncertainty, which is determined for each sample based on counting statistics and other known dominant sources of uncertainty (pipet, standard certificate value, etc). Calculations are carried out using a spreadsheet maintained in accordance with ADS-WI00023.

Pa-231

Aliquots of dissolution are spiked with Pa-233 tracer (in the form of Np-237) which will be used to trace the separation efficiency on a sample-by-sample basis. The dissolutions are decontaminated with AMP- and quaternary amine-based resins to facilitate the removal of interfering radionuclides. Protactinium species are then extracted from the matrix using a CMPO/TBP-based extraction scheme. Pa-233 tracer concentrations are measured using a high purity germanium spectrometer with an appropriate efficiency calibration to convert peak size and counting duration to dpm. The Pa-231 is measured using ICP-MS. The Pa-separation yields determined for each sample are used to correct the ICP-MS result for losses during the radiochemical separation process.


I-129

Aliquots of material are spiked with an elemental iodide carrier which will be used to trace the separation efficiency on a sample-by-sample basis. Samples, with the added KI carrier, are then are dissolved in concentrated acid. Actinide and AMP resins are added to the mixture to facilitate removal of interfering radionuclides. Sodium sulfite is added to the material to reduce the iodine. Silver nitrate is added to the solution to precipitate the iodine as AgI, which is separated via filtration. The purified iodide-containing precipitate is analyzed for I-129 content using low energy photon/x-ray, thin-windowed, semi-planar, high purity germanium spectrometer with an appropriate efficiency calibration to convert peak size and counting duration to dpm.

Iodide carrier yields are measured by NAA, and are used to correct the I-129 analyses for any iodide losses from the radiochemical separation. The quality of the tracing is indicated by the successful quantification of the activated tracer (tracer activity is greater than MDA for each individual count) as well as sufficient recovery to provide the customer-requested sensitivity. For instance, if the separation yield is low, and the I-129 concentration is less than the minimum detectable activity, then the low yield could elevate the MDA to a value above the customer requested detection limit.

When possible, an I-129 laboratory standard is analyzed with the batch of samples. The quality of the tracing is indicated by the successful laboratory spike containing I-129. The % recovery for the I-129 [(measured dpm/added dpm)*100] for the I-129 laboratory spike is used as a data quality indicator.

Each batch contains a method blank, a laboratory spike (when possible), and ≤20 samples. Results are reported with 1-sigma uncertainty, which is determined for each sample based on counting statistics and other known dominant sources of uncertainty (pipet, standard certificate value, etc). Calculations are carried out using a spreadsheet maintained in accordance with ADS-WI00023.

C-14

When carrying out C-14 analyses, the material is added to a mixture of sodium hydroxide and sodium carbonate/sodium hydroxide. A series of oxidation and reduction steps designed to liberate C-14 containing carbon dioxide are carried out, which selectively traps the volatile C-14 in a basic solution. Finally, carbon dioxide containing the purified C-14 is captured in Carbosorb E and measured by liquid scintillation analysis. Aliquots of the C-14 containing Carbosorb E are added to liquid scintillation cocktail and analyzed by liquid scintillation analysis with an appropriate quench curve/efficiency calibration to convert cpm to dpm.


Th-229, Th-230, Ac-227

Paired aliquots of material for each sample undergo radiochemical separations and analyses. One aliquot of the pair is analyzed without a spike, and one aliquot of the pair is spiked with a known quantity of Th-229 to determine separation yield.

Thorium is extracted from the matrix using two stages of a quaternary amine-based solid phase extraction and purified further via co-precipitation with cerium. Th-227, Th-229 and Th-230 concentrations in the final purified precipitate are measured using PIPS alpha spectrometers with known efficiencies. The Th-229 tracer yields are used to correct the results of each sample for any thorium losses from the radiochemical separations. Ac-227 activities are calculated from the Th-227 results.

Each batch contains a method blank, a matrix spike for each sample, a laboratory spike (Th-228), and ≤20 samples. Results are reported with 1-sigma uncertainty, which is determined for each sample based on counting statistics and other known dominant sources of uncertainty (pipet, standard certificate value, etc). Calculations are carried out using a spreadsheet maintained in accordance with ADS-WI00023.

Cl-36

Aliquots of each sample are dissolved using known quantities of hydrochloric acid and nitric acid. The dissolved material is then aggressively decontaminated from interfering radionuclides. Eventually, the samples are distilled to further decontaminate by isolating the chlorine-containing fraction. Following the distillation, Cl-36 is precipitated as AgCl. The AgCl precipitate is counted for gross beta activity using a gas flow proportional counter and an accompanying Cl-36 counting efficiency. The same precipitate is then analyzed by NAA to trace the separation. The yield of the radiochemical separation is determined for each individual sample using NAA of the chlorine which was added during the dissolution.

Each batch contains a method blank and ≤20 samples. Results are reported with 1-sigma uncertainty, which is determined for each sample based on counting statistics and other known dominant sources of uncertainty (pipet, standard certificate value, etc), as described in the AOP. Calculations are carried out using a spreadsheet maintained in accordance with ADS-WI00023.

K-40

Aliquots of dissolved material are subjected to a series of decontamination processes to remove cesium, strontium, and tri-, tetra-, and hexavalent radionuclides. Following the extractions (which selectively remove interferences in the matrix yet do not impact the potassium), the samples are analyzed by coaxial high purity germanium spectrophotometers with an appropriate efficiency and energy calibration to convert peak energy, peak size and counting duration to dpm.


Pt-193

Aliquots of dissolution are spiked with stable platinum which will be used to trace the separation efficiency on a sample-by-sample basis. The platinum species are extracted from the matrix using several types of extractant (AMP to remove cesium and TEVA to separate the platinum from other interferences). Following the radiochemical separation schemes, an aliquot of the extracted platinum-containing material is transferred to a stainless-steel plate (for Pt-193 analysis). An additional aliquot is sent to the ICP-ES laboratory to determine the platinum content in the separated material, and thus the separation yield.

Pt-193 concentrations are measured using low energy photon/x-ray, thin-windowed, semi-planar high purity germanium spectrometers with an appropriate efficiency to convert peak size and counting duration to dpm. Elemental platinum carrier yields are measured by ICP-ES, and are used to correct the Pt-193 analyses for any platinum losses from the radiochemical separations. The quality of the tracing is indicated by the successful quantification of the tracer (tracer activity is greater than MDA for each individual count) as well as sufficient recovery to provide the customer-requested sensitivity. For instance, if the separation yield is low, and the Pt-193 concentration is less than the minimum detectable

activity, then the low yield could elevate the MDA to a value above the customer requested detection limit.


Nb-94

Aliquots of dissolved material are spiked with Zr-95 (which decays to Nb-95) which will be used to trace the separation efficiency on a sample-by-sample basis. The niobium species are extracted from the matrix using an anion exchange process following decontamination from interfering radionuclides. Aliquots of the niobium-containing aliquots are analyzed using a high purity germanium gamma-ray spectrophotometer with an appropriate efficiency calibration to convert peak energy, peak size and counting duration to dpm for both Nb-94 and Nb-95. Yields for Nb-95 are used to correct the radioactive niobium species’ analyses for any losses from the radiochemical separations. The Nb-94 values are yield-corrected using the Nb-95 recoveries [(dpm Nb-94/(dpm Nb-95 recovered/dpm Nb-95 added)]. The quality of the tracing is indicated by the successful quantification of the tracer (tracer activity is greater than MDA for each individual count) as well as sufficient recovery to provide the customer-requested sensitivity. For instance, if the Nb-94 concentration is less than the minimum detectable activity and the separation yield is low, then the low yield could elevate the MDA to a value above the customer requested detection limit.


Pd-107

Aliquots of dissolved material are decontaminated from interfering radionuclides using a combination of resins. Eventually, the palladium is extracted from the samples using a DMG-based extractant. The purified palladium-containing aliquots are analyzed using the ICP-MS to measure Pd-107/Pd-105 mass ratios. After accounting for the mass-107 interference from silver, the ratio for each sample is then multiplied by the Pd-105 concentration for the same sample which was obtained by simple ICP-MS analysis of dissolved material which did not undergo the radiochemical separation steps. This results in a Pd-107 result which has been traced using Pd-105 inherent to each individual sample’s matrix.

Each batch contains a method blank and ≤20 samples. Results are reported with 1-sigma uncertainty, as reported by the ICP-MS results reports. Calculations are carried out using a spreadsheet maintained in accordance with ADS-WI00023.

Zr-93

Zirconium is extracted from aliquots of dissolved material using a CMPO/TBP based extraction system. The purified ziconium-containing aliquots are analyzed using the ICP-MS

to measure Zr-93/Zr-91 mass ratios. The ratio for each sample is then multiplied by the Zr-91 concentration for the dissolved, un-extracted sample which was obtained by simple ICP-MS analysis of dissolved material. This results in a Zr-93 result which has been traced using Zr-91 inherent to each individual sample’s matrix.


Pu-242, 244

Plutonium is extracted from aliquots of dissolved material using Eichrom TEVA resin. The purified plutonium-containing aliquots are analyzed using the ICP-MS to measure Pu-242, Pu-244 and Pu-239 mass ratios. The ratios for each sample are then multiplied by the Pu-239 concentration for the same sample which was obtained by the traced radiochemical separation and analysis scheme discussed previously in the Pu-238, 239/240, 241 section. This provides Pu-242 and Pu-244 results which have been traced by virtue of the Pu-239 value determined by an independent method.


U-233, U-234, U-235, U-236

Uranium is extracted from aliquots of dissolved material using Eichrom UTEVA resin. The purified uranium-containing aliquots are analyzed using the ICP-MS to measure U-233, U-234, U-235, U-236, and U-238 mass ratios. The mass ratios for each sample are then multiplied by the concentration of the best uranium isotope option (which is matrix dependent) in the same sample which was obtained by the simple ICP-MS analysis of dissolved, un-extracted material. This results in uranium results which have been traced using uranium inherent to each individual sample’s matrix. For example, if the ICP-MS of dissolved material provides a mass concentration for U-235, then the U-233/U-235 mass ratio from the U-extract would be multiplied by the U-235 mass concentration in the dissolved, un-extracted sample to obtain a U-233 mass concentration. This would then be converted to U-233 activity concentration using the specific activity of U-233.



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Attachment 3: Data Verification Checklists

To Be Determined


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Attachment 4: Records Checklists

To Be Determined


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Attachment 5: Data Validation Procedures and Checklists

To Be Determined