Effective Date Status Final - Newtown Creeknewtowncreek.info/docs2/2 Remedial Investigation... · EFGS-SOP-054-R09 Revision: 9 Effective Date: 5/20/2013 Page 1 of 30 COMPANY CONFIDENTIAL

Document Title: Determination of Trace Metals by

ICPMS

Eurofins Document Reference: EFGS-SOP-054-R09

Revision: 9 Effective Date: 5/20/2013 Page 1 of 30

COMPANY CONFIDENTIAL. All Eurofins Frontier Global Sciences standard operating procedures contain proprietary information and are protected by Washington State Law. Proprietary information must be maintained with the strictest of confidence and must not be used or appropriated to benefit any party without prior written consent from Eurofins Frontier Global Sciences.

Eurofins Document Reference EFGS-SOP-054-R09 Revision 9

Effective Date 5/20/2013 Status Final

Historical/Local Document Number FGS-SOP-054.09

Local Document Level Level 3

Local Document Type SOP

Local Document Category NA

Prepared by Monica Garcia-Strickland

Reviewed and Approved by

Dave Wunderlich and Patrick Garcia-Strickland

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Table of Contents

1 Revision Log: ......................................................................................................................... 4 2 Reference: ............................................................................................................................. 4 3 Cross Reference: ................................................................................................................... 4 4 Purpose: ................................................................................................................................ 5 5 Scope: .................................................................................................................................... 5 6 Basic Principles: .................................................................................................................... 5 7 Reference Modifications: ....................................................................................................... 6 8 Definitions: ............................................................................................................................. 7 9 Interferences: ......................................................................................................................... 9 10 Safety Precautions, Pollution Prevention and Waste Handling: .......................................... 11 11 Personnel Training and Qualifications: ................................................................................ 13 12 Sample Collection, Preservation, and Handling: ................................................................. 14 13 Apparatus and Equipment: .................................................................................................. 14 14 Reagents and Standards: .................................................................................................... 15 15 Calibration: ........................................................................................................................... 18 16 Procedure: ........................................................................................................................... 18 17 Calculations: ........................................................................................................................ 21 18 Statistical Information/Method Performance: ....................................................................... 22 19 Quality Assurance/Quality Control: ...................................................................................... 22 20 Corrective Action ................................................................................................................. 25 21 List of Attachments .............................................................................................................. 25 Table 1: EPA 1638 Performance Based Acceptance Limits ....................................................... 27 Table 2: Example of an Analytical Sequence ............................................................................. 29 Appendix D: Example - Standard Operating Procedure Training Record .................................. 30

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Approvals:

Prepared by: Date:

Approved by: Date:

Approved by: Date:

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1 Revision Log: Revision: 09 Effective Date: This version Section Justification ChangesCover Required change Changed company name from Frontier Global Sciences to

Eurofins Frontier Global Sciences. All Formatting requirement per LOM

SOP-LAB-201 Reformatted document to new corporate specifications.

2.8, App C Required Added reference and procedures for Nexion 300X 5.4 Required Updated analyte list

2 Reference: 2.1 EPA Method 1638, January 1996.

2.2 Software Guide – ELAN6000 Inductively Coupled Plasma Mass Spectrometer Software Guide, Sciex Part Number 016629 Rev. C, Perkin-Elmer Part Number 0993-8968 Rev. F, June, 1997, Perkin Elmer Sciex, Perkin-Elmer Sciex Instruments, 71 Four Valley Drive, Concord, ON L4K 4V8.

2.3 Software Guide – ELAN 6100 Inductively Coupled Plasma Mass Spectrometer Software Guide, Sciex Part Number 017227, May, 2000, Perkin-Elmer Sciex, Perkin-Elmer Sciex Instruments, 71 Four Valley Drive, Concord, ON L4K 4V8.

2.4 Hardware Guide – ELAN 6000 Inductively Coupled Plasma Mass Spectrometer Hardware Guide, Perkin-Elmer Part Number 0993-8969, 1995, Perkin-Elmer Corporation, 761 Main Ave., Norwalk, CT 06859-0012.

2.5 Software Guide – ELAN Version 3.0, PerkinElmerSCIEX part number 1006920, 2003, PerkinElmer/MDS SCIEX Instruments.

2.6 Hardware Guide – ELAN 6100 DRC Inductively Coupled Plasma Mass Spectrometry Hardware Guide, Perkin Elmer part number WE01-7228, 2000, Perkin-Elmer SCIEX Instruments, 761 Main Avenue, Norwalk, CT 06859-0010.

2.7 Hardware Guide – NexIon 300X Inductively Coupled Plasma Mass Spectrometry Maintenance Guide, Perkin-Elmer SCIEX Instruments, 761 Main Avenue, Norwalk, CT 06859-0010.

2.8 National Environmental Laboratory Accreditation Conference, NELAC Standard September 8, 2009.

2.9 Department of Defense Quality Systems Manual for Environmental Laboratories, prepared by DoD Environmental Quality Workgroup, Final Version 4.2, October 2010.

3 Cross Reference: Document Document Title SOP FGS-003 Pipette Verification, Calibration & Maintenance SOP FGS-008 Ultra Clean Aqueous Sample Collection SOP FGS-029 Ultra-Clean Sample Filtration SOP FGS-032 Extraction of Ag, Cd, Cu, Pb, and Ni from Water by Co-APDC Coprecipitation SOP FGS-052 Total Recoverable Metals Digestion by Oven Heating SOP-FGS-065 Cleaning of Sampling Equipment and Bottles for Analysis of Trace Metals SOP FGS-094, App F Standard Operating Procedure Training Record

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Document Document Title SOP FGS-099 Waste Disposal Procedure for Client Sample Waste SOP FGS-109 Reductive Precipitation SOP FGS-111 HF/HNO3/HCl Bomb Digestion SOP FGS-126 Health and Safety Evaluation and Auditing SOP FGS-141 Total Recoverable Metals Using Nitric Acid Oven Bomb Digestion SOP FGS-146 Total Recoverable Metals in Solids via Microwave Oven Digestion

4 Purpose: 4.1 This SOP describes the method for measuring metals at trace concentrations in water

and diluted digested solids by ICP-MS.

5 Scope: 5.1 This method is used for the determination of dissolved, total, and total recoverable

elements in waters and dilute digested solids using inductively coupled plasma - mass spectrometry (ICP-MS). It is intended for use in analyzing low-total dissolved solids (TDS) samples, or samples diluted sufficiently to produce a low-TDS aliquot (ideally, less than 500 mg/L TDS, but no higher than 1,000 mg/L TDS). The calibration range for this method can be from 0.004 to 20,000µg/L, depending on the analyte of interest. Method Detection Limit (MDL) studies for all analytes applicable to this method are kept on file in the QA Office.

5.2 This method should be followed to ensure the accuracy and reproducibility of the sample results generated by all ICP-MS analysts at EFGS. Only fully trained, experienced ICP-MS analysts, or those under the direct supervision of an experienced ICP-MS analyst, shall be allowed to use this method. Qualified ICP-MS analysts must be thoroughly trained in the interpretation of spectral and matrix interferences, procedures for their correction, as well as ultra-clean sample handling.

5.3 This method shall be followed to analyze for a very large list of analytes; however, at the time of the last revision of this SOP, this method has only been fully validated for the analysis of the following metals: Ag, Al, As, B, Ba, Be, Ca, Cd, Co, Cr, Cu, Fe, Hg, K, Mg, Mn, Mo, Na, Ni, P, Pb, Sb, Se, Sn, Sr, Ti, Tl, V, and Zn. Research-level analyses that generally follow this method shall also be performed for other elements, e.g., rare earth elements, uranium, thorium, phosphorus, lithium, etc.

6 Basic Principles: 6.1 An aliquot of a well-mixed, homogeneous sample is prepared for analysis. For

determination of dissolved elements, the sample must be filtered either in the field or in the laboratory through a filter unit according to ultra-clean sample handling techniques (SOP FGS-029, “Ultra-Clean Sample Filtration”), and then preserved with acid. For the determination of total/total recoverable elements in waters, the samples are prepared by solubilizing the analytes through heating with acid, or extracting the analytes from the sample matrix. Acidification will not be performed only at the request of the project managers for special projects.

6.2 Solid samples shall be analyzed by this method after the appropriate digestion steps. All preparation procedures are detailed in separate SOPs. PUBLIC


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6.3 Prepared samples are introduced into a radio frequency (RF) plasma where energy-transfer processes cause desolvation, atomization, and ionization. The ions are extracted from the plasma through a differentially-pumped vacuum interface and separated based on their mass-to-charge ratio (m/z) by a mass spectrometer. A solid-state detector detects ions transmitted through the mass analyzer and the resulting current is processed by a data handling system.

7 Reference Modifications: 7.1 Comparison of EFGS 054.09 and EPA 1638:

EFGS 054-09 Method 1638 Sample Preparation

Dissolved aqueous samples are preserved with 1% nitric acid. Total recoverable aqueous samples are prepared with 1% nitric acid or 1% nitric acid and 0.5% hydrochloric acid and digested in closed containers, in an oven at 85°C.

Dissolved aqueous samples are preserved with 1% nitric acid. Total recoverable aqueous samples are prepared with 1% nitric acid and 0.5% hydrochloric acid and digested in closed containers, in an oven at 85°C.

Matrices Can be used for various matrices: waters, dilute digested solids, biological tissues, and geological samples.

For aqueous samples only.

Prep./Analysis Blanks

Continuing Calibration Blanks and Method Blanks must be < PQL.**

Continuing Calibration Blanks and Method Blanks must be < MDL.

Field/Equip. Blanks

Recommended Recommended

ICV/CCV ICV (SDS) immediately after calibration CCVs (SDS) every 10 samples

ICV (PDS) immediately after calibration CCVs (PDS) every 10 samples

OPR (LCS) LCS (PDS or SDS) per 10 (1 OPR (PDS or SDS) per 10)

1 OPR (SDS) per 10

MD None required but can be added at the request of the project manager or client.

None

MS/MSD MS/MSD pair per 10, spiked at the mid-level of the calibration range. An AS/ASD is performed after each MS/MSD set.

MS/MSD pair per 10. Usually in mid-level calibration range but must be at least 1-5 times the PQL.

Elements run by method

Ag, Al, As, B, Ba, Be, Ca, Cd, Co, Cr, Cu, Fe, K, Mg, Mn, Mo, Na, Ni, Pb, Sb, Se, Sn, Sr, Ti, Tl, V, and Zn.

Ag, Cd, Cu, Pb, Ni, Sb, Se, Tl, and Zn.

Internal Standards

Internal standardization typically consists of Sc, Ge*, In, Pt, Ga, Rh. Lu, Li6, Te, Tb, Bi and Y. Recovery must be 60-125%. *See Section 9.7 regarding Germanium use.

Internal standardization utilizes at least three of the following analytes: Bi, Y, In, Sc and Tb. Recovery must be 60-125%.

EFGS 054-09 Method 1638

Daily Tuning Solution

Be, Mg, Cu, Rh, Ce, Pb or Be, Mg, Cu, Rh, Ce, Pb

Be, Mg, Co, In, Pb at 100 µg/L PUBLIC


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Instrument Calibration

Calibration is based on a minimum 5-point calibration curve with a correlation coefficient (R) > 0.995 using a Linear Thru Zero calibration. Calibration Blank is used in Calibration as stated in 1638 section 18.4.

Calibration is based on a 3-point calibration with a RF of <20%.

Control Limits

ICV/CCV/LCS/LCSD/MS/MSD based on 1638 element-specific acceptance criteria defined in Table 1. Elements outside of the 1638 list, acceptance criteria based on 200.8 control limits.

Element-specific acceptance criteria defined in EPA 1638, Table 2.

8 Definitions: 8.1 Analytical Run – the continuous analysis of one or more batches. An analytical run

requires a calibration curve, ICV, ICB, and CCV/CCB every ten samples. An analytical run must conclude with a CCV/CCB.

8.2 Batch – comprising no more than 20 samples unless otherwise specified. A batch must contain one Preparation Blank, MS and MSD, and a LCS (OPR) per 10 samples.

8.3 Calibration Standards (CAL) – a series of standards that will be used to calibrate the instrument, made from a PDS. A calibration blank plus at least five different concentrations are required, beginning with one at or below the PQL concentration.

8.4 Certified Reference Material (CRM) – a standard of known composition that is certified by a recognized authority and representing a sample matrix. It is used to verify the accuracy of a method.

8.5 Control Limit (CL) – the limit of the range of acceptability for the quality control samples

8.6 Dissolved analyte – the concentration of analyte in water after passing through a membrane filter assembly prior to sample acidification .

8.7 Filtration Blank (FB) - an aliquot of reagent water that is treated exactly as a sample at the time of filtration. The Filtration Blank is used to determine if method analytes or other interferences are present in the filtration paper and/or apparatus. The filter blank is added to client workorder and is treated as a discreet sample.

8.8 Initial Calibration Verification (ICV) – a standard used to check initial calibration and is prepared from a SDS. This standard is run at mid-level concentration and verifies instrument calibration. It is always followed by an ICB.

8.9 Initial and Continuing Calibration Blank (ICB and CCB) for evaluation of instrument drift, sensitivity, and contamination. ICB must be analyzed directly after the ICV, and the CCBs every 10 samples immediately after CCVs. ICB and CCBs must individually be less than one-half of the Practical Quantitation Limit.

8.10 Internal Standard – an element added at the same concentration to all samples and standards in an analytical batch, and used to correct the relative responses of other method analytes in the sample to account for instrument drift. The internal standard must be an element that is not a sample component. PUBLIC


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8.11 Laboratory Control Sample (LCS) – the LCS is processed and analyzed exactly like a sample, and its purpose is to determine whether method performance is within acceptable control limits. The LCS can be a reference material, especially in the case of a solid reference material (e.g., a sediment, fish, etc.), or a reagent water to which known quantities of the method analytes are spiked (Also called an Ongoing Precision Recovery sample (OPR)). A PDS or an SDS is used to spike this solution.

8.12 Linear Dynamic Range (LDR) – the concentration range over which the analytical curve remains linear.

8.13 Method Blank or Preparation Blank – an aliquot of reagent water that is treated exactly as a sample at the time of preparation, including exposure to all lab ware, equipment, reagents, and acids that are used with other samples. The Method Blank is used to determine if method analytes or other interferences are present in the laboratory environment, the reagents, or apparatus.

8.14 Method Detection Limit (MDL) – the minimum concentration of an analyte that can be identified, measured, and reported with 99% confidence that the analyte concentration is greater than zero as defined in 40 CFR Part 136, Appendix B.

8.15 Method Duplicate (MD) – a second separate sample, taken from the same source sample and analyzed in the laboratory separately at the request of the client. A MSD may be used as a duplicate.

8.16 Matrix Spike (MS) and Matrix Spike Duplicate (MSD) – designated sample (representative of the batch) is spiked with a known concentration of analytes. In the absence of such information, mid-concentration on the calibration curve is desirable. The PDS or an SDS is used to spike the matrix samples.

8.17 May: This action, activity, or procedural step is optional.

8.18 May Not: This action, activity, or procedural step is prohibited.

8.19 Ongoing Precision Recovery (OPR) - A method blank spiked with known quantities of analytes from a secondary source at 30 ng/L, or a known certified reference material. Its purpose is to assure that the results produced by the laboratory remain within the limits specified in the referenced methods for precision and accuracy. See LCS.

8.20 Practical Quantitation Limit (PQL) – minimum concentration necessary for quantitative detection by the given method, often described as being 3 -10x higher than MDL. EFGS defines as the minimum concentration necessary for obtaining 70-130%, with the exception of some elements as well as non-routine analytes at a 50-150%.

8.21 Primary Dilution Standard (PDS) – a standard that is used to make a series of calibration standards for this method; can also be used for IDOC/CDOC.

8.22 Quality control sample (QCS)—A sample containing all or a subset of the analytes at known concentrations. The QCS is obtained from a source external to the laboratory or is prepared from a source of standards different from the source of calibration standards. It is used to check laboratory performance with test materials prepared external to the normal preparation process. This sample is analyzed within a batch as an LCS and is performed on a quarterly basis. PUBLIC


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8.23 Stock Standard Solution (SSS) – a standard of analyte that is purchased from a certified source for the preparation of working standards.

8.24 Secondary Dilution Standard (SDS) – a sample of standard from an alternate SSS, used to prepare the ICV, CCV, LCS, LCSD, OPR, MS, and MSD standards, and can also be used for IDOC/CDOC.

8.25 Shall: This action, activity, or procedure is required.

8.26 Should: This action, activity, or procedure is suggested, but not required.

8.27 Total analyte – the concentration of analyte in water after digestion in an HNO3/HF mix.

8.28 Total recoverable analyte – the concentration of analyte in water after digestion in an HNO3 or HNO3/HCl.

8.29 .dac – Optimization filename extension.

8.30 .mth – method file name

8.31 .rop– report file name extension

8.32 .tun - Tuning filename extension

8.33 .swz – smart tune file extension

8.34 RF–Response Factor, percentage units.

9 Interferences: 9.1 Contamination

9.1.1 Sampling

9.1.1.1 Contamination of the aqueous samples during the sample collection is a great risk, and it is imperative that extreme care be taken to avoid this. EFGS’s SOP on sample collection and handling (EFGS-008) must be consulted to ensure minimum contamination during sampling of aqueous samples.

9.1.1.2 If samples are collected in bottles other than those provided by EFGS, bottle blanks should be submitted by the client to test for background contamination. If the samples are preserved in the field, bottle blanks should also be preserved to test for metals contamination in the preservation acid.

9.1.1.3 If samples are collected using any equipment such as tubing, pumps, or filters, that equipment and apparatus should be tested for trace metal contamination through the analysis of equipment blanks. It is suggested that the client analyze trip blanks to assess contamination occurring during the shipment of bottles and equipment.

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9.1.2.1 All new vendor labware (including sample bottles, pipette tips, digestion bottles, extraction apparatus, and ICP-MS autosampler tubes) must be tested for trace metals, and, if necessary, acid-cleaned following established protocols (SOP EFGS-065, “Cleaning of Sampling Equipment and Bottles for Analysis of Trace Metals”).

9.1.2.2 All reagents used are tested for the presence of trace metals.

9.1.2.3 The laboratory must be kept free from all sources of contamination.

9.2 Interferences

9.2.1 Isobaric Elemental Interference

9.2.1.1 Isotopes of different elements that form singly or doubly charged ions of the same m/z and cannot be resolved by the mass spectrometer cause this type of interference.

9.2.1.2 Wherever possible, efforts must be made to choose an isotope that is un-interfered.

9.2.2 Polyatomic Isobaric Interference

9.2.2.1 These types of interferences are caused by ions consisting of more than one atom which have the same m/z as the isotope of interest, and which cannot be resolved by the mass spectrometer.

9.2.2.2 Most of the common polyatomic interferences have been identified, and when they cannot be avoided by selection of an alternative mass, appropriate corrections must be made to the data.

9.2.3 Abundance Sensitivity: The potential for “wing overlap” interference exists when small m/z peaks are being measured adjacent to large ones.

9.2.4 Physical Interference

9.2.4.1 Physical interference results in differences between instrument responses for the sample and the calibration standards.

9.2.4.2 The use of internal standards effectively reduces the effects from most physical interferences.

9.2.5 Carryover

9.2.5.1 Memory effects on the probe, nebulizer, mixing block, cones, torch, spray chamber, and autosampler are minimized by flushing the system.

9.2.5.2 If carryover interference is suspected, the sample must be reanalyzed at an alternate dilution after a rinse, under the same analytical conditions of the analytical run or after the analysis of an acceptable blank (less than half the PQL). Each rinse is to be treated as a discreet injection.

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10 Safety Precautions, Pollution Prevention and Waste Handling: 10.1 Personnel will don appropriate laboratory attire according to the Chemical Hygiene

Plan. This includes, but is not limited to, laboratory coat, safety goggles and nitrile gloves under clean gloves.

10.2 The toxicity or carcinogenicity of reagents used in this method has not been fully established. Each chemical should be regarded as a potential health hazard and exposure to these compounds should be as low as reasonably achievable. Chemists should refer to the MSDS (Material Safety Data Sheets) for each chemical they are working with.

10.3 All personnel handling environmental samples known to contain or to have been in contact with human waste should be immunized against known disease-causative agents. Eurofins Frontier will reimburse the expense of Hepatitis A and B immunizations for any laboratory staff member who desires this protection.

10.4 Hydrofluoric Acid (HF) is used for many purposes including mineral digestion, surface cleaning, etching, and biological staining. HF’s unique properties make it significantly more hazardous than many of the other acids used on site.

10.4.1 Always wear HF apron, face shield, tyvex sleeves and double gloves when working with HF.

10.4.2 Check PPE after you have finished working for broken PPE.

10.4.3 For spills, briefly spray with Boric acid and then neutralize. Make sure the acids have fully reacted before disposing of the neutralized waste.

10.4.4 If HF is spill on you rinse for at least 15 minutes and then apply Calcium Gluconate.

10.4.5 Ventilation

10.4.5.1 HF should be used with adequate ventilation to minimize inhalation of vapor. Concentrations greater than 5% should always be handled inside a properly functioning chemical fume hood. The chemical fume hood needs to have a current inspection sticker (see FGS-126). Notify EH&S if there are any issues with the hood.

10.4.6 Eye Protection

10.4.6.1 Always use chemical splash goggles together with a face shield when handling concentrated HF. Due to HF’s highly corrosive nature, safety glasses with side shields do not provide adequate eye protection.

10.4.7 Body Protection

10.4.7.1 Wear laboratory coat with a chemical splash apron made out of natural rubber, neoprene, or viton. Never wear short pants or open-toed shoes when handling HF or other corrosive chemicals.

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10.4.8.1 Typically, medium or heavyweight viton, nitrile, or natural rubber gloves are worn when working with HF. Always consult the manufacturer’s glove selection guide when selecting a glove for HF. If you have any questions about which glove to choose, contact EH&S. A second pair of nitrile exam gloves should be worn under the gloves for protection against leaks. Gloves that have not been contaminated with HF may be disposed of in the common trash. If gloves become contaminated with HF, remove them immediately, thoroughly wash your hands, and check your hands for any sign of contamination. Contact the EH&S Officer if your skin has been exposed to any direct HF.

10.5 Nitric acid (HNO3): Corrosive. Strong oxidizer. Contact with other material may cause a fire. Causes eye and skin burns. May cause severe respiratory tract irritation with possible burns. May cause severe digestive tract irritation with possible burns.

10.5.1 Eye Contact

10.5.1.1 Causes severe eye burns. Direct contact with liquid may cause blindness or permanent eye damage.

10.5.2 Skin Contact

10.5.2.1 Causes skin burns. May cause deep, penetrating ulcers of the skin. Concentrated nitric acid dyes human skin yellow on contact.

10.5.3 Inhalation

10.5.3.1 Effects may be delayed. Causes chemical burns to the respiratory tract. Inhalation may be fatal as a result of spasm, inflammation, edema of the larynx and bronchi, chemical pneumonitis and pulmonary edema. Aspiration may lead to pulmonary edema. May cause systemic effects. May cause acute pulmonary edema, asphyxia, chemical pneumonitis, and upper airway obstruction caused by edema. Depending on the conditions, the vapor or fumes of nitric acid may actually be a mixture of nitric acid and various oxides of nitrogen. The composition may vary with temperature, humidity, and contact with other organic materials.

10.5.4 Ingestion

10.5.4.1 May cause severe and permanent damage to the digestive tract. Causes gastrointestinal tract burns. May cause perforation of the digestive tract. May cause systemic effects.

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10.5.5.1 Exposure to high concentrations of nitric acid vapor may cause pneuomonitis and pulmonary edema which may be fatal. Symptoms may or may not be delayed. Continued exposure to the vapor & mist of nitric acid may result in a chronic bronchitis, & more severe exposure results in a chemical pneumonitis. The vapor & mists of nitric acid may erode the teeth, particularly affecting the canines & incisors.

10.6 See Eurofins Frontier Global Sciences Chemical Hygiene Plan (CHP) for general information regarding employee safety, waste management, and pollution prevention.

10.7 Pollution prevention information can be found in the current Eurofins Frontier Global Sciences Chemical Hygiene Plan (CHP), which details and tracks various waste streams and disposal procedures.

10.8 All laboratory waste is accumulated, managed, and disposed of in accordance with all federal, state, and local laws and regulations. Any waste generated by this procedure should be disposed of according to SOP FGS-099 “Waste Disposal Procedure for Client Sample Waste,” which provides instruction on dealing with laboratory and client waste.

11 Personnel Training and Qualifications: 11.1 An analyst must perform an initial demonstration of capability (IDOC) that includes four

replicates of a secondary source before being qualified to analyze samples without supervision. Continuing DOC will be maintained and monitored via performance on CRMs and other QC samples, as well as obtaining acceptable results on proficiency testing exercises.

11.2 Training is documented by the employee and supervisor, and is kept on file in the QA Office. The employee must read, understand, and by signing the training document, agree to perform the procedures as stated in all Standard Operating Procedures (SOPs) related to this method.

11.3 Reading of the SOP must be documented on the correct form such as “Standard Operating Procedure Training Record,” Appendix F in FGS-094, the last page of this SOP, Appendix D “Standard Operating Procedure Training Record” or a similar document.”

11.4 All employees must also, on a yearly basis, read the Quality Manual (QM), and complete the yearly Ethics training.

11.5 All training documents including IDOCs, CDOCs, SOP reading, Initial QA orientation, and Ethics training are stored by the Quality Assurance Manager in the employees training file for ten years after the employee is no longer working for Eurofins Frontier Global Sciences.

11.6 Chemical Safety Training, Compressed Gas Training, Chemical Hygiene Plan documentation, and Shipping of Hazardous goods, are stored by the Health and Safety Officer for ten years after the employee is no longer working for Eurofins Frontier Global Sciences. PUBLIC


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12 Sample Collection, Preservation, and Handling: 12.1 All aqueous samples must be collected according to the protocols described in SOP

FGS-008, “Ultra Clean Aqueous Sample Collection” (equivalent to EPA 1669). Solid samples must be collected in polyethylene or fluoropolymer jars.

12.2 Samples for dissolved metals determination must be filtered through a 0.45μm or a 0.2μm pre-cleaned disposable filter unit. Eurofins Frontier recommends that the samples shall be filtered at the laboratory within 48-hours of sample collection and prior to preservation, if the samples are not filtered in the field as per EPA requirements. Filtering procedures are described in SOP FGS-029, “Ultra-Clean Sample Filtration.”

12.3 Aqueous samples must be preserved to an acidity of pH 2 or less, see Section 12.8 for non-preserved samples. Solid samples require no preservation; however, refrigeration at -14-18°C is required for soil and/or biological tissue samples. Other solid samples may be stored at room temperature. In general, one of the following preservation schemes is followed for aqueous samples

12.3.1 Preserve with HNO3 for Cobalt-APDC (FGS 032, “Extraction of Ag, Cd, Cu, Pb, and Ni from Water by Extraction with Co-APDC”) and Reductive Co-precipitation (FGS 109, “Reductive Precipitation”) extraction.

12.3.2 Preserve with HNO3 or HNO3 with HCl for total recoverable metals digestions (EFGS-052 “Total Recoverable Metals Digestion by Oven Heating”).

12.3.3 For dissolved metals determinations, preserve filtered sample with same acid as ‘total’ partner in either Specifics can be found in EFGS-052.

12.4 When preserving samples, the pipette tip must be pre-cleaned with HNO3 prior to the pipetting of acids.

12.5 Preserved samples must be stored for a minimum of 48 hours at 0-4° Celsius before preparation and/or analysis to completely dissolve the metals adsorbed on the bottle walls for EPA 1638.

12.6 Preserved samples must be stored for a minimum of 16 hours at room temperature before preparation and/or analysis to completely dissolve the metals adsorbed on the bottle walls for EPA 200.8. Preserved samples must be must be stored in a secure area of the laboratory with the COC.

12.7 Clients requesting acid soluble samples must be preserved for a minimum of 16 hours and filtered through a pre-cleaned filter and labeled acid soluble.

12.8 Preservation will not be performed only at the request of the project managers for special projects. Samples that have not been preserved will be stored 0-4° Celsius until digestion/analysis and must be stored in a secure area of the laboratory with the COC. Refer to FGS 052, “Total Recoverable Metals Digestion by Oven Heating” for digestion modification.

13 Apparatus and Equipment: 13.1 LIMS PUBLIC


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13.2 Facility: A clean laboratory environment is crucial to the success of producing good data for ultra-low levels of trace metals.

13.3 Instrumentation: ICP-MS equipped with autosampler.

13.4 Other Apparatus and Materials:

13.4.1 Analytical balance capable of measuring to 0.1mg

13.4.2 Convection oven capable of maintaining 85°C

13.4.3 pH paper

13.4.4 Sample bottles – can be constructed of fluoropolymer (FEP, PTFE), polyethylene (HDPE, LDPE), polycarbonate (PC), polypropylene (PP), or glass. All bottles must be cleaned according to SOP FGS-065, “Cleaning of Sampling Equipment and Bottles for Analysis of Trace Metals.” Glass must not be used with HF, or for analyses requiring measurement of Si, B, Al, alkaline, or alkaline-earth metals.

13.4.5 Clean-room gloves

13.4.6 Autosampler vials, 15mL and 50mL

13.4.7 Plastic zip-type bags, various sizes

13.4.8 Volumetric flasks, Class-A (cleaned according to SOP FGS-065, “Cleaning of Sampling Equipment and Bottles for Analysis of Trace Metals”), Glass volumetric flasks can only be used for preparation and not storage.

13.4.9 Assorted calibrated pipettes (calibrated according to SOPs FGS-003, “Pipette Verification, Calibration & Maintenance” and FGS-155, “Calibration of Volumetric Dispensers”).

13.4.10 Solution storage bottles, 125mL to 2000mL

13.4.11 Disposable filter units, 150mL to 500mL

13.4.12 Vacuum pump and tubing connections for filtering

14 Reagents and Standards: Reagents may contain elemental impurities that could affect the integrity of analytical data. Because of the high sensitivity of ICP-MS, high-purity reagents must be used. (The highest grade does not necessarily mean a reagent has the lowest trace element concentration.) Each reagent lot must be tested for the metals of interest.

14.1 Reagent Water: 18-MΩ ultra pure deionized water starting from a pre-purified (distilled, R.O., etc.) source is used.

14.2 Nitric Acid (HNO3): Concentrated low trace-metal grade nitric acid. This reagent shall be entered into LIMS and the expiration date is set to 3 years after receipt date.

14.3 Hydrofluoric Acid, HF: Concentrated low trace-metals grade hydrofluoric acid (previously analyzed and tested low). This reagent shall be entered into LIMS and the expiration date is set to 3 years after receipt date.

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14.4 Stock Standard Solutions (SSS) – shall be purchased from a reputable commercial source.

14.4.1 It is recommended to have a single element standard for each of the commonly determined metals as well as any metals that shall be used as internal standards or interference check samples.

14.4.2 For calibration verification, a second source is required for all elements being determined. (SDS, see section 8.30).

14.5 Multi-element stock standard solutions – care must be taken in the preparation of multi-element stock standards so that the elements are compatible and stable. Examples of current multi-element standards are provided here, though other multi-element standards shall be prepared and used for analysis while still being compliant with this SOP. Likewise, the concentrations of these named standards shall change based on results of periodic MDL studies. All standard preparation requires appropriate and comprehensive documentation.

14.5.1 Dilute single element stock standards appropriately to make the following multi-element standards. These standards are stable for at least one year.

14.5.2 “MLA” Standard: This solution is stable for one year or at the manufacturer’s expiration.

14.5.3 “MLB” Standard: This solution is stable for one year or at the manufacturer’s expiration.

14.5.4 “SM-1411-002” table below lists elements.

Element Sb, Be, Tl, Ag Cd Pb Mo, Sr, Co Cr, As, Se, V, Ti, Mn Ni, Cu Ba Zn Ba Fe Al B Na, Mg, Ca, K, Hardness by calculation

14.5.5 Additional elements (such as Sn, Li, Th, U, etc.) shall be prepared as a separate standard, or added to the standards, if care is taken to avoid incompatibility issues and internal standard conflicts. PUBLIC


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14.6 Internal standard solution – dilute stock standard solutions of the elements in table below.

6Li Sc Ga Ge Rh In Lu Pt Bi Y Te Tb

This solution is stable at the earliest expiration of the standards used. The date and initials of the analyst who prepares this standard must be entered into Laboratory Management System (LIMS) and a label printed. The label must have LIMS ID, preparation date, prep by and expiration date. If a large volume is prepared, >2L, analyst must indicate the number of containers made. All containers are combined to make a uniform solution.

14.7 Calibration standards – Fresh calibration standards must be prepared as needed. The standards used, date and analyst’s initials must be recorded in the ICP-MS calibration logbook each time the curve is prepared.

14.7.1 Dilute the multi-element stock standard solutions in autosampler vials with HNO3. Curve matrix is determined by type of sample matrix, as follows. As per Trace Metals Laboratory Manager or a Project Manager request, an alternate curve can be used to achieve lower detection limits or extending the linear range.

14.7.1.1 Only use calibrated mechanical pipettes when preparing the calibration standards.

14.8 ICV – Initial calibration verification solution is made up from standards that are from a secondary source (SDS) to verify the validity of the calibration curve and must be analyzed immediately following the calibration curve. The ICV used shall vary depending on the analytes being measured, and is left to the discretion of the analyst.

14.9 ‘”Daily”’ Tuning solution.

14.9.1 Dilute stock standard solutions of at least Be, Mg, Cu, Rh, Ce, Ba and Pb - or -

14.9.2 Dilute stock standard solutions of at least Be, Mg, Cu, Rh, Ce, Ba, and Pb.

14.10 Dual Detector Calibration solution – dilute stock standard solutions of all elements of interest (including internal standards) to with HNO3K and Si.

14.11 Certified reference materials of various waters (e.g., river water, seawater, estuarine water, etc)

14.12 Quality control sample (QCS) — The QCS must be prepared from a source different from that used to produce the calibration standards. The calibration standards and PUBLIC


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acceptable instrument performance must be verified with the preparation and analyses of a QCS on quarterly basis.

15 Calibration: 15.1 After instrument optimization, the calibration standards described in 14.7 are analyzed.

15.2 Calibration is based on a minimum 5-point calibration curve with a correlation coefficient (R) > 0.995.

15.3 The first calibration standard shall be at or below the PQL.

16 Procedure: 16.1 Sample Preparation:

16.1.1 For the determination of total and total recoverable analytes, there are several different preparation procedures to choose from. The decision of which method to use is based on the client’s needs and requests, the required MDLs, the matrix of the sample, and how the data will be used.

16.1.1.1 Refer to SOP FGS-052 (Total Recoverable Metals Digestion by Oven Heating) for procedures on digesting fresh waters with metals levels above ambient levels, sea or wastewaters with high levels of metals (amenable to dilution).

16.1.1.2 Refer to SOP FGS-032 (Extraction of Ag, Cd, Cu, Pb, and Ni from Water by Co-APDC Coprecipitation) for procedures for chelating metals from samples with high matrix constituents (i.e. seawater or mining effluent), or from fresh waters if very low detection limits are required.

16.1.1.3 Refer to SOP FGS-058 (Total Recoverable Metals Digestion for Solid, Animal or Plant Materials) for applicable procedures.

16.1.1.4 Refer to SOP FGS-111 (HF/HNO3/HCl Bomb Digestion of Sediments, Soils, Rocks, and Bayer Process Solids and Slurries for Mercury, followed by Repeated HNO3 Evaporation for other Metals) for applicable procedures.

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16.1.1.5 Refer to SOP FGS-109 (Reductive Precipitation) for applicable procedures.

16.1.1.6 Refer to SOP FGS-084 (Oven Aqua Regia Bomb) for applicable procedures.

16.1.1.7 Refer to SOP FGS-141 (Oven Nitric Bomb) for applicable procedures.

16.1.1.8 Refer to SOP EFGS-146 (Total Recoverable Metals in Solids via Microwave Digestion) for applicable procedures.

16.1.1.9 Refer to SOP EFGS-149 (Total recoverable metals in aqueous ceuticals by oven heating) for applicable procedures.

16.1.1.10 When the general metal concentrations of a sample are unknown, it is suggested the samples be diluted or analyzed by “Total Quant” before analyzing undiluted. This protects the cones and the detector.

16.1.2 For determination of dissolved elements, samples must be acidified, following filtration. Pour filtered preserved sample into an autosampler tube. If the samples are suspected to be high in metals or dissolved solids, they must be diluted to achieve an approximate TDS level in the diluted sample of 500-1000mg/L.

16.2 Sample Analysis

16.2.1 Start-up: Reboot on a daily basis to ensure all updates are installed properly. Turn on the computer and monitor and start up the software.

16.2.2 Check the chiller and the argon supply to be sure both are at operating levels.

16.2.3 Check the condition of the sample introduction system. Refer to the maintenance section for more details if any item is in need of cleaning or replacement.

16.2.4 Check sampler and skimmer cones. Clean or replace as needed.

16.2.5 Check the plasma torch.

16.2.6 Inspect the RF load coil.

16.2.7 Replace sample and rinse pump tubing. Waste tubing shall be replaced as needed.

16.2.8 After placing the pump tubing correctly on the pump, replace the tubing clamps for each channel and swing the cam levers over to apply tension to the clamps. Turn on the peristaltic pump.

16.2.9 Check that the sample, reagent, pump, and drain tubing are in good condition. Check the level of the sample waste container, if full, neutralize and dispose.

16.2.10 Lower the autosampler probe into the rinse vessel.

16.2.11 Document vacuum pressure and ignite plasma. PUBLIC


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16.2.12 Lower the autosampler probe into the rinse vessel.

16.2.13 Optimize X-Y Adjustment

16.2.14 Optimize instrument signal

16.2.14.1 Instrument Performance Check (“Daily”)

16.2.14.1.1 Review the results of the daily in the Reports window. Minimum performance specifications are listed on page 3-14 of the Software Guide.

16.2.14.1.2 If the daily is not satisfactory, manually adjust the nebulizer flow and perform a Tune analysis. If the Daily is still not satisfactory, a full optimization may be necessary only after it has been determined that replacing and cleaning parts does not improve sensitivity. This may or may not solve the problem. If after a full optimization the Daily is still not satisfactory, call a service engineer.

16.2.15 Tune the Instrument. The tuning controls are used to perform either of two operations:

16.2.15.1.1 A mass calibration that is used to adjust the instrument’s electronics to assure the accuracy of the mass spectrometer.

16.2.15.1.2 A resolution check/adjustment is done to assure that the resolution at each mass of interest in within the defined range of units.

16.2.15.1.3 Full Optimization: A full optimization must be performed when the status of the instrument is completely unknown, after a major subsystem has been serviced, or when other optimizations do not produce a satisfactory Daily. A full optimization must only be performed after the other optimizations listed above. The full optimization procedures optimize the detector.

16.2.16 The instrument is ready for analyzing samples. The following provides some general guidance on the subject:

16.2.16.1 Define the desired Method. It is useful to start with an all-encompassing method, and delete or edit to suit the needs of that day’s run. Save the method under a file name corresponding to the date (example, Year Month Day and method number i.e. -130511-1. Check to see that the name of the report file the data will be saved to (in the Reports page in the dataset folder) also corresponds to the Year Month Day and method number.

16.2.16.2 All blanks, standards, and samples must have internal standard solution added to them at the same ratio. This is achieved by direct addition of the internal standard solution via the peristaltic pump.

16.2.16.3 Before any analysis is initiated, the instrument must be allowed to rinse out any analytes from the system that may be temporarily retained during

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the optimization step. Check for a stable base line and then proceed with the calibration.

16.2.16.4 When setting up an analytical run, the following guidelines must be observed:

16.2.16.4.1 The ICV standard must always immediately follow the calibration curve. In addition, if EPA Method 6020 is performed a low level ICV (LLICV) solution is also analyzed.

16.2.16.4.2 The initial calibration blank (ICB) must be run immediately after the ICV as an indication of analyte carry-over.

16.2.16.4.3 A continuing calibration verification (CCV) sample shall be the same solution as the ICV solution, and represent the mid-range of the calibration curve. It must be analyzed every 10 samples, and must be run at the conclusion of analysis. In addition, if EPA Method 6020 is performed a low level CCV (LLCCV) solution is also analyzed every at the end of analysis.

16.2.16.4.4 A continuing calibration blank (CCB) must be analyzed after each CCV to monitor for carry-over.

16.2.16.4.5 The start of a preparation batch all preparation blank(s) and LCS/LCSD pairs or OPR must be analyzed prior to running samples. Note this is for batches that have not been analyzed. Samples requesting reanalysis with passing QC need only analyze ICV/ICB, samples requested for analysis and CCV/CCB pairs per 10 samples.

16.2.16.4.6 Volume permitting an analytical spiked sample (AS/ASD) should be analyzed. Analytical spikes, wherever appropriate and/or possible, should be spiked at approximately mid-level of the calibration.

16.2.16.5 Total Quant: A Total Quant scan is a way of screening a sample to determine the approximate concentrations of many elements very quickly. To perform a total quant, calibrate on only a blank and a high level standard, then analyze the samples without the addition of internal standards. Refer to the Software Guide for more information on this subject.

16.2.17 Shutdown: When all analyses are complete, flush the system with reagent water for at least five minutes, followed by flushing with air for at least five minutes, and extinguish the plasma. Please refer to Appendix A-C and the Software Guide for additional information.

17 Calculations: 17.1 Instrument concentrations are calculated by the software.

17.2 Instrument concentrations are imported into a Laboratory information management system and are calculated as follow for a final concentration of ppb.

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Instrumental Value (µg/L) * F.V. (mL) *

D.F. I.V. or Mass (mL or g)

17.3 The values for the calibration standards are recalculated against the newly created calibration curve. The solution is not re-analyzed.

17.4 The samples are not blank corrected.

17.5 Hardness is calculated from separate determinations of calcium and magnesium, according to Standard Method 2340B. Hardness (mg equiv. CaCO3/L) = 2.497 [Ca, mg/L] + 4.118 [Mg, mg/L]:

18 Statistical Information/Method Performance: 18.1 The Method Detection Limit (MDL) is determined according to 40 CFR Part 136 Section

B. Ten replicates (9 degrees of freedom) spiked 3-10 times the expected MDL are run. The standard deviation (s) is taken from the resulting data and the MDL is calculated as follows: MDL=2.821*s. This value should not be interpreted as the method reporting limit.

18.2 The Practical Quantitation Limit (PQL) is the reporting limit for this method and is included as part of the calibration (2003 NELAC regulation 5.5.5.2.2.1.h.3). The PQL is determined by running ten replicate samples with a concentration that will produce a recovery of 70-130% for most analytes, but the recovery requirements are analyte dependent. The PQL is referred to as the Method Reporting Limit (MRL) in LIMS.

18.3 Current LODs and PQLs are stored at: General and Admin\Quality Assurance\MDLs & PQLs.

19 Quality Assurance/Quality Control: NOTE: The quality control criteria specified in this SOP are consistent with EPA Method 1638, which, at the time of this writing, is not a promulgated method, though widely accepted.

For projects requiring QC criteria other than those specified herein, please refer to the relevant method and clearly document the method and criteria being used in the appropriate logbook and in the dataset. Use of any QC criteria other than the following requires an approval of the Trace Metals Laboratory Manager, Project Manager, and QA Manager. Alternate QC criteria must be recorded in the QA Office as a special project.

19.1 Preventative maintenance – the user shall refer to the Hardware Guide, which details extensively all daily, weekly, and monthly preventative maintenance for the instrument. All maintenance must be documented in the instrument maintenance logbook. Correct instrument optimization is a crucial part of the quality control.

19.2 The Daily instrument check must meet the requirements.

19.3 The correlation coefficients of calibration curves (R) for each element must be ≥0.995 on at least five standards to proceed with sample analysis or ≥0.998 for EPA Method 6020 analysis. If the correlation coefficients for any element do not meet the requirement, results for that element must not be reported from that run. PUBLIC


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Note: Calibration points can only be removed from the low and high end. Mid points can never be removed.

19.3.1 The first calibration standard shall be at or below the PQL. The recovery of the standard shall be between 70-130% with the exception of some elements as well as non-routine analytes at a 50-150%. For EPA Method 6020 the LLICV and LLCCV standards are used instead of the low standard recovery. The recovery of the LLICV and LLCCV standard shall be within 70-130%.

19.3.2 If a sample concentration exceeds that of the highest calibration standard, the sample must be diluted so that it is within the calibrated concentration range.

19.4 The ICV must be analyzed following the calibration. The CCV must be analyzed per 10 samples.

19.5 The ICB and CCBs shall be monitored for the effects of carry-over. In most cases, carry-over of analyte must not exceed the PQL for specifics please refer to the Data Review Flow Chart. The ICB must be analyzed following the ICV. The CCB must be analyzed following the CCV and must be analyzed per 10 samples. An analytical sequence will end with the analysis of a CCV/CCB pair. The absolute value of the ICB/CCB must be less than the PQL or ½ the PQL for DOD projects.

19.6 Each digestion batch (or analytical batch for the analysis of dissolved elements) must have at least one associated preparation blank, FGS suggests one preparation blank per 10 samples. These are treated exactly the same as the samples, and must go through all of the same preparative steps. The absolute value of the preparation blank must be less than the PQL or ½ the PQL for DOD projects.

19.7 Per Eurofins Frontier Global Sciences internal Quality Control Standards, the preparation blank for the batch and the absolute value of the associated ICB/CCBs must be less than the PQL or ½ the PQL for DOD projects for the samples to be reportable.

19.7.1 The preparation blanks and the absolute value of the ICB/CCBs must be less than the MDL in the EPA 1638 Table 1 below for the associated samples to be reported for regulatory compliance purposes according to Method 1638, for clients located in the State of Louisiana, or clients that must meet LELAP (Louisiana Environmental Laboratory Accreditation Program) requirements.

(EPA 1638 Table 1)

Analyte MDL (µg/L) RL (µg/L) EFGS

MDL (µg/L)

EFGS

RL (µg/L)

Antimony 0.0097 0.02 0.0021 0.02

Cadmium 0.025 0.1 0.004 0.02

Copper 0.087 0.2 0.011 0.1

Lead 0.015 0.05 0.004 0.04

Nickel 0.33 1 0.0136 0.1 PUBLIC


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Selenium 0.45 1 0.1938 0.6

Silver 0.029 0.1 0.006 0.02

Thallium 0.0079 0.02 0.0011 0.005

Zinc 0.14 0.5 0.101 0.2

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19.8 One or more rinse blanks, comprised of only dilute acid, must be run after any samples suspected to be high in metals content. Each rinse is to be treated as a discreet injection

19.9 A matrix duplicate (MD) sample analysis may be performed. Depending on client-specified preferences, the MD shall be client-specific or batched between two or more clients. The relative percent difference (RPD) for the replicates must be ≤20% if the sample concentrations are greater than 10 times the PQL. A duplicate matrix spike (MSD) shall be substituted for the MD, with the same control limit applying.

19.10 For each set of 10 or less samples, a matrix spike (MS) and a matrix spike duplicate (MSD) analysis shall be performed. Depending on client-specified preferences, the MS and MSD shall be client-specific or batched between two or more clients. Refer to Table 1 for acceptance criteria.

19.11 For each set of 10 samples, a LCS or OPR analysis shall be performed.

19.12 The acceptable range for internal standard recoveries is between 60-125% or above 70% for EPA Method 6020 only. Samples falling outside of these criteria can be validated with passing QC. i.e. if a sample has a Germanium recovery of 146% and the CCV has a Germanium recovery of 148% with all analytes bracketing the internal standard in control, with a minimum of 30%.Anything below will need approval by the Trace Metal Laboratory Manager, Technical Director and the QA Manager.

20 Corrective Action 20.1 The Quality Control data obtained during the analyses provide an indication of the

quality of the sample data. The QC limits are defined in the QC section and determine if the preparation batch must be reanalyzed.

20.2 Corrective action is required if quality assurance parameters are out, or if the analyst believes it is necessary. First, a careful re-evaluation of the calculations involved must be done.

20.3 Corrective action will then be carried out as decided by the Trace Metals Laboratory Manager and QC Manager. Some data can be qualified, but must be left up to Laboratory Manager/QA Manager for final approval.

20.4 The Quarterly Check Standard: Determine the mean concentration from three analyses, the QCS must be within ± 10% of the stated QCS value and is performed on a quarterly basis. If the QCS is not within the required limits, an immediate second analysis of the QCS is recommended to confirm unacceptable performance. If the QCS continues to fail and calibration standards and/or acceptable instrument performance cannot be verified, the source of the problem must be identified and corrected before proceeding with further analyses for that metal.

21 List of Attachments Table 1: EPA 1638 and performance based acceptance limits for ICV, CCV, LCS, MS,

and MSD

Table 2: Example of an Analytical Sequence PUBLIC


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Appendix D: Example - Standard Operating Procedure Training Record

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Table 1 EPA 1638 and Performance-Based Acceptance Limits for ICV, CCV, LCS, MS, and MSD

Analyte ICV/CCV

Recovery(%)

LCS and OPR

Recovery (%)MS Recovery

(%) Ag 81–107 74–119 74–119 Cd 91–105 84–113 84–113 Cu 76–120 51–145 51–145 Ni 86–116 68–134 68–134 Pb 91–120 72–143 72–143 Sb 90–111 79–122 79–122 Se 69–127 59–149 59–149 Tl 82–118 64–137 64–137 Zn 76–121 46–146 46–146 Al 85-115 85-115 80-115 As 85-115 85-115 85-115 B 75-125 75-135 75-135

Ba 85-115 85-115 80-120 Be 75-125 75-125 75-125 Ca 85-115 80-120 70-130 Co 85-115 85-115 80-115 Cr 85-115 85-115 85-115 Fe 80-120 80-120 75-125 K 85-115 85-115 85-115

Mg 85-115 85-115 80-120 Mn 85-115 85-115 80-120 Mo 85-115 85-115 80-115 Na 80-120 80-120 75-125 Sr 80-120 80-120 80-120 U 80-120 80-120 70-130 V 85-115 85-115 75-125

When EPA 200.8 is analyzed, the recovery control limits are for the ICV/CCV 90-110%, MS/MSD 70-130%, and LCS/LCSD 85-115%. The low standard recovery is 70-130% or 50-150% depending on element of interest.

When AOAC 993.14, USP 730, USP 232 or USP 233 are analyzed, the recovery control limits are for the ICV/CCV 90-110%, MS/MSD 75-125%, and LCS/LCSD 80-120%. The low standard recovery is 70-130% or 50-150% depending on element of interest.

When EPA 6020 is analyzed the recovery control limits are for the ICV/CCV 90-110%, MS/MSD 75-125%, and LCS/LCSD 80-120%. The low standard recovery is 70-130% or 50-150% PUBLIC


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depending on element of interest. The LLICV and LLCCV solution must recover within 70-130%.

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Table 2 Example of an Analytical Sequence

EFGS-054.09 EPA 1638 ICV-SDS ICV-PDS

ICB ICB OPR1-SDS (BS1) OPR1-SDS

OPR2-SDS (BSD1) MB1 MB1 Sample #1 MB2 Sample #2

Sample #1 Sample #3 Sample #2 Sample #4 Sample #3 Sample #5 Sample #4 Sample #6 Sample #5 Sample #7 Sample #6 Sample #8 CCV1-SDS CCV1-PDS

CCB1 CCB1 Sample #7 Sample #9 Sample#8 Sample#10 Sample#9 MS1

Sample#10 MSD1 MS1 OPR2-SDS

MSD1 MB2 Sample #11 Sample #11 Sample #12 Sample #12 Sample #13 Sample #13 Sample #14 Sample #14 CCV2-SDS CCV2-PDS

CCB2 CCB2 Sample #15 Sample #15 Sample #16 Sample #16 Sample #17 Sample #17 Sample #18 Sample #18 Sample #19 Sample #19 Sample#20 Sample#20

MS2 MS2 MSD2 MSD2

CCV3-SDS CCV3-PDS CCB3 CCB3

**The preparation blanks and the absolute value of the ICB/CCBs must be less than the MDL in the EPA 1638 table 1 below for the associated samples to be reported for regulatory compliance purposes for EPA Method 1638, for clients located in the State of Louisiana, or clients that must meet LELAP (Louisiana Environmental Laboratory Accreditation Program) requirements. Note this requirement is for clients requiring strict 1638. All other 1638 clients not requiring strict 1638 are evaluated down to the PQL or ½ the PQL for DoD projects.

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Appendix D: Example - Standard Operating Procedure Training Record

By signing this document, I the employee, certifies to have read, understood and agreed to follow the test method and quality procedure as described in this procedure. Reading of SOP EFGS-054.09: Determination of Trace Metals by ICPMS.

SOP name and Revision number

Employee name (print)

Employee name (sign) Date:

Supervisor name (sign) Date:

Initial SOP Training (leave blank if not applicable)

Initial reading of method and training Initials Date Supervisor 1. Read method 2. Observe the method 3. Detailed review of method and associated literature 4. Supervised practice of method with trainer 5. Unsupervised practice of the method with trainer 6. Review of work with trainer and/or peer-review 7. IDOC to determine precision and accuracy 8. Determination of blanks

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