Synoptic Evaluation of Drinking Water Constituents of ......The June 2016 Synoptic Evaluation of Drinking Water Constituents of Concern in the Sacramento River Basinstudy is being

Synoptic Evaluation of Drinking Water Constituents of

Concern in the Sacramento River Basin

Final Quality Assurance Project Plan

June 2016

2Synoptic Evaluation 2016 Final QAPP

A2, Element 2. Table of Contents A1, Element 1. Title and Approval Sheet ................................................................................ 2

A2, Element 2. Table of Contents ............................................................................................ 3

A3, Element 3. Distribution List .............................................................................................. 8

A4, Element 4. Project/Task Organization .............................................................................. 8

Involved parties and roles..................................................................................................................... 9

Quality Assurance Offer – State Water Board ...................................................................................... 9

Field and Lab Personnel ........................................................................................................................ 9

Monitoring Lead ................................................................................................................................... 9

A5, Element 5. Problem Statement/Background ...................................................................11

Problem statement: ...........................................................................................................11

Decisions or outcomes ......................................................................................................11

Water quality or regulatory criteria .....................................................................................11

A6, Element 6. Project/Task Description ...............................................................................22

Work statement and produced products ............................................................................22

Constituents to be monitored and measurement techniques .............................................22

Project schedule ................................................................................................................24

Geographical setting .........................................................................................................24

Constraints ........................................................................................................................24

A7, Element 7. Quality Objectives and Criteria for Measurement Data ...............................25

Measurement Quality Objectives .......................................................................................25

Accuracy ...........................................................................................................................26

Precision ...........................................................................................................................26

Contamination ...................................................................................................................27

Comparability ....................................................................................................................27

Completeness ...................................................................................................................27

Representativeness ...........................................................................................................27

Method Detection Limit and Sensitivity ..............................................................................28

A8, Element 8. Special Training Needs/Certification ............................................................62

Specialized training or certifications ..................................................................................62

Training personnel .............................................................................................................62

A9, Element 9. Documents and Records ...............................................................................63

QAPP updates and distribution..........................................................................................63

Records to be included in data reports ..............................................................................63

Persons responsible for maintaining records .....................................................................63


Electronic records..............................................................................................................63

B1, Element 10. Sampling Process Design ...........................................................................64

Type and Total Number of Samples ..................................................................................64

Sampling Location .............................................................................................................65

Inaccessible Sample Sites .................................................................................................65

Project Activity Schedule ...................................................................................................65

Bias – Sources and Minimization .......................................................................................65

B2, Element 11. Sampling Methods .......................................................................................66

Field preparation ...............................................................................................................67

Sample volume and bottle type .........................................................................................67

Sample preservation and holding times .............................................................................68

Sample equipment ............................................................................................................69

Sample collection procedures............................................................................................72

Responsible person ...........................................................................................................72

B3, Element 12. Sample Handling and Custody ...................................................................73

Maximum holding times .....................................................................................................73

Sample Handling ...............................................................................................................73

Transport ...........................................................................................................................73

Sample Transfer ................................................................................................................73

Sample Handling and Custody Documentation .................................................................74

Responsible Individuals .....................................................................................................74

Sample Identification .........................................................................................................74

Chain of Custody Procedures ............................................................................................74

B4, Element 13. Analytical Methods and Field Measurements ............................................75

Field analytical procedures ................................................................................................75

Instruments to be used in Field ..........................................................................................88

Equipment to be used for laboratory analysis ....................................................................88

Method Performance Criteria ............................................................................................89

Corrective Actions .............................................................................................................91

Sample Disposal Procedures ............................................................................................91

Laboratory Turnaround Times ...........................................................................................91

B5, Element 14. Quality Control .............................................................................................92

Quality Control Activities ....................................................................................................92

Quality Control Samples ....................................................................................................92

Laboratory Blank ...........................................................................................................92

Matrix Spike and Matrix Spike Duplicate ........................................................................93


Laboratory Control Spike and Laboratory Control Spike Duplicate ................................93

Surrogates .....................................................................................................................93

Calibration Check Samples ...........................................................................................93

Travel Blank ..................................................................................................................93

Field Duplicates .............................................................................................................94

Laboratory Duplicates ....................................................................................................94

Quality Assurance Frequency of Analysis and Measurement Quality Objectives ...............94

Corrective Actions .............................................................................................................95

B6, Element 15. Instrument/Equipment Testing, Inspection, and Maintenance .................96

Periodic Maintenance ........................................................................................................96

Testing Criteria ..................................................................................................................96

Persons Responsible for Testing, Inspection and Maintenance .........................................96

Spare Parts .......................................................................................................................96

Deficiencies .......................................................................................................................96

B7, Element 16. Instrument/Equipment Calibration and Frequency....................................99

B8, Element 17. Inspection/Acceptance of Supplies and Consumables ........................... 100

B9, Element 18. Non-Direct Measurements (Existing Data) ............................................... 102

Existing Data ................................................................................................................... 102

Usage Limits ................................................................................................................... 102

B10, Element 19. Data Management .................................................................................... 103

Data/information Handling and Storage ........................................................................... 103

Computerized Information System Maintenance ............................................................. 103

SWAMP Information Management System...................................................................... 104

C1, Element 20. Assessments and Response Actions ....................................................... 105

Project assessments ....................................................................................................... 105

Assessment reports ......................................................................................................... 106

Corrective action ............................................................................................................. 106

C2, Element 21. Reports to Management ............................................................................ 108

Interim and final reports ................................................................................................... 108

Quality Assurance Reports .............................................................................................. 108

D1, Element 22. Data Review, Verification, and Validation Requirements ........................ 109

Responsibility for Data Review ........................................................................................ 109

Checking for Common Errors .......................................................................................... 109

Checking Against MQOs ................................................................................................. 109

Checking Against QA/QC ................................................................................................ 109

Checking Lab Data .......................................................................................................... 109


Data Verification .............................................................................................................. 110

Data Validation ................................................................................................................ 110

Responsibility for Data Validation .................................................................................... 110

Data Separation .............................................................................................................. 110

D2, Element 23. Verification and Validation Methods ......................................................... 111

D3, Element 24. Reconciliation with User Requirements ................................................... 112

APPENDICES......................................................................................................................... 113

Appendix 1. Sampling Sites ............................................................................................. 114

Appendix 2. Map of Sampling Sites ................................................................................. 115

Appendix 3. Monitoring Plan ............................................................................................ 116

I. INTRODUCTION ...................................................................................................... 118II. BACKGROUND ....................................................................................................... 118III. STUDY DESIGN OVERVIEW ................................................................................. 118

III.a. Monitoring Design ............................................................................................ 120

III.b. Sampling Locations ......................................................................................... 120

III.c. Parameters ...................................................................................................... 123

III.c.1 Field Parameters ........................................................................................ 123

III.c.2 Laboratory Analyses .................................................................................. 123

III.d. Frequency and Sampling ................................................................................. 133

III.e. Spatial and Temporal Scale ............................................................................. 133

III.f. Data Management ............................................................................................ 133

IV. REVIEW STRATEGY ............................................................................................. 133

V. QUALITY ASSURANCE .......................................................................................... 133

V.a. Field Equipment ............................................................................................... 133

V.b. Laboratory Method and Costs .......................................................................... 133

VI. REFERENCES....................................................................................................... 137Appendix 4. Sampling Event Preparation ........................................................................ 147

Appendix 5. Field of Protocols ......................................................................................... 148

Appendix 6. Sample Collection ........................................................................................ 149

Appendix 7. List of Constituents within Each Scan including RLs and MDLs ................... 151

Appendix 8. Field Sheets (SWAMP) ................................................................................ 161

Appendix 9. Bacterial Processing Lab Sheet (SWAMP) .................................................. 162

Appendix 10. ExcelChem Environmental Laboratories (Chain of Custody) ...................... 163

Appendix 11. ExcelChem Environmental Laboratories QA/QC Manual ........................... 164

Appendix 12. ExcelChem Environmental Laboratories Analytical Methods SOPs ........... 203

Appendix 13. SWAMP QAPP .......................................................................................... 290


Appendix 14. ASWA Procedure Manual .......................................................................... 291

Appendix 15. References ................................................................................................ 343

LIST OF TABLES Table 1 Distribution List .............................................................................................................. 8 Table 2 Personnel Responsibilities ............................................................................................ 9 Table 3 Project Schedule ..........................................................................................................24 Table 4 Measurement Quality Objectives ..................................................................................29 Table 5 Sacramento River Basin Monitoring Sites ....................................................................65 Table 6 Field and Laboratory Analytical Methods ......................................................................75 Table 7 Quality Control Checks .................................................................................................92 Table 8 Quality Assurance Frequency of Analysis and Measurement Quality Objectives ..........94 Table 9 Corrective Actions ........................................................................................................95 Table 10 Testing, Inspection, Maintenance of Sampling Equipment ..........................................98 Table 11 Inspection/Acceptance Testing Requirements for Consumables and Supplies ......... 101 Table 12 QA Management Reports ......................................................................................... 108 Table 13 Sacramento River Basin Monitoring Sites ................................................................ 121 Table 14 List of Constituents within Each Scan including RLs and MDLs................................ 124 Table 15 Laboratory Costs for Chemical Parameters .............................................................. 135 LIST OF FIGURES Figure 1 Organizational Chart ...................................................................................................10


A3, Element 3. Distribution List Central Valley Regional Water Quality Control Board (Central Valley Water Board) staff listed in Table 1 below will receive copies of this Quality Assurance Project Plan (QAPP) and any approved revisions of this plan. The QAPP plan will be available on the project website and to any interested party by requesting a copy from True Khang. Table 1 Distribution List Title: Name (Affiliation): E-Mail.: No. of

copies Project Lead, Senior Environmental Scientist

Anne Littlejohn (Central Valley Water Board)

[email protected] 1

Monitoring Lead, Environmental Scientist

True Khang (Central Valley Water Board)

[email protected] 1

Project Coordinator, Environmental Scientist

Cindy Au-Yeung (Central Valley Water Board)

[email protected] 1

A4, Element 4. Project/Task Organization The June 2016 Synoptic Evaluation of Drinking Water Constituents of Concern in the Sacramento River Basin study is being sponsored by the Central Valley Regional Water Quality Control Board (Central Valley Water Board) in conjunction with the Central Valley Salinity Alternatives for Long-Term Sustainability (CV-SALTS) initiative. The Municipal and Domestic Supply (MUN) Beneficial Use is defined as uses of water for community, military, or individual water supply systems including, but not limited, drinking water supply. The purpose of this study is to provide a one-day snapshot of water quality in the Sacramento River Basin at the main stem of the Sacramento and Feather River against criteria developed to protect human health; specifically Title 22 primary and secondary Maximum Contaminant Levels (MCLs), California Toxics Rule (CTR), and other numeric water quality criteria listed in Table 3 for constituents without a MCL or CTR. The constituents analyzed and sampling sites will be selected from Tables 3 and 6, respectively, and will be subject to available funding. The final amount of available funding and selection of sampling sites will be noted in the final report. The study will be conducted over a one-day period, with each designated site being sampled a single time. Sampling sites consist of: • Locations utilized by other programs gathering water quality data • Locations representative of the main stem Sacramento and Feather Rivers Table 2 identifies all personnel involved with this study. Descriptions of each person’s responsibilities follow the table. Figure 1 shows relationships between personnel.


Involved parties and roles Table 2 Personnel Responsibilities

Name Organizational Affiliation Title Project Title/

Responsibility

Contact Information (Telephone number, fax number, email address.)

Anne Littlejohn

Central Valley Water Board

Senior Environmental Scientist

Project Lead

Tel: 916-464-4840 Email: [email protected]

Cindy Au Yeung


Environmental Scientist

Project Coordinator


True Khang Central Valley Water Board


Monitoring Lead


Renee Spears State Water Board

Senior Environmental Scientist Specialist

QA Officer


Quality Assurance Offer – State Water Board The Quality Assurance Officer for the State Water Board works independently from the Monitoring Lead, field staff, and laboratory staff, and is responsible for ensuring that the data meets all quality objectives. Field and Lab Personnel Central Valley Water Board staff trained in sample collection will coordinate all field collection activities and collect the majority of water samples. ExcelChem Environmental Lab personnel will conduct laboratory analyses. Monitoring Lead The Monitoring Lead will be responsible for maintaining the official and approved QA Project Plan.


Figure 1 Organizational Chart

Project LeadCentral Valley Water Board

Anne Littlejohn

Sample Analysis ExcelChem Environmental Labs

Lab Staff

Monitoring LeadCentral Valley Water Board

True Khang

QA OfficerState Water Board

Renee Spears

Project Coordinator Central Valley Water Board

Cindy Au-Yeung

Monitoring Support Central Valley Water Board

Field Staff


A5, Element 5. Problem Statement/Background Problem statement: Please see Monitoring Plan in Appendix 3. Via the State Water Resources Control Board Sources of Drinking Water Policy (88-63), the Central Valley Regional Water Quality Control Board Basin Plans (Basin Plans) designate the Municipal and Domestic Supply (MUN) beneficial use to all water bodies unless they are specifically listed as water bodies without MUN. The Basin Plans state that water bodies designated for MUN must not exceed MCLs for chemical constituents, pesticides, and radionuclides. This project will provide a one-time snapshot of the water quality in the Sacramento River Basin at the main stem of the Sacramento and Feather River as compared to criteria developed to protect human health. The findings from this study may change how compliance for MUN will be enforced in new NPDES permits. Main goal of the monitoring is to determine:

Key Question

• Is water quality in the main stem of the Sacramento and Feather River being protected for human health?

Decisions or outcomes The primary objectives of this monitoring project are:

• Collect representative samples in main stem Sacramento and Feather River; • Determine spatial distribution of any detectible constituent concentrations of concerns;

and, • Identify whether criteria developed to protect human health are exceeded

Water quality or regulatory criteria To evaluate whether water quality may be suitable for the MUN beneficial use, data will be compared to Maximum Contaminant Levels (MCLs) specified in provisions of Title 22 of the California Code of Regulations, California Toxics Rule (CTR) criteria, and other numeric water quality criteria listed in Table 3 for constituents without a MCL or CTR criteria. For constituents with both a MCL and CTR criteria, the most conservative numeric threshold will be selected for water quality evaluation. For constituents without a MCL and CTR criteria, the most appropriate numeric water quality criteria for protecting MUN beneficial use will be selected for water quality


evaluation. In addition, E. coli will be added to the monitoring effort and will be compared to the USEPA Recreational Guideline for Designated Beach Area at 235 MPN/100mL (USEPA, 1986). This numeric water quality criterion will be strictly used as a tool for evaluation to put values into context in terms of spatial and temporal trends.


Table 3 PARAMETERS AND CRITERIA The following list all of the constituents that have MUN water quality evaluation criteria. Please note that not all of these constituents were tested for due to scan variations provided by the laboratory.

Analyte Primary MCL

Secondary MCL CTR Other Evaluation Criteria/Guideline

1,1,1-Trichloroethane 200 ug/L 1,1,2,2-Tetrachloroethane 1 ug/L 0.17 ug/L 1,1,2,Trichloro-1,2,2-Trifluoroethane (Freon 113) 1200 ug/L

1,1,2-Trichloroethane 5 ug/L 0.6 ug/L 1,1-Dichloroethane 5 ug/L 1,1-Dichloroethylene 6 ug/L 0.057 ug/L 1,2,4-Trichlorobenzene 5 ug/L 1,2,4-Trimethylbenzene 330 ug/L (DDW Drinking Water Notification Levels) 1,2-Dibromo-3chloropropane (DBCP) 0.2 ug/L

1,2-Dibromoethane (Ethylene Dibromide) (EDB) 0.05 ug/L

1,2-Dichlorobenzene 600 ug/L 2,700 ug/L 1,2-Dichloroethane (Ethylene dichloride) 5 ug/L 0.38 ug/L

1,2-Dichloropropane 5 ug/L 0.52 ug/L 1,2-Diphenylhydrazine 0.04 ug/L 1,3 Dichlorobenzene 400 ug/L 1,3,5-Trimethylbenzene 330 ug/L (DDW Drinking Water Notification Levels) 1,3-Dichloropropene 0.5 ug/L 10 ug/L 1,4-Dichlorobenzene 5 ug/L 400 ug/L


Analyte Primary MCL


2,3,7,8-TCDD (Dioxin) 0.00003 ug/L 1.3x10-8 ug/L 2,4,5-TP (Silvex) 50 ug/L 2,4,6-Trichlorophenol 2.1 ug/L 2,4-Dichlorophenol 93 ug/L 2,4-Dichlorophenoxyacetic acid (2,4-D) 70 ug/L

2,4-Dichlorophenoxybutyric acid (2,4-DB) 56 ug/L (USEPA IRIS Reference Dose)

2,4-Dimethylphenol 540 ug/L 2,4-Dinitrophenol 70 ug/L 2,4-Dinitrotoluene 0.11 ug/L 2-Chloronaphthalene 1,700 ug/L 2-Chlorophenol 120 ug/L 2-Methyl-4,6-Dinitrophenol 13.4 ug/L 3,3'-Dichlorobenzidine 0.04 ug/L 4,4'-DDD 0.00083 ug/L 4,4'-DDE 0.00059 ug/L 4,4'-DDT 0.00059 ug/L Acenaphthene 1,200 ug/L Acrolein 320 ug/L Acrylonitrile 0.059 ug/L Alachlor 2 ug/L Aldrin 0.00013 ug/L Alpha-BHC (alpha-Benzene hexachloride) 0.0039 ug/L

Aluminum 1,000 ug/L 200 ug/L


Analyte Primary MCL


Ammonia 1,500 ug/L [Odor Threshold (Amoore and Huatala)] Anthracene 9,600 ug/L Antimony 6 ug/L 14 ug/L Arsenic 10 ug/L

Asbestos 7 Million Fiber/Liter 7 Million

Fibers/Liter

Atrazine 1 ug/L Barium 1,000 ug/L Bentazon 18 ug/L Benzene 1 ug/L 1.2 ug/L Benzidine 0.00012 ug/L Benzo(a)Anthracene [1,2-Benzanthracene] 0.0044 ug/L

Benzo(a)pyrene 0.2 ug/L 0.0044 ug/L Benzo(b)Fluoranthene [3,4-Benzofluoranthene] 0.0044 ug/L

Benzo(k)Fluoranthene 0.0044 ug/L Beryllium 4 ug/L

Beta/photon emitters

4 millirem/year annual dose equivalent to the total body or any internal organ

Beta-BHC (beta-Benzene hexachloride) 0.014 ug/L

Bis(2-Chloroethyl)Ether 0.031 ug/L


Analyte Primary MCL


Bis(2-Chloroisopropyl)Ether 1,400 ug/L Boron 1,000 ug/L (DDW Notification Level for Drinking Water) Bromoform 4.3 ug/L Butylbenzyl Phthalate 3,000 ug/L Cadmium 5 ug/L Carbofuran 18 ug/L Carbon Tetrachloride 0.5 ug/L .25 ug/L Chlordane 0.1 ug/L 0.00057 ug/L

Chloride 250,000 ug/L

Chlorobenzene (Monochlorobenzene) 70 ug/L 680 ug/L

Chlorodibromomethane 0.401 ug/L

Chloroform 1.8 ug/L [CalEPA Cancer Potency Factor as a Drinking Water Level (assume 70kg body weight & 2 liters per day drinking water consumption)]

Chlorpyrifos 2 ug/L (USEPA, OPP Drinking Water Health Advisory- Non-cancer)

Chromium 50 ug/L Chromium VI (Hexavalent Chromium) 10 ug/L

Chrysene 0.0044 ug/L Cis1,2-Dichloroethylene 6 ug/L Color 15 units Copper 1,000 ug/L 1,300 ug/L Cyanide 150 ug/L 700 ug/L Dalapon 200 ug/L Di(2-ethylhexyl)adipate 400 ug/L


Analyte Primary MCL


Di(2-ethylhexyl)phthalate (DEHP) (Bis(2-ethylhexyl) phthalate)

4 ug/L

Diazinon 1.2 ug/L (DDW Drinking Water Notification Level) Dibenzo(ah)Anthracene 0.0044 ug/L Dichlorobromomethane 0.56 ug/L Dichloromethane (Methylene Chloride) 5 ug/L 4.7 ug/L

Dieldrin 0.00014 ug/L Diethyl Phthalate 23,000 ug/L Di-isopropyl ether (Isopropyl ether) (DIPE) 0.8 ug/L [Odor Threshold (Amoore and Hautala)]

Dimethyl Phthalate 313,000 ug/L Di-n-Butyl Phthalate 2,700 ug/L Dinoseb 7 ug/L Diquat 20 ug/L

E. coli 235 MPN/100ml [USEPA Recreational Guideline for Designated Beach Area (Upper 75% Confidence Level)]

Endosulfan I (Alpha-Endosulfan) 110 ug/L

Endosulfan II (Beta-Endosulfan) 110 ug/L Endosulfan Sulfate 110 ug/L Endothall 100 ug/L Endrin 2 ug/L 0.76 ug/L Endrin Aldehyde 0.76 ug/L Ethylbenzene 300 ug/L 3,100 ug/L Fluoranthene 300 ug/L


Analyte Primary MCL


Fluorene 1,300 ug/L Fluoride 2,000 ug/L Foaming Agents (MBAS) 500 ug/L Gamma-BHC (gamma-Benzene hexachloride) (Lindane)

0.2 ug/L 0.019 ug/L

Glyphosate 700 ug/L Gross Alpha particle activity (excluding radon and uranium) 15 pCi/L

Haloacetic acids (HAAs) 60 ug/L Heptachlor 0.4 ug/L 0.01 ug/L Heptachlor Epoxide 0.2 ug/L 0.001 ug/L Hexachlorobenzene 1 ug/L 0.00075 ug/L Hexachlorobutadiene 0.44 ug/L Hexachlorocyclopentadiene 50 ug/L 240 ug/L Hexachloroethane 1.9 ug/L Indeno(1,2,3-cd) Pyrene 0.0044 ug/L Iron 300 ug/L Isophorone 8.4 ug/L Lead 15 ug/L Manganese 50 ug/L Mercury 2 ug/L 0.05 ug/L Methoxychlor 30 ug/L Methyl Bromide (Bromomethane) 48 ug/L

Methyl-tert-butyl ether (MTBE) 13 ug/L 5 ug/L


Analyte Primary MCL


Molinate 20 ug/L Nickel 100 ug/L 610 ug/L Nitrate (as NO3) 45,000 ug/L Nitrate+Nitrite (sum as nitrogen) 10,000 ug/L Nitrite (as Nitrogen) 1000 ug/L Nitrobenzene 17 ug/L N-Nitrosodimethylamine (NDMA) 0.00069 ug/L

N-Nitrosodi-n-Propylamine 0.005 ug/L N-Nitrosodiphenylamine 5 ug/L

Odor 3 TON (Threshold units)

Oxamyl 50 ug/L Pentachlorophenol 1 ug/L 0.28 ug/L Perchlorate 6 ug/L

pH 6.5 – 8.5 units

Phenol 21,000 ug/L Picloram 500 ug/L Polychlorinated Biphenyls (PCBs) 0.5 ug/L 0.00017 ug/L

Pyrene 960 ug/L

Radium-226

5 pCi/L (combined radium- 226 & -228


Analyte Primary MCL


Radium-228


Selenium 50 ug/L Silver 100 ug/L Simazine 4 ug/L

Sodium 20,000 ug/L (USEPA Drinking Water Advisory for Persons on Restricted Sodium Diet)

Specific Conductance 900 µS/cm

Strontium-90

8 pCi/L (=4 millirem/yr dose to bone marrow)

Styrene 100 ug/L

Sulfate 250,000 ug/L

Tetrachloroethylene (Tetrachloroethene) (PCE) 5 ug/L 0.8 ug/L

Thallium 2 ug/L 1.7 ug/L Thiobencarb 70 ug/L 1 ug/L Toluene 150 ug/L 6,800 ug/L

Total Dissolved Solids 500,000 ug/L

Total Triahlomethanes 80 ug/L Toxaphene 3 ug/L 0.00073 ug/L Trans-1,2-Dichloroethylene 10 ug/L 700 ug/L Trichloroethylene (TCE) 5 ug/L 2.7 ug/L


Analyte Primary MCL


Trichlorofluoromethane (Freon 11) 150 ug/L

Tritium

20000 pCi/L (=4 millirem/yr dose to total body)

Turbidity 5 NTU Uranium 20 pCi/L Vanadium 50 ug/L (DDW Drinking Water Notification Levels) Vinyl Chloride 0.5 ug/L 2 ug/L Xylenes 1,750 ug/L Zinc 5,000 ug/L

NOTE: Not all of the analytes listed above were analyzed for this study.

Acronyms CalEPA California Environmental Protection Agency CTR California Toxics Rule DDW Division of Drinking Water IRIS Integrated Risk Information System MCL Maximum Contaminant Level OPP Office of Pesticide Programs USEPA United States Environmental Protection Agency


A6, Element 6. Project/Task Description Work statement and produced products This project will provide a one-day snapshot of the water quality in the main stem of the Sacramento and Feather River as compared to criteria developed to protect human health. The water quality data will be compared to the MCLs specified in provisions of Title 22 of the California Code of Regulations, CTR criteria, and other numeric water quality criteria as an evaluation of the MUN beneficial use. Constituents to be monitored and measurement techniques Field measurements for DO, SC, pH, and temperature will be collected using a YSI EXO 1 Sonde (Sonde). Turbidity measurements will be collected using a portable Hach 2100P turbidimeter. Photo documentation at all monitoring sites will be conducted when collecting field measurements. Samples will be analyzed for all MCLs specified in Title 22 of the California Code of Regulations, with the exceptions of asbestos and radionuclides. In addition, select constituents with human health criteria in the CTR will be analyzed, as well as E. coli, which has been identified as a trigger for possible reductions in pathogen levels by the Division of Drinking Water at the State Water Resources Control Board. Analyses will be conducted at ExcelChem utilizing the following methods: EPA method 200.7: This method will be used to analyzed hardness, barium, antimony, beryllium, cadmium, chromium, nickel, copper, silver, zinc, selenium, boron, sodium, total aluminum, total iron, and total manganese by inductively coupled plasma – mass spectrometry (ICP MS). This method is used for determination of dissolved elements and total recoverable element concentrations in surface waters, drinking water, and wastewaters. EPA method 200.9: This method will be used to analyze total lead and thallium by stabilized temperature graphite furnace atomic absorption. This method is used for determination of total recoverable elements in surface water, drinking water, storm runoff, industrial and domestic wastewater. EPA method 300: This method will be used to analyze sulfate, chloride, total fluoride, nitrate as nitrogen and nitrite as nitrogen by ion chromatography. This method is used on drinking water, surface water, mixed domestic and industrial wastewaters.


EPA method 5540C: This method will be used to analyze MBAs, or foaming agents, by observing the intensity of the cationic dye through ion pair formation. This method is used for drinking water samples. EPA method 8260B: This method will be used to analyze volatile organic compounds by gas chromatography/mass spectrometry (GC/MS) in surface water. Organohalides, particularly the trihalomethanes, are present in most chlorinated water systems; especially those using surface waters as a water source. EPA method 8151A: This method will be used to analyze chlorinated herbicides by capillary gas chromatography (GC) in surface water. EPA method 8141A: This method will be used to analyze organo-phosphorus pesticides by capillary gas chromatography (GC) in surface water. EPA method 8082A: This method will be used to analyze polychlorinated biphenyls by capillary gas chromatography (GC) in surface water. EPA method 8290: This method will be used to analyze polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans by high-resolution gas chromatography and high-resolution mass spectrometry (HRGC/HRMS) on purified sample extracts of surface water. EPA method 8318: This method will be used to analyze carbamate pesticides by high performance liquid chromatography (HPLC) in surface water. EPA method 8081A: This method will be used to analyze organo-chlorinated herbicides by capillary gas chromatography (GC) in surface water. EPA method 8270C: This method will be used to analyze semivolatile organic compounds by gas chromatography/mass spectrometry (GC/MS) on purified sample extracts of surface water. EPA method 2540: This method will be used to analyze total dissolved solids by drying in an oven at a defined temperature using a filter on surface water samples.


EPA method 350.2: This method will be used to analyze ammonia as nitrogen by distillation of the surface water. EPA method 206.3 This method will be used to analyze total arsenic by gaseous hydride generation – atomic absorption in drinking water. Project schedule The project schedule is outlined in Table 4. Table 4 Project Schedule

Date Activity June 20, 2016 Field Sampling (Sacramento River Basin)

June 21-June 29, 2014 Lab Analysis Geographical setting The Central Valley Regional Water Quality Control Plan (Basin Plan) covers the entire area included in the Sacramento River and San Joaquin River drainage basins. The basins are bound by the crests of the Sierra Nevada on the east and the Coast Range and Klamath Mountains on the west. The Sacramento River and San Joaquin River Basins cover about one fourth of the total area of the State and over 30% of the State’s irrigable land. The Sacramento and San Joaquin Rivers furnish roughly 51% of the State’s water supply. Surface waters from the two drainage basins meet and form the Delta, which ultimately drains to San Francisco Bay. The selected areas of this monitoring study are located within the Sacramento River Basin. The Sacramento River Basin covers 27,210 square miles and includes the entire area drained by the Sacramento River. The Sacramento River is the largest river in the watershed, with an annual average stream flow volume of 22 million acre-feet. All watersheds tributary to the Sacramento River north of the Cosumnes River watershed and the closed basin of Goose Lake and drainage sub-basins of Cache and Putah Creeks are included in the Sacramento River Basin. Further description of the study area can be found in the monitoring plan located at: http://www.waterboards.ca.gov/centralvalley/water_issues/basin_plans/sacsjr.pdf Constraints The primary constraints for this project are personnel, funding, and logistics. Other constraints may be identified throughout the course of the study.


http://www.waterboards.ca.gov/centralvalley/water_issues/basin_plans/sacsjr.pdf

Personnel: Currently, only two Central Valley Water Board staff are available for monitoring. The limited availability of staff limits the number of sites that can be monitored and the frequency of monitoring. Funding: The maximum budget for this project is $15,000 and has the potential to change unannounced. With a varying budget, it will be difficult to pinpoint exactly how much will be allocated to this project, possibly affecting the number of sites and constituents sampled. Logistics: Logistical constraints include hold times. The sampling sites are at least an hour from the Central Valley Water Board’s contracted laboratory. The shortest hold time is 48 hours for Nitrate as Nitrogen, Nitrite as Nitrogen, and MBAs. The Volatile Organic Compound scan has a hold time of 14 days. Boron, total iron, sodium, total aluminum, total arsenic, and total manganese have hold times of 6 months. Once sampling concludes for the day, the samples will be transported to ExcelChem Environmental Labs. A7, Element 7. Quality Objectives and Criteria for Measurement Data Measurement Quality Objectives This section contains the measurement quality objectives of this study and includes analyses in the field. Data quality indicators for this study will consist of the following: Measurement or Analysis Type Applicable Data Quality Objective Field Measurements (DO, SC, pH, Temp, turbidity)

Accuracy, Precision, Completeness

Boron, sodium, nitrate as nitrogen, nitrite as nitrogen, volatile organic compounds, MBAs; Total: iron, aluminum, fluoride, arsenic, manganese, barium, lead, antimony, beryllium, cadmium, nickel, thallium, copper, silver, zinc, selenium; E. coli, total dissolved solids, ammonia as nitrogen, hardness, sulfate, chloride, chlorinated herbicides, organo-phosphorus pesticides, PCB’s, dioxin, carbamate pesticides, organochlorine pesticides, and semi-volatile organic compounds.

Accuracy, Precision, Contamination, Completeness


There are two types of quality objectives. Measurement Quality Objectives (MQOs) refer to the quality of a given measurement (e.g. accuracy or precision). The Data Quality Objectives (DQOs) refer to the ability of an entire data set to provide answers to a study question (e.g. completeness or representativeness). DQOs for the proposed project will be based on MQOs for the analytes listed in Table 5. All monitoring data obtained will be kept in Excel files in order to make reviews easier. The data will eventually be loaded into the California Environmental Data Exchange Network (CEDEN) as resources become available. The MQOs for field measurements are listed in Table 5. Additional MQOs for data acceptability, test conditions, water chemistry, and sample handling are listed in Appendix A of the SWAMP QAPP. MQOs for the equipment used to measure water temperature, dissolved oxygen, specific conductivity, pH, and turbidity in this project are detailed in Table 5. With proper calibration, the range, accuracy, and resolution of each instrument will meet the manufacturer’s specifications and meet the MQOs for individual parameters. These parameters are detailed in 7.1 through 7.6. Accuracy Accuracy is the relationship between a measurement of a known concentration against a measured value. Accuracy is measured by determining the percent recovery of known concentrations of analytes spiked into field sample or reagent water before extraction. This is a laboratory quality assurance that ExcelChem Environmental Labs will perform while analyzing water samples. Precision Precision is a Data Quality Indicator (DQI) that measures the variability of repeated measurements of the same parameter in the same sample under the same analytical condition. Precision measurements are determined by field and laboratory duplicate samples, and will be evaluated by having the same analyst complete the procedure for duplicate field samples or laboratory duplicates. Our expectation is that duplicate samples will be ≥80% concordant (i.e., ≥80% agreement between pairs of samples). YSIs will be used in this study, which automatically take multiple measurements and display an average of the results. Where these types of instruments are used, replicate readings are not


necessary. For turbidity, samples will be collected and results recorded in triplicate. Analytical precision for key constituent analysis will be evaluated at a frequency of 5% of the total samples for the project for field duplicates for each key constituent. Contamination Contamination is the unintentional addition of analytical constituents to a sample or system. To test for contamination during sample transport, a travel blank for each key constituent will be transported with field samples. Travel blanks for each key constituent will be analyzed at a frequency of 5% of the total samples for the project. Laboratory blanks are analyzed per analytical batch. Comparability Comparability is the degree to which data can be compared directly to data from similar studies. Methods for field parameters and key constituents are either EPA approved methods or are found in Standard Methods. Completeness Completeness is the fraction of planned data that must be collected in order to fulfill the statistical criteria of the project. It is expected that 100% of field measurements and analysis of key constituents will be taken. This accounts for adverse weather conditions, safety concerns, and equipment problems. Central Valley Water Board staff will determine completeness by comparing the number of measurements that were planned to be collected against the number of measurements that were actually collected that were also deemed valid. No analysis at a “dry” site will be considered a “sample” since part of the effort is to characterize the hydrology of the water bodies. An invalid measurement would be one that does not meet the sampling method requirements and the data quality objectives. Completeness results will be checked for each sampling season. This will allow Central Valley Water Board staff to identify and correct problems. Representativeness Representativeness describes the relevance of data to the actual environmental condition. Bias or lack of representativeness can occur if: Samples are taken in a stream reach that fails to describe the area of interest; Samples are collected in an unusual location (For example: a stagnant pool instead of

the flowing portion of the water body);


Samples are not preserved, stored, or analyzed appropriately, causing the condition of the sample to change

Representativeness and resulting bias are addressed through the overall sampling design. Sites were selected to characterize receiving waters and where hold times could be met. Sample collection specifications are described in Appendix 5. Method Detection Limit and Sensitivity The Method Detection Limit (MDL) is defined as the minimum concentration of a substance that can be measured and reported with 99% confidence that the analyte concentration is greater than zero. It is important to record MDLs of any pollutants analyzed for because it cannot be determined that a pollutant was not present, only that it could not be detected. Sensitivity is the ability of the instrument to detect one concentration from the next. Sensitivities (Target Reporting Limits) for field data and lab data are noted in Table 5.


Table 5 Measurement Quality Objectives

Sample Type Analyte Accuracy Precision

Target Reporting

Limit

Method Detection

Limit Unit Test Method Completeness

Central Valley Water Board Field Testing (YSI EXO1) Dissolved Oxygen 1% 0.1% air sat. 0.01 mg/L N/A mg/l 6562 Rapid

Pulse Sensor 100%

Field Testing (YSI EXO1) pH +0.1 pH units 0.01 units NA N/A pH

units 6561 pH Sensor 100%

Field Testing (YSI EXO1) Specific Conductivity

±0.5% of reading or ±0.001 mS/cm

0.0001 to 0.01 mS/cm (range-dependent)

0.001 µS/cm N/A µS/cm

6560 Conductivity Sensor

100%

Field Testing (YSI EXO1) Water Temperature -5 to 35°C:

+0.01°C 0.001°C NA N/A °C 6560 Temperature Sensor

100%

Field Testing (Hach 2100P)

Turbidity

± 2% of reading plus stray light from 0-1000 NTU

±1% of reading or 0.01 NTU, whichever is greater

0 to 1,000NTU N/A NTU

Ratio Nephelometric signal (90°) scatter light ratio to transmitted light

100%

Laboratory Analysis Total Coliform and E. coli P/A

Lab and Field duplicate samples, per SM

1 N/A MPN Colilert-18 100%

ExcelChem Environmental Lab

Laboratory Analysis 1, 1-Dichloroethane LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.04 µg/L EPA 8260B 100%

Laboratory Analysis 1,1,1,2-Tetrachloroethane LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.08 µg/L EPA 8260B 100%

Laboratory Analysis 1,1,1-Trichloroethane LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.05 µg/L EPA 8260B 100%



Target Reporting

Limit

Method Detection



MS & MSD 50-150%; RPD<25%

0.5 0.4 µg/L EPA 8260B 100%


MS & MSD 50-150%; RPD<25%

0.5 0.1 µg/L EPA 8260B 100%

Laboratory Analysis 1,1-Dichloroethene LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.05 µg/L EPA 8260B 100%

Laboratory Analysis 1,1-Dichloropropene LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.03 µg/L EPA 8260B 100%

Laboratory Analysis 1,2,3-Trichlorobenzene LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.05 µg/L EPA 8260B 100%

Laboratory Analysis 1,2,3-Trichloropropane LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.06 µg/L EPA 8260B 100%


MS & MSD 50-150%; RPD<25%

0.5 0.02 µg/L EPA 8260B 100%

Laboratory Analysis 1,2,4-Trimethylbenzene LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.04 µg/L EPA 8260B 100%

Laboratory Analysis

1,2-Dibromo-3-chloropropane LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.07 µg/L EPA 8260B 100%

Laboratory Analysis 1,2-Dibromoethane (EDB) LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.1 µg/L EPA 8260B 100%

Laboratory Analysis 1,2-Dichlorobenzene LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.06 µg/L EPA 8260B 100%



Target Reporting

Limit

Method Detection


Laboratory Analysis 1,2-Dichloroethane LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.04 µg/L EPA 8260B 100%

Laboratory Analysis 1,2-Dichloropropane LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.06 µg/L EPA 8260B 100%


MS & MSD 50-150%; RPD<25%

0.5 0.03 µg/L EPA 8260B 100%


MS & MSD 50-150%; RPD<25%

0.5 0.06 µg/L EPA 8260B 100%


MS & MSD 50-150%; RPD<25%

0.5 0.05 µg/L EPA 8260B 100%

Laboratory Analysis 2-Butanone LCS 70-130%

MS & MSD 50-150%; RPD<25%

5 0.1 µg/L EPA 8260B 100%

Laboratory Analysis 2-Chlorotoluene LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.03 µg/L EPA 8260B 100%

Laboratory Analysis 2-Hexanone LCS 70-130%

MS & MSD 50-150%; RPD<25%

5 0.1 µg/L EPA 8260B 100%


MS & MSD 50-150%; RPD<25%

0.5 0.05 µg/L EPA 8260B 100%

Laboratory Analysis 4-Isopropyltoluene LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.04 µg/L EPA 8260B 100%

Laboratory Analysis 4-Methyl1-2pentanone LCS 70-130%

MS & MSD 50-150%; RPD<25%

5 0.05 µg/L EPA 8260B 100%



Target Reporting

Limit

Method Detection


Laboratory Analysis Acetone LCS 70-130%

MS & MSD 50-150%; RPD<25%

5 0.1 µg/L EPA 8260B 100%

Laboratory Analysis Benzene LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.03 µg/L EPA 8260B 100%

Laboratory Analysis Bromobenzene LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.05 µg/L EPA 8260B 100%

Laboratory Analysis Bromochloromethane LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.07 µg/L EPA 8260B 100%

Laboratory Analysis Bromodichloromethane LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.05 µg/L EPA 8260B 100%

Laboratory Analysis Bromoform LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.03 µg/L EPA 8260B 100%

Laboratory Analysis Bromomethane LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.05 µg/L EPA 8260B 100%

Laboratory Analysis Carbon disulfide LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.06 µg/L EPA 8260B 100%

Laboratory Analysis Carbon tetrachloride LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.02 µg/L EPA 8260B 100%

Laboratory Analysis Chlorobenzene LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.03 µg/L EPA 8260B 100%

Laboratory Analysis Chloroethane LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.08 µg/L EPA 8260B 100%



Target Reporting

Limit

Method Detection


Laboratory Analysis Chloroform LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.05 µg/L EPA 8260B 100%

Laboratory Analysis Chloromethane LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.06 µg/L EPA 8260B 100%

Laboratory Analysis cis-1,2-Dichloroethane LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.03 µg/L EPA 8260B 100%

Laboratory Analysis cis-1,3-Dichloropropene LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.04 µg/L EPA 8260B 100%

Laboratory Analysis Dibromochloromethane LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.07 µg/L EPA 8260B 100%

Laboratory Analysis Dibromomethane LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.07 µg/L EPA 8260B 100%

Laboratory Analysis Dichlorodifluoromethane LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.07 µg/L EPA 8260B 100%

Laboratory Analysis Di-isopropyl ether LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.1 µg/L EPA 8260B 100%

Laboratory Analysis Ethyl tert-Butyl Ether LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.04 µg/L EPA 8260B 100%

Laboratory Analysis Ethylbenzene LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.03 µg/L EPA 8260B 100%

Laboratory Analysis Hexachlorobutadiene LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.07 µg/L EPA 8260B 100%



Target Reporting

Limit

Method Detection


Laboratory Analysis Iodomethane LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.03 µg/L EPA 8260B 100%

Laboratory Analysis Isopropylbenzene LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.04 µg/L EPA 8260B 100%

Laboratory Analysis m,p-Xylene LCS 70-130%

MS & MSD 50-150%; RPD<25%

1 0.09 µg/L EPA 8260B 100%

Laboratory Analysis Methyl tert-Butyl Ether LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.05 µg/L EPA 8260B 100%

Laboratory Analysis Methylene chloride LCS 70-130%

MS & MSD 50-150%; RPD<25%

5 0.08 µg/L EPA 8260B 100%

Laboratory Analysis Naphthalene LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.04 µg/L EPA 8260B 100%

Laboratory Analysis n-Butylbenzene LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.04 µg/L EPA 8260B 100%

Laboratory Analysis n-Propylbenzene LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.04 µg/L EPA 8260B 100%

Laboratory Analysis o-Xylene LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.04 µg/L EPA 8260B 100%

Laboratory Analysis sec-Butylbenzene LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.03 µg/L EPA 8260B 100%

Laboratory Analysis TBA LCS 70-130%

MS & MSD 50-150%; RPD<25%

1 0.1 µg/L EPA 8260B 100%



Target Reporting

Limit

Method Detection


Laboratory Analysis Tert-Amyl Methyl Ether LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.03 µg/L EPA 8260B 100%

Laboratory Analysis tert-Butylbenzene LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.02 µg/L EPA 8260B 100%

Laboratory Analysis Tetrachloroethene LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.08 µg/L EPA 8260B 100%

Laboratory Analysis Toluene LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.04 µg/L EPA 8260B 100%

Laboratory Analysis trans-1,2-Dichloroethane LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.04 µg/L EPA 8260B 100%

Laboratory Analysis trans-1,3-Dichloropropene LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.04 µg/L EPA 8260B 100%

Laboratory Analysis Trichloroethane LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.06 µg/L EPA 8260B 100%

Laboratory Analysis Trichlorofluoromethane LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.05 µg/L EPA 8260B 100%

Laboratory Analysis Trichlorotrifluoroethane LCS 70-130%

MS & MSD 50-150%; RPD<25%

1 0.05 µg/L EPA 8260B 100%

Laboratory Analysis Vinyl chloride LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.06 µg/L EPA 8260B 100%

Laboratory Analysis Xylenes, total LCS 70-130%

MS & MSD 50-150%; RPD<25%

1 0.1 µg/L EPA 8260B 100%



Target Reporting

Limit

Method Detection



MS & MSD 50-150%; RPD<25%

0.5 0.08 µg/L EPA 524 100%


MS & MSD 50-150%; RPD<25%

0.5 0.05 µg/L EPA 524 100%


MS & MSD 50-150%; RPD<25%

0.5 0.04 µg/L EPA 524 100%


MS & MSD 50-150%; RPD<25%

0.5 0.1 µg/L EPA 524 100%

Laboratory Analysis 1,1,-Dichloroethane LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.04 µg/L EPA 524 100%

Laboratory Analysis 1,1-Dichloroethene LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.05 µg/L EPA 524 100%

Laboratory Analysis 1,1-Dichloropropene LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.03 µg/L EPA 524 100%


MS & MSD 50-150%; RPD<25%

0.5 0.05 µg/L EPA 524 100%

Laboratory Analysis 1,2,3-Trichloropropane LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.06 µg/L EPA 524 100%


MS & MSD 50-150%; RPD<25%

0.5 0.02 µg/L EPA 524 100%


MS & MSD 50-150%; RPD<25%

0.5 0.04 µg/L EPA 524 100%



Target Reporting

Limit

Method Detection


Laboratory Analysis

1,2-Dibromo-3-chloropropane LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.07 µg/L EPA 524 100%

Laboratory Analysis 1,2-Dibromoethane (EDB) LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.1 µg/L EPA 524 100%


MS & MSD 50-150%; RPD<25%

0.5 0.06 µg/L EPA 524 100%

Laboratory Analysis 1,2-Dichloroethane LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.06 µg/L EPA 524 100%


MS & MSD 50-150%; RPD<25%

0.5 0.06 µg/L EPA 524 100%


MS & MSD 50-150%; RPD<25%

0.5 0.03 µg/L EPA 524 100%


MS & MSD 50-150%; RPD<25%

0.5 0.03 µg/L EPA 524 100%


MS & MSD 50-150%; RPD<25%

0.5 0.06 µg/L EPA 524 100%


MS & MSD 50-150%; RPD<25%

0.5 0.05 µg/L EPA 524 100%


MS & MSD 50-150%; RPD<25%

0.5 0.06 µg/L EPA 524 100%

Laboratory Analysis 2-Butanone LCS 70-130%

MS & MSD 50-150%; RPD<25%

5 0.1 µg/L EPA 524 100%



Target Reporting

Limit

Method Detection



MS & MSD 50-150%; RPD<25%

0.5 0.03 µg/L EPA 524 100%

Laboratory Analysis 2-Hexanone LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.1 µg/L EPA 524 100%


MS & MSD 50-150%; RPD<25%

0.5 0.05 µg/L EPA 524 100%

Laboratory Analysis 4-Isopropyltoluene LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.04 µg/L EPA 524 100%

Laboratory Analysis 4-Methyl-2-pentanone LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.05 µg/L EPA 524 100%

Laboratory Analysis Acetone LCS 70-130%

MS & MSD 50-150%; RPD<25%

5 0.1 µg/L EPA 524 100%

Laboratory Analysis Benzene LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.03 µg/L EPA 524 100%

Laboratory Analysis Bromobenzene LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.05 µg/L EPA 524 100%

Laboratory Analysis Bromochloromethane LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.07 µg/L EPA 524 100%

Laboratory Analysis Bromodichloromethane LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.05 µg/L EPA 524 100%

Laboratory Analysis Bromoform LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.03 µg/L EPA 524 100%



Target Reporting

Limit

Method Detection


Laboratory Analysis Bromomethane LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.05 µg/L EPA 524 100%

Laboratory Analysis Carbon disulfide LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.06 µg/L EPA 524 100%

Laboratory Analysis Carbon tetrachloride LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.02 µg/L EPA 524 100%

Laboratory Analysis Chlorobenzene LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.03 µg/L EPA 524 100%

Laboratory Analysis Chloroethane LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.08 µg/L EPA 524 100%

Laboratory Analysis Chloroform LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.05 µg/L EPA 524 100%

Laboratory Analysis Chloromethane LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.06 µg/L EPA 524 100%

Laboratory Analysis cis-1,2-Dichloroethane LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.03 µg/L EPA 524 100%

Laboratory Analysis cis-1,3-Dichloropropene LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.04 µg/L EPA 524 100%

Laboratory Analysis Dibromochloromethane LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.07 µg/L EPA 524 100%

Laboratory Analysis Dibromomethane LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.07 µg/L EPA 524 100%



Target Reporting

Limit

Method Detection


Laboratory Analysis Dichlorodifluoromethane LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.07 µg/L EPA 524 100%

Laboratory Analysis Di-isopropyl ether LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.1 µg/L EPA 524 100%

Laboratory Analysis Ethyl tert-Butyl Ether LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.04 µg/L EPA 524 100%

Laboratory Analysis Ethylbenzene LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.03 µg/L EPA 524 100%


MS & MSD 50-150%; RPD<25%

0.5 0.07 µg/L EPA 524 100%

Laboratory Analysis Iodomethane LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.03 µg/L EPA 524 100%

Laboratory Analysis Isopropylbenzene LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.04 µg/L EPA 524 100%

Laboratory Analysis m,p-Xylene LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.09 µg/L EPA 524 100%

Laboratory Analysis Methyl tert-Butyl Ether LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.05 µg/L EPA 524 100%

Laboratory Analysis Methylene chloride LCS 70-130%

MS & MSD 50-150%; RPD<25%

1 0.08 µg/L EPA 524 100%


MS & MSD 50-150%; RPD<25%

0.5 0.04 µg/L EPA 524 100%



Target Reporting

Limit

Method Detection


Laboratory Analysis n-Butylbenzene LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.04 µg/L EPA 524 100%

Laboratory Analysis n-Propylbenzene LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.04 µg/L EPA 524 100%

Laboratory Analysis o-Xylene LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.04 µg/L EPA 524 100%

Laboratory Analysis sec-Butylbenzene LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.03 µg/L EPA 524 100%

Laboratory Analysis Styrene LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.09 µg/L EPA 524 100%

Laboratory Analysis TBA LCS 70-130%

MS & MSD 50-150%; RPD<25%

1 0.1 µg/L EPA 524 100%

Laboratory Analysis Tert-Amyl Methyl Ether LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.03 µg/L EPA 524 100%

Laboratory Analysis tert-Butylbenzene LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.02 µg/L EPA 524 100%

Laboratory Analysis Tetrachloroethene LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.08 µg/L EPA 524 100%

Laboratory Analysis Toluene LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.04 µg/L EPA 524 100%

Laboratory Analysis Total Trihalomethanes LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.5 µg/L EPA 524 100%



Target Reporting

Limit

Method Detection


Laboratory Analysis trans-1,2-Dichloroethane LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.04 µg/L EPA 524 100%

Laboratory Analysis trans-1,3-Dichloropropene LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.04 µg/L EPA 524 100%

Laboratory Analysis Trichloroethane LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.06 µg/L EPA 524 100%

Laboratory Analysis Trichlorofluoromethane LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.05 µg/L EPA 524 100%

Laboratory Analysis Trichlorotrifluoroethane LCS 70-130%

MS & MSD 50-150%; RPD<25%

1 0.05 µg/L EPA 524 100%

Laboratory Analysis Vinyl chloride LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.06 µg/L EPA 524 100%

Laboratory Analysis Xylenes, total LCS 70-130%

MS & MSD 50-150%; RPD<25%

1 0.1 µg/L EPA 524 100%

Laboratory Analysis 4,4'-DDD LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.1 0.006 µg/L EPA 8081A 100%

Laboratory Analysis 4,4'-DDE LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.1 0.005 µg/L EPA 8081A 100%

Laboratory Analysis 4,4'-DDT LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.1 0.004 µg/L EPA 8081A 100%

Laboratory Analysis Aldrin LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.1 0.011 µg/L EPA 8081A 100%



Target Reporting

Limit

Method Detection


Laboratory Analysis alpha-BHC LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.1 0.011 µg/L EPA 8081A 100%

Laboratory Analysis alpha-Chlordane LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.1 0.006 µg/L EPA 8081A 100%

Laboratory Analysis beta-BHC LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.1 0.011 µg/L EPA 8081A 100%

Laboratory Analysis delta-BHC LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.1 0.021 µg/L EPA 8081A 100%

Laboratory Analysis Dieldrin LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.1 0.006 µg/L EPA 8081A 100%

Laboratory Analysis Endosulfan I LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.1 0.007 µg/L EPA 8081A 100%

Laboratory Analysis Endosulfan II LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.1 0.021 µg/L EPA 8081A 100%

Laboratory Analysis Endosulfan sulfate LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.1 0.005 µg/L EPA 8081A 100%

Laboratory Analysis Endrin LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.1 0.007 µg/L EPA 8081A 100%

Laboratory Analysis Endrin aldehyde LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.1 0.006 µg/L EPA 8081A 100%

Laboratory Analysis Endrin Ketone LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.1 0.005 µg/L EPA 8081A 100%



Target Reporting

Limit

Method Detection


Laboratory Analysis gamma-BHC (Lindane) LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.1 0.013 µg/L EPA 8081A 100%

Laboratory Analysis gamma-Chlordane LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.1 0.005 µg/L EPA 8081A 100%

Laboratory Analysis Heptachlor LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.1 0.016 µg/L EPA 8081A 100%

Laboratory Analysis Heptachlor epoxide LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.1 0.02 µg/L EPA 8081A 100%

Laboratory Analysis Methoxychlor LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.1 0.013 µg/L EPA 8081A 100%

Laboratory Analysis Aroclor 1016 LCS 70-130%

MS & MSD 50-150%; RPD<25%

1 0.06 µg/L EPA 8081A 100%


MS & MSD 50-150%; RPD<25%

1 0.13 µg/L EPA 8081A 100%


MS & MSD 50-150%; RPD<25%

1 0.1 µg/L EPA 8081A 100%


MS & MSD 50-150%; RPD<25%

1 0.06 µg/L EPA 8081A 100%


MS & MSD 50-150%; RPD<25%

1 0.06 µg/L EPA 8081A 100%


MS & MSD 50-150%; RPD<25%

1 0.09 µg/L EPA 8081A 100%



Target Reporting

Limit

Method Detection



MS & MSD 50-150%; RPD<25%

1 0.08 µg/L EPA 8081A 100%

Laboratory Analysis PCBs LCS 70-130%

MS & MSD 50-150%; RPD<25%

1 0.08 µg/L EPA 8081A 100%


MS & MSD 50-150%; RPD<25%

2 0.6 µg/L EPA 8270C 100%


MS & MSD 50-150%; RPD<25%

2 0.4 µg/L EPA 8270C 100%

Laboratory Analysis 2,4,5-Trichlorophenol LCS 70-130%

MS & MSD 50-150%; RPD<25%

5 1.6 µg/L EPA 8270C 100%

Laboratory Analysis 2,4,6-Trichlorophenol LCS 70-130%

MS & MSD 50-150%; RPD<25%

5 1.6 µg/L EPA 8270C 100%

Laboratory Analysis 2,4-Dichlorophenol LCS 70-130%

MS & MSD 50-150%; RPD<25%

2 0.8 µg/L EPA 8270C 100%

Laboratory Analysis 2,4-Dimethylphenol LCS 70-130%

MS & MSD 50-150%; RPD<25%

2 0.8 µg/L EPA 8270C 100%

Laboratory Analysis 2,4-Dinitrophenol LCS 70-130%

MS & MSD 50-150%; RPD<25%

10 0.3 µg/L EPA 8270C 100%

Laboratory Analysis 2,4-Dinitrotoluene LCS 70-130%

MS & MSD 50-150%; RPD<25%

2 0.8 µg/L EPA 8270C 100%

Laboratory Analysis 2,6-Dinitrotoluene LCS 70-130%

MS & MSD 50-150%; RPD<25%

2 0.8 µg/L EPA 8270C 100%



Target Reporting

Limit

Method Detection


Laboratory Analysis 2-Chloronaphthalene LCS 70-130%

MS & MSD 50-150%; RPD<25%

2 0.2 µg/L EPA 8270C 100%

Laboratory Analysis 2-Chlorophenol LCS 70-130%

MS & MSD 50-150%; RPD<25%

2 0.8 µg/L EPA 8270C 100%

Laboratory Analysis 2-Methylnaphthalene LCS 70-130%

MS & MSD 50-150%; RPD<25%

2 0.6 µg/L EPA 8270C 100%

Laboratory Analysis 2-Methylphenol LCS 70-130%

MS & MSD 50-150%; RPD<25%

2 0.4 µg/L EPA 8270C 100%

Laboratory Analysis 2-Nitroaniline LCS 70-130%

MS & MSD 50-150%; RPD<25%

2 0.4 µg/L EPA 8270C 100%

Laboratory Analysis 2-Nitrophenol LCS 70-130%

MS & MSD 50-150%; RPD<25%

2 1.2 µg/L EPA 8270C 100%

Laboratory Analysis 3,3´-Dichlorobenzidine LCS 70-130%

MS & MSD 50-150%; RPD<25%

5 0.8 µg/L EPA 8270C 100%


MS & MSD 50-150%; RPD<25%

2 0.5 µg/L EPA 8270C 100%

Laboratory Analysis 4,6-Dinitro-2-methylphenol LCS 70-130%

MS & MSD 50-150%; RPD<25%

10 2.2 µg/L EPA 8270C 100%

Laboratory Analysis 4-Bromophenyl phenyl ether LCS 70-130%

MS & MSD 50-150%; RPD<25%

2 0.8 µg/L EPA 8270C 100%

Laboratory Analysis 4-Chloro-3-methylphenol LCS 70-130%

MS & MSD 50-150%; RPD<25%

2 0.6 µg/L EPA 8270C 100%



Target Reporting

Limit

Method Detection


Laboratory Analysis 4-Chloroaniline LCS 70-130%

MS & MSD 50-150%; RPD<25%

2 0.5 µg/L EPA 8270C 100%

Laboratory Analysis 4-Chlorophenyl phenyl ether LCS 70-130%

MS & MSD 50-150%; RPD<25%

2 0.5 µg/L EPA 8270C 100%


MS & MSD 50-150%; RPD<25%

2 0.6 µg/L EPA 8270C 100%


MS & MSD 50-150%; RPD<25%

5 0.1 µg/L EPA 8270C 100%

Laboratory Analysis Acenaphthene LCS 70-130%

MS & MSD 50-150%; RPD<25%

2 0.6 µg/L EPA 8270C 100%

Laboratory Analysis Acenaphthylene LCS 70-130%

MS & MSD 50-150%; RPD<25%

2 0.3 µg/L EPA 8270C 100%

Laboratory Analysis Aniline LCS 70-130%

MS & MSD 50-150%; RPD<25%

2 0.3 µg/L EPA 8270C 100%

Laboratory Analysis Anthracene LCS 70-130%

MS & MSD 50-150%; RPD<25%

2 0.3 µg/L EPA 8270C 100%

Laboratory Analysis Azobenzene LCS 70-130%

MS & MSD 50-150%; RPD<25%

2 0.4 µg/L EPA 8270C 100%

Laboratory Analysis Benzidine LCS 70-130%

MS & MSD 50-150%; RPD<25%

5 0.2 µg/L EPA 8270C 100%

Laboratory Analysis Benzo (a) anthracene LCS 70-130%

MS & MSD 50-150%; RPD<25%

2 0.4 µg/L EPA 8270C 100%



Target Reporting

Limit

Method Detection


Laboratory Analysis Benzo (a) pyrene LCS 70-130%

MS & MSD 50-150%; RPD<25%

5 1.2 µg/L EPA 8270C 100%

Laboratory Analysis Benzo (b) fluoranthene LCS 70-130%

MS & MSD 50-150%; RPD<25%

2 0.8 µg/L EPA 8270C 100%

Laboratory Analysis Benzo (g,h,i) perylene LCS 70-130%

MS & MSD 50-150%; RPD<25%

2 1.3 µg/L EPA 8270C 100%

Laboratory Analysis Benzo (k) fluoranthene LCS 70-130%

MS & MSD 50-150%; RPD<25%

2 1 µg/L EPA 8270C 100%

Laboratory Analysis Benzoic acid LCS 70-130%

MS & MSD 50-150%; RPD<25%

30 0.5 µg/L EPA 8270C 100%

Laboratory Analysis Benzyl alcohol LCS 70-130%

MS & MSD 50-150%; RPD<25%

2 0.4 µg/L EPA 8270C 100%

Laboratory Analysis Bis(2-chloroethoxy)methane LCS 70-130%

MS & MSD 50-150%; RPD<25%

2 0.4 µg/L EPA 8270C 100%

Laboratory Analysis Bis(2-chloroethyl)ether LCS 70-130%

MS & MSD 50-150%; RPD<25%

2 0.6 µg/L EPA 8270C 100%

Laboratory Analysis Bis(2-chloroisopropyl)ether LCS 70-130%

MS & MSD 50-150%; RPD<25%

2 0.4 µg/L EPA 8270C 100%

Laboratory Analysis Bis(2-ethylhexyl)phthalate LCS 70-130%

MS & MSD 50-150%; RPD<25%

5 0.7 µg/L EPA 8270C 100%

Laboratory Analysis Butyl benzyl phthalate LCS 70-130%

MS & MSD 50-150%; RPD<25%

2 1 µg/L EPA 8270C 100%



Target Reporting

Limit

Method Detection


Laboratory Analysis Carbazole LCS 70-130%

MS & MSD 50-150%; RPD<25%

2 0.6 µg/L EPA 8270C 100%

Laboratory Analysis Chrysene LCS 70-130%

MS & MSD 50-150%; RPD<25%

2 0.5 µg/L EPA 8270C 100%

Laboratory Analysis Dibenz (a,h) anthracene LCS 70-130%

MS & MSD 50-150%; RPD<25%

2 1.6 µg/L EPA 8270C 100%

Laboratory Analysis Dibenzofuran LCS 70-130%

MS & MSD 50-150%; RPD<25%

2 0.3 µg/L EPA 8270C 100%

Laboratory Analysis Diethyl phthalate LCS 70-130%

MS & MSD 50-150%; RPD<25%

2 0.6 µg/L EPA 8270C 100%

Laboratory Analysis Dimethyl phthalate LCS 70-130%

MS & MSD 50-150%; RPD<25%

2 0.8 µg/L EPA 8270C 100%

Laboratory Analysis Di-n-butyl phthalate LCS 70-130%

MS & MSD 50-150%; RPD<25%

2 0.4 µg/L EPA 8270C 100%

Laboratory Analysis Di-n-octyl phthalate LCS 70-130%

MS & MSD 50-150%; RPD<25%

5 0.7 µg/L EPA 8270C 100%

Laboratory Analysis Fluoranthene LCS 70-130%

MS & MSD 50-150%; RPD<25%

2 0.6 µg/L EPA 8270C 100%

Laboratory Analysis Fluorene LCS 70-130%

MS & MSD 50-150%; RPD<25%

2 0.5 µg/L EPA 8270C 100%

Laboratory Analysis Hexachlorobenzene LCS 70-130%

MS & MSD 50-150%; RPD<25%

2 0.6 µg/L EPA 8270C 100%



Target Reporting

Limit

Method Detection



MS & MSD 50-150%; RPD<25%

2 0.6 µg/L EPA 8270C 100%

Laboratory Analysis Hexachlorocyclopentadiene LCS 70-130%

MS & MSD 50-150%; RPD<25%

2 0.6 µg/L EPA 8270C 100%

Laboratory Analysis Hexachloroethane LCS 70-130%

MS & MSD 50-150%; RPD<25%

2 0.5 µg/L EPA 8270C 100%

Laboratory Analysis Indeno (1,2,3-cd) pyrene LCS 70-130%

MS & MSD 50-150%; RPD<25%

5 1.6 µg/L EPA 8270C 100%

Laboratory Analysis Isophorone LCS 70-130%

MS & MSD 50-150%; RPD<25%

2 0.3 µg/L EPA 8270C 100%


MS & MSD 50-150%; RPD<25%

2 0.5 µg/L EPA 8270C 100%

Laboratory Analysis Nitrobenzene LCS 70-130%

MS & MSD 50-150%; RPD<25%

2 0.7 µg/L EPA 8270C 100%

Laboratory Analysis N-Nitrosodimethylamine LCS 70-130%

MS & MSD 50-150%; RPD<25%

2 0.4 µg/L EPA 8270C 100%

Laboratory Analysis N-Nitrosodi-n-propylamine LCS 70-130%

MS & MSD 50-150%; RPD<25%

2 0.3 µg/L EPA 8270C 100%

Laboratory Analysis N-Nitrosodiphenylamine LCS 70-130%

MS & MSD 50-150%; RPD<25%

2 0.6 µg/L EPA 8270C 100%

Laboratory Analysis Pentachlorophenol LCS 70-130%

MS & MSD 50-150%; RPD<25%

10 2.4 µg/L EPA 8270C 100%



Target Reporting

Limit

Method Detection


Laboratory Analysis Phenanthrene LCS 70-130%

MS & MSD 50-150%; RPD<25%

2 0.4 µg/L EPA 8270C 100%

Laboratory Analysis Phenol LCS 70-130%

MS & MSD 50-150%; RPD<25%

2 0.3 µg/L EPA 8270C 100%

Laboratory Analysis Pyrene LCS 70-130%

MS & MSD 50-150%; RPD<25%

2 1 µg/L EPA 8270C 100%

Laboratory Analysis Azinphos-methyl LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.2 0.027 µg/L EPA 8141A 100%

Laboratory Analysis Bolstar LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.2 0.086 µg/L EPA 8141A 100%

Laboratory Analysis Coumaphos LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.2 0.168 µg/L EPA 8141A 100%

Laboratory Analysis Demeton LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.2 0.105 µg/L EPA 8141A 100%

Laboratory Analysis Demeton-O LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.2 0.101 µg/L EPA 8141A 100%

Laboratory Analysis Demeton-S LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.2 0.105 µg/L EPA 8141A 100%

Laboratory Analysis Diazinon LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.25 0.065 µg/L EPA 8141A 100%

Laboratory Analysis Dichlorvos LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.2 0.156 µg/L EPA 8141A 100%



Target Reporting

Limit

Method Detection


Laboratory Analysis Dimethoate LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.2 0.071 µg/L EPA 8141A 100%

Laboratory Analysis Disulfoton LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.2 0.069 µg/L EPA 8141A 100%

Laboratory Analysis Dursban (Chlorpyrifos) LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.2 0.071 µg/L EPA 8141A 100%

Laboratory Analysis EPN LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.2 0.124 µg/L EPA 8141A 100%

Laboratory Analysis Ethoprop LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.2 0.077 µg/L EPA 8141A 100%

Laboratory Analysis Fensulfothion LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.2 0.139 µg/L EPA 8141A 100%

Laboratory Analysis Fenthion LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.2 0.067 µg/L EPA 8141A 100%

Laboratory Analysis Gardona (Stirophos) LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.2 0.11 µg/L EPA 8141A 100%

Laboratory Analysis Malathion LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.2 0.159 µg/L EPA 8141A 100%

Laboratory Analysis Merphos LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.2 0.097 µg/L EPA 8141A 100%

Laboratory Analysis Mevinphos LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.2 0.115 µg/L EPA 8141A 100%



Target Reporting

Limit

Method Detection


Laboratory Analysis Molinate LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.2 0.044 µg/L EPA 8141A 100%

Laboratory Analysis Monocrotophos LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.2 0.015 µg/L EPA 8141A 100%

Laboratory Analysis Naled LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.2 0.169 µg/L EPA 8141A 100%

Laboratory Analysis Parathion LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.2 0.079 µg/L EPA 8141A 100%

Laboratory Analysis Parathion-methyl LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.2 0.077 µg/L EPA 8141A 100%

Laboratory Analysis Phorate LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.2 0.083 µg/L EPA 8141A 100%

Laboratory Analysis Ronnel LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.2 0.066 µg/L EPA 8141A 100%

Laboratory Analysis Sulfotep LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.2 0.095 µg/L EPA 8141A 100%

Laboratory Analysis TEPP LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.2 0.151 µg/L EPA 8141A 100%

Laboratory Analysis Tokuthion (Prothiofos) LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.2 0.077 µg/L EPA 8141A 100%

Laboratory Analysis Trichloronate LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.2 0.067 µg/L EPA 8141A 100%



Target Reporting

Limit

Method Detection


Laboratory Analysis 2,4,5-T LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.097 µg/L EPA 8151A 100%

Laboratory Analysis 2,4,5-TP (Silvex) LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.5 0.095 µg/L EPA 8151A 100%

Laboratory Analysis 2,4-D LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.4 0.086 µg/L EPA 8151A 100%

Laboratory Analysis 2,4-DB LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.8 0.157 µg/L EPA 8151A 100%

Laboratory Analysis 3,5-Dichlorobenzoic acid LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.8 0.17 µg/L EPA 8151A 100%


MS & MSD 50-150%; RPD<25%

0.6 0.117 µg/L EPA 8151A 100%

Laboratory Analysis Acifluorfen LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.8 0.157 µg/L EPA 8151A 100%

Laboratory Analysis Bentazon LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.6 0.11 µg/L EPA 8151A 100%

Laboratory Analysis Chloramben LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.8 0.008 µg/L EPA 8151A 100%

Laboratory Analysis Dalapon LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.6 0.115 µg/L EPA 8151A 100%

Laboratory Analysis DCPA LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.4 0.015 µg/L EPA 8151A 100%



Target Reporting

Limit

Method Detection


Laboratory Analysis Dicamba LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.4 0.08 µg/L EPA 8151A 100%

Laboratory Analysis Dichloroprop LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.8 0.196 µg/L EPA 8151A 100%

Laboratory Analysis Dinoseb LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.4 0.083 µg/L EPA 8151A 100%

Laboratory Analysis MCPP LCS 70-130%

MS & MSD 50-150%; RPD<25%

10 0.891 µg/L EPA 8151A 100%

Laboratory Analysis Pentachlorophenol LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.3 0.053 µg/L EPA 8151A 100%

Laboratory Analysis Picloram LCS 70-130%

MS & MSD 50-150%; RPD<25%

0.8 0.02 µg/L EPA 8151A 100%

Laboratory Analysis Hexavalent Chromium LCS 80-120%

MS & MSD 80-120%, RPD<25%

1 0.1 µg/L EPA 218.6 100%

Laboratory Analysis Chloride LCS 80-120%

MS & MSD 80-120%, RPD<25%

0.5 0.04 mg/L EPA 300.0 100%

Laboratory Analysis Fluoride LCS 90%-110%

MS & MSD 75-125%, RPD<20%

0.1 0.02 mg/L EPA 300.0 100%

Laboratory Analysis Nitrate as Nitrogen LCS 90%-110%

MS & MSD 75-125%, RPD<20%

0.11 0.009 mg/L EPA 300.0 100%

Laboratory Analysis Nitrite as Nitrogen LCS 90%-110%

MS & MSD 75-125%, RPD<20%

0.15 0.03 mg/L EPA 300.0 100%



Target Reporting

Limit

Method Detection


Laboratory Analysis Sulfate as SO4 LCS 80-120%

MS & MSD 80-120%, RPD<25%

5 0.7 mg/L EPA 300.0 100%

Laboratory Analysis Perchlorate LCS 85%-115%

MS & MSD 75-125%, RPD<20%

2 0.094 µg/L EPA 314.0 100%

Laboratory Analysis Specific Conductance (EC) N/A N/A 5 1.09 µS/cm EPA 120.1 100%

Laboratory Analysis Total Dissolved Solids N/A N/A 15 7.68 mg/L SM 2540C 100%

Laboratory Analysis Cyanide LCS 70%-130%

MS & MSD 70-130%, RPD<30%

0.005 0.0009 mg/L SM 4500CN E 100%

Laboratory Analysis pH N/A N/A 0.1 0.1 pH

Units SM 4500-H+ B 100%

Laboratory Analysis Ammonia as N LCS 90-110%

MS & MSD 80-120%, RPD<25%

0.1 0.04 mg/L SM 4500-NH3 B/H 100%

Laboratory Analysis MBAS LCS 90-110% No MS & MSD 0.1 0.06 mg/L SM 5540C 100%

Laboratory Analysis Total Alkalinity LCS 80-120%

MS & MSD 80-120%, RPD<20%

5 2.37 mg/L SM2320B 100%

Laboratory Analysis Total Hardness LCS 80-120%

MS & MSD 75-125%, RPD<20%

5 2.86 mg/L SM2340B 100%

Laboratory Analysis Aluminum LCS 80-120%

MS & MSD 80-120%, RPD<25%

50 24.5 µg/L EPA 200.7 100%

Laboratory Analysis Antimony LCS 80-120%

MS & MSD 80-120%, RPD<25%

10 1.3 µg/L EPA 200.7 100%



Target Reporting

Limit

Method Detection


Laboratory Analysis Arsenic LCS 80-120%

MS & MSD 80-120%, RPD<25%

10 1 µg/L EPA 200.7 100%

Laboratory Analysis Barium LCS 80-120%

MS & MSD 80-120%, RPD<25%

5 1.2 µg/L EPA 200.7 100%

Laboratory Analysis Beryllium LCS 80-120%

MS & MSD 80-120%, RPD<25%

5 0.09 µg/L EPA 200.7 100%

Laboratory Analysis Boron LCS 80-120%

MS & MSD 80-120%, RPD<25%

50 0.8 µg/L EPA 200.7 100%

Laboratory Analysis Cadmium LCS 80-120%

MS & MSD 80-120%, RPD<25%

5 0.1 µg/L EPA 200.7 100%

Laboratory Analysis Calcium LCS 80-120%

MS & MSD 80-120%, RPD<25%

100 79 µg/L EPA 200.7 100%

Laboratory Analysis Chromium LCS 80-120%

MS & MSD 80-120%, RPD<25%

5 0.3 µg/L EPA 200.7 100%

Laboratory Analysis Copper LCS 80-120%

MS & MSD 80-120%, RPD<25%

5 0.8 µg/L EPA 200.7 100%

Laboratory Analysis Iron LCS 80-120%

MS & MSD 80-120%, RPD<25%

20 11.5 µg/L EPA 200.7 100%

Laboratory Analysis Lead LCS 80-120%

MS & MSD 80-120%, RPD<25%

5 0.9 µg/L EPA 200.7 100%

Laboratory Analysis Magnesium LCS 80-120%

MS & MSD 80-120%, RPD<25%

50 15.6 µg/L EPA 200.7 100%



Target Reporting

Limit

Method Detection


Laboratory Analysis Manganese LCS 80-120%

MS & MSD 80-120%, RPD<25%

10 0.6 µg/L EPA 200.7 100%

Laboratory Analysis Nickel LCS 80-120%

MS & MSD 80-120%, RPD<25%

5 0.6 µg/L EPA 200.7 100%

Laboratory Analysis Selenium LCS 80-120%

MS & MSD 80-120%, RPD<25%

20 1.3 µg/L EPA 200.7 100%

Laboratory Analysis Silver LCS 80-120%

MS & MSD 80-120%, RPD<25%

5 0.4 µg/L EPA 200.7 100%

Laboratory Analysis Sodium LCS 80-120%

MS & MSD 80-120%, RPD<25%

200 120 µg/L EPA 200.7 100%

Laboratory Analysis Thallium LCS 80-120%

MS & MSD 80-120%, RPD<25%

20 2.2 µg/L EPA 200.7 100%

Laboratory Analysis Titanium LCS 80-120%

MS & MSD 80-120%, RPD<25%

50 1.2 µg/L EPA 200.7 100%

Laboratory Analysis Zinc LCS 80-120%

MS & MSD 80-120%, RPD<25%

10 0.3 µg/L EPA 200.7 100%

Laboratory Analysis Dissolved Aluminum LCS 80-120%

MS & MSD 80-120%, RPD<25%

50 24.5 µg/L EPA 200.7 100%

Laboratory Analysis Dissolved Arsenic LCS 80-120%

MS & MSD 80-120%, RPD<25%

10 1 µg/L EPA 200.7 100%

Laboratory Analysis Dissolved Iron LCS 80-120%

MS & MSD 80-120%, RPD<25%

20 11.5 µg/L EPA 200.7 100%



Target Reporting

Limit

Method Detection


Laboratory Analysis Dissolved Lead LCS 80-120%

MS & MSD 80-120%, RPD<25%

5 0.9 µg/L EPA 200.7 100%

Laboratory Analysis 1,2,3,4,6,7,8-HpCDD LCS 70-130%

MS & MSD 50-150%; RPD<25%

50 2.17 pg/L 1613B 100%

Laboratory Analysis 1,2,3,4,6,7,8-HpCDF LCS 70-130%

MS & MSD 50-150%; RPD<25%

50 3.77 pg/L 1613B 100%

Laboratory Analysis 1,2,3,4,7,8,9-HpCDF LCS 70-130%

MS & MSD 50-150%; RPD<25%

50 4.61 pg/L 1613B 100%

Laboratory Analysis 1,2,3,4,7,8-HxCDD LCS 70-130%

MS & MSD 50-150%; RPD<25%

50 3.98 pg/L 1613B 100%

Laboratory Analysis 1,2,3,4,7,8-HxCDF LCS 70-130%

MS & MSD 50-150%; RPD<25%

50 3.66 pg/L 1613B 100%


MS & MSD 50-150%; RPD<25%

50 5.34 pg/L 1613B 100%


MS & MSD 50-150%; RPD<25%

50 3.97 pg/L 1613B 100%


MS & MSD 50-150%; RPD<25%

50 4.68 pg/L 1613B 100%


MS & MSD 50-150%; RPD<25%

50 8.74 pg/L 1613B 100%

Laboratory Analysis 1,2,3,7,8-PeCDD LCS 70-130%

MS & MSD 50-150%; RPD<25%

50 2.29 pg/L 1613B 100%



Target Reporting

Limit

Method Detection


Laboratory Analysis 1,2,3,7,8-PeCDF LCS 70-130%

MS & MSD 50-150%; RPD<25%

50 2.58 pg/L 1613B 100%


MS & MSD 50-150%; RPD<25%

50 4.97 pg/L 1613B 100%

Laboratory Analysis 2,3,4,7,8-PeCDF LCS 70-130%

MS & MSD 50-150%; RPD<25%

50 2.36 pg/L 1613B 100%

Laboratory Analysis 2,3,7,8-TCDD LCS 70-130%

MS & MSD 50-150%; RPD<25%

10 2.2 pg/L 1613B 100%

Laboratory Analysis 2,3,7,8-TCDF LCS 70-130%

MS & MSD 50-150%; RPD<25%

10 2.01 pg/L 1613B 100%

Laboratory Analysis OCDD LCS 70-130%

MS & MSD 50-150%; RPD<25%

100 4.32 pg/L 1613B 100%

Laboratory Analysis OCDF LCS 70-130%

MS & MSD 50-150%; RPD<25%

100 6.25 pg/L 1613B 100%

Laboratory Analysis TEQ LCS 70-130%

MS & MSD 50-150%; RPD<25%

N/A N/A pg/L 1613B 100%

Laboratory Analysis Total HpCDD LCS 70-130%

MS & MSD 50-150%; RPD<25%

50 3.06 pg/L 1613B 100%

Laboratory Analysis Total HpCDF LCS 70-130%

MS & MSD 50-150%; RPD<25%

50 4.61 pg/L 1613B 100%

Laboratory Analysis Total HxCDD LCS 70-130%

MS & MSD 50-150%; RPD<25%

50 5.34 pg/L 1613B 100%



Target Reporting

Limit

Method Detection


Laboratory Analysis Total HxCDF LCS 70-130%

MS & MSD 50-150%; RPD<25%

50 8.74 pg/L 1613B 100%

Laboratory Analysis Total PeCDD LCS 70-130%

MS & MSD 50-150%; RPD<25%

50 2.29 pg/L 1613B 100%

Laboratory Analysis Total PeCDF LCS 70-130%

MS & MSD 50-150%; RPD<25%

50 2.58 pg/L 1613B 100%

Laboratory Analysis Total TCDD LCS 70-130%

MS & MSD 50-150%; RPD<25%

10 2.2 pg/L 1613B 100%

Laboratory Analysis Total TCDF LCS 70-130%

MS & MSD 50-150%; RPD<25%

10 2.01 pg/L 1613B 100%

List of Acronym LCS Laboratory Control Spike MS Matrix Spike MSD Matrix Spike Duplicate RPD Relative Percent Difference P/A Presence/Absence


A8, Element 8. Special Training Needs/Certification Specialized training or certifications No specialized training or certifications are required for field staff for this project. The State Water Resources Control Board’s Division of Drinking Water has certified ExcelChem Environmental Labs. The QA officer for ExcelChem lab is responsible for overseeing training of lab staff to achieve and maintain high standards of quality. All staff involved will be familiar with the field guidelines, fully trained in the Rinsing Technique and Sample Collection method of water sample collection, and procedures as outlined in the Sample Procedures Manual (Appendix 14). If necessary, additional training will be provided by Central Valley Water Board staff. Field staff will be required to review the SWAMP training manuals on field measurements and water sampling techniques, sample processing procedures, and the procedures outlined in Appendices 3 – 13 of this QAPP, as needed. Training personnel Central Valley Water Board staff is trained annually on field procedures. Training is overseen by program managers who are responsible for their area of expertise. Training records for Central Valley Water Board staff are maintained at the Central Valley Water Board office. Laboratory safety manual and safety training records are maintained in the Central Valley Water Board’s main lab.


A9, Element 9. Documents and Records Documents and records generated from this project will be organized and stored in compliance with this QAPP. This will allow for future retrieval, and for specifying the location and holding times of all records. QAPP updates and distribution All originals of the first and subsequent amended QAPPs will be held at the Central Valley Water Board office by the Monitoring Lead. The Monitoring Lead will be responsible for the distribution of the QAPP and posting to the project website. Any future amended QAPPs will be held and distributed. Records to be included in data reports Data reports for each sampling event will include field data, laboratory data, chain of custody forms, and associated QA reports. All field data will be recorded at the time of completion, using the field data sheet (see Appendix 8). Samples being sent to the ExcelChem Environmental Labs in Rocklin, CA will include a Chain of Custody (CoC) form (Appendix 10). The laboratory will generate records for sample receipt and storage, analyses and reporting. All records will be delivered to the Central Valley Water Board Monitoring Lead, True Khang, within 45 days of sample submission. Persons responsible for maintaining records The Monitoring Lead will maintain the project file, to include the original QAPP and Monitoring Plan, and subsequent revisions. The project file will also contain correspondence regarding decisions made, data reports, draft project report and final project report. Electronic records All data verified by the Monitoring Lead (field measurements) will be entered and stored in Excel spreadsheets. Key constituent data will be verified first by the Laboratory Director for ExcelChem. After verification, key constituents data and laboratory QA will be forwarded electronically in PDF format to the Monitoring Lead. All key constituents data will be stored in Excel spreadsheets in order to more readily review the data. The Monitoring Lead will store the data reports on the Central Valley Water Board network drive, which is backed up nightly.


B1, Element 10. Sampling Process Design The monitoring will be conducted at 6 sampling locations over a one-day period (June 20, 2016) in order to demonstrate water quality in the main stem of the Sacramento and Feather Rivers. Final design was reviewed by the CV-SALTS Technical Committee. For all sites, safety and all-weather access are priorities for sampling activities. Based on field and weather conditions, the sampling plan may be modified by the project team during the sampling event to provide for field safety and make the collection accurate and thorough. Any changes will be documented on SWAMP field sheets. Type and Total Number of Samples All field parameters and bacteria will be monitored once at all sites, with the exception of turbidity, which will be monitored three times per site. This study will analyze for all primary and secondary MCLs specified in Title 22, except for asbestos and radionuclides. In addition, E. coli and drinking water constituents of concern will be measured, and field measurements (DO, SC, pH, temperature, and turbidity) will be taken. Travel blanks and field duplicates will be taken at a frequency of 5% of the total project sample count.


Table 6 Sacramento River Basin Monitoring Sites

Map Label Station Code Site Latitude Longitude

1 519SACVER Sacramento River Below Verona 38.78093 -121.60609 2 515FRNVxx Feather River near Verona 38.79316 -121.62785 3 520SUT003 Sacramento River above Colusa Basin Drain 38.81440 -121.72350

4 Sacramento River by Rough and Ready Pumping Plant 38.86585 -121.79476

519SUT002 Sacramento River below Knights Landing 38.76064 -121.67824

5 Sacramento River at Elkhorn Boat Launch Facility 38.67245 -121.62500

Sampling Location Sampling sites were selected based on accessibility, presence of water, and overall representative of water body. Consideration was also given to potential use of the resulting data by other programs and agencies. GPS coordinates have been obtained from site reconnaissance conducted by the Central Valley Water Board staff in May 2016, and or retrieved from the SWAMP database. A description of each sampling site is included in Appendix 1. Inaccessible Sample Sites If sampling locations become inaccessible, field crews will look for an alternate site within 100 yards of the original sampling site. If no alternative site can be located, no sample will be collected. Project Activity Schedule Sampling events will take place within the sample collection periods listed in the project schedule in A6 Element 6. Field parameters will be measured on site. Samples to be analyzed in labs and will be transported to the respective labs at the end of the field run. Bias – Sources and Minimization Sample misrepresentation occurs at the level of an individual sample or field measurement (e.g., collecting a water sample at a backwater pool that does not represent the bulk of the flow) and will be minimized by using SWAMP compliant training and sampling methods. Representativeness and bias are addressed in more detail in A7, Element 7.


B2, Element 11. Sampling Methods Grab samples are to be collected at stream banks at the location of greatest flow (at least one inch below the surface) by direct submersion of the sample bottle. Stagnant water will not be sampled and photographs will be taken of the stagnant pool. Samples will be collected using the Rinsing Technique and Sample Collection located in the Procedures Manual for Water Quality Monitoring (Appendix 6). Rinsing Technique and Sample Collection: When rinsing, rinse and discard sample water down-stream of where the sample is to be taken. Try not to disturb sediment or any other debris that could alter the sample. Avoid floating impurities, sediment disturbed by sampling, and organic material. Stream Bank Grab Sample Collection 1. Remove lid. 2. Submerse bottle into sample water area filling about ¼ of the way. 3. Lift sample out of water and move away/downstream from sampling spot. 4. Agitate sample thoroughly, to rinse the inside of the container, and pour out. 5. Repeat Steps 2-4 two more times. 6. Collect the sample by submerging the bottle below the surface of the water and facing it

up stream. Be sure to collect a full bottle and not disturb the bottom sediment. 7. Pour a small amount of the sample into the cap for rinsing, discard rinse water, and cap

the sample. The Rinsing Technique and Sample Collection method will be used to fill the 125 mL polyethylene bottles. The 125 mL bottles will be analyzed for MBAs, Total Dissolved Solids, Nitrate as Nitrogen, and Nitrite as Nitrogen. The 250 mL polyethylene bottles contain nitric acid (HNO3) and cannnot be rinsed. A separate 500 mL bottle will be filled using the Rinsing Technique and Sample Collection method. Once the 500 mL bottle is filled, it will then be transferred to the 250 mL bottle. The 250 mL bottles with nitric acid preservative will be analyzed for boron, total iron, sodium, total aluminum, total


arsenic, and total manganese. Three 40 mL VOA vials contain hydrochloric acid (HCL) and also cannot be rinsed. The three VOA vials will be used to analyze the full list for volatile organic compounds. An additional VOA vial will be used to analyze Carbamate pesticides. A stainless steel cup attached to a metal pole to perform steps 2-6 of the Rinsing Technique and Sample Collection method. The stainless steel cup will then be used to transfer sample water into all four VOA vials until the surface tension builds a meniscus and then capped tightly to avoid bubbles. Organochlorine pesticides, PCBs, Organophosphates, Chlorinated Herbicides, Semi-Volatile Organics, and Dioxin analysis will all need to be collected in amber glass containers. The amber glass containers will all contain preservatives, thus the amber glass containers will not be rinsed with sample water. A stainless steel cup attached to a metal pole to perform steps 2-6 of the Rinsing Technique and Sample Collection method. The stainless steel cup will then be used to transfer sample water into the appropriate amber glass container. Dioxin analysis will require two 1 Liter glass amber containers. Chlorinated herbicides, organophosphates, PCBs, Organochlorine pesticides, and semi-volatiles analysis each require 1 Liter glass amber containers Field preparation Field run preparation will consist of preparing field sheets (Appendix 8), bacteria processing sheet (Appendix 9), chain of custody forms (Appendix 10), sample labels, sample collection bottles, and verifying equipment functionality and availability. Central Valley Water Board staff will be responsible for preparing all forms and obtaining sample bottles from ExcelChem environmental labs. On the day of the field run, prior to leaving the office, CVWB field personnel must sign out on the Ag and Surface Water Assessment Unit/Ag Regulatory Planning (ASWAU/ARP) sign out board located in the ASWAU/ARP section. Noting a mobile phone number and providing a map and anticipated schedule for sample collection. Additionally, prior to leaving the office, CVWB samplers will need to complete the vehicle travel log and check the vehicle's tire pressure, oil, coolant, lights, etc. in order to avoid problems and/or delays while in the field. Report any major maintenance needed to the appropriate personnel and if needed retrieve an alternate truck. Sample volume and bottle type Specific conductivity, temperature, pH, and dissolved oxygen will be taken on site and do not require a sample volume or collection bottle. Turbidity will be analyzed three times using the portable turbidimeter model 2100P from Hach.


Sample water will be collected using a stainless steel cup on a metal pole using the Rinsing Technique and Sample Collection method. The sample water will then be transferred from the stainless steel cup to a 15 mL sample cell. The 15 mL sample cell will then be placed into the turbidimeter to analyze for turbidity. Samples collected for boron, total iron, sodium, total aluminum, total arsenic, total manganese, and cyanide will be collected in 250 mL pre-acidified plastic bottles supplied by ExcelChem environmental labs. Samples collected for dissolved metals will be collected in 500 mL plastic bottles supplied by ExcelChem environmental labs. The water samples will not be field filtered, and filtering will be conducted by ExcelChem environmental labs. Samples collected for nitrate as nitrogen, nitrite as nitrogen, ammonia, perchlorate, chromium VI, and MBAs will be collected in individual 125 mL plastic bottles supplied by ExcelChem environmental labs. Samples collected for the volatile organic compound scan and Carbamate pesticide scan will be collected in four 40 mL pre-acidified VOA vials supplied by ExcelChem environmental labs. There will be emphasis on no headspace in filling the VOA vials. Samples collected for semi-volatiles, Organo-Chlorinated Pesticides, Organo-Phosphorus Pesticide, Polychlorinated Biphenyls, Dioxins/Furans, Chlorinated Herbicide will be collected in individual 1 L amber glass bottles supplied by ExcelChem environmental labs. Sample preservation and holding times Samples collected for volatile organic compounds will be collected using sample bottles pre-preserved with hydrochloric acid from ExcelChem environmental labs. Water samples analyzed for boron, sodium, iron, aluminum, arsenic, manganese, and dissolved metals will be preserved by using ExcelChem environmental labs sample bottles containing nitric acid. Samples collected for ammonia will be collected using sample bottles pre-acidified with sulfuric acid. Samples collected for carbamate will be collected with sample bottles containing with sodium thiosulfate. Samples collected for chromium VI will be collected with sample bottles containing chromium VI buffer. Samples collected for cyanide will be collected with sample bottles containing sodium hydroxide. All samples to be analyzed in the lab will be preserved on ice at ≤5°C and transported in coolers (darkness) to the analytical labs.


Sample equipment All sample collection items are located in the Central Valley Water Board office. Most items are stored in areas specifically designated for the Ag Surface Water and Assessment Unit (ASWAU). The Calibration Room is a laboratory prep room located adjacent to the ASWAU lab, which is separate from the Central Valley Water Board’s main lab. Sample collection equipment will consist of the following items: Safety:

Equipment Location Roadside Emergency Kit Garage ASWAU Locker Toolbox Garage ASWAU Locker First Aid Kit Garage ASWAU Locker Jumper Cables Garage ASWAU Locker Rain Gear (as needed) Garage ASWAU Locker Floatation Vests (1 per sampler) Garage ASWAU Locker

Field run requirements:

Equipment Location Ag/RB/SWAMP Field Books Calibration Room Clipboards w/field sheets Calibration Room pH/SC Kit (Includes Myron L) Calibration Room Bucket (w/ Rope and Insect Repellant) Garage ASWAU Locker Potable Water Garage ASWAU Shelf Map Books (North + South) Calibration Room Shovel Garage ASWAU Locker SC Box Garage ASWAU Shelf Polyethylene 5-gal Bucket Back-up Bottles

Garage ASWAU Shelf Garage ASWAU Shelf

Vehicle Travel Pouch Admin office (Reserved vehicle) Sample collection:

Equipment Location Camera (charge battery) Calibration Room Sample Poles Garage ASWAU Locker Sample Coolers (sample containers) Calibration Room Ice Garage Ice Machine YSI MDS + Sonde Calibration Room

All field equipment should be checked prior to each field event to verify functionality. In addition, the following procedures apply to selected equipment:


Field monitoring books: The field monitoring books contain summarized monitoring information (e.g. site location maps, contact information, etc.), access keys and emergency information for field personnel and provide directions to and contact information for the analytical laboratories. Should there be any changes made to the monitoring schedules, the field monitoring books will be updated as well. Field Sheets: Attach the field data sheet to the clipboard with a pencil, extra blank labels, and a photograph sheet of the monitoring sites. Multipurpose meter/sonde: Retrieve the YSI multi-meter from the calibration room shelf. Record the identification number of the meter/sonde in the space provided on the field data sheet. Make sure the battery is fully charged and the DO membrane is good (i.e. with no bubbles) for the next day’s use. Also include in the YSI bag a full service kit and a screwdriver. Included in the full service kit are:

• DO membranes • Fine sanding disks • O rings • KCL Solution • Grease • Probe installation tool • Tube brush • Q tips • Batteries

Tracking the YSI meters/sondes used in the field is important for proper maintenance. Calibration of the meter will be conducted the morning of sampling before leaving the office according to the instructions/cheat sheets (as detailed in the Procedures Manual for the San Joaquin River Water Quality Monitoring Program (Draft), July 2008) located in the calibration room cabinets. The YSI will also be checked or recalibrated at the end of the run and any time during the run if values seem not “normal.” These results are then recorded on the field data sheet in the space provided (Appendix 8). A Myron L SC/pH meter should be included as a back-up for the field runs and stored in the pH/SC kit. Calibration of the meter should be conducted prior to use as a back-up. Calibration instructions for the Myron are on the back of the meter pH/SC kit: The pH/SC kit is an ice chest containing items used for QA/QC during field sampling runs. Reorganize this cooler and augment any supplies as needed. The supplies include:

• SC calibration solution (1417µmhos) (1000 ml bottle) • pH calibration solutions (4, 7, and 10) (1000 ml bottles) • DI water (1000 ml bottle) • Tap water (1000 ml bottle) • Disposable nitrile gloves (in all sizes) • Waterproof marker, ball-point pen, pencil, safety glasses, paper towels • Myron L SC/pH meter • Liquid soap • Alcohol spray bottle w/extra alcohol


• Stainless steel cup

Sampling poles: Sampling poles are used to retrieve a sample up to six feet from the bank. Extensions are available and should be used as necessary. Additionally, a stainless steel cup attached to a pole by a clamp attachment will be used to collect volatile organic compound samples. Bucket and rope: A stainless steel bucket (triple rinse) and rope can be used for sampling off a bridge when there is no safe access to the bank or the distance is too great for the extensions. Additionally, the bucket can be used to carry sampling bottles to and from the site. Cellular telephone: The field crew must have one cellular phone with them in case for emergencies. Life vests: Even the best swimmers can succumb to hypothermia. The ASWAU/ARP has three life vests and additional life vests are available in the office. Life vests should be worn when sampling from bridges, boats, unstable banks, or during periods of extremely high flow. Toolbox (blue) and road emergency box (red): Periodically inspect the toolbox and road emergency box to ensure that the appropriate contents are present and in working order. Contents are listed below: Shovel/spades: Carry a shovel or spade in the truck in case the truck gets stuck and must be dug out. Boots: Each sampler is responsible for being fit for their own rubber boots. If no boots fit the sampler, it will be necessary to have boots ordered. Hip waders can also be ordered as needed. Ice: Prepare bags of ice the day prior to sampling and leave these bags inside the ice machine to be pulled by the sampling crew. Water and food: Drinking water is necessary to maintain normal bodily functions. Bring plenty of water for a day. During the summer, double the amount of water you bring to avoid dehydration. While in the field, convenience food stores are not always available, therefore,

Tool Box Road Emergency Box Screwdriver, pliers Flares Flashlight Reflector triangles Graduated cylinder Fire extinguisher Duct tape First aid kit Utility knife Chain w/ locks W-D 40 Sigma tubing Toilet paper Spare field keys Spare C Batteries w/ YSI Cover Utility Saw Desiccant


pack a lunch and some snacks for the day. Wash your hands prior to eating as we are sampling waterways that may contain unknown contaminants. There are extra water coolers available to carry water for washing hands. Personal protective gear: It is the responsibility of each sampler to think ahead and watch the weather forecast in order to dress appropriately for field monitoring. Rain gear is available in the ASWAU/ARP locker located in the garage area. Items that you may want to consider bringing from home are:

• Hiking boots • Heavy coat/sweater/sweatshirt • Hat • Warm gloves • Sunglasses • Sunscreen

Other personal items: All field personnel will need a CRWQCB identification card that can be obtained from Scott Mills, 916-464-4688. Carry this card in case you are asked to identify yourself by other agencies or the local growers. Money is also helpful for those unexpected necessities. Double Check: After coolers with samples are placed out in the garage with the appropriate equipment, check all equipment off the checklist. The checklist is located in the garage on the ASWAU shelf. Sample collection procedures Sample collection procedures are summarized in Appendix 6. Responsible person The Monitoring Lead is ultimately responsible for coordinating field activities. However, staff may be delegated responsibilities for conducting the work to ensure all activities are completed. For instance, Central Valley Water Board staff and/or scientific aids may be tasked to prepare field sheets, label sample bottles, and conduct sample collection on field runs. Any issues that cannot be readily corrected should be brought to the attention of the Monitoring Lead and noted on the field sheet. The Monitoring Lead will be responsible for investigating and resolving the issue.


B3, Element 12. Sample Handling and Custody Maximum holding times Field parameters do not have a holding time since the results will be determined on site. For all key constituent samples, the samples will be immediately placed on ice in a cooler for transport to the laboratories. Samples will be delivered to ExcelChem environmental laboratories at the end of the field run on June 20 by the sampling crew. Maximum holding time stated in the Surface Water Ambient Monitoring Program Quality Assurance Program Plan (QAPrP) is 6 months after preservation for boron, iron, sodium, aluminum, arsenic, and manganese. The maximum hold time for volatile organic compounds scan is 14 days. Nitrate as Nitrogen, Nitrite as Nitrogen, and MBAs have a maximum hold time of 48 hours. The data generated from the samples collected are intended to characterize the main stem of the Sacramento and Feather River as compared to criteria to protect human health. ExcelChem Environmental Labs hold time for key constituents can be found in Appendix 11. Sample Handling Identification information for each sample will be recorded on the label on the sample bottles when the sample is collected. The same identification information on the bottles utilized for collecting the sample will also be on the field sheet and chain of custody (COC) forms. Transport Samples will be stored in coolers with ice, at a temperature of ≤5°C. Samples to be analyzed for key constituents will be delivered to: ExcelChem Environmental Labs 1135 W. Sunset Blvd, Suite A Rocklin, CA 95765 Tel: 916-543-4445 Maps to the appropriate laboratories are located within the field monitoring books. Sample Transfer


Field crew will deliver June 20th samples and Chain of Custody (COC) forms to ExcelChem staff designated to receive samples. Samples collected will be verified against field sheets and chain of custody forms. Discrepancies and any additional notes, such as holding time exceedances, incorrect sample identification information, inappropriate sample handing, or missing/inadequate field equipment calibration information, will be noted on the field sheets and chain of custody forms, as needed by the staff receiving the samples. Sample Handling and Custody Documentation All samples will be handled so as to minimize contamination. Sample containers will be clearly labeled. All caps and lids will be checked for tightness prior to transport. Samples will be placed in the ice chests with enough ice, or other packing, to include empty sample collection bottles, to completely fill the ice chest. Chain of custody forms will be placed in an envelope and taped to the top of the ice chest or they may be placed in a plastic bag and taped to the inside of the ice chest lid. Samples will be handled using aseptic technique to minimize chance for contamination. Responsible Individuals The Monitoring Lead and Lab Director will have ultimate responsibility for ensuring samples are properly handled and transferred. However, it is also the responsibility of the persons collecting, relinquishing, and receiving samples to initially verify correct sample handling and transfer. Sample Identification Appendix 4 details the sample ID conventions, information that will be included on each bottle, and how samples will be labeled. Chain of Custody Procedures Field measurements do not require specific custody procedures since they will be conducted on site at the sample collection location. Copies of chain of custody forms and all field sheets will be kept in a project binder in the Monitoring Lead’s office.


B4, Element 13. Analytical Methods and Field Measurements Field analytical procedures Table 7 Field and Laboratory Analytical Methods

Analyte

Target Reporting

Limit

Unit

Analytical Method Achievable Laboratory Limits Analytical

Method/SOP Modified for Method:

yes/no Method Detection

Limit Test Method

Central Valley Water Board Dissolved Oxygen N/A mg/l 360.1 No N/A N/A Specific Conductivity N/A µS/cm b/120.1 No N/A N/A

pH N/A pH Units a/150.1 No N/A N/A

Water Temperature N/A °C Temperature No N/A N/A

Turbidity N/A NTU *SM 2130B/ EPA 180.1 No N/A N/A

ExcelChem Environmental Lab 1,1-Dichloroethane 0.5 µg/L GC/MS No 0.04 EPA 8260B 1,1,1,2-Tetrachloroethane 0.5 µg/L GC/MS No 0.08 EPA 8260B 1,1,1-Trichloroethane 0.5 µg/L GC/MS No 0.05 EPA 8260B 1,1,2,2-Tetrachloroethane 0.5 µg/L GC/MS No 0.4 EPA 8260B 1,1,2-Trichloroethane 0.5 µg/L GC/MS No 0.1 EPA 8260B 1,1-Dichloroethane 0.5 µg/L GC/MS No 0.05 EPA 8260B 1,1-Dichloropropene 0.5 µg/L GC/MS No 0.03 EPA 8260B 1,2,3-Trichlorobenzene 0.5 µg/L GC/MS No 0.05 EPA 8260B 1,2,3-Trichloropropane 0.5 µg/L GC/MS No 0.06 EPA 8260B 1,2,4-Trichlorobenzene 0.5 µg/L GC/MS No 0.02 EPA 8260B 1,2,4-Trimethylbenzene 0.5 µg/L GC/MS No 0.04 EPA 8260B 1,2-Dibromo-3-chloropropane 0.5 µg/L GC/MS No 0.07 EPA 8260B 1,2-Dibromoethane (EDB) 0.5 µg/L GC/MS No 0.1 EPA 8260B 1,2-Dichlorobenzene 0.5 µg/L GC/MS No 0.06 EPA 8260B 1,2-Dichloroethane 0.5 µg/L GC/MS No 0.04 EPA 8260B 1,2-Dichloropropane 0.5 µg/L GC/MS No 0.06 EPA 8260B


Analyte

Target Reporting

Limit

Unit




Limit Test Method

1,3-Dichlorobenzene 0.5 µg/L GC/MS No 0.03 EPA 8260B 1,3-Dichloropropane 0.5 µg/L GC/MS No 0.06 EPA 8260B 1,4-Dichlorobenzene 0.5 µg/L GC/MS No 0.05 EPA 8260B 2-Butanone 5 µg/L GC/MS No 0.1 EPA 8260B 2-Chlorotoluene 0.5 µg/L GC/MS No 0.03 EPA 8260B 2-Hexanone 5 µg/L GC/MS No 0.1 EPA 8260B 4-Chlorotoluene 0.5 µg/L GC/MS No 0.05 EPA 8260B 4-Isopropyltoluene 0.5 µg/L GC/MS No 0.04 EPA 8260B 4-Methyl1-2pentanone 5 µg/L GC/MS No 0.05 EPA 8260B Acetone 5 µg/L GC/MS No 0.1 EPA 8260B Benzene 0.5 µg/L GC/MS No 0.03 EPA 8260B Bromobenzene 0.5 µg/L GC/MS No 0.05 EPA 8260B Bromochloromethane 0.5 µg/L GC/MS No 0.07 EPA 8260B Bromodichloromethane 0.5 µg/L GC/MS No 0.05 EPA 8260B Bromoform 0.5 µg/L GC/MS No 0.03 EPA 8260B Bromomethane 0.5 µg/L GC/MS No 0.05 EPA 8260B Carbon disulfide 0.5 µg/L GC/MS No 0.06 EPA 8260B Carbon tetrachloride 0.5 µg/L GC/MS No 0.02 EPA 8260B Chlorobenzene 0.5 µg/L GC/MS No 0.03 EPA 8260B Chloroethane 0.5 µg/L GC/MS No 0.08 EPA 8260B Chloroform 0.5 µg/L GC/MS No 0.05 EPA 8260B Chloromethane 0.5 µg/L GC/MS No 0.06 EPA 8260B cis-1,2-Dichloroethane 0.5 µg/L GC/MS No 0.03 EPA 8260B cis-1,3-Dichloropropene 0.5 µg/L GC/MS No 0.04 EPA 8260B Dibromochloromethane 0.5 µg/L GC/MS No 0.07 EPA 8260B Dibromomethane 0.5 µg/L GC/MS No 0.07 EPA 8260B Dichlorodifluoromethane 0.5 µg/L GC/MS No 0.07 EPA 8260B Di-isopropyl ether 0.5 µg/L GC/MS No 0.1 EPA 8260B Ethyl tert-Butyl Ether 0.5 µg/L GC/MS No 0.04 EPA 8260B Ethylbenzene 0.5 µg/L GC/MS No 0.03 EPA 8260B Hexachlorobutadiene 0.5 µg/L GC/MS No 0.07 EPA 8260B


Analyte

Target Reporting

Limit

Unit




Limit Test Method

Iodomethane 0.5 µg/L GC/MS No 0.03 EPA 8260B Isopropylbenzene 0.5 µg/L GC/MS No 0.04 EPA 8260B m,p-Xylene 1 µg/L GC/MS No 0.09 EPA 8260B Methyl tert-Butyl Ether 0.5 µg/L GC/MS No 0.05 EPA 8260B Methylene chloride 5 µg/L GC/MS No 0.08 EPA 8260B Naphthalene 0.5 µg/L GC/MS No 0.04 EPA 8260B n-Butylbenzene 0.5 µg/L GC/MS No 0.04 EPA 8260B n-Propylbenzene 0.5 µg/L GC/MS No 0.04 EPA 8260B o-Xylene 0.5 µg/L GC/MS No 0.04 EPA 8260B sec-Butylbenzene 0.5 µg/L GC/MS No 0.03 EPA 8260B TBA 1 µg/L GC/MS No 0.1 EPA 8260B Tert-Amyl Methyl Ether 0.5 µg/L GC/MS No 0.03 EPA 8260B tert-Butylbenzene 0.5 µg/L GC/MS No 0.02 EPA 8260B Tetrachloroethene 0.5 µg/L GC/MS No 0.08 EPA 8260B Toluene 0.5 µg/L GC/MS No 0.04 EPA 8260B trans-1,2-Dichloroethane 0.5 µg/L GC/MS No 0.04 EPA 8260B trans-1,3-Dichloropropene 0.5 µg/L GC/MS No 0.04 EPA 8260B Trichloroethane 0.5 µg/L GC/MS No 0.06 EPA 8260B Trichlorofluoromethane 0.5 µg/L GC/MS No 0.05 EPA 8260B Trichlorotrifluoroethane 1 µg/L GC/MS No 0.05 EPA 8260B Vinyl chloride 0.5 µg/L GC/MS No 0.06 EPA 8260B Xylenes, total 1 µg/L GC/MS No 0.1 EPA 8260B 1,1,1,2-Tetrachloroethane 0.5 µg/L GC/MS No 0.08 EPA 524 1,1,1-Trichloroethane 0.5 µg/L GC/MS No 0.05 EPA 524 1,1,2,2-Tetrachloroethane 0.5 µg/L GC/MS No 0.04 EPA 524 1,1,2-Trichloroethane 0.5 µg/L GC/MS No 0.1 EPA 524 1,1,-Dichloroethane 0.5 µg/L GC/MS No 0.04 EPA 524 1,1-Dichloroethane 0.5 µg/L GC/MS No 0.05 EPA 524 1,1-Dichloropropene 0.5 µg/L GC/MS No 0.03 EPA 524 1,2,3-Trichlorobenzene 0.5 µg/L GC/MS No 0.05 EPA 524 1,2,3-Trichloropropane 0.5 µg/L GC/MS No 0.06 EPA 524


Analyte

Target Reporting

Limit

Unit




Limit Test Method

1,2,4-Trichlorobenzene 0.5 µg/L GC/MS No 0.02 EPA 524 1,2,4-Trimethylbenzene 0.5 µg/L GC/MS No 0.04 EPA 524 1,2-Dibromo-3-chloropropane 0.5 µg/L GC/MS No 0.07 EPA 524 1,2-Dibromoethane (EDB) 0.5 µg/L GC/MS No 0.1 EPA 524 1,2-Dichlorobenzene 0.5 µg/L GC/MS No 0.06 EPA 524 1,2-Dichloroethane 0.5 µg/L GC/MS No 0.06 EPA 524 1,2-Dichloropropane 0.5 µg/L GC/MS No 0.06 EPA 524 1,3,5-Trimethylbenzene 0.5 µg/L GC/MS No 0.03 EPA 524 1,3-Dichlorobenzene 0.5 µg/L GC/MS No 0.03 EPA 524 1,3-Dichloropropane 0.5 µg/L GC/MS No 0.06 EPA 524 1,4-Dichlorobenzene 0.5 µg/L GC/MS No 0.05 EPA 524 2,2-Dichloropropane 0.5 µg/L GC/MS No 0.06 EPA 524 2-Butanone 5 µg/L GC/MS No 0.1 EPA 524 2-Chlorotoluene 0.5 µg/L GC/MS No 0.03 EPA 524 2-Hexanone 0.5 µg/L GC/MS No 0.1 EPA 524 4-Chlorotoluene 0.5 µg/L GC/MS No 0.05 EPA 524 4-Isopropyltoluene 0.5 µg/L GC/MS No 0.04 EPA 524 4-Methyl-2-pentanone 0.5 µg/L GC/MS No 0.05 EPA 524 Acetone 5 µg/L GC/MS No 0.1 EPA 524 Benzene 0.5 µg/L GC/MS No 0.03 EPA 524 Bromobenzene 0.5 µg/L GC/MS No 0.05 EPA 524 Bromochloromethane 0.5 µg/L GC/MS No 0.07 EPA 524 Bromodichloromethane 0.5 µg/L GC/MS No 0.05 EPA 524 Bromoform 0.5 µg/L GC/MS No 0.03 EPA 524 Bromomethane 0.5 µg/L GC/MS No 0.05 EPA 524 Carbon disulfide 0.5 µg/L GC/MS No 0.06 EPA 524 Carbon tetrachloride 0.5 µg/L GC/MS No 0.02 EPA 524 Chlorobenzene 0.5 µg/L GC/MS No 0.03 EPA 524 Chloroethane 0.5 µg/L GC/MS No 0.08 EPA 524 Chloroform 0.5 µg/L GC/MS No 0.05 EPA 524 Chloromethane 0.5 µg/L GC/MS No 0.06 EPA 524


Analyte

Target Reporting

Limit

Unit




Limit Test Method

cis-1,2-Dichloroethane 0.5 µg/L GC/MS No 0.03 EPA 524 cis-1,3-Dichloropropene 0.5 µg/L GC/MS No 0.04 EPA 524 Dibromochloromethane 0.5 µg/L GC/MS No 0.07 EPA 524 Dibromomethane 0.5 µg/L GC/MS No 0.07 EPA 524 Dichlorodifluoromethane 0.5 µg/L GC/MS No 0.07 EPA 524 Di-isopropyl ether 0.5 µg/L GC/MS No 0.1 EPA 524 Ethyl tert-Butyl Ether 0.5 µg/L GC/MS No 0.04 EPA 524 Ethylbenzene 0.5 µg/L GC/MS No 0.03 EPA 524 Hexachlorobutadiene 0.5 µg/L GC/MS No 0.07 EPA 524 Iodomethane 0.5 µg/L GC/MS No 0.03 EPA 524 Isopropylbenzene 0.5 µg/L GC/MS No 0.04 EPA 524 m,p-Xylene 0.5 µg/L GC/MS No 0.09 EPA 524 Methyl tert-Butyl Ether 0.5 µg/L GC/MS No 0.05 EPA 524 Methylene chloride 1 µg/L GC/MS No 0.08 EPA 524 Naphthalene 0.5 µg/L GC/MS No 0.04 EPA 524 n-Butylbenzene 0.5 µg/L GC/MS No 0.04 EPA 524 n-Propylbenzene 0.5 µg/L GC/MS No 0.04 EPA 524 o-Xylene 0.5 µg/L GC/MS No 0.04 EPA 524 sec-Butylbenzene 0.5 µg/L GC/MS No 0.03 EPA 524 Styrene 0.5 µg/L GC/MS No 0.09 EPA 524 TBA 1 µg/L GC/MS No 0.1 EPA 524 Tert-Amyl Methyl Ether 0.5 µg/L GC/MS No 0.03 EPA 524 tert-Butylbenzene 0.5 µg/L GC/MS No 0.02 EPA 524 Tetrachloroethene 0.5 µg/L GC/MS No 0.08 EPA 524 Toluene 0.5 µg/L GC/MS No 0.04 EPA 524 Total Trihalomethanes 0.5 µg/L GC/MS No 0.5 EPA 524 trans-1,2-Dichloroethane 0.5 µg/L GC/MS No 0.04 EPA 524 trans-1,3-Dichloropropene 0.5 µg/L GC/MS No 0.04 EPA 524 Trichloroethane 0.5 µg/L GC/MS No 0.06 EPA 524 Trichlorofluoromethane 0.5 µg/L GC/MS No 0.05 EPA 524 Trichlorotrifluoroethane 1 µg/L GC/MS No 0.05 EPA 524


Analyte

Target Reporting

Limit

Unit




Limit Test Method

Vinyl chloride 0.5 µg/L GC/MS No 0.06 EPA 524 Xylenes, total 1 µg/L GC/MS No 0.1 EPA 524 4,4'-DDD 0.1 µg/L GC No 0.006 EPA 8081A 4,4'-DDE 0.1 µg/L GC No 0.005 EPA 8081A 4,4'-DDT 0.1 µg/L GC No 0.004 EPA 8081A Aldrin 0.1 µg/L GC No 0.011 EPA 8081A alpha-BHC 0.1 µg/L GC No 0.011 EPA 8081A alpha-Chlordane 0.1 µg/L GC No 0.006 EPA 8081A beta-BHC 0.1 µg/L GC No 0.011 EPA 8081A delta-BHC 0.1 µg/L GC No 0.021 EPA 8081A Dieldrin 0.1 µg/L GC No 0.006 EPA 8081A Endosulfan I 0.1 µg/L GC No 0.007 EPA 8081A Endosulfan II 0.1 µg/L GC No 0.021 EPA 8081A Endosulfan sulfate 0.1 µg/L GC No 0.005 EPA 8081A Endrin 0.1 µg/L GC No 0.007 EPA 8081A Endrin aldehyde 0.1 µg/L GC No 0.006 EPA 8081A Endrin Ketone 0.1 µg/L GC No 0.005 EPA 8081A gamma-BHC (Lindane) 0.1 µg/L GC No 0.013 EPA 8081A gamma-Chlordane 0.1 µg/L GC No 0.005 EPA 8081A Heptachlor 0.1 µg/L GC No 0.016 EPA 8081A Heptachlor epoxide 0.1 µg/L GC No 0.02 EPA 8081A Methoxychlor 0.1 µg/L GC No 0.013 EPA 8081A Aroclor 1016 1 µg/L GC No 0.06 EPA 8081A Aroclor 1221 1 µg/L GC No 0.13 EPA 8081A Aroclor 1232 1 µg/L GC No 0.1 EPA 8081A Aroclor 1242 1 µg/L GC No 0.06 EPA 8081A Aroclor 1248 1 µg/L GC No 0.06 EPA 8081A Aroclor 1254 1 µg/L GC No 0.09 EPA 8081A Aroclor 1260 1 µg/L GC No 0.08 EPA 8081A PCBs 1 µg/L GC No 0.08 EPA 8081A 1,2,4-Trichlorobenzene 2 µg/L GC/MS No 0.6 EPA 8270C


Analyte

Target Reporting

Limit

Unit




Limit Test Method

1,4-Dichlorobenzene 2 µg/L GC/MS No 0.4 EPA 8270C 2,4,5-Trichlorophenol 5 µg/L GC/MS No 1.6 EPA 8270C 2,4,6-Trichlorophenol 5 µg/L GC/MS No 1.6 EPA 8270C 2,4-Dichlorophenol 2 µg/L GC/MS No 0.8 EPA 8270C 2,4-Dimethylphenol 2 µg/L GC/MS No 0.8 EPA 8270C 2,4-Dinitrophenol 10 µg/L GC/MS No 0.3 EPA 8270C 2,4-Dinitrotoluene 2 µg/L GC/MS No 0.8 EPA 8270C 2,6-Dinitrotoluene 2 µg/L GC/MS No 0.8 EPA 8270C 2-Chloronaphthalene 2 µg/L GC/MS No 0.2 EPA 8270C 2-Chlorophenol 2 µg/L GC/MS No 0.8 EPA 8270C 2-Methylnaphthalene 2 µg/L GC/MS No 0.6 EPA 8270C 2-Methylphenol 2 µg/L GC/MS No 0.4 EPA 8270C 2-Nitroaniline 2 µg/L GC/MS No 0.4 EPA 8270C 2-Nitrophenol 2 µg/L GC/MS No 1.2 EPA 8270C 3,3´-Dichlorobenzidine 5 µg/L GC/MS No 0.8 EPA 8270C 3-Nitroaniline 2 µg/L GC/MS No 0.5 EPA 8270C 4,6-Dinitro-2-methylphenol 10 µg/L GC/MS No 2.2 EPA 8270C 4-Bromophenyl phenyl ether 2 µg/L GC/MS No 0.8 EPA 8270C 4-Chloro-3-methylphenol 2 µg/L GC/MS No 0.6 EPA 8270C 4-Chloroaniline 2 µg/L GC/MS No 0.5 EPA 8270C 4-Chlorophenyl phenyl ether 2 µg/L GC/MS No 0.5 EPA 8270C 4-Nitroaniline 2 µg/L GC/MS No 0.6 EPA 8270C 4-Nitrophenol 5 µg/L GC/MS No 0.1 EPA 8270C Acenaphthene 2 µg/L GC/MS No 0.6 EPA 8270C Acenaphthylene 2 µg/L GC/MS No 0.3 EPA 8270C Aniline 2 µg/L GC/MS No 0.3 EPA 8270C Anthracene 2 µg/L GC/MS No 0.3 EPA 8270C Azobenzene 2 µg/L GC/MS No 0.4 EPA 8270C Benzidine 5 µg/L GC/MS No 0.2 EPA 8270C Benzo (a) anthracene 2 µg/L GC/MS No 0.4 EPA 8270C Benzo (a) pyrene 5 µg/L GC/MS No 1.2 EPA 8270C


Analyte

Target Reporting

Limit

Unit




Limit Test Method

Benzo (b) fluoranthene 2 µg/L GC/MS No 0.8 EPA 8270C Benzo (g,h,i) perylene 2 µg/L GC/MS No 1.3 EPA 8270C Benzo (k) fluoranthene 2 µg/L GC/MS No 1 EPA 8270C Benzoic acid 30 µg/L GC/MS No 0.5 EPA 8270C Benzyl alcohol 2 µg/L GC/MS No 0.4 EPA 8270C Bis(2-chloroethoxy)methane 2 µg/L GC/MS No 0.4 EPA 8270C Bis(2-chloroethyl)ether 2 µg/L GC/MS No 0.6 EPA 8270C Bis(2-chloroisopropyl)ether 2 µg/L GC/MS No 0.4 EPA 8270C Bis(2-ethylhexyl)phthalate 5 µg/L GC/MS No 0.7 EPA 8270C Butyl benzyl phthalate 2 µg/L GC/MS No 1 EPA 8270C Carbazole 2 µg/L GC/MS No 0.6 EPA 8270C Chrysene 2 µg/L GC/MS No 0.5 EPA 8270C Dibenz (a,h) anthracene 2 µg/L GC/MS No 1.6 EPA 8270C Dibenzofuran 2 µg/L GC/MS No 0.3 EPA 8270C Diethyl phthalate 2 µg/L GC/MS No 0.6 EPA 8270C Dimethyl phthalate 2 µg/L GC/MS No 0.8 EPA 8270C Di-n-butyl phthalate 2 µg/L GC/MS No 0.4 EPA 8270C Di-n-octyl phthalate 5 µg/L GC/MS No 0.7 EPA 8270C Fluoranthene 2 µg/L GC/MS No 0.6 EPA 8270C Fluorene 2 µg/L GC/MS No 0.5 EPA 8270C Hexachlorobenzene 2 µg/L GC/MS No 0.6 EPA 8270C Hexachlorobutadiene 2 µg/L GC/MS No 0.6 EPA 8270C Hexachlorocyclopentadiene 2 µg/L GC/MS No 0.6 EPA 8270C Hexachloroethane 2 µg/L GC/MS No 0.5 EPA 8270C Indeno (1,2,3-cd) pyrene 5 µg/L GC/MS No 1.6 EPA 8270C Isophorone 2 µg/L GC/MS No 0.3 EPA 8270C Naphthalene 2 µg/L GC/MS No 0.5 EPA 8270C Nitrobenzene 2 µg/L GC/MS No 0.7 EPA 8270C N-Nitrosodimethylamine 2 µg/L GC/MS No 0.4 EPA 8270C N-Nitrosodi-n-propylamine 2 µg/L GC/MS No 0.3 EPA 8270C N-Nitrosodiphenylamine 2 µg/L GC/MS No 0.6 EPA 8270C


Analyte

Target Reporting

Limit

Unit




Limit Test Method

Pentachlorophenol 10 µg/L GC/MS No 2.4 EPA 8270C Phenanthrene 2 µg/L GC/MS No 0.4 EPA 8270C Phenol 2 µg/L GC/MS No 0.3 EPA 8270C Pyrene 2 µg/L GC/MS No 1 EPA 8270C Azinphos-methyl 0.2 µg/L GC No 0.027 EPA 8141A Bolstar 0.2 µg/L GC No 0.086 EPA 8141A Coumaphos 0.2 µg/L GC No 0.168 EPA 8141A Demeton 0.2 µg/L GC No 0.105 EPA 8141A Demeton-O 0.2 µg/L GC No 0.101 EPA 8141A Demeton-S 0.2 µg/L GC No 0.105 EPA 8141A Diazinon 0.25 µg/L GC No 0.065 EPA 8141A Dichlorvos 0.2 µg/L GC No 0.156 EPA 8141A Dimethoate 0.2 µg/L GC No 0.071 EPA 8141A Disulfoton 0.2 µg/L GC No 0.069 EPA 8141A Dursban (Chlorpyrifos) 0.2 µg/L GC No 0.071 EPA 8141A EPN 0.2 µg/L GC No 0.124 EPA 8141A Ethoprop 0.2 µg/L GC No 0.077 EPA 8141A Fensulfothion 0.2 µg/L GC No 0.139 EPA 8141A Fenthion 0.2 µg/L GC No 0.067 EPA 8141A Gardona (Stirophos) 0.2 µg/L GC No 0.11 EPA 8141A Malathion 0.2 µg/L GC No 0.159 EPA 8141A Merphos 0.2 µg/L GC No 0.097 EPA 8141A Mevinphos 0.2 µg/L GC No 0.115 EPA 8141A Molinate 0.2 µg/L GC No 0.044 EPA 8141A Monocrotophos 0.2 µg/L GC No 0.015 EPA 8141A Naled 0.2 µg/L GC No 0.169 EPA 8141A Parathion 0.2 µg/L GC No 0.079 EPA 8141A Parathion-methyl 0.2 µg/L GC No 0.077 EPA 8141A Phorate 0.2 µg/L GC No 0.083 EPA 8141A Ronnel 0.2 µg/L GC No 0.066 EPA 8141A Sulfotep 0.2 µg/L GC No 0.095 EPA 8141A


Analyte

Target Reporting

Limit

Unit




Limit Test Method

TEPP 0.2 µg/L GC No 0.151 EPA 8141A Tokuthion (Prothiofos) 0.2 µg/L GC No 0.077 EPA 8141A Trichloronate 0.2 µg/L GC No 0.067 EPA 8141A 2,4,5-T 0.5 µg/L GC No 0.097 EPA 8151A 2,4,5-TP (Silvex) 0.5 µg/L GC No 0.095 EPA 8151A 2,4-D 0.4 µg/L GC No 0.086 EPA 8151A 2,4-DB 0.8 µg/L GC No 0.157 EPA 8151A 3,5-Dichlorobenzoic acid 0.8 µg/L GC No 0.17 EPA 8151A 4-Nitrophenol 0.6 µg/L GC No 0.117 EPA 8151A Acifluorfen 0.8 µg/L GC No 0.157 EPA 8151A Bentazon 0.6 µg/L GC No 0.11 EPA 8151A Chloramben 0.8 µg/L GC No 0.008 EPA 8151A Dalapon 0.6 µg/L GC No 0.115 EPA 8151A DCPA 0.4 µg/L GC No 0.015 EPA 8151A Dicamba 0.4 µg/L GC No 0.08 EPA 8151A Dichloroprop 0.8 µg/L GC No 0.196 EPA 8151A Dinoseb 0.4 µg/L GC No 0.083 EPA 8151A MCPP 10 µg/L GC No 0.891 EPA 8151A Pentachlorophenol 0.3 µg/L GC No 0.053 EPA 8151A Picloram 0.8 µg/L GC No 0.02 EPA 8151A Hexavalent Chromium 1 µg/L IC No 0.1 EPA 218.6 Chloride 0.5 mg/L IC No 0.04 EPA 300.0 Fluoride 0.1 mg/L IC No 0.02 EPA 300.0 Nitrate as Nitrogen 0.11 mg/L IC No 0.009 EPA 300.0 Nitrite as Nitrogen 0.15 mg/L IC No 0.03 EPA 300.0 Sulfate as SO4 5 mg/L IC No 0.7 EPA 300.0 Perchlorate 2 µg/L IC No 0.094 EPA 314.0 Specific Conductance (EC) 5 µS/cm Conductivity Meter No 1.09 EPA 120.1 Total Dissolved Solids 15 mg/L Wet Chemistry No 7.68 SM 2540C Cyanide 0.005 mg/L Wet Chemistry No 0.0009 SM 4500CN E


Analyte

Target Reporting

Limit

Unit




Limit Test Method

pH 0.1 pH Units Wet Chemistry No 0.1 SM 4500-H+ B

Ammonia as N 0.1 mg/L Wet Chemistry No 0.04 SM 4500-NH3 B/H

MBAS 0.1 mg/L Wet Chemistry No 0.06 SM 5540C Total Alkalinity 5 mg/L Wet Chemistry No 2.37 SM2320B Total Hardness 5 mg/L Wet Chemistry No 2.86 SM2340B Aluminum 50 µg/L ICP-MS No 24.5 EPA 200.7 Antimony 10 µg/L ICP-MS No 1.3 EPA 200.7 Arsenic 10 µg/L ICP-MS No 1 EPA 200.7 Barium 5 µg/L ICP-MS No 1.2 EPA 200.7 Beryllium 5 µg/L ICP-MS No 0.09 EPA 200.7 Boron 50 µg/L ICP-MS No 0.8 EPA 200.7 Cadmium 5 µg/L ICP-MS No 0.1 EPA 200.7 Calcium 100 µg/L ICP-MS No 79 EPA 200.7 Chromium 5 µg/L ICP-MS No 0.3 EPA 200.7 Copper 5 µg/L ICP-MS No 0.8 EPA 200.7 Iron 20 µg/L ICP-MS No 11.5 EPA 200.7 Lead 5 µg/L ICP-MS No 0.9 EPA 200.7 Magnesium 50 µg/L ICP-MS No 15.6 EPA 200.7 Manganese 10 µg/L ICP-MS No 0.6 EPA 200.7 Nickel 5 µg/L ICP-MS No 0.6 EPA 200.7 Selenium 20 µg/L ICP-MS No 1.3 EPA 200.7 Silver 5 µg/L ICP-MS No 0.4 EPA 200.7 Sodium 200 µg/L ICP-MS No 120 EPA 200.7 Thallium 20 µg/L ICP-MS No 2.2 EPA 200.7 Titanium 50 µg/L ICP-MS No 1.2 EPA 200.7 Zinc 10 µg/L ICP-MS No 0.3 EPA 200.7 Dissolved Aluminum 50 µg/L ICP-MS No 24.5 EPA 200.7 Dissolved Arsenic 10 µg/L ICP-MS No 1 EPA 200.7 Dissolved Iron 20 µg/L ICP-MS No 11.5 EPA 200.7


Analyte

Target Reporting

Limit

Unit




Limit Test Method

Dissolved Lead 5 µg/L ICP-MS No 0.9 EPA 200.7 1,2,3,4,6,7,8-HpCDD 50 pg/L HRMS No 2.17 1613B 1,2,3,4,6,7,8-HpCDF 50 pg/L HRMS No 3.77 1613B 1,2,3,4,7,8,9-HpCDF 50 pg/L HRMS No 4.61 1613B 1,2,3,4,7,8-HxCDD 50 pg/L HRMS No 3.98 1613B 1,2,3,4,7,8-HxCDF 50 pg/L HRMS No 3.66 1613B 1,2,3,6,7,8-HxCDD 50 pg/L HRMS No 5.34 1613B 1,2,3,6,7,8-HxCDF 50 pg/L HRMS No 3.97 1613B 1,2,3,7,8,9-HxCDD 50 pg/L HRMS No 4.68 1613B 1,2,3,7,8,9-HxCDF 50 pg/L HRMS No 8.74 1613B 1,2,3,7,8-PeCDD 50 pg/L HRMS No 2.29 1613B 1,2,3,7,8-PeCDF 50 pg/L HRMS No 2.58 1613B 2,3,4,6,7,8-HxCDF 50 pg/L HRMS No 4.97 1613B 2,3,4,7,8-PeCDF 50 pg/L HRMS No 2.36 1613B 2,3,7,8-TCDD 10 pg/L HRMS No 2.2 1613B 2,3,7,8-TCDF 10 pg/L HRMS No 2.01 1613B OCDD 100 pg/L HRMS No 4.32 1613B OCDF 100 pg/L HRMS No 6.25 1613B TEQ pg/L HRMS No 1613B Total HpCDD 50 pg/L HRMS No 3.06 1613B Total HpCDF 50 pg/L HRMS No 4.61 1613B Total HxCDD 50 pg/L HRMS No 5.34 1613B Total HxCDF 50 pg/L HRMS No 8.74 1613B Total PeCDD 50 pg/L HRMS No 2.29 1613B Total PeCDF 50 pg/L HRMS No 2.58 1613B Total TCDD 10 pg/L HRMS No 2.2 1613B Total TCDF 10 pg/L HRMS No 2.01 1613B

(*) Standard Methods for the Examination of Water and Wastewater, 20th edition.


List of Acronyms ICP-MS Inductively Coupled Plasma Mass Spectrometry HRMS High-resolution mass spectrometry IC Ion Chromatography

GC Gas Chromatography GC/MS Gas Chromatography/Mass Spectrometry

Laboratory Protocols See Appendices 10 and 11


Instruments to be used in Field Field measurements for DO, EC, pH, and temperature will be collected using the YSI EXO 1 Sonde. A probe guard will be attached at the end of the YSI to avoid fouling and protect the probes. If using the probe guard is not sufficient, the YSI may be hung by the bail from a sampling pole while the probe readings stabilize and are recorded. Turbidity measurements will be collected using the Hach 2100P turbidimeter. Samples will be collected by using a stainless steel cup that is attached to a sampling pole and then poured into the glass vial. Care will be taken to minimize disturbance of the bottom of the stream bed. Should sediment be disturbed as a result of sample collection activities, the sampler will wait for the sediment to wash downstream before collecting the sample. Equipment to be used for laboratory analysis Equipment to be used for analysis of total metals and minerals: Inductively Coupled Plasma (ICP)/Mass Spectrophotometer (MS) Laboratory ware Air displacement pipets Analytical balance Sample preparation apparatus Clean hood Equipment to be used for analysis of poly-chlorinated-dibenzo-p-Dioxin/Furan (HRMS):

High Resolution Gas Chromatograph/High-Resolution Mass Spectrometer/Data System (HRMS)

GC Injection Port Gas Chromatography/Mass Spectrometer Mass Spectrometer

Data System GC Columns

Equipment to be used for analysis of Carbamate Pesticides: High Performance Liquid Chromatography (HPLC) HPLC system C-18 reverse phase HPLC column Post Column Reactor with two solvent delivery systems Fluorescence detector


Equipment to be used for analysis of volatile organic compounds, pesticides, herbicides: Purge and trap system Purging device Trap Gas chromatograph (GC) Capillary GC columns Column 1, 2, 3, 4 Mass spectrometer Purge and trap – GC/MS interface Data system Syringes Syringe valves Microsyringes Bottles Equipment to be used for analysis of MBAs (Foaming Agents): Colorimetric equipment Spectrophotometer Filter photometer Separatory funnels Equipment to be used for analysis of Nitrate and Nitrite as Nitrogen: Spectrophotometer Filter photometer (Nitrite as N analysis only) Method Performance Criteria Unless otherwise noted, SWAMP reporting limits do not exist for constituents to be monitored in this study. YSI EXO 1 300/301 Probes (http://www.ysi.com/productsdetail.php?EXO1-Water-Quality-Sonde-89) Temperature Sensor Type Thermistor Range -5 to 50°C Accuracy ±0.01 °C (-5-35°C) ±0.05 °C (35-50°C) Resolution 0.001°C Depth 200 meters


Rapid Pulse Dissolved Oxygen, % saturation, mg/L (Calculated from %air saturation, temperature and salinity) Sensor Type Optical, luminescence lifetime Range 0 to 50 mg/L 0 to 500% air sat.

Accuracy ±1% of the reading or 0.1 mg/L, whichever is greater (0-20 mg/L)

±5% of reading (20-50 mg/L) ±1% reading or 1% air sat., whichever is greater (0-200%)

±5% reading (200-500%) Resolution 0.01mg/L 0.1% air sat. Depth 200 meters pH Sensor Type Glass combination electrode Range 0 to 14 units Accuracy ±0.1 units within 10°C of calibration temperature ±0.2 pH units for entire temp range Resolution 0.01 units Temperature range -5 to 50°C Depth 200 meters Conductivity Sensor Type 4 electrode nickel cell Range 0 to 200 mS/cm SWAMP RL 2.5mS/cm

Accuracy ±0.5% of reading +0.001 mS/cm, whichever is greater (0-100 mS/cm)

±1% of reading (100-200 mS/cm) Resolution 0.0001 mS/cm to 0.01 mS/cm (range-dependent) Temperature Range -5 to 50°C Depth 200 meters


Hach 2100P Turbidimeter (http://www.hach.com/fmmimghach?/CODE%3AL1619_09-0713836%7C1) Method EPA Method 180.1 (Nephelometric Ratio) Range 0 to 1000 NTU SWAMP RL 0.5 NTU Accuracy ±2% of reading plus stray light Precision ±1% of reading, or 0.01 NTU, whichever is greater

Resolution 0.01 on lowest range Temperature Range 0 to 50°C Depth 200 meters Sample Required 15 mL Sample Cells 60X25 mm borosilicate glass with screw caps Corrective Actions When failures in the laboratory occur, the Monitoring Lead and Lab Director will each be responsible for corrections in their respective laboratories. All failures will be documented on the field sheet and with the data report, along with the corrective action that was made. Additionally, corrections will be annotated in any applicable maintenance logs. Sample Disposal Procedures All samples collected will be transferred to ExcelChem Environmental. The laboratory will properly dispose of water samples after three months upon receipt of samples. Laboratory Turnaround Times Samples analyzed for key constituents will have results 2 weeks from the time ExcelChem Environmental Labs received the samples.


B5, Element 14. Quality Control This section describes the field quality control samples to be used in this study. Quality Control Activities The following checks will be utilized to ensure quality control: Table 8 Quality Control Checks QC Check Information Provided

BLANKS Travel blank Transport bias

Laboratory blank Assessment of background level of target analyte resulting from sample preparation and analysis

CALIBRATION CHECK SAMPLES Zero check Calibration drift and memory effect Span check Calibration drift and memory effect Mid-range check Calibration drift and memory effect

REPLICATES Field replicates Precision of all steps after acquisition Laboratory replicates Analytical precision Quality Control Samples Laboratory quality control samples (laboratory blank, laboratory control spike, laboratory control spike duplicate, matrix spike, matrix spike duplicate, laboratory duplicate, and surrogates) will be created by ExcelChem Environmental to be analyzed with field samples. Specific field quality control sample types are described below.

Laboratory Blank Laboratory blanks (also known as method blanks) provide bias information on possible contaminants for the entire laboratory analytical system. These samples will be made from sterile purified water that is known to have no detectable levels of the target analytes. Laboratory blanks will be analyzed along with the project samples to document background contamination of the analytical measurement system. The lab results must be less than the Reporting Limit of the target analytes to be acceptable.


Matrix Spike and Matrix Spike Duplicate Matrix spikes and matrix spike duplicates measure precision and accuracy by determining if the methodology is in control for the particular matrix being analyzed. Matrix spikes are client samples to which a known amount of analyte has been added prior to sample extraction/digestion and instrumental analysis. The lab results must have percent recoveries between 80-120% and the matrix spike duplicate must have a relative percent difference below 25% to be considered acceptable.

Laboratory Control Spike and Laboratory Control Spike Duplicate Laboratory control spike and laboratory control spike duplicates measure accuracy by determining if the methodology has been performed to meet criteria established by regulation, method or laboratory control chart data. Laboratory control spikes (LCS) and LCS duplicates are generated by spiking the analyte into a relatively inert matrix. The lab results must have percent recoveries between 80-120% and the LCS duplicate must have a relative percent difference below 25% to be considered acceptable.

Surrogates Surrogates are utilized in organic analytical methods in order to measure precision. Surrogates are organic compounds which behave similarly to the analytes of interest, but are not normally found in environmental samples. Lab results must have percent recoveries between 70-130%

Calibration Check Samples Field measurement equipment will be checked for calibration against standards of known concentrations for pH and SC. Checks will be run at the beginning of the field run, after ten samples, and/or at the end of the field run.

Travel Blank Travel blanks help isolate contamination associated with sample transport. Travel blanks are not opened during the sample collection. These blanks are created by using deionized water from the Central Valley Water Board Lab to fill sample containers. Travel blanks will be preserved, packaged, and sealed exactly like the surface water samples and will be submitted blind to the lab. The lab results must be less than the reporting limit of the target analytes to be acceptable.


Field Duplicates Field duplicates shall be collected immediately following the collection of normal samples. In cases where multiple intermediate bottles are used for a single analysis, field duplicates and normal sample containers should be filled in an alternating sequence (i.e., normal-duplicate-normal-duplicate). Field duplicates should be submitted “blind” to the laboratories. Five percent of total project sample count will be managed for field duplicates.

Laboratory Duplicates Laboratory duplicates provide precision information on the analytical methods with the target analytes. The laboratory will generate the duplicate samples by splitting one sample for duplicate analysis. Lab results must have a relative percent difference (RPD) less than 25. Quality Assurance Frequency of Analysis and Measurement Quality Objectives Quality control checks above will be conducted at the frequencies described below. Evaluation will be based on the measurement quality objectives listed in Table 9: Table 9 Quality Assurance Frequency of Analysis and Measurement Quality Objectives LABORATORY QUALITY CONTROL

FREQUENCY OF ANALYSIS MEASUREMENT QUALITY OBJECTIVE

Matrix Spike and Matrix Spike Duplicate

10% of samples 75-125% Recovery RPD < 25

Laboratory Control Spike and Laboratory Control Spike Duplicate

10% of samples 75-125% Recovery RPD < 25

Laboratory Blank Per 20 samples or per analytical batch, whichever is more frequent

<RL for target analyte

Laboratory Duplicate Per 10 samples RPD < 25% Surrogates (VOC analysis) All samples and Lab QA 70-130% Recovery FIELD QUALITY CONTROL FREQUENCY OF ANALYSIS MEASUREMENT QUALITY

OBJECTIVE Field Duplicate 5% of total project sample

count RPD < 25%

Travel Blank Per method Blanks <RL for target analyte


Corrective Actions The Contract Manager/QA officer is ultimately responsible for ensuring samples meet QA requirements and that appropriate corrective actions are followed. However, this does not exclude the ExcelChem Environmental Labs Lab Director and QA Officer from maintaining responsibility for following QA/QC procedures for analyses conducted by ExcelChem personnel. The following table identifies QC samples and the corresponding corrective actions to be taken should problems arise. Table 10 Corrective Actions Laboratory Quality Control Corrective Action Matrix Spike and Matrix Spike Duplicate

If it is determined that there is a matrix effect, analyses may be resumed. Otherwise, analyses are suspended while the issue is resolved.

Laboratory Control Spike and LCS Duplicate

If LCS or LCS Duplicate fails, the data can be reported with a qualifier. If acceptable recoveries are not obtained, further analyses are halted until a cause can be identified and corrective action taken.

Surrogate Spikes Analyses are suspended while the issue is resolved. Laboratory Blank The source of the contamination will be investigated and corrected,

if possible. Flag associated samples as determined by the Monitoring Lead.

Laboratory Duplicate Investigate possibility of analyst error. Field Quality Control

(Bacteria) Corrective Action

Field Duplicate Investigate possibility of analyst error. Travel Blank If contamination of the travel blanks and associated samples is

known or suspected, the laboratory should qualify the affected data, and notify the Project Lead and/or Monitoring Lead, who in turn will follow the process detailed in the method.

Field Quality Control (Field measurements)

Corrective Action

DO, SC, pH, Temperature, Turbidity

The instrument should be recalibrated following its manufacturer’s cleaning and maintenance procedures. If measurements continue to fail measurement quality objectives, affected data should not be reported and the instrument should be returned to the manufacturer for maintenance. All troubleshooting and corrective actions should be recorded on the Central Valley Water Board field sheet (Appendix 7)


B6, Element 15. Instrument/Equipment Testing, Inspection, and Maintenance Periodic Maintenance Field measurement equipment will be checked in accordance with the manufacturer’s specifications. This includes battery checks and cleaning. All equipment will be inspected when first handed out and when returned from use for damage. Equipment will be maintained in accordance with its SOPs, which include those specified by the manufacturer and those specified by the method used in this study. Field equipment inspection is carried out prior to each trip in the field. Testing is not conducted if equipment appears visibly worn or if field technicians report problems with the equipment upon returning from the field. Laboratory instruments at ExcelChem are calibrated at specified frequency and within acceptance limits published by EPA. In cases in which specific guidelines are not available, ExcelChem applies either the manufacturer’s recommended guidelines or in-house guidelines. ExcelChem SOPs for analytical methods can be found in Appendix 12. Testing Criteria See Table 11 Testing, Inspection, and Maintenance of Sampling Equipment and Analytical Instruments. See Appendix 11 for equipment testing at ExcelChem. Persons Responsible for Testing, Inspection and Maintenance The Monitoring Lead is responsible for ensuring equipment relevant to their team is properly tested, inspected and maintained. Staff may be delegated the responsibility of carrying out these tasks. Spare Parts Location of spare parts for each piece of equipment is listed in Table 11 Testing, Inspection, and Maintenance of Sampling Equipment and Analytical Instruments. See Appendix11 for equipment testing at ExcelChem. Deficiencies If deficiencies are found, the necessary maintenance will be performed and then the equipment


will be recalibrated and re-inspected. A pre- and post-calibration will be run to determine if the problem has been fixed. If this does not correct the problem, then the equipment will be taken out of use and sent to the manufacturer for servicing. Deficiencies that cannot be immediately corrected will be annotated on the field sheets, as applicable, and noted in the maintenance/calibration logs.


Table 11 Testing, Inspection, Maintenance of Sampling Equipment

Group Equipment / Instrument

Maintenance Activity, Testing Activity or Inspection Activity

Responsible Person

Testing/ Inspection Frequency

Location of Spare Parts

SOP Reference


pH probe (YSI) Calibration Check Monitoring Lead

Per field run Calibration Room YSI User’s Manual

DO probe (YSI) Calibration Check Monitoring Lead


EC probe (YSI) Calibration Check Monitoring Lead


Temperature probe (YSI)

Inspection Monitoring Lead


Hach 2100P turbidimeter

Calibration Check Monitoring Lead

Per field run Calibration Room Hach User’s Manual

Incubator Temperature check Contract Manager

Per field run Order as needed Fisher Scientific, Binder User’s Manuals

UV Lamp Inspection Contract Manager

Per field run

Spare UV Lamp located in main Central Valley Water Board lab

Central Valley Water Board Bacteria Monitoring Procedures

Sealer Cleaning, Inspection Contract Manager Monthly Order as needed Idexx Sealer

Manual


B7, Element 16. Instrument/Equipment Calibration and Frequency All equipment and instruments are operated and calibrated according to the manufacturer’s recommendations. Operation and calibration are performed by personnel properly trained in these procedures. Documentation of all calibration information is recorded in the appropriate logs. If equipment is not meeting the listed criteria (Table 11) it is the responsibility of the field crews to notify the Monitoring Lead and Project Lead, who will be responsible for addressing the problem. Correction may include repair or replacement of equipment. All corrective actions are documented in the appropriate log.


B8, Element 17. Inspection/Acceptance of Supplies and Consumables Upon receipt and prior to use, all calibration standards will be inspected by the field staff for broken seals and to compare the age of each reagent to the manufacturer’s designated shelf life. The Monitoring Lead and Project Lead are each responsible for inspection and acceptance of supplies and consumables used by their respective portions of this study. Details for each consumable are included in Table 12.


Table 12 Inspection/Acceptance Testing Requirements for Consumables and Supplies Project-Related Supplies / Consumables*

Inspection / Testing Specifications

Acceptance Criteria Frequency Responsible Individual

pH 7 Calibration Solution

Used to calibrate pH probe on YSI

Bottle tightly closed Upon arrival and prior to use

Monitoring Lead




Monitoring Lead




Monitoring Lead

1417 Calibration Solution

Lowest solution used to calibrate conductivity probe on YSI


Monitoring Lead


B9, Element 18. Non-Direct Measurements (Existing Data) Existing Data Data Quality Indicators (DQIs) will be used to judge whether the external data meets acceptance criteria. These include, for example, precision, accuracy, representativeness, comparability, completeness, bias, and sensitivity. Measurement performance information such as method detection limits (MDLs), method quantification levels, and the selectivity of a method (or lack of sensitivity) for the target analytes will be used to judge whether the external data meets acceptance criteria. Acceptance of external data for use will depend on the relevance of the matrix, location of the samples, and the methods that were used for collection and/or analysis (for example, field versus laboratory-based methods, the method of collection and analysis, etc.). Water chemistry and field measurement data collected through this project will be stored in Excel spreadsheets until more resources become available. Additionally, data collection stations for parameters such as flow and precipitation can be accessed through the California Data Exchange Center (http://cdec.water.ca.gov). Where appropriate, this data may be assessed in this study in order to better characterize long term trends. Usage Limits If and when external data does not meet acceptance criteria, it will, at the very least, be flagged as such. Flagged data may possibly be used under certain conditions, but its use will be limited and clearly designated.


http://cdec.water.ca.gov/

B10, Element 19. Data Management Data will be maintained as established in Element 9 above. All data from this study will be stored in Excel files until resources are available to transfer the information to a statewide data base. The Monitoring Lead maintains overall responsibility for proper data handling. Specific tasks may be delegated to other participants in this study. The Monitoring Lead will keep hard copies of monitoring related project documents in a dedicated binder. Monitoring related documents include: the Monitoring Plan (MP), the Quality Assurance Project Plan (QAPP), field logs, field data forms, COC forms and laboratory reports. Data/information Handling and Storage Recording, transcribing, digitizing, and downloading data: Central Valley Water Board staff will prepare field sheets (Appendices 6 and 7) prior to the field run to include sample run and sample location identification information. The sheets will be printed on waterproof paper. Field crews will record observations and field measurement data at the sampling locations, using pencil. Prior to leaving the field site, field data sheets will be checked for completeness and accuracy. Transmittal See A9, Element 9 Management See A9, Element 9 Storage See A9, Element 9. Retrieval: The main contact for records will be through the Monitoring Lead, who will maintain the official project file. Contact information can be found in Table 2, A4, Element 4. Computerized Information System Maintenance Official electronic files will be maintained by the Monitoring Lead once the data reports are received. The file will be located on the Central Valley Water Board network at R:\RB5\R5SSections\TMDL Basin NPS Delta\aCross Section\Ag Dominated WBs\MUN BPAs\MONITORING\Synoptic Study_2016\Monitoring Data.


The Central Valley Water Board Information Technology unit performs backup nightly on all network drives. SWAMP Information Management System Field measurement and key constituents data will be verified as meeting QA/QC requirements by the Monitoring Lead. Once the data is verified acceptable, it will be entered into Excel spreadsheets by the Monitoring Lead.


C1, Element 20. Assessments and Response Actions Assessment and oversight involves field activities to ensure that the QA Project Plan is being implemented as planned and that the project activities are on track. By implementing proper assessment and oversight, finding critical problems toward the end of the project is minimized, when it may be too late to apply corrections to remedy them. Two types of assessments may be used in this project: field assessments and laboratory assessments. Field assessments will include:

o Readiness reviews to verify field teams are properly prepared prior to starting field activities;

o Field activity audits to assess field team activities during their execution; and o Post sampling event reviews to assess field sampling and measurement activities

methodologies and documentation at the end of all events or a selected event.

Laboratory assessments may involve two types of activities:

o Data reviews of each data package submitted by a laboratory; and o Audits of laboratory practices and methodologies.

o Field duplicates and travel blanks will be submitted blind to the laboratories to assess precision and contamination.

Project assessments Readiness reviews will be conducted by the Monitoring Lead prior to each sampling run. All sampling personnel will be given a brief review of the sampling procedures, the equipment that will be used during sampling, and the goals and objectives of the sampling event. Readiness reviews will consist of the following activities:

o Equipment checks – It is important that all field equipment be clean and ready to use when it is needed. Therefore, prior to using all sampling and/or field measurement equipment, each piece of equipment will be checked to make sure that it is in proper working order.

o Equipment maintenance records – Equipment maintenance records will be checked to ensure that all field instruments have been properly maintained and that they are ready for use.

o Supply checks – Adequate supplies of all items in B2, Element 11 will be checked before each field event to make sure that there are sufficient supplies to successfully support


each sampling event. o Paperwork checks – It is important to make sure that all field activities and

measurements are properly recorded in the field. Therefore, prior to starting each field event, necessary paperwork such as field sheets, chain of custody record forms, etc. will be checked to ensure that sufficient amounts are available during the field event.

Field activity audits are held per the Central Valley Water Board’s Procedures Manual to assess the sample collection methodologies, field measurement procedures, and record keeping of the field crew in order to ensure that the activities are being conducted as planned and as documented in this QAPP. Post sampling event reviews will be conducted by the Monitoring Lead following each sampling event in order to ensure that all information is complete and any deviations from planned methodologies are documented. Activities include reviewing field measurement documentation in order to help ensure that all information is complete. Laboratory data review will be conducted by ExcelChem’s QA Officer upon receipt of data from each lab. Data will be checked for completeness, accuracy, specified methods were used, and that all related QC data was provided with the sample analytical results. Laboratory audits will include blind sample submission to the labs by the monitoring lead for each sampling run. The results of the lab’s analysis will be compared to the known analytes (e.g. lab blanks) or acceptable ranges (e.g. lab duplicates) Assessment reports Separate assessment reports will not be generated for readiness reviews, field activity audits, or post sampling event reviews. Instead, problem areas such as sample collection or transport of samples will be notated on field sheets. The monitoring lead will be responsible for correcting or minimizing the problem for the next sampling event after reviewing the notes on the field sheets. Laboratory assessment information (data review and audit) will be included in the laboratory data sets. Corrective action If a problem arises, prompt action to correct the immediate problem and identify its root causes is imperative. Any related systematic problems must also be identified. Problems regarding field data quality that may require corrective action will be documented in


the field data sheets. Deficiencies that cannot be immediately corrected will be noted on the Central Valley Water Board field sheet and brought to the attention of the Monitoring Lead. The Monitoring Lead will coordinate with the Central Valley Water Board staff to correct the deficiencies. The results of the resolution of the discrepancy will be documented in writing on the field sheet and on a separate log that will be kept in the project file. Individual laboratory data quality will be reviewed by the Monitoring Lead. Deficiencies and corrective actions taken will be noted on the ExcelChem report and on the Excel spreadsheets to which the data will be transferred. Overall laboratory data quality will be reviewed by the Monitoring Lead. The Monitoring Lead and Project Lead have the authority to issue stop work orders to stop all sampling and analysis activities until the discrepancy can be resolved.


C2, Element 21. Reports to Management

Interim and final reports The ExcelChem Lab Director will review draft reports to ensure the accuracy of data analysis and data interpretation. Table 13 QA Management Reports

Type of Report

Frequency Projected Delivery Dates(s)

Person(s) Responsible for Report Preparation

Report Recipients

Data report Per field run 7 days after receipt of samples

ExcelChem Lab Director

Monitoring Lead

Quality Assurance Reports Separate quality assurance reports will not be generated. Quality assurance information annotated on field and lab sheets will be included with the Data reports.


D1, Element 22. Data Review, Verification, and Validation Requirements Data review, verification, and validation procedures help to ensure that project data will be reviewed in an objective and consistent manner. Data review is the in-house examination to ensure that the data have been recorded, transmitted, and processed correctly. Responsibility for Data Review The Monitoring Lead will be responsible for data review. This includes checking that all technical criteria have been met, documenting any problems that are observed and, if possible, ensuring that deficiencies noted in the data are corrected. Checking for Common Errors Data produced from the project will be examined in-house to check for common types of data errors. This will include reviewing the data for errors pertaining to entry, transcription, transformation, and calculation. Checking Against MQOs Data generated by project activities will be reviewed against method quality objectives (MQOs). This will ensure that the data is of acceptable quality and it is be SWAMP-comparable with respect to minimum expected MQOs. Checking Against QA/QC QA/QC requirements were developed and documented in B3, Element 12; B4, Element 13; B5, Element 14; B7, Element 16; and B8, Element 17 and the data will be checked against this information. Checks will include evaluation of field and laboratory duplicate results; and field and laboratory blank data pertinent to each method and analytical data set. This will ensure that the data will be SWAMP-comparable with respect to quality assurance and quality control procedures. Checking Lab Data Lab data consists of all information obtained during sample analysis. Initial review of laboratory data will be performed by the laboratory QA/QC Officer in accordance with the lab’s internal data review procedures. However, once the Central Valley Water Board receives the lab data, independent checks will be performed to ensure that the data is complete, consistent, and meets management requirements of the data management section of this QAPP.


Data Verification Data verification is the process of evaluating the completeness, correctness, and conformance/compliance of a specific data set against the method, procedural, or contractual specifications. Data Validation Data validation is an analyte- and sample-specific process that evaluates the information after the verification process (i.e., determination of method, procedural, or contractual compliance) to determine analytical quality and any limitations. The Central Valley Water Board will conduct data validation in order to ensure that the data is able to be used in evaluating the MUN beneficial use. Responsibility for Data Validation The Monitoring Lead will be responsible for validation of data. Data Separation Data will be separated into three categories for use with making decisions based upon it. These categories are:

1. Data that meets all acceptance requirements 2. Data that has been determined to be unacceptable for use 3. Data that may be conditionally used and that is flagged as per SWAMP specification


D2, Element 23. Verification and Validation Methods Defining the methods for data verification and validation helps to ensure that project data are evaluated objectively and consistently. Information on these methods is provided below. All data records for the proposed project will be checked visually and will be recorded as checked by the checker’s initials as well as with the dates on which the records were checked. All of the laboratory’s data will be checked as part of the verification methodology process. Any data that is discovered to be incorrect or missing during the verification or validation process will immediately be reported to the Monitoring Lead. If errors involve laboratory data then this information will also be reported to the Monitoring Lead. If there are any data quality problems, the monitoring lead will try to identify whether the problem is a result of project design issues, sampling issues, analytical methodology issues, or QA/QC issues (from laboratory or non-laboratory sources). If the source of the problems can be traced to one or more of these basic activities then the person or people in charge of the areas where the issues lie will be contacted and efforts will be made to immediately resolve the problem. If the issues are too broad or severe to be easily corrected then appropriate people involved will be assembled to discuss and try to resolve the issue(s) as a group. The Monitoring Lead has the final authority to resolve any issues that may be identified during the verification and validation process.


D3, Element 24. Reconciliation with User Requirements Information from field data reports (including field activities, post sampling events, corrective actions, and audits), laboratory data reviews (including errors involving data entry, transcriptions, omissions, and calculations and laboratory audit reports), reviews of data versus MQOs, reviews against Quality Assurance and Quality Control (QA/QC) requirements, data verification reports, data validation reports, independent data checking reports, and error handling reports will be used to determine whether or not the project’s objectives have been met. Data from all monitoring measurements will be summarized in tables. During the quarterly review, data that show significant changes over time during the monitoring period will be plotted in graphs and charts. There are no known limitations that are inherent to the data to be collected for this study. Explanations will be provided for any data determined unacceptable for use or flagged for QA/QC concerns. The proposed project will provide data for the selected analytes described in Element 6. All data will be readily available to all those involved in this project. The above evaluations will provide a comprehensive assessment of how well the project meets its objectives. No other evaluations will be used. The Project Lead and Monitoring Lead will be responsible for reporting project reconciliation. This will include measurements of how well the project objectives were met. When resources become available, the data will be entered into CEDEN templates in order to be loaded into the CEDEN database. This section describes how validated data will be evaluated to see if it answers the project objectives outlined in A5, Element 5.


APPENDICES


Appendix 1. Sampling Sites

Map Label Station Code Site Latitude Longitude

1 519SUT008 Sacramento River Below Verona at Joes Landing 38.77715 -121.60097 2 515FRNVxx Feather River near Verona 38.79252 -121.62755

3 520SUT011 Sacramento River above Colusa Basin Drain at Cranmore Road 38.81440 -121.72350

4 520SUT012 Sacramento River Upstream of Rough and Ready Pumping Plant 38.86585 -121.79476

5 519SUT002 Sacramento River below Knights Landing 38.76064 -121.67824

6 519SUT108 Sacramento River at Elkhorn Boat Launch Facility 38.67245 -121.62500

NOTE: Map Labels match locations depicted in Appendix 2.


Appendix 2. Map of Sampling Sites Sacramento River Basin Sampling Sites


Appendix 3. Monitoring Plan

Synoptic Evaluation of Drinking Water

Constituents of Concern in the Sacramento River Basin

Final Monitoring Plan June 2016


TABLE OF CONTENTS I. INTRODUCTION ................................................................................................................. 118

II. BACKGROUND .................................................................................................................. 118

III. STUDY DESIGN OVERVIEW ............................................................................................ 118

III.a. Monitoring Design .................................................................................................... 120

III.b. Sampling Locations .................................................................................................. 120

III.c. Parameters .............................................................................................................. 123

III.c.1 Field Parameters ................................................................................................... 123 III.c.2 Laboratory Analyses .............................................................................................. 123 III.d. Frequency and Sampling ......................................................................................... 133

III.e. Spatial and Temporal Scale ..................................................................................... 133

III.f. Data Management .................................................................................................... 133

IV. REVIEW STRATEGY ........................................................................................................ 133

V. QUALITY ASSURANCE .................................................................................................... 133

V.a. Field Equipment ....................................................................................................... 133

V.b. Laboratory Method and Costs .................................................................................. 133

VI. REFERENCES .................................................................................................................. 137

List of Tables Table 1 Sacramento River Basin Monitoring Sites .................................................................. 121 Table 2 List of Constituents within Each Scan including RLs and MDLs ................................. 124 Table 3 Laboratory Costs for Chemical Parameters ................................................................ 135 List of Figures Figure 1 Sacramento River Basin............................................................................................ 119 Figure 2 Sacramento River Basin Monitoring Sites ................................................................. 122 Appendix APPENDIX A PARAMETERS AND CRITERIA ....................................................................... 138


I. INTRODUCTION This plan documents the monitoring aspects of the Synoptic Evaluation of Drinking Water Constituents of Concern in the Sacramento River Basin that will be conducted in June 2016. The purpose of this study is to evaluate the current water quality within the Sacramento River Basin against Maximum Contaminant Levels (MCLs) specified in provisions of the Title 22 of the California Code of Regulations, California Toxics Rule (CTR) criteria, and other numeric water quality criteria listed in Appendix A for constituents without a MCL or CTR criteria developed to protect human health. Sampling of the study’s sites will be conducted over the course of one day. Sampling sites consist of:

• Locations that are utilized by other programs gathering water quality data • Locations in the main river stems

II. BACKGROUND Via the incorporation of the State Water Resources Control Board Sources of Drinking Water Policy (Resolution 88-63) into the Sacramento River and San Joaquin River Basins Water Quality Control Plan (Basin Plan), the municipal and domestic supply (MUN) beneficial applies to all surface and ground water bodies in the region unless they are specifically listed as water bodies that are not designated as supporting the MUN beneficial use. The Basin Plan states that water bodies designated for MUN must not exceed Maximum Contaminant Levels (MCLs) for chemical constituents, pesticides and radionuclides. This project will provide a one-day snapshot of the water quality in the Sacramento River Basin at the main stem of the Sacramento and Feather River as compared to criteria developed to protect human health.

III. STUDY DESIGN OVERVIEW This Monitoring Plan has been formatted to reflect California’s Surface Water Ambient Monitoring Program (SWAMP) template. The following sections provide details of the plan, including questions to be answered, constituents to be analyzed, sampling sites, and frequency. Figure 1 displays the study area.


Figure 2 Sacramento River Basin


III.a. Monitoring Design This monitoring effort will evaluate water quality along the Sacramento River and Feather River against criteria developed to protect human health; specifically the Title 22 primary and secondary MCLs and select constituents identified in the California Toxics Rule. The analytes and their associated criteria are listed in Appendix A. Not all of the analytes listed in Appendix A were analyzed for this study. The main question being asked by this study is: During a one-time snapshot of the Sacramento River Basin, does water quality in the Sacramento and Feather River exceed potable water quality criteria? The primary objectives of this project are:

• Collect representative samples in the Sacramento River and Feather River; • Determine spatial distribution of any detectible constituent concentrations of concern;

and • Identify whether criteria developed to protect human health are exceeded.

All aspects of this study, including all samples and field measurements collected, will be conducted in accordance with the Procedures Manual for the San Joaquin River Water Quality Monitoring Program (Central Valley Water Board, 2010), which is compliant with the 2008 SWAMP Quality Assurance Program Plan (QAPrP) for the State of California’s Surface Water Ambient Monitoring Program (State Water Board, 2008). III.b. Sampling Locations Six sites have been selected for sampling (Table 1). Depending on available funding, not all six sites would be sampled. The final amount of available budget and selection of sites will be noted in the final report. Sites were selected based on accessibility, presence of water, representativeness of the main river stems and historical issues with contaminants. Considerations were also given to potential use of the resulting data by other program and agencies. Figure 2 is a map of the sampling locations.


Table 14 Sacramento River Basin Monitoring Sites Map

Label Station Code Site Latitude Longitude

1 519SUT008 Sacramento River Below Verona at Joes Landing 38.77715 -121.60097 2 515FRNVxx Feather River near Verona 38.79252 -121.62755

3 520SUT011 Sacramento River above Colusa Basin Drain at Cranmore Road 38.81440 -121.72350

4 520SUT012 Sacramento River Upstream of Rough and Ready Pumping Plant 38.86585 -121.79476

5 519SUT002 Sacramento River below Knights Landing 38.76064 -121.67824

6 519SUT108 Sacramento River at Elkhorn Boat Launch Facility 38.67245 -121.62500

NOTE: Map labels match locations depicted in Figure 2.


Figure 3 Sacramento River Basin Monitoring Sites


III.c. Parameters III.c.1 Field Parameters Collection of field parameters will include temperature, dissolved oxygen, pH, specific conductivity, and turbidity. One photo upstream of sampling location, one photo looking straight ahead at sampling location, and one photo downstream of sampling location will be taken. III.c.2 Laboratory Analyses This study will analyze for MCLs specified in provisions of Title 22 of the California Code of Regulations, CTR criteria, and other numeric quality criteria listed in Appendix A for constituents without a MCL or CTR criteria. For constituents with both a MCL and CTR criteria, the most conservative numeric threshold was selected for water quality evaluation. For constituents without a MCL and CTR criteria, the most appropriate for protecting MUN beneficial use numeric water quality criteria was selected for water quality evaluation. Table 2 lists the major analytical scans that will be conducted by ExcelChem Environmental Labs. In addition to the constituents listed in Table 2, E. coli samples will be collected.


Table 15 List of Constituents within Each Scan including RLs and MDLs

Scan Analyte RL MDL Unit Test Method Volatile Organic Compounds (VOCs) by GC/MS

1, 1-Dichloroethane 0.5 0.04 µg/L EPA 8260B 1,1,1,2-Tetrachloroethane 0.5 0.08 µg/L EPA 8260B 1,1,1-Trichloroethane 0.5 0.05 µg/L EPA 8260B 1,1,2,2-Tetrachloroethane 0.5 0.4 µg/L EPA 8260B 1,1,2-Trichloroethane 0.5 0.1 µg/L EPA 8260B 1,1-Dichloroethane 0.5 0.05 µg/L EPA 8260B 1,1-Dichloropropene 0.5 0.03 µg/L EPA 8260B 1,2,3-Trichlorobenzene 0.5 0.05 µg/L EPA 8260B 1,2,3-Trichloropropane 0.5 0.06 µg/L EPA 8260B 1,2,4-Trichlorobenzene 0.5 0.02 µg/L EPA 8260B 1,2,4-Trimethylbenzene 0.5 0.04 µg/L EPA 8260B 1,2-Dibromo-3-chloropropane 0.5 0.07 µg/L EPA 8260B

1,2-Dibromoethane (EDB) 0.5 0.1 µg/L EPA 8260B 1,2-Dichlorobenzene 0.5 0.06 µg/L EPA 8260B 1,2-Dichloroethane 0.5 0.04 µg/L EPA 8260B 1,2-Dichloropropane 0.5 0.06 µg/L EPA 8260B 1,3-Dichlorobenzene 0.5 0.03 µg/L EPA 8260B 1,3-Dichloropropane 0.5 0.06 µg/L EPA 8260B 1,4-Dichlorobenzene 0.5 0.05 µg/L EPA 8260B 2-Butanone 5 0.1 µg/L EPA 8260B 2-Chlorotoluene 0.5 0.03 µg/L EPA 8260B 2-Hexanone 5 0.1 µg/L EPA 8260B 4-Chlorotoluene 0.5 0.05 µg/L EPA 8260B 4-Isopropyltoluene 0.5 0.04 µg/L EPA 8260B 4-Methyl1-2pentanone 5 0.05 µg/L EPA 8260B Acetone 5 0.1 µg/L EPA 8260B Benzene 0.5 0.03 µg/L EPA 8260B Bromobenzene 0.5 0.05 µg/L EPA 8260B Bromochloromethane 0.5 0.07 µg/L EPA 8260B Bromodichloromethane 0.5 0.05 µg/L EPA 8260B Bromoform 0.5 0.03 µg/L EPA 8260B Bromomethane 0.5 0.05 µg/L EPA 8260B Carbon disulfide 0.5 0.06 µg/L EPA 8260B Carbon tetrachloride 0.5 0.02 µg/L EPA 8260B Chlorobenzene 0.5 0.03 µg/L EPA 8260B

Chloroethane 0.5 0.08 µg/L EPA 8260B


Scan Analyte RL MDL Unit Test Method

Volatile Organic Compounds (VOCs) by GC/MS

Chloroform 0.5 0.05 µg/L EPA 8260B Chloromethane 0.5 0.06 µg/L EPA 8260B cis-1,2-Dichloroethane 0.5 0.03 µg/L EPA 8260B cis-1,3-Dichloropropene 0.5 0.04 µg/L EPA 8260B Dibromochloromethane 0.5 0.07 µg/L EPA 8260B Dibromomethane 0.5 0.07 µg/L EPA 8260B Dichlorodifluoromethane 0.5 0.07 µg/L EPA 8260B Di-isopropyl ether 0.5 0.1 µg/L EPA 8260B Ethyl tert-Butyl Ether 0.5 0.04 µg/L EPA 8260B Ethylbenzene 0.5 0.03 µg/L EPA 8260B Hexachlorobutadiene 0.5 0.07 µg/L EPA 8260B Iodomethane 0.5 0.03 µg/L EPA 8260B Isopropylbenzene 0.5 0.04 µg/L EPA 8260B m,p-Xylene 1 0.09 µg/L EPA 8260B Methyl tert-Butyl Ether 0.5 0.05 µg/L EPA 8260B Methylene chloride 5 0.08 µg/L EPA 8260B Naphthalene 0.5 0.04 µg/L EPA 8260B n-Butylbenzene 0.5 0.04 µg/L EPA 8260B n-Propylbenzene 0.5 0.04 µg/L EPA 8260B o-Xylene 0.5 0.04 µg/L EPA 8260B sec-Butylbenzene 0.5 0.03 µg/L EPA 8260B TBA 1 0.1 µg/L EPA 8260B Tert-Amyl Methyl Ether 0.5 0.03 µg/L EPA 8260B tert-Butylbenzene 0.5 0.02 µg/L EPA 8260B Tetrachloroethene 0.5 0.08 µg/L EPA 8260B Toluene 0.5 0.04 µg/L EPA 8260B trans-1,2-Dichloroethane 0.5 0.04 µg/L EPA 8260B trans-1,3-Dichloropropene 0.5 0.04 µg/L EPA 8260B Trichloroethane 0.5 0.06 µg/L EPA 8260B Trichlorofluoromethane 0.5 0.05 µg/L EPA 8260B Trichlorotrifluoroethane 1 0.05 µg/L EPA 8260B Vinyl chloride 0.5 0.06 µg/L EPA 8260B Xylenes, total 1 0.1 µg/L EPA 8260B 1,1,1,2-Tetrachloroethane 0.5 0.08 µg/L EPA 524 1,1,1-Trichloroethane 0.5 0.05 µg/L EPA 524 1,1,2,2-Tetrachloroethane 0.5 0.04 µg/L EPA 524 1,1,2-Trichloroethane 0.5 0.1 µg/L EPA 524 1,1,-Dichloroethane 0.5 0.04 µg/L EPA 524 1,1-Dichloropropene 0.5 0.03 µg/L EPA 524 1,2,3-Trichlorobenzene 0.5 0.05 µg/L EPA 524




1,2,3-Trichloropropane 0.5 0.06 µg/L EPA 524 1,2,4-Trichlorobenzene 0.5 0.02 µg/L EPA 524 1,2,4-Trimethylbenzene 0.5 0.04 µg/L EPA 524 1,2-Dibromo-3-chloropropane 0.5 0.07 µg/L EPA 524

1,2-Dibromoethane (EDB) 0.5 0.1 µg/L EPA 524 1,2-Dichlorobenzene 0.5 0.06 µg/L EPA 524 1,2-Dichloroethane 0.5 0.06 µg/L EPA 524 1,2-Dichloropropane 0.5 0.06 µg/L EPA 524 1,3,5-Trimethylbenzene 0.5 0.03 µg/L EPA 524 1,3-Dichlorobenzene 0.5 0.03 µg/L EPA 524 1,3-Dichloropropane 0.5 0.06 µg/L EPA 524 1,4-Dichlorobenzene 0.5 0.05 µg/L EPA 524 2,2-Dichloropropane 0.5 0.06 µg/L EPA 524 2-Butanone 5 0.1 µg/L EPA 524 2-Chlorotoluene 0.5 0.03 µg/L EPA 524 2-Hexanone 0.5 0.1 µg/L EPA 524 4-Chlorotoluene 0.5 0.05 µg/L EPA 524 4-Isopropyltoluene 0.5 0.04 µg/L EPA 524 4-Methyl-2-pentanone 0.5 0.05 µg/L EPA 524 Acetone 5 0.1 µg/L EPA 524 Benzene 0.5 0.03 µg/L EPA 524 Bromobenzene 0.5 0.05 µg/L EPA 524 Bromochloromethane 0.5 0.07 µg/L EPA 524 Bromodichloromethane 0.5 0.05 µg/L EPA 524 Bromoform 0.5 0.03 µg/L EPA 524 Bromomethane 0.5 0.05 µg/L EPA 524 Carbon disulfide 0.5 0.06 µg/L EPA 524 Carbon tetrachloride 0.5 0.02 µg/L EPA 524 Chlorobenzene 0.5 0.03 µg/L EPA 524 Chloroethane 0.5 0.08 µg/L EPA 524 Chloroform 0.5 0.05 µg/L EPA 524 Chloromethane 0.5 0.06 µg/L EPA 524 cis-1,2-Dichloroethane 0.5 0.03 µg/L EPA 524 cis-1,3-Dichloropropene 0.5 0.04 µg/L EPA 524 Dibromochloromethane 0.5 0.07 µg/L EPA 524 Dibromomethane 0.5 0.07 µg/L EPA 524 Dichlorodifluoromethane 0.5 0.07 µg/L EPA 524 Di-isopropyl ether 0.5 0.1 µg/L EPA 524 Ethyl tert-Butyl Ether 0.5 0.04 µg/L EPA 524




Ethylbenzene 0.5 0.03 µg/L EPA 524 Hexachlorobutadiene 0.5 0.07 µg/L EPA 524 Iodomethane 0.5 0.03 µg/L EPA 524 Isopropylbenzene 0.5 0.04 µg/L EPA 524 m,p-Xylene 0.5 0.09 µg/L EPA 524 Methyl tert-Butyl Ether 0.5 0.05 µg/L EPA 524 Methylene chloride 1 0.08 µg/L EPA 524 Naphthalene 0.5 0.04 µg/L EPA 524 n-Butylbenzene 0.5 0.04 µg/L EPA 524 n-Propylbenzene 0.5 0.04 µg/L EPA 524 o-Xylene 0.5 0.04 µg/L EPA 524 sec-Butylbenzene 0.5 0.03 µg/L EPA 524 Styrene 0.5 0.09 µg/L EPA 524 TBA 1 0.1 µg/L EPA 524 Tert-Amyl Methyl Ether 0.5 0.03 µg/L EPA 524 tert-Butylbenzene 0.5 0.02 µg/L EPA 524 Tetrachloroethene 0.5 0.08 µg/L EPA 524 Toluene 0.5 0.04 µg/L EPA 524 Total Trihalomethanes 0.5 0.5 µg/L EPA 524 trans-1,2-Dichloroethane 0.5 0.04 µg/L EPA 524 trans-1,3-Dichloropropene 0.5 0.04 µg/L EPA 524 Trichloroethane 0.5 0.06 µg/L EPA 524 Trichlorofluoromethane 0.5 0.05 µg/L EPA 524 Trichlorotrifluoroethane 1 0.05 µg/L EPA 524 Vinyl chloride 0.5 0.06 µg/L EPA 524 Xylenes, total 1 0.1 µg/L EPA 524

Pesticides by GC/ECD

4,4'-DDD 0.1 0.006 µg/L EPA 8081A 4,4'-DDE 0.1 0.005 µg/L EPA 8081A 4,4'-DDT 0.1 0.004 µg/L EPA 8081A Aldrin 0.1 0.011 µg/L EPA 8081A alpha-BHC 0.1 0.011 µg/L EPA 8081A alpha-Chlordane 0.1 0.006 µg/L EPA 8081A beta-BHC 0.1 0.011 µg/L EPA 8081A delta-BHC 0.1 0.021 µg/L EPA 8081A Dieldrin 0.1 0.006 µg/L EPA 8081A Endosulfan I 0.1 0.007 µg/L EPA 8081A Endosulfan II 0.1 0.021 µg/L EPA 8081A Endosulfan sulfate 0.1 0.005 µg/L EPA 8081A Endrin 0.1 0.007 µg/L EPA 8081A Endrin aldehyde 0.1 0.006 µg/L EPA 8081A




Endrin Ketone 0.1 0.005 µg/L EPA 8081A gamma-BHC (Lindane) 0.1 0.013 µg/L EPA 8081A gamma-Chlordane 0.1 0.005 µg/L EPA 8081A Heptachlor 0.1 0.016 µg/L EPA 8081A Heptachlor epoxide 0.1 0.02 µg/L EPA 8081A Methoxychlor 0.1 0.013 µg/L EPA 8081A

PCBs by GC/ECD

Aroclor 1016 1 0.06 µg/L EPA 8081A Aroclor 1221 1 0.13 µg/L EPA 8081A Aroclor 1232 1 0.1 µg/L EPA 8081A Aroclor 1242 1 0.06 µg/L EPA 8081A Aroclor 1248 1 0.06 µg/L EPA 8081A Aroclor 1254 1 0.09 µg/L EPA 8081A Aroclor 1260 1 0.08 µg/L EPA 8081A PCBs 1 0.08 µg/L EPA 8081A

SemiVolatile Organic Compounds by GC/MS

1,2,4-Trichlorobenzene 2 0.6 µg/L EPA 8270C 1,4-Dichlorobenzene 2 0.4 µg/L EPA 8270C 2,4,5-Trichlorophenol 5 1.6 µg/L EPA 8270C 2,4,6-Trichlorophenol 5 1.6 µg/L EPA 8270C 2,4-Dichlorophenol 2 0.8 µg/L EPA 8270C 2,4-Dimethylphenol 2 0.8 µg/L EPA 8270C 2,4-Dinitrophenol 10 0.3 µg/L EPA 8270C 2,4-Dinitrotoluene 2 0.8 µg/L EPA 8270C 2,6-Dinitrotoluene 2 0.8 µg/L EPA 8270C 2-Chloronaphthalene 2 0.2 µg/L EPA 8270C 2-Chlorophenol 2 0.8 µg/L EPA 8270C 2-Methylnaphthalene 2 0.6 µg/L EPA 8270C 2-Methylphenol 2 0.4 µg/L EPA 8270C 2-Nitroaniline 2 0.4 µg/L EPA 8270C 2-Nitrophenol 2 1.2 µg/L EPA 8270C 3,3´-Dichlorobenzidine 5 0.8 µg/L EPA 8270C 3-Nitroaniline 2 0.5 µg/L EPA 8270C 4,6-Dinitro-2-methylphenol 10 2.2 µg/L EPA 8270C 4-Bromophenyl phenyl ether 2 0.8 µg/L EPA 8270C

4-Chloro-3-methylphenol 2 0.6 µg/L EPA 8270C 4-Chloroaniline 2 0.5 µg/L EPA 8270C 4-Chlorophenyl phenyl ether 2 0.5 µg/L EPA 8270C

4-Nitroaniline 2 0.6 µg/L EPA 8270C 4-Nitrophenol 5 0.1 µg/L EPA 8270C Acenaphthene 2 0.6 µg/L EPA 8270C




Acenaphthylene 2 0.3 µg/L EPA 8270C Aniline 2 0.3 µg/L EPA 8270C Anthracene 2 0.3 µg/L EPA 8270C Azobenzene 2 0.4 µg/L EPA 8270C Benzidine 5 0.2 µg/L EPA 8270C Benzo (a) anthracene 2 0.4 µg/L EPA 8270C Benzo (a) pyrene 5 1.2 µg/L EPA 8270C Benzo (b) fluoranthene 2 0.8 µg/L EPA 8270C Benzo (g,h,i) perylene 2 1.3 µg/L EPA 8270C Benzo (k) fluoranthene 2 1 µg/L EPA 8270C Benzoic acid 30 0.5 µg/L EPA 8270C Benzyl alcohol 2 0.4 µg/L EPA 8270C Bis(2-chloroethoxy)methane 2 0.4 µg/L EPA 8270C

Bis(2-chloroethyl)ether 2 0.6 µg/L EPA 8270C Bis(2-chloroisopropyl)ether 2 0.4 µg/L EPA 8270C Bis(2-ethylhexyl)phthalate 5 0.7 µg/L EPA 8270C Butyl benzyl phthalate 2 1 µg/L EPA 8270C Carbazole 2 0.6 µg/L EPA 8270C Chrysene 2 0.5 µg/L EPA 8270C Dibenz (a,h) anthracene 2 1.6 µg/L EPA 8270C Dibenzofuran 2 0.3 µg/L EPA 8270C Diethyl phthalate 2 0.6 µg/L EPA 8270C Dimethyl phthalate 2 0.8 µg/L EPA 8270C Di-n-butyl phthalate 2 0.4 µg/L EPA 8270C Di-n-octyl phthalate 5 0.7 µg/L EPA 8270C Fluoranthene 2 0.6 µg/L EPA 8270C Fluorene 2 0.5 µg/L EPA 8270C Hexachlorobenzene 2 0.6 µg/L EPA 8270C Hexachlorobutadiene 2 0.6 µg/L EPA 8270C Hexachlorocyclopentadiene 2 0.6 µg/L EPA 8270C Hexachloroethane 2 0.5 µg/L EPA 8270C Indeno (1,2,3-cd) pyrene 5 1.6 µg/L EPA 8270C Isophorone 2 0.3 µg/L EPA 8270C Naphthalene 2 0.5 µg/L EPA 8270C Nitrobenzene 2 0.7 µg/L EPA 8270C

Organophosphorus Pesticides

N-Nitrosodimethylamine 2 0.4 µg/L EPA 8270C N-Nitrosodi-n-propylamine 2 0.3 µg/L EPA 8270C N-Nitrosodiphenylamine 2 0.6 µg/L EPA 8270C Pentachlorophenol 10 2.4 µg/L EPA 8270C




Phenanthrene 2 0.4 µg/L EPA 8270C Phenol 2 0.3 µg/L EPA 8270C Pyrene 2 1 µg/L EPA 8270C Azinphos-methyl 0.2 0.027 µg/L EPA 8141A Bolstar 0.2 0.086 µg/L EPA 8141A Coumaphos 0.2 0.168 µg/L EPA 8141A Demeton 0.2 0.105 µg/L EPA 8141A Demeton-O 0.2 0.101 µg/L EPA 8141A Demeton-S 0.2 0.105 µg/L EPA 8141A Diazinon 0.25 0.065 µg/L EPA 8141A Dichlorvos 0.2 0.156 µg/L EPA 8141A Dimethoate 0.2 0.071 µg/L EPA 8141A Disulfoton 0.2 0.069 µg/L EPA 8141A Dursban (Chlorpyrifos) 0.2 0.071 µg/L EPA 8141A EPN 0.2 0.124 µg/L EPA 8141A Ethoprop 0.2 0.077 µg/L EPA 8141A Fensulfothion 0.2 0.139 µg/L EPA 8141A Fenthion 0.2 0.067 µg/L EPA 8141A Gardona (Stirophos) 0.2 0.11 µg/L EPA 8141A Malathion 0.2 0.159 µg/L EPA 8141A Merphos 0.2 0.097 µg/L EPA 8141A Mevinphos 0.2 0.115 µg/L EPA 8141A Molinate 0.2 0.044 µg/L EPA 8141A Monocrotophos 0.2 0.015 µg/L EPA 8141A Naled 0.2 0.169 µg/L EPA 8141A Parathion 0.2 0.079 µg/L EPA 8141A Parathion-methyl 0.2 0.077 µg/L EPA 8141A Phorate 0.2 0.083 µg/L EPA 8141A Ronnel 0.2 0.066 µg/L EPA 8141A Sulfotep 0.2 0.095 µg/L EPA 8141A TEPP 0.2 0.151 µg/L EPA 8141A Tokuthion (Prothiofos) 0.2 0.077 µg/L EPA 8141A Trichloronate 0.2 0.067 µg/L EPA 8141A

Chlorinated Herbicides

2,4,5-T 0.5 0.097 µg/L EPA 8151A

2,4,5-TP (Silvex) 0.5 0.095 µg/L EPA 8151A 2,4-D 0.4 0.086 µg/L EPA 8151A 2,4-DB 0.8 0.157 µg/L EPA 8151A 3,5-Dichlorobenzoic acid 0.8 0.17 µg/L EPA 8151A 4-Nitrophenol 0.6 0.117 µg/L EPA 8151A




Acifluorfen 0.8 0.157 µg/L EPA 8151A Bentazon 0.6 0.11 µg/L EPA 8151A Chloramben 0.8 0.008 µg/L EPA 8151A Dalapon 0.6 0.115 µg/L EPA 8151A DCPA 0.4 0.015 µg/L EPA 8151A Dicamba 0.4 0.08 µg/L EPA 8151A Dichloroprop 0.8 0.196 µg/L EPA 8151A Dinoseb 0.4 0.083 µg/L EPA 8151A MCPP 10 0.891 µg/L EPA 8151A Pentachlorophenol 0.3 0.053 µg/L EPA 8151A Picloram 0.8 0.02 µg/L EPA 8151A

Ion Chromatography

Hexavalent Chromium 1 0.1 µg/L EPA 218.6 Chloride 0.5 0.04 mg/L EPA 300.0 Fluoride 0.1 0.02 mg/L EPA 300.0 Nitrate as Nitrogen 0.11 0.009 mg/L EPA 300.0 Nitrite as Nitrogen 0.15 0.03 mg/L EPA 300.0 Sulfate as SO4 5 0.7 mg/L EPA 300.0 Perchlorate 2 0.094 µg/L EPA 314.0

Wet Chemistry

Specific Conductance (EC) 5 1.09 µS/cm EPA 120.1 Total Dissolved Solids 15 7.68 mg/L SM 2540C

Cyanide 0.005 0.0009 mg/L SM 4500CN E

pH 0.1 0.1 pH Units

SM 4500-H+ B

Ammonia as N 0.1 0.04 mg/L SM 4500-NH3 B/H

MBAS 0.1 0.06 mg/L SM 5540C Total Alkalinity 5 2.37 mg/L SM2320B Total Hardness 5 2.86 mg/L SM2340B

Total Recoverable Metals

Aluminum 50 24.5 µg/L EPA 200.7 Antimony 10 1.3 µg/L EPA 200.7 Arsenic 10 1 µg/L EPA 200.7 Barium 5 1.2 µg/L EPA 200.7 Beryllium 5 0.09 µg/L EPA 200.7 Boron 50 0.8 µg/L EPA 200.7 Cadmium 5 0.1 µg/L EPA 200.7 Calcium 100 79 µg/L EPA 200.7 Chromium 5 0.3 µg/L EPA 200.7 Copper 5 0.8 µg/L EPA 200.7 Iron 20 11.5 µg/L EPA 200.7 Lead 5 0.9 µg/L EPA 200.7




Magnesium 50 15.6 µg/L EPA 200.7 Manganese 10 0.6 µg/L EPA 200.7 Nickel 5 0.6 µg/L EPA 200.7 Selenium 20 1.3 µg/L EPA 200.7 Silver 5 0.4 µg/L EPA 200.7 Sodium 200 120 µg/L EPA 200.7 Thallium 20 2.2 µg/L EPA 200.7 Titanium 50 1.2 µg/L EPA 200.7 Zinc 10 0.3 µg/L EPA 200.7

Dissolved Metals

Dissolved Aluminum 50 24.5 µg/L EPA 200.7 Dissolved Arsenic 10 1 µg/L EPA 200.7 Dissolved Iron 20 11.5 µg/L EPA 200.7 Dissolved Lead 5 0.9 µg/L EPA 200.7

Dixoin/Furan

1,2,3,4,6,7,8-HpCDD 50 2.17 pg/L 1613B 1,2,3,4,6,7,8-HpCDF 50 3.77 pg/L 1613B 1,2,3,4,7,8,9-HpCDF 50 4.61 pg/L 1613B 1,2,3,4,7,8-HxCDD 50 3.98 pg/L 1613B 1,2,3,4,7,8-HxCDF 50 3.66 pg/L 1613B 1,2,3,6,7,8-HxCDD 50 5.34 pg/L 1613B 1,2,3,6,7,8-HxCDF 50 3.97 pg/L 1613B 1,2,3,7,8,9-HxCDD 50 4.68 pg/L 1613B 1,2,3,7,8,9-HxCDF 50 8.74 pg/L 1613B 1,2,3,7,8-PeCDD 50 2.29 pg/L 1613B 1,2,3,7,8-PeCDF 50 2.58 pg/L 1613B 2,3,4,6,7,8-HxCDF 50 4.97 pg/L 1613B 2,3,4,7,8-PeCDF 50 2.36 pg/L 1613B 2,3,7,8-TCDD 10 2.2 pg/L 1613B 2,3,7,8-TCDF 10 2.01 pg/L 1613B OCDD 100 4.32 pg/L 1613B OCDF 100 6.25 pg/L 1613B TEQ pg/L 1613B Total HpCDD 50 3.06 pg/L 1613B Total HpCDF 50 4.61 pg/L 1613B Total HxCDD 50 5.34 pg/L 1613B Total HxCDF 50 8.74 pg/L 1613B Total PeCDD 50 2.29 pg/L 1613B Total PeCDF 50 2.58 pg/L 1613B Total TCDD 10 2.2 pg/L 1613B Total TCDF 10 2.01 pg/L 1613B


III.d. Frequency and Sampling All field, bacteria, and chemical parameters will be monitored once at the 6 sites listed in Table 1. III.e. Spatial and Temporal Scale Sampling sites are located along the Sacramento and Feather River. The study will be conducted on June 20, 2016. III.f. Data Management All data collected during this study will be managed in accordance with the California Environmental Data Exchange Network (CEDEN) templates provided by the Central Valley Regional Data Center (CVRDC). The Central Valley Water Board will load field and chemical data into the templates provided from the CVRDC. The time period to enter all data from this study into the templates will be determined as more resources become available. When the data is entered into the CEDEN database, the data can be accessed by the public via www.ceden.org.

IV. REVIEW STRATEGY This document and the study report will be reviewed by CV-SALTS program staff from the Central Valley Water Board.

V. QUALITY ASSURANCE V.a. Field Equipment A YSI multiparameter water quality monitor will be used to collect data for temperature, dissolved oxygen, pH, and specific conductivity. Turbidity measurements will be collected with a Hach turbidimeter. The field equipment is calibrated using certified calibration standards and manufacturer specifications prior to each sampling event and the calibration is checked for accuracy following each sampling event. Calibration records are maintained at the Central Valley Water Board office and are used to determine instrument accuracy. Specific model numbers and calibration dates for the field equipment will be noted on the field sheets and in the final report. A digital camera will be used to take sampling location photos. V.b. Laboratory Method and Costs The lab analyses of chemical parameters will be conducted by ExcelChem Environmental Labs in Rocklin, California. The E. coli samples will be processed by qualified staff members at the Central Valley Water Board using an IDEXX system and methods specified in the Procedures Manual for the San Joaquin River Water Quality Monitoring Program (Central Valley Water Board, 2010).


http://www.ceden.org/

Sampling cost estimates are outlined in Table 3 and include submittal of two QA/QC samples.


Table 16 Laboratory Costs for Chemical Parameters Bid Group Analysis Test Method Rate Qty Cost

1 Polychlorinated Biphenyls (PCB's) 8082A $60.00 6 $360.00 1 Gas Chromatography/ Mass Spectrometer (GC/MS) Semivolatiles 8270C $75.00 6 $450.00 1 Volatile Organic Compound & Oxygenated Additive 8260B $125.00 6 $750.00

1 Poly-Chlorinated-Dibenzo-p-Dioxin/Furan High Resolution Mass Spectrometer (HRMS) 1613B $500.00 6 $3,000.00

1 Drinking Water Volatile Organic Compounds 524.2 $80.00 6 $480.00 2 Organo-Chlorinated Pesticide 8081A $60.00 6 $360.00 2 Organo-Phosphorus Pesticide 8141A $60.00 6 $360.00 2 Chlorinated Herbicide 8151A $60.00 6 $360.00 2 1,2-DB-3-CP, 1,2-DCEthene, 1,2,3-TPPane 8260B $40.00 6 $240.00 2 Carbamate Pesticide 8318/632 $125.00 6 $750.00 4 Perchlorate 314.1 $50.00 6 $300.00 7 Aluminum 200.7/200.8 $15.00 6 $90.00 7 Barium 200.7/200.8 $4.00 6 $24.00 7 Boron 200.7/200.8 $15.00 6 $90.00 7 Iron 200.7/200.8 $15.00 6 $90.00 7 Thallium 200.7/200.8 $4.00 6 $24.00

9 Antimony, Berryllium, Cadmium, Chromium, Copper, Lead, Nickel, Selenium, Silver, Titanium, Zinc, Arsenic Thorium, Chromium IV, Cyanide 200.8 ICP/MS $80.00 6 $480.00

14 Flouride Salts 300 $5.00 6 $30.00 16 Ammonia Nitrogen 4500-NH3 $30.00 6 $180.00 16 Nitrate Nitrogen 300 $30.00 6 $180.00 16 Nitrite Nitrogen 300 $10.00 6 $60.00

20

General Minerals (Title 22): Alkalinity, Calcium, Chloride, Copper, Iron, Methylene Blue Active Substances (MBAs), Manganese, Magnesium, pH, Sodium, Sulfate, Total Dissolved Solids (TDS), Total Hardness, Total Conductivity, Zinc

$105.00 6 $630.00

Aluminum (dissolved) 200.7 $15.00 6 $90.00


Bid Group Analysis Test Method Rate Qty Cost Arsenic (dissolved) 200.7 $20.00 6 $120.00 Lead (dissolved) 200.7 $15.00 6 $90.00 Iron (dissolved) 200.7 $15.00 6 $90.00

23 Dissolved filtering fee for dissolved metals $20/hour/sample (4 dissolved metals) $80.00 6 $480.00

Total cost per site $1,693.00 Total cost for 6 sites $10,158.00 Total cost for QA samples 2 $3386.00 DI Water (gallon) $10 3 $30

Grand total for lab analyses $13,574.00


VI. REFERENCES Central Valley Regional Water Quality Control Board (Central Valley Water Board). 2015. The Water Quality Control Plan for the Sacramento River Basin and San Joaquin River Basin (Basin Plan), 4th Edition. Central Valley Water Board. 2010. Procedures Manual for the San Joaquin River Water Quality Monitoring Program. State Water Resources Control Board (State Water Board). 2008. SWAMP Quality Assurance Program Plan.


Synoptic Evaluation of Drinking Water Constituents of Concern in the Sacramento River Basin, Draft QAPP, May 2016 138

APPENDIX A PARAMETERS AND CRITERIA

The following list all of the constituents that have MUN water quality evaluation criteria. Please note that not all of these constituents were tested for due to scan variations provided by the laboratory and this list does not include all drinking water evaluation criteria. All constituents were evaluated against MCLs specified in provisions of Title 22 of the California Code of Regulations, the CTR, and other evaluation criteria/guideline listed for constituents without a MCL or CTR criteria. Evaluation criteria were obtained from the State Water Board’s Water Quality Goals Database. Please note that not all of these constituents were tested for due to scan variations provided by each laboratory.

Analyte Primary MCL


1,1,1-Trichloroethane 200 ug/L 1,1,2,2-Tetrachloroethane 1 ug/L 0.17 ug/L 1,1,2,Trichloro-1,2,2-Trifluoroethane (Freon 113) 1200 ug/L

1,1,2-Trichloroethane 5 ug/L 0.6 ug/L 1,1-Dichloroethane 5 ug/L 1,1-Dichloroethylene 6 ug/L 0.057 ug/L 1,2,4-Trichlorobenzene 5 ug/L 1,2,4-Trimethylbenzene 330 ug/L (DDW Drinking Water Notification Levels) 1,2-Dibromo-3chloropropane (DBCP) 0.2 ug/L

1,2-Dibromoethane (Ethylene Dibromide) (EDB) 0.05 ug/L

1,2-Dichlorobenzene 600 ug/L 2,700 ug/L 1,2-Dichloroethane (Ethylene dichloride) 5 ug/L 0.38 ug/L

1,2-Dichloropropane 5 ug/L 0.52 ug/L 1,2-Diphenylhydrazine 0.04 ug/L 1,3 Dichlorobenzene 400 ug/L



Analyte Primary MCL


1,3,5-Trimethylbenzene 330 ug/L (DDW Drinking Water Notification Levels) 1,3-Dichloropropene 0.5 ug/L 10 ug/L 1,4-Dichlorobenzene 5 ug/L 400 ug/L 2,3,7,8-TCDD (Dioxin) 0.00003 ug/L 1.3x10-8 ug/L 2,4,5-TP (Silvex) 50 ug/L 2,4,6-Trichlorophenol 2.1 ug/L 2,4-Dichlorophenol 93 ug/L 2,4-Dichlorophenoxyacetic acid (2,4-D) 70 ug/L

2,4-Dichlorophenoxybutyric acid (2,4-DB) 56 ug/L (USEPA IRIS Reference Dose)

2,4-Dimethylphenol 540 ug/L 2,4-Dinitrophenol 70 ug/L 2,4-Dinitrotoluene 0.11 ug/L 2-Chloronaphthalene 1,700 ug/L 2-Chlorophenol 120 ug/L 2-Methyl-4,6-Dinitrophenol 13.4 ug/L 3,3'-Dichlorobenzidine 0.04 ug/L 4,4'-DDD 0.00083 ug/L 4,4'-DDE 0.00059 ug/L 4,4'-DDT 0.00059 ug/L Acenaphthene 1,200 ug/L Acrolein 320 ug/L Acrylonitrile 0.059 ug/L Alachlor 2 ug/L Aldrin 0.00013 ug/L



Analyte Primary MCL


Alpha-BHC (alpha-Benzene hexachloride) 0.0039 ug/L

Aluminum 1,000 ug/L 200 ug/L Ammonia 1,500 ug/L [Odor Threshold (Amoore and Huatala)] Anthracene 9,600 ug/L Antimony 6 ug/L 14 ug/L Arsenic 10 ug/L

Asbestos 7 Million Fiber/Liter 7 Million

Fibers/Liter

Atrazine 1 ug/L Barium 1,000 ug/L Bentazon 18 ug/L Benzene 1 ug/L 1.2 ug/L Benzidine 0.00012 ug/L Benzo(a)Anthracene [1,2-Benzanthracene] 0.0044 ug/L

Benzo(a)pyrene 0.2 ug/L 0.0044 ug/L Benzo(b)Fluoranthene [3,4-Benzofluoranthene] 0.0044 ug/L

Benzo(k)Fluoranthene 0.0044 ug/L Beryllium 4 ug/L



Analyte Primary MCL


Beta/photon emitters

4 millirem/year annual dose equivalent to the total body or any internal organ

Beta-BHC (beta-Benzene hexachloride) 0.014 ug/L

Bis(2-Chloroethyl)Ether 0.031 ug/L Bis(2-Chloroisopropyl)Ether 1,400 ug/L Boron 1,000 ug/L (DDW Notification Level for Drinking Water) Bromoform 4.3 ug/L Butylbenzyl Phthalate 3,000 ug/L Cadmium 5 ug/L Carbofuran 18 ug/L Carbon Tetrachloride 0.5 ug/L .25 ug/L Chlordane 0.1 ug/L 0.00057 ug/L Chloride 250,000 ug/L Chlorobenzene (Monochlorobenzene) 70 ug/L 680 ug/L

Chlorodibromomethane 0.401 ug/L

Chloroform 1.8 ug/L [CalEPA Cancer Potency Factor as a Drinking Water Level (assume 70kg body weight & 2 liters per day drinking water consumption)]

Chlorpyrifos 2 ug/L (USEPA, OPP Drinking Water Health Advisory- Non-cancer)

Chromium 50 ug/L



Analyte Primary MCL


Chromium VI (Hexavalent Chromium) 10 ug/L

Chrysene 0.0044 ug/L Cis1,2-Dichloroethylene 6 ug/L Color 15 units Copper 1,000 ug/L 1,300 ug/L Cyanide 150 ug/L 700 ug/L Dalapon 200 ug/L Di(2-ethylhexyl)adipate 400 ug/L Di(2-ethylhexyl)phthalate (DEHP) (Bis(2-ethylhexyl) phthalate)

4 ug/L

Diazinon 1.2 ug/L (DDW Drinking Water Notification Level) Dibenzo(ah)Anthracene 0.0044 ug/L Dichlorobromomethane 0.56 ug/L Dichloromethane (Methylene Chloride) 5 ug/L 4.7 ug/L

Dieldrin 0.00014 ug/L Diethyl Phthalate 23,000 ug/L Di-isopropyl ether (Isopropyl ether) (DIPE) 0.8 ug/L [Odor Threshold (Amoore and Hautala)]

Dimethyl Phthalate 313,000 ug/L Di-n-Butyl Phthalate 2,700 ug/L Dinoseb 7 ug/L Diquat 20 ug/L

E. coli 235 MPN/100ml [USEPA Recreational Guideline for Designated Beach Area (Upper 75% Confidence Level)]



Analyte Primary MCL


Endosulfan I (Alpha-Endosulfan) 110 ug/L

Endosulfan II (Beta-Endosulfan) 110 ug/L Endosulfan Sulfate 110 ug/L Endothall 100 ug/L Endrin 2 ug/L 0.76 ug/L Endrin Aldehyde 0.76 ug/L Ethylbenzene 300 ug/L 3,100 ug/L Fluoranthene 300 ug/L Fluorene 1,300 ug/L Fluoride 2,000 ug/L Foaming Agents (MBAS) 500 ug/L Gamma-BHC (gamma-Benzene hexachloride) (Lindane)

0.2 ug/L 0.019 ug/L

Glyphosate 700 ug/L Gross Alpha particle activity (excluding radon and uranium) 15 pCi/L

Haloacetic acids (HAAs) 60 ug/L Heptachlor 0.4 ug/L 0.01 ug/L Heptachlor Epoxide 0.2 ug/L 0.001 ug/L Hexachlorobenzene 1 ug/L 0.00075 ug/L Hexachlorobutadiene 0.44 ug/L Hexachlorocyclopentadiene 50 ug/L 240 ug/L Hexachloroethane 1.9 ug/L Indeno(1,2,3-cd) Pyrene 0.0044 ug/L



Analyte Primary MCL


Iron 300 ug/L Isophorone 8.4 ug/L Lead 15 ug/L Manganese 50 ug/L Mercury 2 ug/L 0.05 ug/L Methoxychlor 30 ug/L Methyl Bromide (Bromomethane) 48 ug/L

Methyl-tert-butyl ether (MTBE) 13 ug/L 5 ug/L Molinate 20 ug/L Nickel 100 ug/L 610 ug/L Nitrate (as NO3) 45,000 ug/L Nitrate+Nitrite (sum as nitrogen) 10,000 ug/L Nitrite (as Nitrogen) 1000 ug/L Nitrobenzene 17 ug/L N-Nitrosodimethylamine (NDMA) 0.00069 ug/L

N-Nitrosodi-n-Propylamine 0.005 ug/L N-Nitrosodiphenylamine 5 ug/L

Odor 3 TON (Threshold units)

Oxamyl 50 ug/L Pentachlorophenol 1 ug/L 0.28 ug/L Perchlorate 6 ug/L

pH 6.5 – 8.5 units



Analyte Primary MCL


Phenol 21,000 ug/L Picloram 500 ug/L Polychlorinated Biphenyls (PCBs) 0.5 ug/L 0.00017 ug/L

Pyrene 960 ug/L

Radium-226


Radium-228


Selenium 50 ug/L Silver 100 ug/L Simazine 4 ug/L

Sodium 20,000 ug/L (USEPA Drinking Water Advisory for Persons on Restricted Sodium Diet)

Specific Conductance 900 µS/cm

Strontium-90

8 pCi/L (=4 millirem/yr dose to bone marrow)

Styrene 100 ug/L Sulfate 250,000 ug/L Tetrachloroethylene (Tetrachloroethene) (PCE) 5 ug/L 0.8 ug/L

Thallium 2 ug/L 1.7 ug/L Thiobencarb 70 ug/L 1 ug/L



Analyte Primary MCL


Toluene 150 ug/L 6,800 ug/L Total Dissolved Solids 500,000 ug/L Total Triahlomethanes 80 ug/L Toxaphene 3 ug/L 0.00073 ug/L Trans-1,2-Dichloroethylene 10 ug/L 700 ug/L Trichloroethylene (TCE) 5 ug/L 2.7 ug/L Trichlorofluoromethane (Freon 11) 150 ug/L

Tritium

20000 pCi/L (=4 millirem/yr dose to total body)

Turbidity 5 NTU Uranium 20 pCi/L Vanadium 50 ug/L (DDW Drinking Water Notification Levels) Vinyl Chloride 0.5 ug/L 2 ug/L Xylenes 1,750 ug/L Zinc 5,000 ug/L

Acronyms CalEPA California Environmental Protection Agency CTR California Toxics Rule DDW Division of Drinking Water IRIS Integrated Risk Information System MCL Maximum Contaminant Level OPP Office of Pesticide Programs USEPA United States Environmental Protection Agency



Appendix 4. Sampling Event Preparation Sample Bottle Labeling All samples will be pre-labeled before each sampling event to the extent practicable. Sample id numbers will correspond with the field sheets. Pre-labeling sample bottles simplifies field activities. Custom labels will be produced using blank water-proof labels. Using this approach will allow the stations and analytical constituent information to be entered into the computer program in advance, and printed as needed prior to each sampling event. Labels shall be placed on the appropriate bottles in a dry environment; attempting to apply labels to sample bottles after filling will cause problems, as labels usually do not adhere to wet bottles. The labels shall be applied to the bottles rather than to the caps. Field labels shall contain the following information: Sampler initials, year, month, date – sample id, parameter identification. Parameter identifications are as follows: M Metals VOC Volatile Organic Compounds N_n Nitrate as Nitrogen and Nitrite as Nitrogen MBA Methylene Blue Active Substances Example: CLG090505-10M CLG090505-10VOC CLG090505-10N_n CLG090505-10MBA



Appendix 5. Field of Protocols Field crews (2 persons per crew, minimum) will only be mobilized for sampling when weather conditions and flow conditions are considered to be safe. For safety reasons, sampling will occur during daylight hours. A sampling event should proceed in the following manner:

1. Before leaving the sampling crew base of operations, notify laboratory, confirm number and type of sample bottles as well as the complete equipment list.

2. Proceed to the first sampling station. 3. Fill-out the general information on the field log sheets (Appendices 6&7). 4. Take field measurements and observations, and record on the field log sheet (Appendix

7). 5. Take the samples indicated on the field log sheet in the manner described in this plan.

Place bottles in the coolers with ice. Double check against the log sheet that all appropriate bottles were filled.

6. Repeat the procedures in steps 3, 4, and 5 for each of the remaining sampling stations. 7. Complete the chain of custody forms (Appendix 8) using the field notes. 8. After collection is completed, deliver the samples to ExcelChem environmental labs at

the end of the field run on June 25th.



Appendix 6. Sample Collection Water Sample Collection All water samples will be collected as grab samples, using aseptic technique. At most stations, grab samples will be collected at approximately six feet from the bank, using sampling poles, by direct submersion of the sample bottle depth. This is the preferred method for grab sample collection; however, due to sampling station configurations and safety concerns, direct filling of sample bottles is not always feasible. Sampling station configuration will dictate grab sample collection technique. Grab samples will be collected directly into the appropriate bottles (containing the required preservations). The grab sample technique that may be employed is described below. Direct Submersion: Where practical, all grab samples will be collected by direct submersion to mid-stream, mid-depth using the following procedures. The collector will be careful to not touch the inside of the sample bottle at any time. If the inside of the sample bottle is accidentally touched another sample bottle will be used. This is the preferred method for grab sample collection, and shall be adhered to as long as the safety of the sampling personnel is not jeopardized by doing so. Modifications are to be made only as necessary, and clean sampling techniques are always to be followed. After collection the samples will be immediately placed on ice in a cooler for transport to the analytical laboratories. All samples will be delivered to ExcelChem environmental labs at the end of the field run (June 25th only). Control samples will be collected at the same time and also immediately placed on ice. The proper COC form (See Appendix 8) will be filled out and signed by the appropriate lab personnel prior to releasing the samples to them. Clean Sampling Techniques Samples will be collected using “clean sampling techniques” to minimize the possibility of sample contamination. For this program, clean techniques must be employed whenever handling bottles, lids, or intermediate containers. Clean sampling techniques are summarized below:

• Samples are collected only into new, clean, laboratory provided sample bottles. • Wearing clean powder-free nitrile gloves at all times are required on sampling

crews. • Clean, powder-free nitrile gloves are changed whenever something not known to

be clean has been touched. • Clean techniques must be employed whenever handling grab sample or

intermediate bottles.



• To reduce the potential for contamination, sample collection personnel must adhere to the following rules while collecting samples: o No smoking. o Never sample near a running vehicle. Do not park vehicles in immediate

sample collection area, even non-running vehicles. o During wet weather events avoid allowing rainwater to drip from rain gear or

any other surface into sample bottles. o Do not eat or drink during sample collection. o Do not breathe, sneeze or cough in the direction of an open sample bottle.

• Wear clean powder-free nitrile gloves when handling bottles and caps. Change gloves if soiled or if the potential for cross-contamination occurs from handling sampling materials or samples;

• Submerge bottle to mid-stream/mid-depth, remove lid, let bottle fill, and replace lid. Place sample on ice;

• Collect remaining samples including control samples, if needed, using the same protocols described above;

• Fill out COC form, note sample collection on field form, and deliver to analytical lab. Field Measurements and Observations Field measurements will be taken and observations made at each sampling station before a sample is collected. Field measurements will include pH, temperature, dissolved oxygen, specific conductance and turbidity. Field measurements will be taken at approximately six feet from the bank. All field measurement results and comments on field observations will be recorded on SWAMP field observations data sheets (Appendix 8), which in turn will be stored in project binders located in the project manager’s cubicle. If at any time the collection of field measurements appears unsafe, an alternate site within 100 yards may be used, or the sample will not be collected. Sample site conditions will be noted on the field sheets, and photos will be taken of the site. In addition to field measurements, observations will be made at each sampling station. Observations will include color, odor, floating materials, presence of wildlife, as well as observations of contact and non-contact recreation. All comments on field observations will be recorded in the field log presented in Appendices 6&7. Chain-of-Custody Chain-of-custody (COC) forms will be filled out for all samples submitted to the analytical laboratory. Sample data, sample location, sample collection crew names, and analysis requested shall be noted on each COC. See Appendix 8 for blank COC forms. Transport to Lab Samples will be stored in coolers with ice and delivered to ExcelChem for the June 25th, 2014 samples, and picked up by ExcelChem for the June 30th, 2014 samples.



Appendix 7. List of Constituents within Each Scan including RLs and MDLs

Scan Analyte RL MDL Unit Test

Method Volatile Organic Compounds (VOCs) by GC/MS

1, 1-Dichloroethane 0.5 0.04 µg/L EPA 8260B 1,1,1,2-Tetrachloroethane 0.5 0.08 µg/L EPA 8260B 1,1,1-Trichloroethane 0.5 0.05 µg/L EPA 8260B 1,1,2,2-Tetrachloroethane 0.5 0.4 µg/L EPA 8260B 1,1,2-Trichloroethane 0.5 0.1 µg/L EPA 8260B 1,1-Dichloroethane 0.5 0.05 µg/L EPA 8260B 1,1-Dichloropropene 0.5 0.03 µg/L EPA 8260B 1,2,3-Trichlorobenzene 0.5 0.05 µg/L EPA 8260B 1,2,3-Trichloropropane 0.5 0.06 µg/L EPA 8260B 1,2,4-Trichlorobenzene 0.5 0.02 µg/L EPA 8260B 1,2,4-Trimethylbenzene 0.5 0.04 µg/L EPA 8260B 1,2-Dibromo-3-chloropropane 0.5 0.07 µg/L EPA 8260B 1,2-Dibromoethane (EDB) 0.5 0.1 µg/L EPA 8260B 1,2-Dichlorobenzene 0.5 0.06 µg/L EPA 8260B 1,2-Dichloroethane 0.5 0.04 µg/L EPA 8260B 1,2-Dichloropropane 0.5 0.06 µg/L EPA 8260B 1,3-Dichlorobenzene 0.5 0.03 µg/L EPA 8260B 1,3-Dichloropropane 0.5 0.06 µg/L EPA 8260B 1,4-Dichlorobenzene 0.5 0.05 µg/L EPA 8260B 2-Butanone 5.0 0.1 µg/L EPA 8260B 2-Chlorotoluene 0.5 0.03 µg/L EPA 8260B 2-Hexanone 5.0 0.1 µg/L EPA 8260B 4-Chlorotoluene 0.5 0.05 µg/L EPA 8260B 4-Isopropyltoluene 0.5 0.04 µg/L EPA 8260B 4-Methyl1-2pentanone 5.0 0.05 µg/L EPA 8260B Acetone 5.0 0.1 µg/L EPA 8260B Benzene 0.5 0.03 µg/L EPA 8260B Bromobenzene 0.5 0.05 µg/L EPA 8260B Bromochloromethane 0.5 0.07 µg/L EPA 8260B Bromodichloromethane 0.5 0.05 µg/L EPA 8260B Bromoform 0.5 0.03 µg/L EPA 8260B Bromomethane 0.5 0.05 µg/L EPA 8260B Carbon disulfide 0.5 0.06 µg/L EPA 8260B Carbon tetrachloride 0.5 0.02 µg/L EPA 8260B Chlorobenzene 0.5 0.03 µg/L EPA 8260B Chloroethane 0.5 0.08 µg/L EPA 8260B Chloroform 0.5 0.05 µg/L EPA 8260B




Chloromethane 0.5 0.06 µg/L EPA 8260B VOCs by GC/MS cont'd

cis-1,2-Dichloroethane 0.5 0.03 µg/L EPA 8260B cis-1,3-Dichloropropene 0.5 0.04 µg/L EPA 8260B Dibromochloromethane 0.5 0.07 µg/L EPA 8260B Dibromomethane 0.5 0.07 µg/L EPA 8260B Dichlorodifluoromethane 0.5 0.07 µg/L EPA 8260B Di-isopropyl ether 0.5 0.1 µg/L EPA 8260B Ethyl tert-Butyl Ether 0.5 0.04 µg/L EPA 8260B Ethylbenzene 0.5 0.03 µg/L EPA 8260B Hexachlorobutadiene 0.5 0.07 µg/L EPA 8260B Iodomethane 0.5 0.03 µg/L EPA 8260B Isopropylbenzene 0.5 0.04 µg/L EPA 8260B m,p-Xylene 1.0 0.09 µg/L EPA 8260B Methyl tert-Butyl Ether 0.5 0.05 µg/L EPA 8260B Methylene chloride 5.0 0.08 µg/L EPA 8260B Naphthalene 0.5 0.04 µg/L EPA 8260B n-Butylbenzene 0.5 0.04 µg/L EPA 8260B n-Propylbenzene 0.5 0.04 µg/L EPA 8260B o-Xylene 0.5 0.04 µg/L EPA 8260B sec-Butylbenzene 0.5 0.03 µg/L EPA 8260B TBA 1.0 0.1 µg/L EPA 8260B Tert-Amyl Methyl Ether 0.5 0.03 µg/L EPA 8260B tert-Butylbenzene 0.5 0.02 µg/L EPA 8260B Tetrachloroethene 0.5 0.08 µg/L EPA 8260B Toluene 0.5 0.04 µg/L EPA 8260B trans-1,2-Dichloroethane 0.5 0.04 µg/L EPA 8260B trans-1,3-Dichloropropene 0.5 0.04 µg/L EPA 8260B Trichloroethane 0.5 0.06 µg/L EPA 8260B Trichlorofluoromethane 0.5 0.05 µg/L EPA 8260B Trichlorotrifluoroethane 1.0 0.05 µg/L EPA 8260B Vinyl chloride 0.5 0.06 µg/L EPA 8260B Xylenes, total 1.0 0.1 µg/L EPA 8260B 1,1,1,2-Tetrachloroethane 0.5 0.08 µg/L EPA 524 1,1,1-Trichloroethane 0.5 0.05 µg/L EPA 524 1,1,2,2-Tetrachloroethane 0.5 0.04 µg/L EPA 524 1,1,2-Trichloroethane 0.5 0.1 µg/L EPA 524 1,1,-Dichloroethane 0.5 0.04 µg/L EPA 524 1,1-Dichloroethane 0.5 0.05 µg/L EPA 524 1,1-Dichloropropene 0.5 0.03 µg/L EPA 524 1,2,3-Trichlorobenzene 0.5 0.05 µg/L EPA 524




1,2,3-Trichloropropane 0.5 0.06 µg/L EPA 524 VOCs by GC/MS cont'd

1,2,4-Trichlorobenzene 0.5 0.02 µg/L EPA 524 1,2,4-Trimethylbenzene 0.5 0.04 µg/L EPA 524 1,2-Dibromo-3-chloropropane 0.5 0.07 µg/L EPA 524 1,2-Dibromoethane (EDB) 0.5 0.1 µg/L EPA 524 1,2-Dichlorobenzene 0.5 0.06 µg/L EPA 524 1,2-Dichloroethane 0.5 0.06 µg/L EPA 524 1,2-Dichloropropane 0.5 0.06 µg/L EPA 524 1,3,5-Trimethylbenzene 0.5 0.03 µg/L EPA 524 1,3-Dichlorobenzene 0.5 0.03 µg/L EPA 524 1,3-Dichloropropane 0.5 0.06 µg/L EPA 524 1,4-Dichlorobenzene 0.5 0.05 µg/L EPA 524 2,2-Dichloropropane 0.5 0.06 µg/L EPA 524 2-Butanone 5.0 0.1 µg/L EPA 524 2-Chlorotoluene 0.5 0.03 µg/L EPA 524 2-Hexanone 0.5 0.1 µg/L EPA 524 4-Chlorotoluene 0.5 0.05 µg/L EPA 524 4-Isopropyltoluene 0.5 0.04 µg/L EPA 524 4-Methyl-2-pentanone 0.5 0.05 µg/L EPA 524 Acetone 5.0 0.1 µg/L EPA 524 Benzene 0.5 0.03 µg/L EPA 524 Bromobenzene 0.5 0.05 µg/L EPA 524 Bromochloromethane 0.5 0.07 µg/L EPA 524 Bromodichloromethane 0.5 0.05 µg/L EPA 524 Bromoform 0.5 0.03 µg/L EPA 524 Bromomethane 0.5 0.05 µg/L EPA 524 Carbon disulfide 0.5 0.06 µg/L EPA 524 Carbon tetrachloride 0.5 0.02 µg/L EPA 524 Chlorobenzene 0.5 0.03 µg/L EPA 524 Chloroethane 0.5 0.08 µg/L EPA 524 Chloroform 0.5 0.05 µg/L EPA 524 Chloromethane 0.5 0.06 µg/L EPA 524 cis-1,2-Dichloroethane 0.5 0.03 µg/L EPA 524 cis-1,3-Dichloropropene 0.5 0.04 µg/L EPA 524 Dibromochloromethane 0.5 0.07 µg/L EPA 524 Dibromomethane 0.5 0.07 µg/L EPA 524 Dichlorodifluoromethane 0.5 0.07 µg/L EPA 524 Di-isopropyl ether 0.5 0.1 µg/L EPA 524 Ethyl tert-Butyl Ether 0.5 0.04 µg/L EPA 524 Ethylbenzene 0.5 0.03 µg/L EPA 524




Hexachlorobutadiene 0.5 0.07 µg/L EPA 524 VOCs by GC/MS cont'd

Iodomethane 0.5 0.03 µg/L EPA 524 Isopropylbenzene 0.5 0.04 µg/L EPA 524 m,p-Xylene 0.5 0.09 µg/L EPA 524 Methyl tert-Butyl Ether 0.5 0.05 µg/L EPA 524 Methylene chloride 1.0 0.08 µg/L EPA 524 Naphthalene 0.5 0.04 µg/L EPA 524 n-Butylbenzene 0.5 0.04 µg/L EPA 524 n-Propylbenzene 0.5 0.04 µg/L EPA 524 o-Xylene 0.5 0.04 µg/L EPA 524 sec-Butylbenzene 0.5 0.03 µg/L EPA 524 Styrene 0.5 0.09 µg/L EPA 524 TBA 1.0 0.1 µg/L EPA 524 Tert-Amyl Methyl Ether 0.5 0.03 µg/L EPA 524 tert-Butylbenzene 0.5 0.02 µg/L EPA 524 Tetrachloroethene 0.5 0.08 µg/L EPA 524 Toluene 0.5 0.04 µg/L EPA 524 Total Trihalomethanes 0.5 0.5 µg/L EPA 524 trans-1,2-Dichloroethane 0.5 0.04 µg/L EPA 524 trans-1,3-Dichloropropene 0.5 0.04 µg/L EPA 524 Trichloroethane 0.5 0.06 µg/L EPA 524 Trichlorofluoromethane 0.5 0.05 µg/L EPA 524 Trichlorotrifluoroethane 1.0 0.05 µg/L EPA 524 Vinyl chloride 0.5 0.06 µg/L EPA 524 Xylenes, total 1.0 0.1 µg/L EPA 524


4,4'-DDD 0.1 0.006 µg/L EPA 8081A 4,4'-DDE 0.1 0.005 µg/L EPA 8081A 4,4'-DDT 0.1 0.004 µg/L EPA 8081A Aldrin 0.1 0.011 µg/L EPA 8081A alpha-BHC 0.1 0.011 µg/L EPA 8081A alpha-Chlordane 0.1 0.006 µg/L EPA 8081A beta-BHC 0.1 0.011 µg/L EPA 8081A delta-BHC 0.1 0.021 µg/L EPA 8081A Dieldrin 0.1 0.006 µg/L EPA 8081A Endosulfan I 0.1 0.007 µg/L EPA 8081A Endosulfan II 0.1 0.021 µg/L EPA 8081A Endosulfan sulfate 0.1 0.005 µg/L EPA 8081A Endrin 0.1 0.007 µg/L EPA 8081A Endrin aldehyde 0.1 0.006 µg/L EPA 8081A Endrin Ketone 0.1 0.005 µg/L EPA 8081A




gamma-BHC (Lindane) 0.1 0.013 µg/L EPA 8081A Pesticides by GC/ECD cont'd

gamma-Chlordane 0.1 0.005 µg/L EPA 8081A Heptachlor 0.1 0.016 µg/L EPA 8081A Heptachlor epoxide 0.1 0.02 µg/L EPA 8081A Methoxychlor 0.1 0.013 µg/L EPA 8081A

PCBs by GC/ECD

Aroclor 1016 1.00 0.0600 µg/L EPA 8081A Aroclor 1221 1.00 0.130 µg/L EPA 8081A Aroclor 1232 1.00 0.100 µg/L EPA 8081A Aroclor 1242 1.00 0.0600 µg/L EPA 8081A Aroclor 1248 1.00 0.0600 µg/L EPA 8081A Aroclor 1254 1.00 0.0900 µg/L EPA 8081A Aroclor 1260 1.00 0.0800 µg/L EPA 8081A PCBs 1.00 0.0800 µg/L EPA 8081A


1,2,4-Trichlorobenzene 2.0 0.6 µg/L EPA 8270C 1,4-Dichlorobenzene 2.0 0.4 µg/L EPA 8270C 2,4,5-Trichlorophenol 5.0 1.6 µg/L EPA 8270C 2,4,6-Trichlorophenol 5.0 1.6 µg/L EPA 8270C 2,4-Dichlorophenol 2.0 0.8 µg/L EPA 8270C 2,4-Dimethylphenol 2.0 0.8 µg/L EPA 8270C 2,4-Dinitrophenol 10.0 0.3 µg/L EPA 8270C 2,4-Dinitrotoluene 2.0 0.8 µg/L EPA 8270C 2,6-Dinitrotoluene 2.0 0.8 µg/L EPA 8270C 2-Chloronaphthalene 2.0 0.2 µg/L EPA 8270C 2-Chlorophenol 2.0 0.8 µg/L EPA 8270C 2-Methylnaphthalene 2.0 0.6 µg/L EPA 8270C 2-Methylphenol 2.0 0.4 µg/L EPA 8270C 2-Nitroaniline 2.0 0.4 µg/L EPA 8270C 2-Nitrophenol 2.0 1.2 µg/L EPA 8270C 3,3´-Dichlorobenzidine 5.0 0.8 µg/L EPA 8270C 3-Nitroaniline 2.0 0.5 µg/L EPA 8270C 4,6-Dinitro-2-methylphenol 10.0 2.2 µg/L EPA 8270C 4-Bromophenyl phenyl ether 2.0 0.8 µg/L EPA 8270C 4-Chloro-3-methylphenol 2.0 0.6 µg/L EPA 8270C 4-Chloroaniline 2.0 0.5 µg/L EPA 8270C 4-Chlorophenyl phenyl ether 2.0 0.5 µg/L EPA 8270C 4-Nitroaniline 2.0 0.6 µg/L EPA 8270C 4-Nitrophenol 5.0 0.1 µg/L EPA 8270C Acenaphthene 2.0 0.6 µg/L EPA 8270C Acenaphthylene 2.0 0.3 µg/L EPA 8270C




Aniline 2.0 0.3 µg/L EPA 8270C Anthracene 2.0 0.3 µg/L EPA 8270C


Azobenzene 2.0 0.4 µg/L EPA 8270C Benzidine 5.0 0.2 µg/L EPA 8270C Benzo (a) anthracene 2.0 0.4 µg/L EPA 8270C Benzo (a) pyrene 5.0 1.2 µg/L EPA 8270C Benzo (b) fluoranthene 2.0 0.8 µg/L EPA 8270C Benzo (g,h,i) perylene 2.0 1.3 µg/L EPA 8270C Benzo (k) fluoranthene 2.0 1.0 µg/L EPA 8270C Benzoic acid 30.0 0.5 µg/L EPA 8270C Benzyl alcohol 2.0 0.4 µg/L EPA 8270C Bis(2-chloroethoxy)methane 2.0 0.4 µg/L EPA 8270C Bis(2-chloroethyl)ether 2.0 0.6 µg/L EPA 8270C Bis(2-chloroisopropyl)ether 2.0 0.4 µg/L EPA 8270C Bis(2-ethylhexyl)phthalate 5.0 0.7 µg/L EPA 8270C Butyl benzyl phthalate 2.0 1.0 µg/L EPA 8270C Carbazole 2.0 0.6 µg/L EPA 8270C Chrysene 2.0 0.5 µg/L EPA 8270C Dibenz (a,h) anthracene 2.0 1.6 µg/L EPA 8270C Dibenzofuran 2.0 0.3 µg/L EPA 8270C Diethyl phthalate 2.0 0.6 µg/L EPA 8270C Dimethyl phthalate 2.0 0.8 µg/L EPA 8270C Di-n-butyl phthalate 2.0 0.4 µg/L EPA 8270C Di-n-octyl phthalate 5.0 0.7 µg/L EPA 8270C Fluoranthene 2.0 0.6 µg/L EPA 8270C Fluorene 2.0 0.5 µg/L EPA 8270C Hexachlorobenzene 2.0 0.6 µg/L EPA 8270C Hexachlorobutadiene 2.0 0.6 µg/L EPA 8270C Hexachlorocyclopentadiene 2.0 0.6 µg/L EPA 8270C Hexachloroethane 2.0 0.5 µg/L EPA 8270C Indeno (1,2,3-cd) pyrene 5.0 1.6 µg/L EPA 8270C Isophorone 2.0 0.3 µg/L EPA 8270C Naphthalene 2.0 0.5 µg/L EPA 8270C Nitrobenzene 2.0 0.7 µg/L EPA 8270C N-Nitrosodimethylamine 2.0 0.4 µg/L EPA 8270C N-Nitrosodi-n-propylamine 2.0 0.3 µg/L EPA 8270C N-Nitrosodiphenylamine 2.0 0.6 µg/L EPA 8270C Pentachlorophenol 10.0 2.4 µg/L EPA 8270C Phenanthrene 2.0 0.4 µg/L EPA 8270C Phenol 2.0 0.3 µg/L EPA 8270C




Pyrene

2.0 1.0 µg/L EPA 8270C


Azinphos-methyl 0.200 0.0270 µg/L EPA 8141A Bolstar 0.200 0.0860 µg/L EPA 8141A Coumaphos 0.200 0.168 µg/L EPA 8141A Demeton 0.200 0.105 µg/L EPA 8141A Demeton-O 0.200 0.101 µg/L EPA 8141A Demeton-S 0.200 0.105 µg/L EPA 8141A Diazinon 0.250 0.0650 µg/L EPA 8141A Dichlorvos 0.200 0.156 µg/L EPA 8141A Dimethoate 0.200 0.0710 µg/L EPA 8141A Disulfoton 0.200 0.0690 µg/L EPA 8141A Dursban (Chlorpyrifos) 0.200 0.0710 µg/L EPA 8141A EPN 0.200 0.124 µg/L EPA 8141A Ethoprop 0.200 0.0770 µg/L EPA 8141A Fensulfothion 0.200 0.139 µg/L EPA 8141A Fenthion 0.200 0.0670 µg/L EPA 8141A Gardona (Stirophos) 0.200 0.110 µg/L EPA 8141A Malathion 0.200 0.159 µg/L EPA 8141A Merphos 0.200 0.0970 µg/L EPA 8141A Mevinphos 0.200 0.115 µg/L EPA 8141A Molinate 0.200 0.0440 µg/L EPA 8141A Monocrotophos 0.200 0.0150 µg/L EPA 8141A Naled 0.200 0.169 µg/L EPA 8141A Parathion 0.200 0.0790 µg/L EPA 8141A Parathion-methyl 0.200 0.0770 µg/L EPA 8141A Phorate 0.200 0.0830 µg/L EPA 8141A Ronnel 0.200 0.0660 µg/L EPA 8141A Sulfotep 0.200 0.0950 µg/L EPA 8141A TEPP 0.200 0.151 µg/L EPA 8141A Tokuthion (Prothiofos) 0.200 0.0770 µg/L EPA 8141A Trichloronate 0.200 0.0670 µg/L EPA 8141A


2,4,5-T 0.500 0.0970 µg/L EPA 8151A 2,4,5-TP (Silvex) 0.500 0.0950 µg/L EPA 8151A 2,4-D 0.400 0.0860 µg/L EPA 8151A 2,4-DB 0.800 0.157 µg/L EPA 8151A 3,5-Dichlorobenzoic acid 0.800 0.170 µg/L EPA 8151A 4-Nitrophenol 0.600 0.117 µg/L EPA 8151A Acifluorfen 0.800 0.157 µg/L EPA 8151A Bentazon 0.600 0.110 µg/L EPA 8151A




Chlorinated Herbicides cont’d

Chloramben 0.800 0.00800 µg/L EPA 8151A Dalapon 0.600 0.115 µg/L EPA 8151A DCPA 0.400 0.0150 µg/L EPA 8151A Dicamba 0.400 0.0800 µg/L EPA 8151A Dichloroprop 0.800 0.196 µg/L EPA 8151A Dinoseb 0.400 0.0830 µg/L EPA 8151A MCPP 10.0 0.891 µg/L EPA 8151A Pentachlorophenol 0.300 0.0530 µg/L EPA 8151A Picloram 0.800 0.0200 µg/L EPA 8151A

Ion Chromatography

Hexavalent Chromium 1.0 0.1 µg/L EPA 218.6 Chloride 0.5 0.04 mg/L EPA 300.0 Fluoride 0.1 0.02 mg/L EPA 300.0 Nitrate as Nitrogen 0.11 0.009 mg/L EPA 300.0 Nitrite as Nitrogen 0.15 0.03 mg/L EPA 300.0 Sulfate as SO4 5.0 0.7 mg/L EPA 300.0 Perchlorate 2.00 0.0940 µg/L EPA 314.0

Wet Chemistry

Specific Conductance (EC) 5.00 1.09 µS/cm

EPA 120.1

Total Dissolved Solids 15.0 7.68 mg/L SM 2540C Cyanide 0.00500 0.000900 mg/L SM 4500CN

E pH 0.100 0.100 pH

Units SM 4500-H+ B

Ammonia as N 0.100 0.0400 mg/L SM 4500-NH3 B/H

MBAS 0.100 0.0600 mg/L SM 5540C Total Alkalinity 5.00 2.37 mg/L SM2320B Total Hardness 5.00 2.86 mg/L SM2340B


Aluminum 50.0 24.5 µg/L EPA 200.7 Antimony 10.0 1.3 µg/L EPA 200.7 Arsenic 10.0 1.0 µg/L EPA 200.7 Barium 5.0 1.2 µg/L EPA 200.7 Beryllium 5.0 0.09 µg/L EPA 200.7 Boron 50.0 0.8 µg/L EPA 200.7 Cadmium 5.0 0.1 µg/L EPA 200.7 Calcium 100 79.0 µg/L EPA 200.7 Chromium 5.0 0.3 µg/L EPA 200.7 Copper 5.0 0.8 µg/L EPA 200.7 Iron 20.0 11.5 µg/L EPA 200.7 Lead 5.0 0.9 µg/L EPA 200.7




Total Recoverable Metals cont'd

Magnesium 50.0 15.6 µg/L EPA 200.7 Manganese 10.0 0.6 µg/L EPA 200.7 Nickel 5.0 0.6 µg/L EPA 200.7 Selenium 20.0 1.3 µg/L EPA 200.7 Silver 5.0 0.4 µg/L EPA 200.7 Sodium 200 120 µg/L EPA 200.7 Thallium 20.0 2.2 µg/L EPA 200.7 Titanium 50.0 1.2 µg/L EPA 200.7 Zinc 10.0 0.3 µg/L EPA 200.7

Dissolved Metals

Dissolved Aluminum 50.0 24.5 µg/L EPA 200.7 Dissolved Arsenic 10.0 1.0 µg/L EPA 200.7 Dissolved Iron 20.0 11.5 µg/L EPA 200.7 Dissolved Lead 5.0 0.9 µg/L EPA 200.7

Dixoin/Furan

1,2,3,4,6,7,8-HpCDD 50 2.17 pg/L 1613B 1,2,3,4,6,7,8-HpCDF 50 3.77 pg/L 1613B 1,2,3,4,7,8,9-HpCDF 50 4.61 pg/L 1613B 1,2,3,4,7,8-HxCDD 50 3.98 pg/L 1613B 1,2,3,4,7,8-HxCDF 50 3.66 pg/L 1613B 1,2,3,6,7,8-HxCDD 50 5.34 pg/L 1613B 1,2,3,6,7,8-HxCDF 50 3.97 pg/L 1613B 1,2,3,7,8,9-HxCDD 50 4.68 pg/L 1613B 1,2,3,7,8,9-HxCDF 50 8.74 pg/L 1613B 1,2,3,7,8-PeCDD 50 2.29 pg/L 1613B 1,2,3,7,8-PeCDF 50 2.58 pg/L 1613B 2,3,4,6,7,8-HxCDF 50 4.97 pg/L 1613B 2,3,4,7,8-PeCDF 50 2.36 pg/L 1613B 2,3,7,8-TCDD 10 2.20 pg/L 1613B 2,3,7,8-TCDF 10 2.01 pg/L 1613B OCDD 100 4.32 pg/L 1613B OCDF 100 6.25 pg/L 1613B TEQ pg/L 1613B Total HpCDD 50 3.06 pg/L 1613B Total HpCDF 50 4.61 pg/L 1613B Total HxCDD 50 5.34 pg/L 1613B Total HxCDF 50 8.74 pg/L 1613B Total PeCDD 50 2.29 pg/L 1613B Total PeCDF 50 2.58 pg/L 1613B Total TCDD 10 2.20 pg/L 1613B Total TCDF 10 2.01 pg/L 1613B



NOTE: RL is Reporting Limit MDL is Method Detection Limit GC/MS is Gas Chromatography—Mass Spectrometry GC/ECD is Gas Chromatography—Electron Capture Detector



Appendix 8. Field Sheets (SWAMP)

SWAMP Field Observations Data Sheet EventType WQ Entered in d-base (initial/date) Page 1 of 1 Pages

Station Description

Personnel: Station ID

Sample Time (first sample): Agency: Citizens Monitoring Group Date: 5/2/2011 Funding: 10SW5S01

Purpose: Project: Group: Protocol:

Walk-in Bridge OtherBank

Left Bank Right Bank NA

None Bridge Pipes ConcreteChannel GradeControl Culvert AerialZiplin

UpStream Down Stream Within Sample Boundry NA

+/- ft

None Sulfides (e.g. rotten eggs) Sewage Manure Petroleum Smoke

Clear Partly Coudy Overcast Fog Smoky Hazy

None Vascular Nonvascular OilySheen Foam Trash

Bedrock Concrete Cobble Gravel Sand Mud Unknown

Clear (see bottom) Cloudy (>4" visibility) Murky (<4" visibility)

None Sulfides (e.g. rotten eggs) Sewage Manure Petroleum Mixed

Colorless Green Yellow Brown

NA Dry Isolated Pool Low Normal High Flood

Yes No Unknown

None Fog Drizzle Rain Snow

None Light Moderate/Heavy Unknown

No <1 year <5 years

Direction Record the direction from which the wind is blowing

Beaufort Scale Use scale 0-8; refer to the scales listed: 6

0 3 7

1 4 8

2 5 9

Bac100ml

Crypto500ml

Giardia 500ml

Sal100ml

Number Bottles: 2 0 0 0Dry

Y Other (explain)

N

N

Light gray cells are for information purposes Field Comments:Uncolored cells need to be populated

N / S / E / W

1

Water Color

Observed Flow

Precipitation

SAMP

LE S

ITE

DESC

RIPT

ION

Occupation Method:

RB / LB / BB / US / DS / ##

Collection Location:Starting Bank

(facing downstream):

GPS Actual Latitude:0

0 Actual Longitude:

Win

d

Light Air: Direction of wind shown by smoke drift, but not by wind vanesLight Breeze: Wind felt on face; leaves rustle; ordinary vanes moved by wind

2 RB / LB / BB / US / DS / ##3

Site Odor

Wadability

Gentle Breeze: Leaves and small twigs in constant motion; wind extends light flag

Evidence of Fires

If there is an IMMEDIATE (within range, potentially affecting sample) hydromodification; Is the hydromodification upstream/downstream/within area of sample; if there is no

Midchannel

GPS Device:

AGPRO_R5S_2010WaterChem / Habitat / Field Measure

38.60094

Precipitation/Runnoff (last 24 hrs)

Sky Code

Other Presence

Dominant Substrate

Water Clarity

Water Odor

Target Longitude:

SAMP

LE

COLL

ECTI

ONHA

BITA

T OB

SERV

ATIO

NS

Sample Type:

Individual Bottles Collected By:

Other:

RB / LB / BB / US / DS / ##PHOT

OS

Moderate Breeze: Raises dust and loose paper; small branches are moved.

Turbidity (ntu)

Sample Failure Reason

Strong Breeze: Large branches in motion; whistling heard in telegraph wires umbrellas used with difficultyNeargale: Whole trees in motion; inconvenience felt when walking against the wind

Neargale: Whole trees in motion; inconvenience felt when walking against the wind

Fresh Breeze: Small trees in leaf begin to sway crested wavelets form on inland waters

Gale: Breaks Twigs and generally impedes progress

Calm; smoke rises vertically

Measurements Collected:

Water Temp (°C) pH

Subsurface

SAMP

LES

XMP110101-20 Grab

Sample ID:Other:

Field Duplicate

Don't forget to fill in the

calibration sheet

FIEL

D ME

ASUR

EMEN

TS

No Access

Flooded

DO (mg/L)SC

(uS/cm)

Field Blank

Lab Duplicate Pole HandPole & beaker

Record if there is evidence of rain or overland runnoff at the site. Light refers to light rain with no overland runoff and Moderate/Heavy refers rain resulting in overland runoff.

Record presence of vegetation IN the water at the immediate sampling area. Vascular refers to terrestrial or aquatic vegetation and Nonvascular refers to plankton, periphyton, If possible, describe the DOMINANT substrate type; use unknown if you cannot see the dominant substrate typeThis describes the clarity of the water while standing creek side.

The color of the water from standing creek side

Visual estimates in cubic feet/second, if able to estimate

In general, is the waterbody being sampled wadeable to the average person at the point of sample?What is happening right now?

Sample ID XMP110101-10III/III

American R @ Discovery Park519AMNDVY

Datum:

Target Latitude:

Hydromodification Location:

SJRRB5_StS_05_FY1011

Describe existing hydromodifications indicated above, such as a grade control, drainage pipes, bridge, culvert.

-121.5055

Record Actual GPS coordinates

Hydromodification Type



Appendix 9. Bacterial Processing Lab Sheet (SWAMP)

Run: Colusa Run Sample Processing Date: 6/29/11

18H 22H 18H 22H 18H 22H 18H 22H 18H 22H 18H 22H 18H 22H 18H 22H 18H 22H 18H 22H 18H 22H 18H 22H 18H 22H 18H 22H

# Large Wells

# Small Wells

Empty Wells

MPN18H 22H 18H 22H 18H 22H 18H 22H 18H 22H 18H 22H 18H 22H 18H 22H 18H 22H 18H 22H 18H 22H 18H 22H 18H 22H 18H 22H

# Large Wells

# Small WellsFalse

Positives

MPN

43 Normal Sample # 4050 Duplicate Sample # 51

Normal

Duplicate

Mean of R log

Normal

Duplicate

Mean of R log

BLANK Field Blank # 52

Distribution:Original: to CLG for QA Tracking and Originals BinderCopy: to Data entryCopy: to Project Managers, as needed

NOTES:

Needs ReviewMean of R log Pass

Pass

~0.24 Pass Needs Review

Pass Needs Review

Pass

51 50 60LAB BLANK520COL006 LD 520COL002 FD

43520COL003 520COL004 FieldBlank

44 45 52Site Code:

Yellow +

520COL006 520COL005 520COL001 520COL002

Needs Review

Incubator Temperature Checks:

LAB DUPLICATES FIELD DUPLICATES

MPN

Mean of R log

Needs ReviewNeeds Review

41 42

Initials: Temp: Time:


0.29

Yellow + Fluorescence

(+)

Media Lot #

MPN

3rd Check ~4 Hrs Before Pull fr Incubator:


Lab Blank # 60

ARW110629 40Sample ID Number:

Pass

Trays Read By:


Sampler Signature / Date / Time Arrived in Lab:

2nd Check - Placed in Incubator:

4th Check - Pulled from Incubator:

Normal Sample #

Duplicate Sample #

1st Check ~4 Hrs After Field Crew Leaves:

Log MPNABS(Normal Log MPN-Dup Log

MPN)

Processer / Date / Time:

Placed in Incubator By / Date / Time:

TOTAL COLIFORM

E. COLI

Light gray fields to be filled in during field run set up.Unshaded fields to be filled in during sample processing, result analysis, and for incubator QA

Mean = Mean of Normal and Duplicate, which is then compared to the individual corresponding CI's to determine acceptability of data. Xave = Mean of Normal and Duplicate, which is used as part of RD% formula. Pass1= Lab Duplicates pass only when RD%<2

Pulled from Incubator By / Date / Time:

0.36

Normal

ABS(Normal Log MPN-Dup Log MPN)Log MPN

Normal

Duplicate

~0.43

Duplicate



Appendix 10. ExcelChem Environmental Laboratories (Chain of Custody)


Appendix 11. ExcelChem Environmental Laboratories QA/QC Manual

Excelchem Environmental Laboratories

Quality Assurance and Quality Control Manual

Initial release date - 1990 Revision –August– 2012


165

EXCELCHEM ENVIRONMENTAL LABS QUALITY ASSURANCE PROGRAM SECTION PAGE # 1.0 – Project Description 3 2.0 – Project Organization & Responsibility 3 3.0 – Quality Assurance Objectives 4 4.0 – Sample Custody 4 5.0 – Calibration Procedures & Frequency 11 6.0 – Analytical Procedures 11 7.0 – Data Reduction, Validation & Reporting 12 8.0 – Internal Quality Control Checks 13 9.0 – Performance & System Audits 15 10.0 – Preventative Maintenance 16 11.0 – Procedures Used to Assess Precision, Accuracy & Completeness 16 12.0 – Corrective Actions 17 13.0 – QA Reports to Management 19 14.0 – Organizational Chart 20 15.0 – Chain-of-Custody 21 16.0 – Mock Report 22


166

SECTION 1.0 – PROJECT DESCRIPTION

Excelchem Environmental Labs proposes to supply analytical support for projects dealing with environmental sampling and analysis of vapor, water, soil, wastewater, and petroleum products. Projects which Excelchem is capable of supporting may include, but are not limited to, the following general descriptions:

1. Buried Tank Investigation 2. California AB 2588 Air Studies 3. Wastewater Pilot Studies 4. Toxicity Bioassay Studies 5. Groundwater Monitoring 6. Hazardous Waste Investigations 7. Soil Gas Studies 8. BTU Value of Gas Determination 9. Compliance Monitoring 10. Expert Testimony

EPA CLP-style or other project-specific data reporting formats can be delivered in support of your individual work orders. SECTION 2.0 – PROJECT ORGANIZATION & RESPONSIBILITY

EXCELCHEM employs a Project Manager system to assure that all work performed by the laboratory is properly managed and otherwise attended to. Our organization chart identifies the responsible personnel. Qualified Project Managers are selected from among the senior technical officers of the company according to the nature of the job itself. The Project Manager, Christine Kimbrell, is responsible for the review of the initial work requests, the assignment of resources, and the review of both the quality assurance data and the data used to generate reports. For example, when a typical request to provide analytical services is delivered to the laboratory, the Sample Control Officer selects a Project Manager. He/she reviews the chain of custody and determines if the analytical methods are appropriate for the analytes requested. Any changes noted as a result of this review are sent back to both the Sample Control Officer and the departments within which the analyses are to be performed. If questions arise, the client is called. An acknowledgement that describes the work to be performed is returned to the client. The Department Heads are responsible for notifying the Project Managers regarding any difficulties which may be complicating the analyses themselves (i.e. a special matrix problem) or which might delay the delivery of results. The analysts are responsible for performing the analysis, performing the necessary quality assurance work and maintaining the “paper trail”, which serves to verify that all procedures were in control while a set of samples was being analyzed. Thus, it can be seen that project performance is a team effort at EXCELCHEM. This system provides for quality review at the following four levels:

1. The Analyst – first level review 2. The QA/QC officer – second level review


167

3. The Project Manager – third level review 4. Signature Review – fourth level review

SECTION 3.0 – QUALITY ASSURANCE OBJECTIVES

The first objective of the Quality Assurance Program at EXCELCHEM is to provide data of known quality. The second objective is to provide data of the highest quality permitted by intended use to which the data will be put. The third objective is to improve the quality of all data leaving the laboratory, regardless of intended use. The methods and organizational structures designed to achieve these worthy objectives are discussed in the sections that follow. Quality, as used to describe the analytical services provided by EXCELCHEM, means the production of results that are accurate, valid and precise. This is reflected in the commitment of Excelchem’s technical resources to the Quality Assurance Program. For example, John Somers, who holds the rank of Laboratory Director, is fully authorized to direct Quality Assurance measures within all departments at all branches of the Company. While the level of Quality Assurance automatically supplied at Excelchem is more sufficient for most intended uses, additional documentation or special report formats can be provided upon request. Charges for additional documentation range from nominal, for such records as injection records, chromatograms and calibration curves, to considerable for presentation of results in full EPA CLP-style format. Quality assurance data already supplied at no additional charge include:

1. Blanks 2. Duplicates 3. Spikes 4. Surrogate Recoveries (when appropriate)

Acceptable criteria for these quality assurance parameters are found in SW-846, Standard Methods and Title 22. SECTION 4.0 – SAMPLE CUSTODY

Sample Control is the department that documents the receipt of incoming samples and initiates all paperwork regarding samples. Excelchem is presently utilizing a Laboratory Information Management System (LIMS). Upon arrival to the lab, the priority of the sample is determined for order of processing. Samples with short holding times take first priority. Second priority are samples with longer holding times, but which are quickly approaching that holding time. The RUSH samples are processed next, followed by any other samples received. Samples waiting processing are held in a refrigerator used only for that purpose; water samples requiring volatile analysis are kept in a separate refrigerator. The refrigerator is kept locked at all times to maintain security and to keep the samples from being mistaken for samples already processed. Documentation received with the sample is then reviewed for accuracy and completeness of information regarding the client, the sampler, the description of the samples, the date samples, and any special request, such as turnaround time, detection limits required, etc.


168

If the samples come to the lab with a chain of custody, as is recommended, the chain of custody document is signed by the Sample Control Officer after it is determined that all samples listed on that chain of custody have arrived. Notes regarding the condition of samples, such as temperature, seals being intact, bottles not received, or bottles broken are made by the Sample Control Officer on the chain of custody document. Inconsistencies require an immediate call to the client. The samples are then organized to determine what, and how many containers of each sample are received. The samples are then logged into the LIMs. Each sample is given a unique log number. The number consists of a Workorder number assigned by the Lims. The first two digits are the year, the second two digits indicate the month, and the last three digits indicate the number of Workorders received so far that month. Each sample in that Workorder is given a designation. For example: the sample 0508100-01 is the first sample of the 100th Workorder received in August 2005. Once the sample is logged in, the sample containers are clearly marked with the correlating sample number. The sample log numbers are also recorded on the chain of custody for future reference. Worksheets are then prepared by Sample Control through the LIMs to notify various groups within the lab of the required analyses. The worksheet includes information such as the client’s name, the project manager’s name, the sample number, the turnaround time required, and the sample location. If a sample is a RUSH, the turnaround time is highlighted to make sure it is identified as such by laboratory personnel. The analysis requested, the holding time for that analysis, the EPA Method number, and the detection limit are also listed as the work is completed. Following log-in, but prior to analysis, a proper location for the storage of the sample is then determined by the Sample Control Officer. Similar sample types are stored in the same locked refrigerators. Once the sample is stored, the worksheets are distributed to proper departments, and key personnel are notified of any unusual or important information such as rushes, unusual matrices, unusual analyses or samples approaching their holding times. The proper containers, with preservatives where appropriate, are provided to the client free of charge. This is to promote the use of the proper containers and preservatives that provide more accurate results. The following six pages contain a chart EPA-recommended sample holding times, containers and preservatives.


169

ORGANICS Parameter Container Preservative Holding Time Volatile Organics 40ml VOA tube Cool to 4 degrees C 14 days w/ teflon lined lid HCL to pH 2 * Base Neutrals/ Acid 2 qt. Amber glass Cool to 4 degrees C 7 days until extraction Extractables w/ teflon lined lid 40 days after extraction Pesticides 1 qt. Amber glass Cool to 4 degrees C 7 days until extraction w/ teflon lined lid 40 days after extraction Phenols (Acids) 1 qt. Amber glass Cool to 4 degrees C 7 days until extraction

40 days after extraction

Herbicides 1 qt. Amber glass Cool to 4 degrees C 7 days until extraction

40 days after extraction

Polychlorinated Biphenyls 1 qt. Amber glass Cool to 4 degrees C 7 days until extraction (PCB's) w/ teflon lined lid 40 days after extraction Purgeable Halocarbons 40ml VOA tube Cool to 4 degrees C 14 days w/ teflon lined lid Purgeable Aromatic 40ml VOA tube Cool to 4 degrees C 14 days Hydrocarbons w/ teflon lined lid HCL to pH 2 * Acrolein and 40ml VOA tube Cool to 4 degrees C 14 days Acrylonitrile w/ teflon lined lid Adjust pH to 4-5 ** Benzene, Toluene, 40ml VOA tube Cool to 4 degrees C 14 days Xylenes (BTEX) w/ teflon lined lid HCL to pH 2 * Total Organic Halogens 500 ml Amber glass Cool to 4 degrees C 14 days w/ teflon lined lid Zero Headspace * Exempt if samples analyzed within 7 days ** pH adjustment only required for Acrylonitrile Note: Any Chlorinated sample should also be neutralized with 0.008% Na2S203


170

INORGANICS Parameter Container Preservative Holding Time Acidity 100 ml P/G Cool to 4 degrees C 14 days Alkalinity 100 ml P/G Cool to 4 degrees C 14 days Ammonia - Nitrogen 100 ml P/G Cool to 4 degrees C 28 days Biochemical Oxygen 500 ml P/G Cool to 4 degrees C 48 hours Demand Bromide 250 ml P/G None required 28 days Chemical Oxygen Demand 100 ml P/G Cool to 4 degrees C 28 days H2SO4 to pH <2 Chloride 200 ml P/G None required 28 days Chlorine Residual 100 ml P/G None required analyze immediately Color 100 ml P/G Cool to 4 degrees C 48 hours Cyanide 100 ml P/G Cool to 4 degrees C 14 days NaOH to pH >12, 0.6g ascorbic acid Fluoride 100 ml P/G None required 28 days Hardness 100 ml P/G NHO3 or H2SO4 6 months to pH <2 Metals 500 ml P/G HNO3 to pH <2 6 months Cr (VI) 500 ml P/G Cool to 4 degrees C 24 hours Mercury 500 ml P/G HNO3 to pH <2 28 days Nitrogen (TKN) 500 ml P/G H2SO4 to pH <2 6 months Nitrate - Nitrogen 100 ml P/G Cool to 4 degrees C 48 hours


171

INORGANICS (continued) Parameter Container Preservative Holding Time Oil & Grease 1 qt. G Cool to 4 degrees C 28 days H2SO4 to pH <2 Total Organic Carbon 100 ml P/G Cool to 4 degrees C 28 days H2SO4 to pH <2 Orthophosphate 100 ml P/G Filter immediately 48 hours Cool to 4 degrees C Oxygen (Dissolved) N/A None required Analyze immediately Phenolics, total 1 qt. G only Cool to 4 degrees C 28 days H2SO4 to pH <2 Phosphorus, total 100 ml G only Cool to 4 degrees C 28 days H2SO4 to pH <2 Solids 100 ml P/G Cool to 4 degrees C 7 days Volatile, Suspended, 100 ml P/G Cool to 4 degrees C 7 days Total & Dissolved Temperature N/A None required Analyze immediately RADIOCHEMISTRY Parameter Container Preservative Holding Time Gross Alpha/ Beta 1/2 gal plastic HNO3 to pH <2 6 months Radium 226 1/2 gal plastic HNO3 to pH <2 6 months Radionuclides - Gamma 1/2 gal plastic HNO3 to pH <2 6 months Radionuclides - Alpha 1/2 gal plastic HNO3 to pH <2 6 months Liquid Scintillation 100 ml plastic As required 6 months


172

MICROBIOLOGY Parameter Container Preservative Holding Time Total Coliform 250 ml Amber glass Cool to 4 degrees C 6 hours sterilized 0.008% Na2S203 Fecal Coliform 250 ml Amber glass Cool to 4 degrees C 6 hours sterilized 0.008% Na2S203 Standard Plate Count 250 ml Amber glass Cool to 4 degrees C 24 hours sterilized 0.008% Na2S203 Yeast and Mold 250 ml Amber glass Cool to 4 degrees C 24 hours sterilized 0.008% Na2S203 Bio-burdon 250 ml Amber glass Cool to 4 degrees C 24 hours sterilized BIOLOGICAL Parameter Container Preservative Holding Time Bioassay - Acute 2 qt. P/G Cool to 4 degrees C 36 hours Ceriodaphnia/ Daphnia Bioassay - Chronic 2 qt. Cool to 4 degrees C 72 hours Ceriodaphnia Bioassay - Chronic 2 qt. Cool to 4 degrees C 72 hours Ceriodaphnia Mini Pass/ Fail Fathead Minnow/ Bluegill 5 gal Cool to 4 degrees C 36 hours (48 hr. acute) Fathead Minnow/ Bluegill 5 gal/ day Cool to 4 degrees C 36 hours (96 hr. acute) Fish Larvae (chronic) 1 gal/ day Cool to 4 degrees C 72 hours


173

PRESERVATION TECHNIQUES FOR SOLID AND HAZARDOUS WASTES Parameter Container Preservative Holding Time Volatile Organics 40 ml VOA tube Cool to 4 degrees C 14 days w/ teflon lined lid HCl Non-Volatile Organics 8 oz wide mouth G Cool to 4 degrees C 7 days until extraction w/ teflon lined lid 40 days after extraction Inorganics 8 oz wide mouth G Cool to 4 degrees C As required w/ teflon lined lid EP Toxicity 2 qt. Amber wide Cool to 4 degrees C N/A mouth G w/ teflon lid Toxicity Characteristic 2 qt. Amber wide Cool to 4 degrees C Leaching Procedure mouth G w/ teflon lid Volatile Organics Cool to 4 degrees C 14 days until extraction 14 days after extraction Semi-Volatile Organics Cool to 4 degrees C 40 days until extraction 40 days after extraction Mercury Cool to 4 degrees C 28 days until extraction 28 days after extraction Other Metals Cool to 4 degrees C 180 days until extraction 180 days after extraction Key: P = Polyethylene G = Glass


174

SECTION 5.0 – CALIBRATION PROCEDURES & FREQUENCY

The calibration of laboratory instruments is performed at the specified frequency and within acceptance limits published by EPA (i.e. the response factors and relative percent deviations for EPA methods 8260 & 8270). In cases in which specific guidelines are not available, Excelchem applies either the manufacturer’s recommended guidelines or in-house guidelines. Where calibration frequencies are not specified by the method itself, verification is generally established at least once daily following the initial development of a multi-point calibration curve. Where available, calibrations are carried out using certified reference materials. (Although these can be very expensive as is the case for certified national Bureau of Standards traceable specialty gas standards, the additional accuracy and credibility are well worth the cost). More importantly, Excelchem analysts are trained to detect calibration problems at the bench and realize that these must be corrected before carrying on with additional analyses.

SECTION 6.0 – ANALYTICAL PROCEDURES

EXCELCHEM employs analytical methods described in the following references: 1. SW-846 with updates I, II, IIa, IIb, and III, 1997

2. Standards Methods for the Examination of Water and Wastewater, 18th

edition, 1992 3. Methods for the Chemical Analysis of Water and Wastes, EPA-300/4-

79/020, 1983 4. Code of Federal Regulations 40, Revised 1985 5. California LUFT Manual, October 1989

Amy Sailor, Excelchems’ Quality Assurance Officer, is responsible for maintaining the company’s Manual of Standard Operating Procedures (SOP). This manual is a collection of published analytical protocols, as well as comments, cautions and equipment-specific instructions. Trainees are required to read and understand specific SOPs before being internally certified to perform a given analysis. Analysts are regularly given updates of those SOPs relating to the analysis they are certified to perform. Department heads maintain copies of all SOPs applying to their departments while the Laboratory Director and higher-ranking officers have complete copies of all SOPs. The SOP system ensures that all analyses are performed to the same high standards throughout the company. More importantly, no analyst is allowed to deviate from the approved SOP without prior approval of the Quality Assurance Officer. The failure of an employee to follow an SOP can be cause for dismissal. Procedures applied are always identified by reference to an EPA method or by reference to some other specific source on all Excelchem analytical reports. Senior Excelchem technical staff is always available to assist clients by discussing the merits of all methods


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performed by the laboratory. By guiding the client in the selection of an appropriate method, Excelchem believes that we will able to provide a more complete and valuable service.

SECTION 7.0 – DATA REDUCTION, VALIDATION & REPORTING

The lines of responsibility for data reduction, validation, and reporting are clearly delineated – everyone is responsible for generating valid data. An elaborate system of internal record keeping has been designed which allows the Quality Assurance Officer (Ms. Sailor) to determine when the sample came in, how it came in, who collected it, who received it, who prepared the work order, where and how the sample was stored, who had each sample, when he had it, how much he used and what he did with it. Sample preparation records are kept which show both the date of preparation and the person who prepared it. Concentration factors and comments are also written in the preparation logbooks. Sample analysis logbooks are kept for each instrument, which show the data analyzed and who ran the equipment. If data is transcribed or calculations are made, the time of transcription or calculation and the analyst’s initials are written on a hard copy where the calculation or transcription is maintained as a permanent record. Standard preparation records are similarly documented in specific logbooks created for this purpose. Thus, it is clear that everyone is responsible for quality at Excelchem. Their various roles have already been explained in Section 2.0. Documentation of this responsibility is what makes the QA/QC system particularly effective. In addition to the workstation and instrument logbook documentation, those providing second and third level data review (Department Heads and Project Managers) must thoroughly review their work. Ultimately, the senior scientist signing the report has final responsibility. Data collected from several different departments are separately evaluated first by the analyst, second by the QA/QC Officer, then collectively by the Project Manager, and finally by the signer of the reports. The collective review may include a check of the ion balance, examination for compatible constituents and whether or not the results make sense. The latter part of the evaluation process, which might be described as certification, includes the review of the quality assurance data. Among the questions considered are:

1. Is the full method blank acceptable? 2. Is the duplicate sufficiently precise? 3. Is the calibration validated? 4. Is an acceptable spike recovery obtained? 5. Do the number of significant figures reflect the precision of the method? 6. Is the method of analysis correctly stated? 7. Is the method of sample preparation correctly stated? 8. Are correct holding times observed? 9. Are the units correct? 10. Are the practical quantitation limits correct? 11. Is an acceptable value obtained for the Certified Reference Material? 12. Are surrogate recoveries acceptable?


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Only after all questions have been satisfactorily answered; is the data considered to be validated. At this point, the report is signed and transmitted to the client. Written acceptance criteria for method blanks, spikes, spike duplicates, and reference samples make it easier for our analysts to identify and correct suspect data. The multiple person review increases the opportunity to eliminate data of suspect quality. The Senior Scientist review applies experience regarding sensibility to detect suspect data.

SECTION 8.0 – INTERNAL QUALITY CONTROL CHECKS

Internal quality control checks include, but are not limited to those items that are discussed separately in the paragraphs that follow. It should be further noted that these are documented as part of the Company’s record keeping practices and are, therefore, available for use in validating the quality of all results generated by Excelchem laboratory facilities. Furthermore, many of these quality control checks incorporate numerical acceptance criteria which require corrective action if exceeded. 8.1 Instrument Performance Criteria – Where available, published instrument performance criteria, such as those developed by EPA for use in connection with the methods for volatile and semi-volatile organic analysis, are employed to verify that instruments are performing according to specifications. These method-specific criteria are kept on file with each instrument and are available for review upon request. In-house criteria, serving the same purpose, have been developed for other instrumentation and are generally based on the manufacturer’s specifications. 8.2 Reasonableness – This highly significant criteria is often overlooked by regulatory documents – presumably because it is subjective rather than quantitative in nature. Furthermore, since the assessment of reasonableness requires experience, not all laboratories are equally qualified to provide this form of internal quality assurance. Reasonableness considers such things as the relationship to other samples from a given site, comparison of the current data with historical data, a knowledge of environmental degradation processes, and a knowledge of the composition of commercial products such as fuels, solvents and pesticides which may be released to the environment. For this reason, all Excelchem generated reports are reviewed by an experienced scientist before signing and release. The experience-based criterion applied may best be summed up as follow: “If it doesn’t make sense, it is suspect!” 8.3 Control Charts – Method-specific, matrix-specific quality control charts have been developed by our laboratory for each of the parameters they determine. These are updated on a quarterly basis and released to the analysts, department head, project managers, technical officers, and to the Quality Assurance Officer. These graphical representations allow analysts at the bench to immediately determine if an analysis is out of control so that corrective action will not be delayed. At higher levels of review, they serve to validate the data that is being reviewed. 8.4 Surrogate Spikes – Wherever possible, compounds closely related to the analytes, but not having commercial use, are added to every sample prior to sample preparation. The recovery of these materials demonstrates that losses have not occurred during sample preparation and that analytes of a similar nature could have been recovered from that sample.


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8.5 Replicate Samples – Results from replicate sample analyses are a measure of precision. One sample in ten is split for duplicated analysis in order to verify that acceptable precision is achieved. If more than one sample matrix is involved, the above criteria apply to each sample matrix. If acceptable precision is not verified, further analyses are halted until a cause has been identified and corrective action taken. If samples are expected to be clean, duplicate blank spikes (Laboratory Control Spikes) are performed in order to evaluate precision. 8.6 Spiked Samples – Results from spiked sample analyses are a measure of accuracy. One sample in ten is spiked with several of the Priority Pollutants in the compound class of classes under investigation. If more than one matrix is involved, the above criteria apply to each sample matrix. Spike recoveries are calculated by the method detailed in ASTM Method D 3856, Section 11.5.1, Annual Book of ASTM Standards, Volume 11.01, Water, (1986). Excelchem usually selects the same sample used for the replicate analysis. In this way, Excelchem can base the percent recovery upon the amount added and the mean of the duplicate determinations, and thereby minimize the effect of precision upon the determination of accuracy. Again, if acceptable recoveries are not obtained, further analyses are halted until a cause has been identified and corrective action taken. 8.6.1 Laboratory Control Spikes – For every ten samples analyzed, Excelchem analyzes a Laboratory Control Spike (LCS) and Spike Duplicate (LCSD) which are comprised of a blank matrix spike with one of several of the priority pollutants in the compound class or classes under investigation. The LCS/LCSD are spiked with standards obtained from a source other than the manufacturer of the standards used to calibrate the instrument. In this way, Excelchem is able to measure the accuracy not only of duplicate spike analyses, but also of the calibration curve itself. If acceptable recoveries are not obtained, further analyses are halted until a cause can be identified and corrective action taken. 8.7 Certified Reference Standards / Secondary Source Standards – To assess methodological and instrumental accuracy, Excelchem analyzes US EPA or NBS certified reference materials along with the samples in order to certify the accuracy of results (see section 8.6.1 above). Since the expected results for standards of this type generated in-house are known, problems may be detected and corrected at a very early stage. Results not within the acceptance range are investigated, and corrective action is taken to insure that results are within the acceptable range prior to the analysis of further samples. 8.8 Internal Standards – Known amounts of internal standards are added to every sample or sample extract for organics analysis that are calibrated via the internal standard technique. This technique permits Excelchem to compensate for minor changes in the instrument performance by relating analyte concentrations to the response of the internal standards. Values for the internal standard response outside the acceptance range established for each instrument constitute grounds for rejecting the data. If a problem is detected the analyst is required to determine the cause of the problem and correct it before reanalyzing the sample. 8.9 Daily Standard and Blank Runs – Each day’s runs are preceded by instrument tuning, initialization of analytical parameters, standard runs containing all of the analytes


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to be determined plus the internal standards, surrogates, and blank runs. Hard copies and computerized records of all such runs are maintained. The blank run is compared with acceptance criteria established for the laboratory. If an acceptable blank is not obtained, the problem must be corrected before samples are processed. 8.10 Verification of Results with an Alternative Method – The range of capabilities available at Excelchem often makes it possible to determine a given parameter by one or more alternate methods. For example, calcium may be determined by atomic absorption or inductively-coupled-plasma spectroscopy. Fuel-related materials may be determined by gas chromatography using either flame ionization detection or scanning ion mass spectrometry. Polychlorinated biphenyls may be determined by gas chromatography followed by electron capture detection or by selective ion mass spectrometric detection. When methodology dictates or results are in question or are know to be the subject of legal action, they are verified with another method. 8.11 Logbooks – Logbooks documenting the preparation of standard and surrogate solutions are maintained. Information regarding the source of the standard, lot number, weight or volume of standard used, date prepared and name of preparer are included. Solvents used to prepare standard and surrogate solutions are checked for purity prior to use. Logbooks documenting the use of each analytical instrument are maintained; a description of every sample (including standards, duplicates, spikes and blanks) is recorded in the logbook as the samples are analyzed. Likewise, logbooks documenting periodic maintenance and repairs to each instrument are maintained.

SECTION 9.0 – PERFORMANCE & SYSTEM AUDITS

The Quality Assurance Officer and/or other corporate executives conduct both performance and systems audits of the laboratory in order to ensure that data of a defensible quality is produced at all times. As part of its laboratory certification program, the State of California also conducts both performance and systems audits. Performance audits are quantitative in nature and are designed to evaluate specific analytical measurement systems. They may be open or blind and may originate with the laboratory, with the client, or with a regulatory agency. Systems audits are qualitative reviews of the laboratory quality control measurement system designed to verify that these systems are being used appropriately. A partial systems audit might be as simple as a short question and answer session with a group or department. These might reveal procedural misunderstandings that could be corrected on the spot and/or by rewriting the Standard Operating Procedure (SOP) with improved clarity. Systems audits may be carried out at any stage of an analytical program. For example, Excelchem certifies analysts for proficiency in the procedures that they are to perform before allowing them to perform them. This activity represents a kind of one-on-one systems audit. Analyst certifications are reviewed annually, as individual procedures are revised, or as new procedures are added. These are all examples of system audits. Items addressed in a typical systems audit include a comparison between actual laboratory practice and the protocol as written in the standard operating procedure.


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While most such audits serve only to verify that laboratory procedures are in control, they are the best way to discover evolutionary variations from the SOP that need to be incorporated formally into the SOP or eliminated. These reviews also provide analysts with an opportunity to communicate problems associated with the existing SOP’s.

SECTION 10.0 – PREVENTATIVE MAINTENACE

Excelchem Environmental Labs has opted to purchase service contracts on selected major instrumentation to ensure the availability of regularly scheduled and periodic maintenance. Since even the typical 72-hour guaranteed response time is not sufficient for the modern laboratory, Excelchem has begun to rely to a greater extent on expanded in-house supplies of spare parts, on improved in-house repair capabilities and on the availability of backup instrumentation from the same manufacturer. For example, when a gas chromatograph system develops a problem, Excelchem is generally able to quickly isolate the problem by swapping parts with one of the operating instruments. The malfunctioning part is then ordered by overnight delivery service, thus often suffering only one day of downtime. In-house preventative maintenance such as filter changes, pump-oil replacement, cleaning of optics, etc. is documented in instrument-specific maintenance logbooks kept with each instrument. Scheduled preventative maintenance is similarly recorded, as are in-house and commercial repairs.

SECTION 11.0 – PROCEDURES USED TO ASSESS PRECISION, ACCURACY & COMPLETENESS

11.1 Precision – Measures the dispersion of repeated measurements of the same parameter in the same sample from one another. The tools employed to routinely assess precision at Excelchem include:

a. Replicate Samples b. Laboratory Control Spikes c. Matrix Spikes d. Sensibility e. Confirmation by an Independent Method f. Quality Control Charts

11.2 Accuracy – Measures the deviation of the reported value from the true value. The tools employed to routinely assess accuracy at Excelchem include:

a. Certified Reference Materials / Secondary Source Standards b. Laboratory Control Spikes (also measure precision) c. Matrix Spikes (also measures precision) d. Sensibility e. Confirmation by an Independent Method f. Quality Control Charts (also measure precision)

11.3 Completeness – The QA definition of completeness refers to the degree to which valid data are produced under a particular QA program. Appropriately enough,


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expressed as a percentage, the job is never done. Since the QA objectives discussed within, and generally adopted by EPA, are based on the ninety-five percent confidence level, about five percent of the tests fail EVEN WHEN THE SITUATION IS FUNCTIONING PROPERLY. Thus the QA target for completeness is ninety-five percent. The actual percent of samples reported vs. samples received, of course will be closer to 100 percent since the statistical five percent, plus the real “out-of-control” results will be repeated, if possible, and matched with acceptable QA data. The measurements used to describe completeness may be calculated according to one of the two formulas presented below:

a. Results provided divided by samples submitted expressed as a percent b. Accepted results generated divided by number of analyses performed.

Typically, Excelchem’s customers are concerned only with the first definition.

SECTION 12.0 – CORRECTIVE ACTIONS

The detection of a Quality Assurance problem at Excelchem, as explained above, may arise at the bench, during review by the Department Head, by the Project Manager, or by the senior chemist who signs the reports. It is the responsibility of the detecting party to initiate corrective action by completing an “Analysis Out of Control” form. These forms have developed a positive acceptance required to make the system a success. These documents may be generated by bench analysts, middle managers and senior technical staff. They are sent upward through the ranks as well as downward and are generally recognized as a form of communication designed to improve quality. It should be noted that because a written response is required, the Excelchem system documents not only the problem but also the solution. The following are among the items that must be inspected; if a problem is discovered a corrective action is required as well as complete documentation. 12.1 Calibration / Instrument Responses – Analysts must initiate retests and take corrective actions anytime these are out of limits. Since valid data cannot be generated in the absence of a proper instrument response, detection of problems must be immediate and corrective action is absolutely required before analyses can be resumed. Detection of a problem is most often achieved by the analyst him/herself. 12.2 Instrument Blanks – Results provided for all analytes must be below the reported practical quantitation limits. Analytes for which a signal is noted but for which the signal is too weak to provide a value above the practical quantitation limit may be reported either as “not detected” or with a calculated value and a footnote explaining that such levels are reported only in the blank. Required actions typically begin with a rerun under the same conditions. If the rerun is acceptable, it is concluded that carryover was the cause and no further action is required. If the rerun is unacceptable, it is concluded that the analytical system is contaminated and more serious corrective actions must then be undertaken before analyses can be resumed, such as cleaning the system, replacing sample contact parts, etc. Generally the recognition of a problem is most often achieved by the analyst.


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12.3 Method Blanks – Method blanks differ from instrument blanks in that they are brought through all sample preparation steps prior to being introduced to the instrument. Thus they describe contamination that may originate in the laboratory as well as within the instrument. The reporting options are the same as have already been described in the previous subsection. Values at or above the practical quantitation limit require corrective action. In this case, a comparison with the corresponding instrument blank may permit the problem to be isolated. If the sample preparation is suspect, an immediate systems audit may pinpoint the source of the problem. If not, further isolation may be necessary. This is accomplished by the use of reagent blanks and sample preparation step blanks. 12.4 Travel Blanks – Travel Blanks are containers of analyte-free water supplied to client by the laboratory and sent back to the laboratory unopened. They serve to detect incidental contamination arising from shipment and storage prior to analysis. If a comparison to the instrument and method blank indicate that the problem is indeed due to shipment and storage, corrective actions might include the replacement the replacement of shipping containers, the cleaning of refrigerators, etc. 12.5 Field Blanks – These are employed to detect contamination arising from contact with sampling equipment, during shipment or during storage. Since they also detect contamination originating during sample preparation and analysis, an unacceptable result requires isolation by comparison with the method blank, the travel blank and the instrument blank. If these are clean, the client is advised that a sample problem may exist. Appropriate corrective actions include the use of properly cleaned samplers, pumps, bailers, etc. 12.6 Spikes – Unacceptable spike data include all points beyond the upper and lower control limits of the Quality Control Charts or three points in a row above or below the warning limit. Potential corrective actions include a systems review between the analyst, the data processor, the person preparing the spike, and the department head. If a surrogate of the same class as the analyte for which a poor recovery was noted is present, it may serve as an indicator of a matrix problem. When such is the case and a duplicate spike provides a low recovery, the likely cause is a matrix effect and analyses may be resumed. Otherwise, analyses are suspended while the issue is resolved. 12.7 Duplicates – Unacceptable precision may indicate a non-homogeneous sample, a dirty instrument, or an instrument malfunction that compromises reproducibility. Corrective actions, again, include a systems review with the analyst and department head plus the physical reexamination of the sample. The signal-to-noise ratio of the instrument should be examined as its deterioration indicated that cleaning may be needed or troubleshooting procedures undertaken. Analyses are to be suspended until the source of the problem has been identified and corrected. 12.8 Sensibility – Unusual results are often detected by the Project Manager or the signing senior chemist, since a higher level of experience is needed to make observations of this type. Because these senior staff have access to all of the analytical data which relate to a project, they are also able to develop and overview of the situation that allows them to spot potential inconsistencies between separate analytical tests involving the same analytes. Examples of data that don’t make sense would include groundwater thought to be contaminated with gasoline but having suspiciously low BTEX concentrations (a possible indication of diesel), or a narrow range petroleum distillate


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described as diesel (probably Stoddard Solvent). Corrective actions usually involve reruns, discussions with the client, performing additional tests, etc. If otherwise sensible results are of a sensational nature, the above actions may be supplemented by re-sampling, reanalysis or even splitting samples with another laboratory. In this case, the concern is that any results that have the potential to require costly remediative actions by the client should not be released without extremely thorough documentation. 12.9 Other Corrective Actions – Instruments suffering from high problem rates or failing to meet performance criteria may be sent back to the manufacturer. Trainees failing to achieve proficiency may be dismissed and analysts repeatedly found to be the source of “out of control” situations are retrained or dismissed. Methods that are subject of frequent “out of control” notices may be revised, replaced, or abandoned.

SECTION 13.0 – QA REPORTS TO MANAGEMENT

Within Excelchem, QA does not just report to management, QA IS Management. Ms. Sailor is the QA Officer of the Company, and reports only to the Lab Director, John Somers. Mr. Somers is authorized to enter into contracts for the company and as such is one of only two persons to be empowered. He becomes heavily involved in major project management as well as in the upgrading of staff through in-house training. In addition to reporting to our management, Excelchem’s Quality Assurance Program is prepared to report to YOUR management. With every batch or reports you will receive:

1. Blank Report 2. Spike Report 3. Full Duplicate Analysis 4. Travel Blank Report (if provided)

In addition, at nominal cost, based on time and materials, a client can elect to receive an overall monthly quality assurance report. The report would summarize the quality assurance results for the month and including relevant instrument performance documentation, copies of the chain-of-custody documents, and task-specific case narratives. From a discussion of conclusions Excelchem may be able to draw from the data parameters such as depth relationships, or source relationships however it would be confined to the data and its interpretation since Excelchem staff members are analysts and would not be certified to include legal, medical, or engineering conclusions.

Section 14.0 Organization Chart for Excelchem Labs

Mindy Somers, President & Chief Executive Officer

John Somers, Laboratory Director

Amy Saylor, QA/QC Officer

Amy Saylor, Lab Manager


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Section 15.0 Mock Chain of Custody


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Section 16.0 Mock Report


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Appendix 12. ExcelChem Environmental Laboratories Analytical Methods SOPs

Standard Operating Procedure for Method 4500 NH3 B/H Revision: 08/2012

Title: Analysis of Ammonia Nitrogen by Discrete Analysis. Scope: This method determines ammonia nitrogen in drinking water, surface

water, saline water, domestic and industrial wastes, groundwater, distillates, and soil extracts according to Standard Method 4500NH3 B/H.

Purpose: The purpose of this procedure is to ensure quality control in the lab and

traceability of possible causes of error in analytical results. Equipment & Conditions: There will be an O-I Analytical Discrete Analyzer 3500

Automated Chemistry Analyzer. Data manipulation and control is via O-I Analytical DA 3500. The absorbance will be measured at 640 nm. A Lachat Instruments Micro Dist will be used for distillation.

Sample Containers and Handling: 1. Collect samples in acid-washed HDPE or glass bottles. 2. Samples can be held for up to 28 days is cooled immediately, stored

at just above freezing (≤ 6ºC), and preserved at pH 2 with sulfuric acid.

Method Start-up and Validation:

1. Calibration standards are analyzed at no fewer than five concentrations. From these standards, a calibration curve is established for each compound. The concentrations will include:

Point #1 0 mg/l NH3-N Point #2 0.1 mg/l NH3-N Point #3 0.5 mg/l NH3-N Point #4 1.0 mg/l NH3-N Point #5 2.0 mg/l NH3-N Point #6 5.0 mg/l NH3-N 2. Continuing instrument calibration will be verified every ten samples

analyses. There will be a CCV analyzed at the beginning and at the end of a sequence of samples.

3. The continuing calibration check standard must not deviate more than

10% from the calibration curve. If the calibration cannot be verified within the specified limits, the analysis must be discontinued and the cause determined. Subsequently, the calibration curve, QC and samples must be reanalyzed after the correction has been made.


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4. All data shall be reported with three significant figures.

5. Stock standards shall be prepared from neat materials. Standards shall be obtained from Fisher Scientific or equivalent.

6. A minimum of one method blank, LCS, LCSD, MS, and MSD for every

matrix and batch of twenty samples.

7. The relative percent difference (RPD) between spiked matrix duplicate determinations is to be calculated as follows:

RPD = __ |D1-D2|__ *100

[(D1 + D2)/2] D1= First sample value D2= Second sample value

8. A control limit of ± 10% RPD or within the documented historical

acceptance limits for each matrix shall be used for sample values greater than ten times the instrument detection limit.

9. The spiked sample or spiked duplicate sample recovery is to be within

20% of the actual value or within the documented historical acceptance limits for each matrix.

10. A minimum of fifteen minutes will be allowed for the lamp to warm up.

Quality Control Preparation: 1. Method Blank – 25 mL DIH2O, then follow sample preparation

beginning with letter b. 2. BS/BSD – 25 mL DIH2O + 500 uL of 100 ppm Ammonia

Spike, then follow sample preparation beginning with letter b. 3. MS/MSD – 25 mL selected sample + 500 uL of 100 ppm

Ammonia Spike, then follow sample preparation beginning with letter b.

Sample Preparation:

1. Distill samples according to the following steps. a. Aliquot 25 mLs of sample into VOA or similar container. b. Add 1.25 mL 0.025 Borate Buffer to all samples and Q.C. c. Adjust pH to 9.45 – 9.54 using 1 N Sodium Hydroxide and

remove any residual chlorine. d. For soil samples, weigh 1 g +/- 0.01 g of sample and dilute to

25 mLs. e. Add 25 mLs of adjusted sample and 4-5 boiling chips to the

boiling tubes. f. Cap boiling tubes with green screw cap. g. Place boiling tubes in the HotBlock. h. Label collection traps with sample number/ Q.C name. i. Pipette 15 mL of 0.016 M H2SO4 solution into the collection

trap.


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j. Attach the collection trap to the boiling tube in the larger port on the cap, and the vacuum manifold.

k. Turn on the Vacuum and adjust each valve to provide a bubble rate of 10-15 bubbles per second for each collection trap.

l. Turn on the HotBlock and set temperature to 135 degrees C. m. Heat samples under vacuum for 60 minutes after 135 degrees

C is reached (1 hour 40 minutes). n. While vacuum is on, remove collection traps from the boiling

tubes. o. Volumize the distillate in the collection trap up to the 25 mL

mark with DI H2O. p. Transfer distillate into a labeled VOA container or similar and

adjust the pH to 4.0 - 7.0. The sample is now ready for analysis by the discrete analyzer.

2. 0.016 M sulfuric acid

a. Add 1.0 mL of concentrate sulfuric acid to 500 mL deionized water in a 1 L volumetric flask.

b. Dilute to 1 L with deionized water and mix well.

3. Borate Buffer (0.025M) a. Add 8.8 mL 1N sodium hydroxide to 500 mL deionized water

and 9.5g sodium tetraborate in a 1 L volumetric flask. b. Dilute to 1 L with deionized water and mix well. Store in

polyethylene bottles. Reagents and Equipment:

1. High purity reagents of sodium phenate, sodium hypochlorite, EDTA, sodium potassium tartrate, sodium nitroprusside, sodium tetraborate, sodium hydroxide, and ammonium chloride shall be used.

2. Trace metal purity concentrated sulfuric acid shall be used.

3. DI water of high enough purity shall be used.

4. All glassware shall be washed and rinsed. The final rinse shall be DI

water. Quality Control:

1. Analysis of the method blank to ensure that the analytical system is

interference free. 2. Quality control data will include a method blank for every matrix batch

of samples. It will also include laboratory control sample and duplicate, matrix sample spike and duplicate for every matrix and batch of twenty samples.


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3. The LCS/LCSD and MS/MSD shall have recovery limits of ± 20%.

4. The relative difference between spikes shall be ± 20%.

5. A MDL study shall be performed to determine the level at which each

analyte can be reported. A low standard that is approximately 3-5 times above the instrument detection level shall be analyzed using sever replicates on three non-consecutive days. An upper range may also be determined for calculation purposes.

6. Samples that are over range shall be diluted and reanalyzed.

Calculations:

1. Sample concentrations will be calculated as follows: A. Samples will be reported in mg NH3-N /L. Formula:

(mg analyte)* (dilution factor) (L of sample)

B. Soil samples will be reported in mg/kg.

Formula:

mg = ug = (mg analyte)*(dilution factor) kg g kg of soil

C. The instrument will be calibrated in mg/L.

2. Average percent spike recovery:

Sum of replicate recoveries______*100 (# of replicates)*(spike concentration)

4. Relative Percent Difference (RPD):

Difference of x and y__ *100 Mean of x and y


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Ammonia Nitrogen Reagents and Standards

1. Stock 1000 ppm NH3-N: Prepare every 6 months a. 3.819 g ammonium chloride in a 1000 mL volumetric flask to

volume with Millipore water.

2. Intermediate calibrant 10 ppm NH3-N: Prepare every 6 months a. 10 mL 1000 ppm NH3-N in a 1000 mL volumetric flask to

volume with Millipore water.

3. CCV standard 2 ppm NH3-N: Prepare daily a. 20 mL 10 ppm NH3-N added to 100 mL of Millipore water.

4. R1- 5% EDTA: Prepare when CCV’s start to fail.

a. Purchased. Located in brown fridge in GC room.

5. R2- Sodium Phenate: Prepare once CCV’s start to fail. a. In a 250 mL beaker, dissolve 8.3 g phenol in 60 mL of Millipore

water. b. In small increments add 3.2 g NaOH with agitation. c. When cool dilute to 100 mL with Millipore water.

6. R3- 2-3% Chlorine : Prepare Daily

a. 10 mL sodium hypochlorite (6% chlorine) added to 10 mL Millipore water.

7. R4- Sodium Nitroprusside: Prepare when CCV’s start to fail.

a. Dissolve 0.05 g sodium nitroprusside (sodium nitroferricyanide) in 100 mL of Millipore water.

8. Spike standard 100 ppm

a. 1:10 dilution of the 1000 ppm standard.


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Standard Operating Procedure for Method 300.0 Title: Analysis of Anions (Bromide, Chloride, Fluoride, Nitrate, Nitrite,

Phosphate and Sulfate) for water and Wastewater. Summary: This method is adapted from EPA Method 300.0 for Bromide (Br-),

Chloride (Cl-), Fluoride (F-), Nitrate-N (NO3--Nitrogen), Nitrite (NO2

--N), Phosphate (HPO4

--P), and Sulfate (SO42-).


traceability of possible causes of error in analytical results. Apparatus & Materials:

DX-600 Ion Chromatograph (Dionex) 3 mL disposable plastic syringe

0.45 μm syringe filters 5 mL plastic vials Vial filter caps Autosampler cassettes

Volumetric Glassware Reagents: Multi-Element IC Stock Standard (Nitrite) – two sources

Multi-Element IC Stock Standard, (Fluoride, Chlorine, Bromide, Nitrate, Phosphate, Sulfate) – two sources.

Eluent Solution – 3.5mM sodium carbonate, 1.0mM sodium bicarbonate 18.2M Water

Interferences:

1. Interferences can be caused by substances with retention times that overlap those of the anions of interest. Large amounts of an anion can interfere with peak resolution of adjacent anions. Dilutions or fortification can be used to solve this issue.

2. The water dip at the beginning of the analysis can interfere with the fluoride peak. A concentrated addition of the eluent added to the sample can help eliminate the problem.

3. Acetate and other anions that are not retained or only slightly retained by the column may co-elute with fluoride.

4. Residual chlorine dioxide is an interferent. If any chlorine dioxide is suspected in the sample, purge sample with an inert gas prior to analysis.

Sample Handling:

1. Collect samples in clean glass or plastic bottle. Store at 4oC (39oF) or

lower if the sample is to be analyzed within 24 to 48 hours.


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2. In a given sample, the anion of interest that requires the most preservation and shortest holding time will determine the preservation treatment.

a. Nitrate, nitrite, and orthophosphate must be analyzed within 48 hours. Cool to 4°C.

b. Chlorite must be analyzed immediately. Preserve with 1 mL of EDA preservation solution if the sample cannot be analyzed within < 10 minutes. Cool to 4°C.

c. Combined nitrate and nitrite requires preservation with concentrated sulfuric acid to pH< 2.

d. All other anions must be analyzed within 28 days and are cooled to 4°C.

3. Just prior to analysis, samples should be filtered through a 0.45 μm filter,

warmed to room temperature, and neutralized with 5.0 N sodium hydroxide solutions, if necessary.

4. Do not use mercury solutions for preservations Method Start-Up, Calibration, and Verification:

1. Create a calibration curve using a blank and a minimum of three standards.

2. Analyze a Quality Control Sample (QCS) on a quarterly basis and after every calibration.

a. The results must be within ±10% of the expected value.

b. The QCS must be prepared from a stock standard obtained from outside the laboratory and different from the source of the calibration standards.

3. Determine the Linear Calibration Range (LCR) initially and verify every six months using a minimum of a blank and three standards.

a. If any verification data exceeds the initial values by ±10%, linearity must be re-established.

4. MDL’s must be determined at least every six months by analyzing seven

replicate aliquots of fortified reagent water and performing the appropriate calculations.

5. At least quarterly, replicates of laboratory fortified blanks (LFB) should be analyzed to determine the precision of the laboratory measurements.


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6. Verify the calibration daily by running a blank and a mid-range check standard at the beginning of the run, after every ten samples, and at the end of the run.

a. The response and retention time must be within ±10% of the expected values.

Quality Control:

1. Analyze reagent water (Method Blank) for every batch

2. Duplicates must be analyzed for every batch of 20 samples.

3. Matrix Spike (MS), Matrix Spike Duplicates (MSD).

a. Spike 10.0 mL of sample with 100 μL of 1000 ppm multi-element standard and 100 μL of 1000 ppm nitrite standard.

b. Spike recovery must be within ±20%.

4. Laboratory Control Spike (LCS), Laboratory Control Spike Duplicate (LCSD)

a. Spike 10.0 mL of reagent water with 100 μL of 1000 ppm multi-element standard and 100 μL of 1000 ppm nitrite standard.

b. Spike recovery must be within ±10%.

5. All glassware must be thoroughly washed and rinsed prior to use.

6. All data is stored on the computer, and a hardcopy is made for the project folder.

Procedure:

1. Turn on the power to the detector and pump module.

2. Create the run sequence in the Chromeleon browser. For any standards, include the concentration and the Standard Logbook number in the sample ID. Begin the sequence with 2-3 system blanks to flush the column.

3. Filter samples using a disposable plastic syringe and 0.45 μm syringe filters.

Prepare any dilutions with filtrate and Millipore water. Pour filtrates and dilutions into 5 mL plastic vials and arrange in an Autosampler cassette.

4. Set a filter cap inside the top of each 5 mL plastic vial and push down into place

using the plastic dowel tool. The filter cap should be flush with the top of the Autosampler cassette.

5. Place cassettes in the Autosampler. Make sure the samples are arranged in the

same order in the cassettes as they are in the sequence in Chromeleon. Press


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the “Hold/Run” button on the Autosampler so the green light is on the right-hand side in the Run position.

6. In Chromeleon, click Batch>Start>Ok to begin the run.

7. Inspect chromatograms carefully and adjust peak integrations as necessary. If

an analyte concentration exceeds the calibration range, the sample must be diluted and re-analyzed.

8. Print two hardcopies of all data: one for the Workorder and one for records.

Include hardcopies of the curve data and QC samples.

References:

1. EPA Method 300.0, Determination of Inorganic Anions by Ion Chromatography, August 1993, Revision 2.3.

2. Dionex Chromeleon Software Manual, June 2006, Version 6.80.


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Standard Operating Procedure for Method 200.7

Title: Analysis of trace elements, including metals, in solution using an inductively coupled argon plasma atomic emission double-view spectrometer.

Scope: Methods EPA 1311, 3010A and 200.7 are used to determine the

concentrations of total and dissolved metals by ICP. A simultaneous ICP with a scanning charge-coupled device (CCD) detector, a dual view optical system, simultaneous background correction, inter-element correction, and a multi-component spectral fitting system is used.


traceability of possible causes of error in analytical results. Equipment & Conditions: There will be a Thermo Scientific ICAP 6000 Series

inductively coupled argon plasma instrument capable of analyzing elements while simultaneously measuring emission lines and background measurements. It will have a Burgener Mira Mist nebulizer.

Argon of 99.996% purity shall be used for the plasma torch fuel. A dryer-filter assembly shall be used in the air line to further clean and

protect the ICP unit from contamination. A chiller/re-circulator unit for cooling the torch assembly shall have a cooling capacity of 1900 watts at 20o C. It will be stable to 1o C. The pump rate shall be 3.8 L / minute.

Sample Containers: Clean plastic containers. Samples are to be preserved with nitric

acid and with the pH being less than 2 for a minimum of 24 hours prior to sample digestion/preparation.


1. A one point calibration is analyzed using known concentrations of a 1ppm calibration standard to construct the calibration curve, subsequently unknowns and other samples are measured against this to determine their concentration. During analysis, the instrument determines intensity ratio values, which are then related to concentration ratios calculated from a calibration curve.

2. An internal standard is used to account for variations in flow and viscosity. The internal standard intensity is measured from the elemental response of yttrium in the calibration blank. The subsequent analyses are all measured versus the internal standard from the blank and the internal standard in the sample. The internal standard must not deviate more than 20% from the calibration curve. If the internal standard fails the sample will be re-analyzed. Samples will be diluted and re-analyzed if the internal standard fails again.

3. The initial calibration verification (ICV) will be analyzed immediately after the calibration from a second source and must not deviate more than 5%


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from the true value. If the ICV cannot be verified within the specified limits, the analysis must be discontinued and the cause determined.

4. Continuing instrument calibration will be verified every ten sample

analyses. There will be a CCV analyzed at the beginning and at the end of a sequence. The continuing calibration check must not deviate more than 10% from the calibration curve. If the calibration can’t be verified within the specified limits, the analysis must be discontinued and the cause determined. Subsequently, the calibration curve, QC and samples must be re-analyzed after the correction has been made.

5. The rinse time between analyses shall be at least one minute.

6. All data shall be reported to three significant figures.

7. Stock standards shall be obtained premixed and dissolved in nitric acid solution. Standards shall be obtained from Aldrich, Perkin-Elmer, Environmental Express and CPI international.

8. Yttrium at a concentration of 1 mg/L shall be added to every blank,

standard and sample before analysis as an internal standard.

9. A minimum of one MB (BLK), BS, BSD, MS and MSD for every matrix and batch of ten samples.

10. Fresh standards shall be made every six months or sooner if upon

analysis the sensitivity of the standards prove to be inadequate for use.

11. The relative percent difference between spiked matrix duplicate determinations is to be calculated as follows:

RPD = (D1-D2) *100% [(D1+D2)] /2

RPD = Relative percent difference D1 = First sample value D2 = Second sample value (duplicate)

12. The spiked sample or spiked duplicate sample recovery is to be within +/- 25% of the actual value or within documented historical acceptance limits for each sample.

13. If spectral overlap or interference is suspected, various techniques can be

used to adjust the data. Spectral overlap can be avoided by using alternate wavelengths, changing resolutions, modifying background correction points, Multi-spectral Component fitting(MSF), and inter-element correction(IEC) factors.


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14. The spectral correction for the MSF model shall have each individual element analyzed for wavelength and peak shape. The MSF correction model can be used for spectral interferences in the methods being used.

15. Any saturation or result above the LDR of an element will be rerun after

dilution of the sample and a subsequent rinsing of the instrument. 16. Optimum sample flow, RF, power, plasma, auxiliary and nebulizer flow

rates will remain constant once established. Flow rates are determined by the type of nebulizer used.

17. A spectral optimization shall be performed every day the instrument is

turned on for analysis.

18. Every time the torch is taken out for inspection or cleaning, the flows are changed, the instrument is moved or any physical change is made to the instrument, torch alignment shall be performed. A 2 mg/L standard of zinc will be used to perform the alignment.

19. An IEC (inter-element Correction) will be utilized to correct for various

kinds of spectral interference. The Thermo Scientific ICAP 6000 Series software manual gives insight into which correction method should be utilized if needed. If interelement correction factors are used then they should be verified periodically according to the specifications listed in EPA 200.7. IECs will be verified daily by analyzing an ICSA and ICSAB solution. ICSA and ICSAB must not deviate more than 20%.

Sample Preparation:

1. Solid samples – 0.5g shall be weighed into a 50mL digestion tube and digested.

2. Aqueous samples – 50mL shall be measured into a 50mL digestion

tube and digested.

3. Unpreserved samples shall be acidified with nitric acid at least 24 hours prior to digestion. The pH must be verified immediately before digestion (pH <2).

4. Sample preparation procedures shall be in accordance with EPA

200.7, 1311, 3010, 3005A, 3010B, 3050B or Title 22WET methods

5. For lower detection limits, larger sample sizes will be measured and smaller final volumes will be utilized.

6. All samples shall be diluted using millipore water with 10% HCl and

2% HNO3 concentrations to ensure minimal interferences and to provide the lowest possible analytical baseline

Reagents & Equipment:


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1. Trace metal purity concentrated nitric and hydrochloric acids shall be used.

2. Millipore water of high enough purity shall be used.

3. The latest versions for digestion procedures shall be followed.

Quality Control:

1. Initial calibration verification (ICV) is analyzed immediately after calibration and is required to be within 95-105% of the true value. A second source from the calibration is used.

2. Continuing calibration verifications (CCV) are run at least every 10

samples and at the end of the analysis, and is required to be within 90-110% of the true value.

3. A calibration blank is used to show the absence of interferences. It is

also used as a reference for the background level when analyzing standards and samples.

a. Interference check standards will be run at the beginning.

ICSA result must be <2 times the reporting limit. ICSAB must be within 20% of the true value.

4. Quality control data will include a method blank for every batch of

samples. It will also include laboratory control sample and duplicate and matrix spike and duplicate for every batch of ten samples.

5. The LCS/LCSD shall have a recovery limit of +/-15%.

6. The MS/MSD shall have a recovery limit of +/-25%.

7. The relative difference between spikes shall be +/- 20%.

8. A MDL study shall be performed to determine the level at which each

element can be reported. A low standard that is approximately 3-5 times above the instrument detection level shall be analyzed using seven replicates.

9. An LDR Study is performed to determine at what point a sample is

over range and must be diluted and re-analyzed. Calculations:

1. Sample concentrations will be calculated as follows:

2. A. Aqueous samples will be reported in ug/L. (ppb)


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Formula: µg analyte * final volume (L) * dilution factor * 1000mL = µg/L (ppb) L initial volume (mL) 1L

B. Soil samples will be reported in mg/kg (ppm).

Formula: µg analyte * final volume (L) * dilution factor * 1000g =mg/Kg (ppm) L initial weight (g) 1Kg

C. WET extract samples will be reported in mg/L (ppm).

Formula: µg analyte * dilution factor * 1mg =mg/Kg (ppm) L 1000 µg

References: Determination of metals and trace elements in water and wastes by Inductively Coupled Plasma-Atomic Emission Spectrometry, EPA 200.7,1994, Revision 4.4


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Standard Operating Procedure for Method SM 2320B Title: Alkalinity, for water, wastewater, and seawater Summary:

This method has been adapted from Standard Methods for the Examination of Water and Wastewater and is equivalent to 2320 B (Titration Method). Alkalinity is a measure of the capacity of water to neutralize acids. Alkalinity of water is due primarily to the presence of bicarbonate, carbonate, and hydroxide ions. Salts of weak acids, such as borates, silicates, and phosphates, also may contribute. Salts of certain organic acids may contribute to alkalinity in polluted or anaerobic water; but their contribution usually is negligible. Bicarbonate is the major form of alkalinity. Carbonates and hydroxide may be significant when algal activity is high and in certain industrial water and wastewater, such as boiler water. Alkalinity is significant in the treatment process for potable water and wastewater. The alkalinity acts as a pH buffer in coagulation and lime soda softening of water. In wastewater treatment, alkalinity is an important parameter in determining the amenability of wastes to the treatment process and control of processes such as anaerobic digestion where bicarbonate alkalinity and any fraction contributed by volatile acid salts become considerations. Alkalinity is expresses as phenolphthalein alkalinity or total alkalinity. Both types can be determined by titration with a standard sulfuric acid solution to an end point pH, evidenced by the color change of a standard indicator solution. The pH also can be determined with a pH meter. Phenolphthalein alkalinity is determined by titration to a pH of 8.3 and registers the total hydroxide and one-half the carbonate present. Total alkalinity is determined by titration to a pH of 5.1, 4.8, 4.5, or 3.7, depending on the amount of carbon dioxide present. The total alkalinity includes all carbonate bicarbonate and hydroxide alkalinity. Sulfuric acid reacts with the free forms of alkalinity converting them to water or carbonic acid. If hydroxide is present, it reacts to form water: 2OH- + H2SO4 ------> 2H2O + SO4

2-

Phenolphthalein alkalinity is determined by titration to and end point pH of 8.3, which corresponds to the conversion of carbonate to bicarbonate. 2CO3

2- + H2SO4 -----> 2HCO3- +SO4

2-

If hydroxide is present, titration to pH 8.3 will indicate the alkalinity due to all of the hydroxide plus one-half of the carbonate. Continued titration to pH 4.5 completed the conversion of carbonate plus any bicarbonate present to carbonic acid. This value is termed total alkalinity.

Apparatus/Materials: Buret, Class A, 25 ml


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Erlenmeyer, 250 ml Graduated cylinder, 50 ml Clippers (for powder pillows) Clamp and stand (for buret) Reagents: Type II water Phenolphthalein powder pillows (942-99) Bromocresol Green-Methyl Red Indicator (943-99) Sulfuric Acid Standard Solution, 0.020 N (203-53) Alkalinity Standard Solution, 0.500N (14278-10) Interferences:

1. Residual chlorine interference with the indicator may be removed by adding a drop of 0.1N sodium thiosulfate.

2. Highly colored or turbid samples may mask the color change at the end point. Use a pH meter for these samples.

Sample Handling:

1. Collect samples in clean plastic or glass bottles. 2. When prompt analysis is not possible, the sample may be stored at 4°C

for 24 hours. Warm to room temperature before analyzing. 3. Avoid excessive agitation and prolonged exposure to air. 4. Fill containers completely and cap tightly.

Quality Control:

1. Analyze reagent water (a Method Blank) for every batch: a. Add 50 ml of Type II water to an Erlenmeyer and analyze as you would a sample.

2. Duplicates must be analyzed for every batch or every 20 samples. 3. Matrix Spike (MS), Matrix Spike Duplicate (MSD):

a. Pipet 0.2 ml of 0.500N Alkalinity Standard Solution into a 50 ml graduated cylinder and fill to the 50 ml graduation with sample. This will give a concentration of equivalent to 100 mg/L total alkalinity, Complete for both the MS and MSD.

b. Analyze as you would a sample. 4. Laboratory Control Spike, Laboratory Control Spike Duplicate:

a. Follow the procedure for the MS and MSD, using a Type II water sample instead of a regular sample.

b. Analyze as you would a sample. 5. All glassware must be thoroughly washed and rinsed prior to use. 6. All data and results must be reported in the Alkalinity logbook.

Procedure:

1. Using a graduated cylinder, transfer 50 ml of sample into a 250 Erlenmeyer flask.

Phenolphthalein Alkalinity:

2. Add 1 Phenolphthalein Indicator powder pillow and swirl gently to mix. 3. Fill a 25 ml buret with 0.020 N Sulfuric Acid.


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4. Titrate the prepared sample, while gently swirling, until the color changes from pink to colorless. a. Record the number of milliliters used by subtracting the initial volume

from the final volume on the buret. 5. Use the following equation to calculate mg/L phenolphthalein alkalinity as

CaCO3: ml titrant x multiplier = mg/L phenolphthalein alkalinity as CaCO3

* multiplier: 20 (because of the 50 ml sample volume)

6. Report results in the Alkalinity logbook. Total Alkalinity:

7. Add 1 Bromcresol Green-methyl Red Indicator powder pillow or [3 drops of Bromocresol Green-Methyl Red aqueous mixed indicator (cat no 1215-16 Ricca Chem Company)] to the titrated samples from Step 6 above and swirl gently to mix.

8. Refill the 25 ml buret with the 0.020N Sulfuric Acid. 9. Titrate the sample until the appropriate end point is reached.

a. Recommended end points

Sample Trait End Point and Color Alkalinity approx. 30 mg/L 5.1 light green blue-gray Alkalinity approx. 150 mg/L 4.8 light violet gray Alkalinity approx. 500 mg/L 4.5 light pink Silicates/phosphates present

4.5 light pink

Industrial wastes 3.7 green (use of Bromphenol Blue Indicator)

10. Use the following equation to calculate mg/L total alkalinity as CaCO3: ml titrant x multiplier = mg/L total alkalinity as CaCO3

* multiplier: 20 (because of the 50 ml sample volume)

11. Report results in the Alkalinity logbook. Determination of Total Alkalinity constituents (hydroxide, carbonate, and bicarbonate):

1. From the results obtained from Steps 6 and 11, determine the alkalinity constituents using this table. a. Report results in the Alkalinity logbook.

-------------IF------------

------------------------------------------THEN--------------------------------------------------------


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Result from titration Hydroxide Alk. Carbonate Alk. Bicarbonate Alk. PhAlk = 0 0 0 Total Alk PhAlk = Total Alk Total Alk 0 0 (2 x PhAlk) < Total Alk

0 (2 x PhAlk) (Total Alk)- (2 x PhAlk)

(2 x PhAlk) = Total Alk

0 Total Alk 0

(2 x PhAlk) > Total Alk

(2 x PhAlk)-(Total Alk) 2 x (Total Alk- PhAlk) 0

PhAlk: Phenolphthalein Alkalinity Alk: Alkalinity References:

1. HACH Water Analysis Handbook, Method 8221, 1997. 2. Standard Methods for the Examination of Water and Wastewater, 18th Ed,

2320B, 1992.


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Standard Operating Procedure for Method SM 2540C

Title: Total Dissolved Solids (Residue, filterable) Summary: As adapted from Standard Methods for the Examination of Water and

Wastewater 2540C. This procedure is used for the determination of filterable residue in drinking, surface, and saline waters and from domestic and industrial wastes. A well-mixed sample is filtered through a glass fiber filter and the filtrate is evaporated and dried to a constant weight at 180oC. * Residue, filterable, is defined as those solids capable of passing through a glass fiber filter and dried to constant weight at 180°C..

Apparatus/Materials: Glass Fiber filters (Whatman 934-AH, 47mm diameter) Analytical Balance (AND HR-120) or equivalent Vacuum Flask, 500mL Vacuum pump (Welch Gem 1.0) Filter support (Gelman Sciences) Graduated cylinders, 100mL Drying oven (Capable of 180 oC) Desiccator, with desiccant Forceps or tongs Watchglasses Beakers Reagents: DI water Interferences:

1. Highly mineralized water containing significant concentrations of calcium, magnesium, chloride, and /or sulfate may be hygroscopic and will require prolonged drying, desiccation and rapid weighing.

2. Samples containing high concentrations of bicarbonate will require careful and possibly prolonged drying to insure that al bicarbonate is converted to carbonate.

3. Excessive residue in the evaporating dish will crust over and entrap water that will not be driven off during drying. Total residue should be limited to about 200mg.

Sample Handling:

1. Preservation of the sample is not practical; analysis should begin as soon as possible. Refrigeration or icing to 4oC to minimize microbiological decomposition of the solids is desirable.


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Quality Control:

1. Analyze distilled water (a Method Blank) for every batch. 2. Duplicates must be analyzed for every batch or every 20 samples. 3. All glassware must be thoroughly washed and rinsed prior to use 4. All data results must be reported in the TDS/TSS logbook

Procedure:

1. Preparation of the glass fiber filter a. Place a filter on the membrane filter apparatus with the

wrinkled surface up. b. Apply a vacuum and wash the filter with 3 successive 20mL

volumes of Type II or distilled water. c. Remove all traces of water by continuing to apply a vacuum

after the water has passed through. d. Discard washings

2. Preparation of the Evaporating dishes (beakers) a. Thoroughly wash and rinse beaker b. Heat the beaker to 180 oC for 1 hour c. Place the beaker in a desiccator with active desiccant and cool

to within 0.2oC of the temperature of the analytical balance. d. Weigh the beaker on the analytical balance and record weight

in TDS logbook. e. Store the beaker in a desiccator until use.

3. Sample analysis a. Assemble the filtration apparatus with a prepared glass filter

from step 1. b. Shake the sample vigorously and rapidly transfer 100mL to the

filtration apparatus using a graduated cylinder. (If filterable residue is low, a larger volume may be filtered.)

c. Filter sample through the glass fiber filter d. If during filtration of this volume the filtration rate drops rapidly

or if filtration time exceeds 10 minutes, the sample should be redone with less sample volume. Sample volume that yields between 2.5mg and 200mg is desirable.

e. Rinse the filter, graduated cylinder, and funnel well with three 10mL portions of distilled water and continue to apply vacuum to remove all traces of water.

f. Dry the sample until evaporated in an oven at 95oC. g. Dry the sample at 180oC for 1 hour. h. Place the beaker in a desiccator with active desiccant and cool

to within 0.2oC of the temperature of the analytical balance. i. Weigh the beaker on the analytical balance and record weight

in the TDS logbook j. Repeat steps f, g, and h until a constant weight is obtained

(weight loss of no more than 0.5mg between bakes). Record the weights of all bakes in the TDS logbook.

4. Calculate filterable residue as follows:


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a. mg/L of filterable ={(A-B)(1000)}/C A: Weight of beaker + residue (mg) B: Weight of beaker (mg) C: Volume of sample filtered (mL) b. Record result in the Dissolved Solids Logbook

References: 1. Standard Method 2540 C


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Standard Operating Procedure for Method 8081A Title: Analysis of organochlorine pesticides using methods EPA 3510, EPA

3550, and EPA 8081A. Scope: Methods EPA 3510, EPA 3550, and EPA 8081A are used to determine

the concentrations of organochlorine pesticides by gas chromatography using an electron capture detector: capillary technique.


traceability of possible causes of error in analytical results. Equipment & Conditions: There will be a Hewlett-Packard 5890 Series II Gas

Chromatograph equipped with two HP electron capture detectors and a Hewlett Packard-7673 series autosampler. Data manipulation and control is via Agilent Technologies-Chemstation (10.02). The chromatographic columns used will be a J&W DB-35MS (30m, 0.32 mm), a J&W DB-XLB (30m, 0.32 mm), and a 5 meter 0.32 mm guard column with an Agilent y-splitter. The carrier gas used will be helium at approximately 2.0 mL/minute and the make-up gas will be nitrogen at approximately 65 mL/minute. Approximate oven parameters will be : initial temperature of 110 ºC for 0.5 minutes and then ramp at a rate of 15 ºC per minute to 320 ºC and hold for 2 minutes for a total instrument runtime of 16.5 minutes.

Sample Preparation: Water samples are extracted by EPA Method 3510. Soil samples are extracted by EPA Method 3550. See the appropriate SOPs for more information. Method Start-up and Validation:

1. Calibration standards are analyzed at no fewer than five concentrations. From these standards, a calibration curve is established for each compound. The concentrations will include: Point #1 25 ug/L Point #2 50 ug/L Point #3 100 ug/L Point #4 200 ug/L Point #5 600 ug/L

2. An average Calibration Factor (CF) will be calculated for each analyte from the calibration curve. The percent Relative Standard Deviation (RSD) will be calculated for each analyte by comparing the average CF of each analyte to the standard deviation of the CFs for each calibration level and analyte. Initial calibration QC parameters will be defined as obtaining a %RSD less than or equal to 20% for each compound.

3. Seven replicates at a low concentration (at or near the expected MDL)

are extracted and analyzed for water and soil. For soil samples, the low concentration standard is spike into a beaker containing clean sand and extracted via method EPA 3550. For water samples, the


225

low concentration standard is spiked into a separatory funnel containing DI water and extracted via method EPA 3510. The method detection limit (MDL) is calculated from these low-level replicates.

4. The method can be utilized on a routine basis upon the determination

that the above data are acceptable. Any changes in laboratory sample preparation or chromatography that may affect the recovery or detection of the compounds requires that this entire section be repeated (i.e. column change).

Instrument Calibration:

1. A calibration blank is analyzed then calibration standards are analyzed at no fewer than five concentrations. From these standards, a calibration curve is established for each compound. The concentrations will include:

Point #1 25 ug/L Point #2 50 ug/L Point #3 100 ug/L Point #4 200 ug/L Point #5 600 ug/L 2. An average Calibration Factor (CF) will be calculated for each analyte

from the calibration curve. The percent Relative Standard Deviation (RSD) will be calculated for each analyte by comparing the average CF of each analyte to the standard deviation of the CFs for each calibration level and analyte. Initial calibration QC parameters will be defined as obtaining a %RSD less than or equal to 20% for each compound.

3. Continuing calibration verification will be done at the beginning and

completion of every analytical batch, every ten samples, or every 12 hours, whichever comes first. If fewer than ten samples are analyzed in a day, no fewer than two continuing calibration checks will be performed (at the start and end of the analytical batch). One day will be considered to be one 24-hour period.

4. Retention time windows for each compound will be calculated upon

each initial calibration. Retention time shifts of the external standards between the initial calibration and continuing calibration standards must be less than plus or minus 2.0%. Corrective action will be taken should these criteria not be met, which may include a new calibration curve being generated.

5. The CFs of the continuing calibration check standards must not

deviate by greater than 15% RPD from the average CFs obtained from the initial calibration. Corrective action will be taken if these criteria are not met, which may include a new calibration curve being generated.


226

6. Stock standards will be obtained from NSI Solutions or equivalent and may contain alpha-BHC, beta-BHC, gamma-BHC, delta-BHC, heptachlor, aldrin, heptachlor epoxide, endosulfan I, dieldrin, 4,4’-DDE, endrin, endosulfan II, 4,4’-DDE, endrin aldehyde, endosulfan sulfate, 4,4’-DDT, endrin ketone, alpha chlordane, gamma chlordane, toxaphene, chlordane, methoxychlor, and the surrogates 2,4,5,6-tetrachloro-m-xylene and decachlorobiphenyl.

7. Standard integrity will be monitored via response factors. Fresh

working standards will be prepared at a minimum of once every 6 months.

Analysis Procedure:

1. Once calibration standards have been run and are in control, a Method Blank must be run to demonstrate that the analytical system is interference free. Clean sand and distilled water will be extracted and used for the matrix blanks.

2. See SOP 3550 for sample preparation in soil and SOP 3510 for sample

preparation in water.

3. All sample extracts are allowed to warm to ambient temperature (20-30º C) before analysis.

4. 2.0 ml sample extracts are injected via HP-7673 autosampler and Agilent Chemstation.

5. Samples are analyzed with a gas chromatograph equipped with two

electron capture detectors.

6. If necessary, extracts will be diluted with hexane to be within the linear range of the instrument. All steps must be performed without delay until the diluted sample is in the gas-tight 2.0 mL vial in order to minimize loss of solvent or analyte.

Quality Control:

1. Analysis of a method blank to ensure that the analytical system is interference free.

2. Precision data review will involve 1 in every 20 samples being analyzed as a

laboratory duplicate. Acceptance criteria for precision is 25% RPD. Should the duplicate fail to meet this criteria, the sample will be analyzed a third time. If the data is still out of control, then a blank and a calibration check standard will be analyzed to verify that the instrument remains in calibration and is interference free.


227

3. The breakdown of DDT and endrin will be measured at no more than 12-hour intervals. If the breakdown is greater than 15% injector maintenance is necessary.

4. One in every 20 samples will be spiked with the analyte of interest and analyzed

as a Matrix Spike and Matrix Spike Duplicate (MS/MSD). Field duplicates will be analyzed and RPDs will be calculated at the client’s request. Upper and lower control limits will be established and maintained on an ongoing basis per EPA SW-846 guidelines.

5. Second column or mass spectrometer confirmations will be performed on all

samples that initially yield a detectable level of analyte.

6. Temperature logbooks will be kept and updated each working day for the standard and sample refrigerators.

7. Surrogate recoveries will be documented for each sample analyzed. Normally

decachlorobiphenyl percent recoveries will be reported. However, if the decachlorobiphenyl recovery is out of control, then the 2,4,5,6-tetrachloro-meta-xylene percent recovery will be reported. If both surrogate recoveries are out of control, then corrective action will be taken, which may involve re-extraction of the sample or flagging the data as “estimated concentration”. Upper and lower surrogate control limits will be established and maintained on an ongoing basis as per EPA SW-846 guidelines.

Calculations:

1. Sample concentrations will be calculated as follows: A. Water samples will be reported in ug/L. Formula:

(ng/ml analyte)* (ml of extract)*(dilution factor) (L of sample extracted)*(1000 ng/ug)


Formula: (ng/ml analyte)* (ml of extract)*(dilution factor)

(grams of soil extracted)/1000 C. The instrument will be calibrated in ug/L (ppb). 2. Method detection limit levels are calculated according to 40 CFR 136,

Appendix B (July 1, 1987). 3. Relative response factors (rrf):

Mass of analyte (ng)____ Area of Peak (relative units)




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6. Calibration Factor: Area of peak (relative units)

Mass of analyte (ng)

7. Percent Relative Standard Deviation (%RSD): Standard deviation of data points*100

Mean of data points

8. Retention time windows for each compound will be calculated upon each initial calibration. The windows will be plus or minus 2.0% of the retention time for each compound from the calibration curve.


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Standard Operating Procedure for Method 314.0

Title: Analysis of Perchlorate in drinking water and wastewater. Summary: This method is adapted from EPA Method 314.0 for Perchlorate. Purpose: The purpose of this procedure is to ensure quality control in the lab and

traceability of possible causes of error in analytical results. Apparatus & Materials: 838 Advanced Sample Processor (Metrohm)

793 IC Sample Prep Module (Metrohm) 709 IC Pump (Metrohm)

830 IC Interface (Metrohm) 819 IC Conductivity Detector (Metrohm) 820 IC Separation Center (Metrohm) 853 CO2 Suppressor Volumetric pipettes Metrohm ASUPP7-250 column and guard column Reagents: Perchlorate Standard – (1000 ppm Perchlorate). Two sources for

calibration curve/quantitation and QC purposes. 10 mM Sodium Carbonate + 35 % Acetonitrile eluent carrier solution. 18.2M Water Interferences: Interferences can be caused by substances with retention times that

overlap that of perchlorate. Large amounts of non-target ions can interfere with peak resolution of perchlorate. Dilutions or fortification can be used to solve this issue.

Other interferences are listed in the EPA Method 314.0. Column damage will occur with samples of low pH. Method Start-up and Validation:

1. Calibration standards are analyzed at no fewer than five concentrations. From these standards, a calibration curve is established. The concentrations will include:

Point #1 0.5 ug/L Perchlorate Point #2 5 ug/L Perchlorate Point #3 10 ug/L Perchlorate Point #4 20 ug/L Perchlorate Point #5 50 ug/L Perchlorate 2. A QCS will be run immediately after calibration. The QCS will not

deviate more than 10% from the calibration curve. 3. An IPC (instrument performance check) standard will be analyzed

before samples are analyzed. The conductance of the IPC must be within 10% of the MCT. The perchlorate recovery must fall between 80% and 120%. The PDA/H must be less than 25%. The perchlorate


230

retention time must not shift by more than 5%. The MCT must be repeated if the IPC fails.

4. An ICCS (initial calibration check standard) will be analyzed after the

IPC. The concentration of the ICCS will be the same as the lowest point on the calibration curve. The perchlorate recovery must fall between 75%-125% of the true value.

5. Continuing instrument calibration will be verified every ten samples

analyses and at the end of a sequence of samples. The concentration of the continuing calibration check standard (CCCS) will alternate between the middle and highest calibration standards.

6. The continuing calibration check standard must not deviate more than

15% from the calibration curve. If the calibration cannot be verified within the specified limits, the analysis must be discontinued and the cause determined. Subsequently, the calibration curve, QC and samples must be reanalyzed after the correction has been made.


8. Stock standards shall be prepared from neat materials. Standards shall be obtained from Fisher Scientific or equivalent.

9. A minimum of one method blank, LCS, LCSD, MS, and MSD for

every matrix and batch of twenty samples.

10. The relative percent difference (RPD) between spiked matrix duplicate

determinations is to be calculated as follows:

RPD = __ |D1-D2|__ *100 [(D1 + D2)/2] D1= First sample value D2= Second sample value

Sample Handling:

1. Collect samples in clean glass or plastic bottle. Store at 4oC (39oF). Analyze samples within 28 days.

2. Before testing the stored solution, warm to room temperature. Confirm that the

pH is between 6-7.

3. Measure the conductivity of each sample prior to analysis. If the MCT is exceeded, dilute the sample. Measure the conductivity of the diluted sample to verify that it is under the MCT. Record the conductivity in the logbook.


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Quality Control:

1. Analyze reagent water (Method Blank) for every batch of 20 samples.

2. Matrix Spike (MS), Matrix Spike Duplicates (MSD).

a. Spike 10.0mLs of sample with 0.5 mL of 100 ug/L perchlorate standard.

b. Analyze. Repeat for MSD. Analyze as you would for a sample.

3. Laboratory Control Spike (LCS), Laboratory Control Spike Duplicate (LCSD) a. Spike 10.0mLs of reagent water with 0.5 mL of 100 ug/L

perchlorate standard Analyze as you would for a sample.

4. All glassware must be thoroughly washed and rinsed prior to use. Calculations:

1. Sample concentrations will be calculated as follows: A. Samples will be reported in ug/L. Formula:

(ug analyte)* (dilution factor) (L of sample)

C. The instrument will be calibrated in ug/L.





References: EPA Method 314.0 Nov, 1999. IC Application Work AW US6-0130-022008, Metrohm-Peak, 2008.


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Perchlorate Reagents and Standards

1. Eluent a. Dissolve 2.112 g sodium carbonate in 500 mL reagent water in a 2 L

volumetric flask. Add 700 mL acetonitrile. Volumize to 2 L with reagent water.

2. Mixed Common Anion Solution: 25 mg/ml

a. 1.0 g sodium chloride, 0.93 g sodium sulfate, and 1.1 g sodium carbonate in a 25 mL volumetric flask to volume with reagent water.

3. Suppressor Reagent

a. Add 5.5 mL H2SO4 to 1L of reagent water.


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Standard Operating Procedure for Method 8082

Title: Analysis of polychlorinated biphenyls (PCBs) using methods EPA 3510, EPA 3550, and EPA 8082.

Scope: Methods EPA 3510, EPA 3550, and EPA 8082 are used to determine the

concentrations and identities of polychlorinated biphenyls (PCBs) by gas chromatography using an electron capture detector: capillary technique.



Chromatograph equipped with two HP electron capture detectors and a Hewlett Packard-7673 series autosampler. Data manipulation and control is via Agilent Technologies-Chemstation (10.02). The chromatographic columns used will be a J&W DB-35MS (30m, 0.32 mm), a J&W DB-XLB (30m, 0.32 mm), and a 5 meter 0.32 mm guard column with an Agilent y-splitter. The carrier gas used will be helium at approximately 2.0 mL/minute and the make-up gas will be nitrogen at approximately 65 mL/minute. Approximate oven parameters will be : initial temperature of 110 ºC for 0.5 minutes and then ramp at a rate of 15 ºC per minute to 320 ºC and hold for 2 minutes for a total instrument runtime of 16.5 minutes.



Point #1 0.5 ug/ml Point #2 1.0 ug/ml Point #3 2.5 ug/ml Point #4 10 ug/ml Point #5 20 ug/ml 5. PCBs will be quantitated by selecting 3 to 5 representative peaks in

each Aroclor standard and calculating the mean of the peaks to determine sample concentration. The instrument will be calibrated by assigning each representative peak the total concentration value of the Aroclor present in the calibration standard injected (i.e. 10 ug/ml). The peaks chosen to represent each Aroclor must be major peaks; they must be at least 25% of the height of the largest peak in that particular Aroclor standard. A preference will be placed on using late-eluting Aroclor peaks due to their generally greater environmental stability.


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6. An average Calibration Factor (CF) will be calculated for each Aroclor peak from the calibration curve. The percent Relative Standard Deviation (%RSD) will be calculated for each Aroclor peak by comparing the average CF of each peak to the standard deviation of the CFs for each calibration level and Aroclor peak. Initial calibration QC parameters will be defined as obtaining a %RSD less than or equal to 20% for each Aroclor peak.


are extracted and analyzed for water and soil for each Aroclor. For soil samples, the low concentration standard is spike into a beaker containing clean sand and extracted via method EPA 3550. For water samples, the low concentration standard is spiked into a separatory funnel containing DI water and extracted via method EPA 3510. The method detection limit (MDL) is calculated from these low-level replicates.





Point #1 0.5 ug/ml Point #2 1.0 ug/ml Point #3 2.5 ug/ml Point #4 10 ug/ml Point #5 20 ug/ml 2. PCBs will be quantitated by selecting 3 to 5 representative peaks in

each Aroclor standard and calculating the mean of the peaks to determine sample concentration. The instrument will be calibrated by assigning each representative peak the total concentration value of the Aroclor present in the calibration standard injected (i.e. 10 ug/ml). The peaks chosen to represent each Aroclor must be major peaks; they must be at least 25% of the height of the largest peak in that particular Aroclor standard. A preference will be placed on using late-eluting Aroclor peaks due to their generally greater environmental stability.

3. An average Calibration Factor (CF) will be calculated for each Aroclor

peak from the calibration curve. The percent Relative Standard Deviation (%RSD) will be calculated for each Aroclor peak by comparing the average CF of each peak to the standard deviation of the CFs for each calibration level and Aroclor peak. Initial calibration


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QC parameters will be defined as obtaining a %RSD less than or equal to 20% for each Aroclor peak.


completion of every analytical batch, every ten samples, or every 12 hours, whichever comes first. If fewer than ten samples are analyzed in a day, no fewer than two continuing calibration checks will be performed (at the start and end of the analytical batch). One day will be considered to be one 24-hour period.

5. Continuing Calibration procedure for PCBs will be as follows:

A. When working with samples from a site expected to contain unknown PCBs, then a continuing calibration mixture of Aroclor 1016 and Aroclor 1260 may be injected during the initial screening of samples. However, when specific Aroclors are identified in the samples, the extracts must be re-injected in a separate batch and bracketed by the appropriate Aroclor standard(s). Continuing Calibration Verification will be done a minimum of once every 12 hours.

B. When working with samples from a site expected to contain specific Aroclors, the appropriate Aroclor standards should be analyzed as Continuing Calibration Verification.

6. Retention time windows for each compound will be calculated upon

each initial calibration. Retention time shifts of the external standards between the initial calibration and continuing calibration standards must be less than plus or minus 2.0%. Corrective action will be taken should these criteria not be met, which may include a new calibration curve being generated.



8. Stock standards will be obtained from NSI Solutions or equivalent and

will include the following Aroclors: 1016, 1221, 1242, 1248, 1254, and 1260. The surrogates 2,4,5,6-tetrachloro-m-xylene and decachlorobiphenyl will also be obtained from NSI Solutions or equivalent.



Analysis Procedure:

1. Once calibration standards have been run and are in control, a matrix blank must be run to demonstrate that the analytical system is


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interference free. Clean sand and distilled water will be extracted and used for the matrix blanks.

2. See SOP 3550 for sample preparation in soil and SOP 3510 for

sample preparation in water.

3. All sample extracts are allowed to warm to ambient temperature (20-30º C) before analysis.

4. 2.0 ml sample extracts are injected via HP-7673 autosampler and

Agilent Chemstation.

5. Samples are analyzed with a gas chromatograph equipped with two electron capture detectors.

6. If necessary, extracts will be diluted with hexane to be within the linear

range of the instrument. All steps must be performed without delay until the diluted sample is in the gas-tight 2.0 mL vial in order to minimize loss of solvent or analyte.

Quality Control:

6. Analysis of a method blank to ensure that the analytical system is interference free.

7. Precision data review will involve 1 in every 20 samples being

analyzed as a laboratory duplicate. Acceptance criteria for precision is 25% RPD. Should the duplicate fail to meet this criteria, the sample will be analyzed a third time. If the data is still out of control, then a blank and a calibration check standard will be analyzed to verify that the instrument remains in calibration and is interference free.

8. One in every 20 samples will be spiked with either Aroclor 1260 or

some other Aroclor (if appropriate to the site) and analyzed as a Matrix Spike and Matrix Spike Duplicate (MS/MSD). Field duplicates will be analyzed and RPDs will be calculated at the client’s request. Upper and lower control limits will be established and maintained on an ongoing basis per EPA SW-846 guidelines.

9. Second column or mass spectrometer confirmations will be performed

on all samples that initially yield a detectable level of analyte.

10. Temperature logbooks will be kept and updated each working day for the standard and sample refrigerators.

11. Surrogate recoveries will be documented for each sample analyzed.

Normally decachlorobiphenyl percent recoveries will be reported. However, if the decachlorobiphenyl recovery is out of control, then the 2,4,5,6-tetrachloro-meta-xylene percent recovery will be reported. If both surrogate recoveries are out of control, then corrective action will


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be taken, which may involve re-extraction of the sample or flagging the data as “estimated concentration”. Upper and lower surrogate control limits will be established and maintained on an ongoing basis as per EPA SW-846 guidelines.

Calculations:


(ug/ml analyte)* (ml of extract)*(dilution factor) (L of sample extracted)


Formula: (ug/ml analyte)* (ml of extract)*(dilution factor)

(grams of soil extracted) C. The instrument will be calibrated in ug/ml (ppm). 2. Method detection limit levels are calculated according to 40 CFR 136,










Mean of data points



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Standard Operating Procedure for Method 8141B

Title: Analysis of organophosphorus pesticides using method EPA 8141B. Scope: EPA Method 8141B is used to determine the concentration of

organophosphorus pesticides by gas chromatography using a flame photometric detector and a nitrogen-phosphorus detector: capillary technique.


traceability of possible causes of error in analytical results. Equipment & Conditions: There will be an Agilent 6890N Gas Chromatograph

equipped with a flame photometric detector, a nitrogen-phosphorus detector, and a 7683 series autosampler. Data manipulation and control is via Agilent Technologies - Chemstation (10.02). The chromatographic columns used will be a J&W DB-35MS (30m, 0.25 mm), a J&W DB-5MS (30m, 0.25mm), and a 5 meter 0.32 mm guard column with an Agilent y-splitter. The carrier gas used will be helium at approximately 1.3 mL/min and the make-up gas will be helium. The carrier plus make-up gas will be kept constant at 60 mL/min for the FPD and 4.0 mL/min for the NPD. Approximate oven parameters will be: initial temperature of 50 ºC for 1 minute and then ramp at a rate of 20 ºC per minute to 250 ºC and hold for 15 minutes.






are extracted and analyzed for water and soil. For soil samples, the low concentration standard is spiked into a beaker containing clean


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sand and extracted via method EPA 3540. For water samples, the low concentration standard is spiked into a separatory funnel containing DI water and extracted via method EPA 3510. The method detection limit (MDL) is calculated from these low-level replicates.








completion of every analytical batch, every ten samples, or every twelve hours, whichever comes first. If fewer than ten samples are analyzed in a day, no fewer than two continuing calibration checks will be performed (at the start and end of the analytical batch). One day will be considered to be one 24-hour period.



5. The retention time windows for each compound will be calculated

upon each initial calibration. Retention time shifts of the external standards between the initial calibration and continuing calibration standards must be less than plus or minus 2.0%. Corrective action will be taken should these criteria not be met, which may include a new calibration curve being generated.


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6. Stock standards will be obtained from NSI Solutions or equivalent, and will include Azinphos methyl, Bolstar, Chlorpyrifos, Coumaphos, Demeton (total), Diazinon, Dichlorvos, Disulfoton, Ethoprop, Fensulfothion, Fenthion, Merphos, Methylparathion, Mevinphos, Naled, Phorate, Ronnel, Stirofos, Tokuthion, Trichlornate, Dimethoate, EPN, Malathion, Monocrotophos, Parathion, Sulfotepp, and TEPP.



Analysis Procedure:

1. Once calibration standards have been run and are in control, a Method Blank must be run to demonstrate that the analytical system is interference free. Clean sand and distilled water will be used for the matrix blanks.

2. All sample extracts are allowed to warm to ambient temperature (20-30º C)

before analysis.

3. 1 ml sample extracts are injected via HP-7683 autosampler and Agilent Chemstation.

4. Samples are analyzed with a gas chromatograph equipped with a flame

photometric detector and a nitrogen phosphorus detector.

5. If necessary, extracts will be diluted with hexane to be within the linear range of the instrument.

Quality Control:

1. Analysis of the method blank to ensure that the analytical system is interference free.

2. Precision data review will involve 1 in every 20 samples being analyzed as a

laboratory duplicate. Acceptance criteria for precision is 20% RPD. Should the duplicate fail to meet this criteria, the sample will be analyzed a third time. If the data is still out of control, then a blank and a calibration check standard will be analyzed to verify that the instrument remains in calibration and is interference free.

3. One in every 20 samples will be spiked with the analyte of interest and analyzed

as a Matrix Spike and Matrix Spike Duplicate (MS/MSD). Field duplicates will be analyzed and RPDs will be calculated at the client’s request. Upper and lower control limits will be established and maintained on an ongoing basis per EPA SW-846 guidelines.


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4. Second column or mass spectrometer confirmations will be performed on all samples that initially yield a detectable level of analyte.

5. Temperature logbooks will be kept and updated each working day for the

standard and sample refrigerators.

6. Surrogate recoveries will be documented for each sample analyzed. The surrogates will be Tributylphosphate and Triphenylphosphate. Triphenylphosphate percent recoveries will be reported. However, if the Triphenylphosphate recovery is out of control, then the Tributylphosphate percent recovery will be reported. If both surrogate recoveries are out of control, then corrective action will be taken, which may involve re-extraction of the sample or flagging the data as “estimated concentration”. Upper and lower surrogate control limits will be established and maintained on an ongoing basis as per EPA SW-846 guidelines.

Calculations: 1. Sample concentrations will be calculated as follows:

A. Water samples will be reported in ug/L. Formula:


B. Soil samples will be reported in mg/kg. Formula:

(ng/ml analyte)* (ml of extract)*(dilution factor) (g of soil extracted)/1000

C. The instrument will be calibrated in ng/ml (ppb).

2. Method detection limit levels are calculated according to 40 CFR 136, Appendix B (July 1, 1987).

3. Relative response factors (rrf):






6. Calibration Factor:


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Area of peak (relative units) Mass of analyte (ng)

7. Percent Relative Standard Deviation (%RSD):

Standard deviation of data points*100 Mean of data points



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Standard Operating Procedure for Method 8151A

Title: Analysis of chlorinated herbicides using method EPA 8151A. Scope: EPA Method 8151A is used to determine the concentration of chlorinated

herbicides by gas chromatography using an electron capture detector: capillary technique.



Chromatograph equipped with two HP electron capture detectors and a Hewlett-Packard 7673 series autosampler. Data manipulation and control is via Agilent Technologies- Chemstation (10.02). The chromatographic columns used will be a J&W DB-35MS (30m, 0.32 mm), a J&W DB-XLB (30m, 0.32 mm), and a 5 meter 0.32 mm guard column with an Agilent y-splitter. The carrier gas used will be helium at approximately 2.0 mL/minute and the make-up gas will be nitrogen at approximately 65 mL/minute. Approximate oven parameters will be : initial temperature of 50 ºC for 0.5 minutes and then ramp at a rate of 25 ºC per minute to 100 ºC and then ramp at 12 ºC per minute to 320 ºC and hold for 3 minutes.

Sample Preparation: Water and soil samples are extracted by EPA Method 8151A. See the 8151A Extraction SOPs for more information. Method Start-up and Validation:





are extracted and analyzed for water and soil. For soil samples, the


245

low concentration standard is spike into a beaker containing clean sand and extracted via method EPA 8151A. For water samples, the low concentration standard is spiked into a separatory funnel containing DI water and extracted via method EPA 8151 A. The method detection limit (MDL) is calculated from these low-level replicates.








completion of every analytical batch, every ten samples, or every twelve hours, whichever comes first. If fewer than ten samples are analyzed in a day, no fewer than two continuing calibration checks will be performed (at the start and end of the analytical batch). One day will be considered to be one 24-hour period.



5. The retention time windows for each compound will be calculated

upon each initial calibration. Retention time shifts of the external standards between the initial calibration and continuing calibration standards must be less than plus or minus 2.0%. Corrective action will be taken should these criteria not be met, which may include a new calibration curve being generated.


246

6. Stock standards will be obtained from NSI Solutions or equivalent, and

will include 2,4-D, 2,4-DB, Dalapon, Dicamba, Dichlorprop, Dinoseb, MCPA, MCPP, Silvex, 2,4,5-T, Acifluorofen, Bentazon, Chloramben, DCPA diacid, 3,5-Dichlorobenzoic acid, 4-Nitrophenol, Pentachlorophenol, and Picloram.



Analysis Procedure:

1. Once calibration standards have been run and are in control, a Method Blank must be run to demonstrate that the analytical system is interference free. Clean sand and distilled water will be used for the matrix blanks.

2. All sample extracts are allowed to warm to ambient temperature (20-

30º C) before analysis. 3. 10 ml sample extracts are injected via HP-7673 autosampler and

Agilent Chemstation.

4. Samples are analyzed with a gas chromatograph equipped with two electron capture detectors.

5. If necessary, extracts will be diluted with hexane to be within the linear

range of the instrument. Quality Control:

1. Analysis of the method blank to ensure that the analytical system is interference free.

2. Precision data review will involve 1 in every 20 samples being

analyzed as a laboratory duplicate. Acceptance criteria for precision is 20% RPD. Should the duplicate fail to meet this criteria, the sample will be analyzed a third time. If the data is still out of control, then a blank and a calibration check standard will be analyzed to verify that the instrument remains in calibration and is interference free.

3. One in every 20 samples will be spiked with the analyte of interest

and analyzed as a Matrix Spike and Matrix Spike Duplicate (MS/MSD). Field duplicates will be analyzed and RPDs will be calculated at the client’s request. Upper and lower control limits will be established and maintained on an ongoing basis per EPA SW-846 guidelines.

4. Second column or mass spectrometer confirmations will be performed

on all samples that initially yield a detectable level of analyte.


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5. Temperature logbooks will be kept and updated each working day for

the standard and sample refrigerators.

6. Surrogate recoveries will be documented for each sample analyzed. The surrogate will be 2,4-dichlorophenylacetic acid (DCAA). If surrogate recovery is out of control, then corrective action will be taken, which may involve re-extraction of the sample or flagging the data as “estimated concentration”. Upper and lower surrogate control limits will be established and maintained on an ongoing basis as per EPA SW-846 guidelines.

Calculations:




Formula:

(ng/ml analyte)* (ml of extract)*(dilution factor) (g of soil extracted)/1000

C. The instrument will be calibrated in ng/ml (ppb). 2. Method detection limit levels are calculated according to 40 CFR 136,










Mean of data points


248


Standard Operating Procedure for Hardness Title: Hardness, Total, for water, wastewater, and seawater


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Summary: This method has been adapted from Standard Methods for the Examination of Water and Wastewater and is equivalent to 2340B (EDTA Titrimetric Method)

Hardness in water is caused by dissolved minerals, primarily divalent

cations including calcium, iron, strontium, magnesium, and manganese. Calcium and magnesium ions usually are the only ions present in significant concentrations; therefore, hardness generally is considered to be a measure of the calcium and magnesium content of water.

The water sample is buffered (using an organic amine and one of its

salts) to a pH of 10.1. An organic dye, calmagite, is added as an indicator for the test. The dye reacts with calcium and magnesium ions to give a red-colored complex. As a titrant, EDTA (ethylenediaminetetraacetic acid), is added. The EDTA will react with all the free calcium and magnesium ions present in the sample. At the end point of the titration, when free magnesium ions are no longer available, EDTA will remove magnesium ions from the indicator, causing a color change from red to blue. Normality and volume of EDTA titrant is then related to the hardness content to determine a final test result, usually expressed in mg/L as calcium carbonate.

Apparatus/Materials: Buret, Class A, 25 ml Erlenmeyer, 250 ml Graduated cylinder, 50 ml Clamp and Stand Reagents: Type II water Man Ver 2 Hardness Indicator powder pillows (851-99) Buffer Solution, Hardness 1 (424-32) TitraVer Hardness Titrant, 0.020N (205-53) Calcium Chloride Standard Solution, 1000 mg/L as CaCO3 (121-53) Interferences:

1. Iron does not interfere up to 15 mg/L. Above this level it causes a red-orange to green end point which is sharp and unusable up to 30 mg/L iron.

2. Manganese titrates directly up to 20 mg/L but masks the end point above this level.

3. Copper and aluminum interfere at levels of 0.10 and 0.20 mg/L, respectively.

4. Cobalt and nickel interfere at all levels and must be absent or masked.

5. Barium, strontium, and zinc titrate directly. 6. Orthophosphate causes a slow end point and polyphosphate must be

absent for accurate results to be obtained. 7. Acidity and alkalinity at 10,000 mg/L (as CaCO3) do not interfere. 8. Saturated sodium chloride solutions do not give a distinct end point

but the titration can be run directly on sea water.


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Sample Handling:

1. Collect samples in plastic or glass bottles that have been washed with a detergent and rinsed with tap water, 1:1 nitric acid, and Type II water.

2. When prompt analysis is not possible, preserve the sample to a pH of less than 2 and store at 4o C.

3. Preserved samples can be stored up to seven days. 4. Preserved samples must be warmed to room temperature and

adjusted to a pH of roughly 7 using sodium hydroxide (5.0 N). Be sure to correct for the addition of the preservative.

Quality Control: 1. Analyze reagent water (a Method Blank) for every batch:

a. Add 50 ml of Type II water to an Erlenmeyer and analyze as you would a sample.

2. Duplicates must be analyzed for every batch or every 20 samples. 3. Matrix spike (MS), Matrix Spike Duplicate (MSD):

a. Pipet 2.50 ml of 1,000 mg/L Calcium Chloride Standard Solution (as CaCO3) to 50 ml graduation with sample. This will give a concentration of 50 mg/L Hardness as CaCO3 (plus the sample concentration). Complete for both the MS and MSD.

b. Analyze as you would a sample. 4. Laboratory Control Spike, Laboratory Control Spike Duplicate:

a. Follow the procedure for MS and MSD, using type II water sample instead of a regular sample

b. Analyze as you would a sample. 5. All glassware must be thoroughly washed and rinsed prior to use. 6. All data and results must be reported in the Total Hardness logbook.

Procedure:

1. Using a graduated cylinder, transfer 50 ml of sample into a 250 ml Erlenmeyer flask.

2. Add 1ml of Hardness 1 Buffer Solution using the calibrated dropper and swirl gently to mix.

3. Add one Man Ver 2 Hardness Indicator powder pillow and swirl gently to mix

4. Fill a 25 ml buret with 0.020N TitraVer Hardness Titrant. 5. Titrate the prepared sample, while gently swirling, until the color

changes from red to purple blue. a. Record the number of milliliters used by subtracting the initial

volume from the final volume on buret. 6. Use the following equation to calculate mg/L Total Hardness as

CaCO3:

ml titrant x multiplier = mg Total Hardness as CaCO3 * multiplier: 20 (20 because 50 ml is 1/20th of 1L)

7. Report in the Total Hardness logbook.

References: 1. HACH Water Analysis Handbook, Method 8226, 1997.


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252

Standard Operating Procedure for Method 8260B 1.0 SCOPE AND APPLICATION

1.1 Method 8260b is used to determine volatile organic compounds in a variety of matrices.

1.2 8260b can be used to quantify most volatile organic compounds that have

boiling points below 200oC and that are insoluble or slightly soluble in water. Volatile water-soluble compounds can be included in these methods; however, for more soluble compounds, the quantitation limits are considerably higher because of poor purging efficiency.

1.3 The practical quantitation limits (PQLS) for 8260b vary from matrix to

matrix but are initially 0.005 for mg/kg soils and solid wastes and 0.5 ug/l for waters. PQLs will be proportionately higher for samples requiring dilution or reduced sample size to avoid saturation of the detector.

1.4 This method is based on a purge-and –trap, gas-chromatographic/mass

spectrometric (GC/MS) procedure.

2.0 SUMMARY OF METHOD

2.1 The volatile compounds are introduced to the gas-chromatograph by the purge-and –trap method or (in limited applications) by direct injection. The components are separated via the gas-chromatograph and detected using a mass spectrometer, which is used to provide both qualitative and quantitative data. The chromatographic conditions, as well as typical mass spectrometer operating parameters, will be given later.

2.2 If the above sample introduction techniques are not applicable, a portion

of the sample is extracted with pesticide-grade methanol to dissolve the organic constituents. A portion of the solution is then diluted in water and analyzed by the normal water method.

2.3 The purge-and–trap process: Helium is bubbled through the solution at

room temperature, and the volatile components are quantitatively transferred from the aqueous phase to the vapor phase. The vapor is passed through a sorbet column, where the organic compounds are trapped. After purging is completed, the sorbets trap is heated and back-flushed with helium to desorb the components onto the gas chromatographic column. The gas chromatographic column is heated to elute the compounds, which are detected with the mass spectrometer.


253

3.0 INTERFERENCES

3.1 Interferences purged or extracted from the samples will vary considerably from source to source, depending on the particular sample or extract being analyzed. However, a method blank is analyzed to ensure that the analytical system is free from interferences under analysis conditions.

3.2 Samples may be contaminated by diffusion of volatile organics (especially

methylene choride and fluorocarbons) through the septum seal during shipment and storage. A field blank is prepared from reagent water free of contaminants and is carried through the sampling and handling to access contamination.

3.3 Cross-contamination may occur when high-level and low-level samples

are analyzed sequentially. Therefore, when highly contaminated samples are analyzed, a system blank may need to be analyzed immediately following to access and prevent cross-contamination. The purge-and–trap system may require several blanks to clean the system of contaminants.

4.0 APPARATUS AND MATERIALS

4.1 Microsyringes: 10ul, 25ul, 100ul, 250ul, 500ul, and 1000ul are available and should only be used for VOA standard preparation and dilution.

4.2 Balance: An analytical balance (accurate to 0.10 gm) for sample

weighing is used. 4.3 VOA vials are used as sample containers and dilution vials. 4.4 Volumetric flasks, spatulas, disposable pipettes, and bulbs are available

for sample preparation. 4.5 Purge –and – trap: A Tekmar lcs3000 coupled with a Varian Archon auto-

sampler.

4.5.1 Needle sparging : The purging apparatus is a VOA vial. The sparging needle must be no more than 5mm from the bottom of the VOA vial. The helium sparging gas must pass through the water containing the solid waste as finely divided bubbles, having diameters no greater than 3mm at inception.

4.5.2 Frit sparging : The purging apparatus is a fritted sparge vessel.

The helium sparging gas must pass through the sample as finely divided bubbles, having diameters no greater than 3mm at inception.

4.5.3 A Supelco Vocarb 3000 trap is used.

4.6 Gas chromatograph/mass spectrometer system:


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4.6.1 A Hewlett Packard, Model 6890, gas chromatograph is used. 4.6.2 Agilent DB-VRX 60M x 0.25RTx column is used.

4.6.3 A Hewlett Packard, model 5973 mass spectrometer is used.

4.6.4 A Hewlett Packard Enviroquant Software data system is used.

The GC/MS and data system are capable of meeting all EPA criteria for GC/MS volatile analytical work.

5.0 REAGENTS

5.1 Stock solutions are purchased as 2000 ppm or some other concentration in methanol. Traceable certified standard mixes or neat from various ISO 9001 approved vendors will only be used.

5.2 The surrogate standards used are dibromofluoromethane, toluene(d8)

and 4- bromofluorobenzene, which are purchased as 2500 ppm solutions from NSI or some other Iso-9001-approved vendor.

5.3 The internal standards used are pentafluorobenzene, 1,4-

difluorobenzene, chlorobenzene (d5), and 1,4-dichlorobenzene(d4) which are purchased as 2500 ppm solutions from NSI or some other Iso-9001-approved vendor.

5.4 The Tuning standard used is a 50 ppm internal standard/surrogate

solution; 1 ul injection, equaling 50 nanograms.

5.5 The calibration standards are prepared as follow: the appropriate stock standard is diluted to 42ppm for waters or 10ppm for soils.

5.6 The matrix spiking standard used is the 42ppm spiking standard at the

mid-point of the curve.

5.7 Great care must be taken to maintain all standard solution integrity. Therefore, all standards are kept below –10 C in the standards freezer. They are removed only for initial and daily calibration standard preparation and are returned to the freezer as quickly as possible. Close observation must be kept on the response factors of the gaseous compounds. These compounds are prone to degrade first and must be replaced more often than the other analytes, typically every three to four weeks.

5.8 Reagent grade water is defined as water that is free of interferences at

the method detection limit for all compounds of interest. The reagent grade water is tested every morning as a method blank. If interfering compounds are found, the cause of the contamination must be found and corrected before analysis continues.


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6.0 INITIAL CALIBRATION FOR PURGE-AND-TRAP ANALYSIS

6.1 Approximate GC/MS operating conditions Electron energy: 70 volts Mass range: 35-300 amu A/D samples: 8 Initial column temperature 40oC Initial column hold time: 10 min. Column temperature progression: 12 C/min. Final column temperature: 190oC Final column hold time: 4 min. Injector temperature: 200oC Interface temperature: 220oC Source temperature: 200oC Carrier gas: UHP Helium

6.2 First, the GC/MS system must meet the ion-abundance criteria daily for a 50ng injection of bromofluorobenzene(BFB). Analysis cannot begin without these criteria having been met. 1.0 ul of 50ppm or 50 nanograms is analyzed.

6.3 Prepare a method blank using a 40-ml VOA vial, completely filled with

organic free water.

6.4 The initial calibration standard is prepared by adding 42ppm standard to a VOA vial filled with organic free water to each of 5 VOA vials and spiking them with the appropriate amount of calibration standard. Analyzing 0.5, 1.0, 5.0, 20.0, 50.0 and 100ul injections of the 42ug/ml calibration standard create these calibration runs. The concentrations are 0.5, 1.0, 5.0, 20.0, 50.0 and 100 ug/l. The internal/surrogate standard solution is added to every blank, spike, standard, and sample to be analyzed with this method. The Archon Auto-sampler will add the appropriate mass of IS/SS to each sample.

6.5 The average response factor (RF) is calculated by the data system for

each compound. The system performance check compounds (SPCCs) are checked for a minimum average response factor. The minimum average “RF” is .30 for chlorobenzene and 1,1,2,2-tetrachloroethane and 0.10 for bromoform, 1,1-dichloroethane and chloromethane. These compounds are checked to verify system cleanliness and performance. Active sites in transfer lines or injector port will cause compound instability and degradation, yielding low average RFs.

6.6 Using the RFs from the initial calibration, the % RSD for a compound

should be equal to or less than 15% for each compound. This criterion must be met before the initial calibration can be used.

7.0 DAILY GC/MS CALIBRATION

7.1 Prior to analyzing a sample, 50ng of BFB must be injected, and the mass spectra must meet the EPA requirements for ion abundances.


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7.2 The initial calibration curve for each compound of interest must be

checked and verified. This is done by analyzing a calibration standard that is at the midrange concentration of the working range (20ug/l).This continuing calibration check must be within 20% of the initial calibration curve. The SPCC and CCV requirements must be met.

7.3 System performances check compounds: All SPCCS must meet the

criteria set forth above. Some possible problems are: standard mixture degradation, injector port liner contamination, contamination at the front end of the analytical column, and active sites in the column or the chromatographic system.

7.4 Continuous calibration verification: After the system performance check is

met, CCVs are used to check the validity of the initial calibration. The percent difference in the response factors is calculated using the average RF from the initial curve and the RF from the continuing calibration run. If the percent difference for all CCVs is less than 20, the initial calibration is assumed to be valid. If the criteria is not met, corrective action must be taken, and a new 5-point calibration must be generated.

7.5 The internal standard responses and retention times in the continuing

calibration standard must be checked immediately after data acquisition. If the retention time of any internal standard changes by more than 30 seconds from the previous continuing calibration check, the chromatographic system must be checked for problems and corrections must be made, as necessary. If the total area for the quantitation ion of any internal standard varies by more than + 50% from the last daily calibration standard run, the mass spectrometer must be inspected for problems, and corrections must be made as appropriate.

8.0 GC/MS ANALYSIS

8.1 Water analysis (8260B)

8.1.1 Visually inspecting a sample helps determine the necessity of dilution before initial analysis. Use good judgment-if a sample appears highly contaminated, it is better to start with a high dilution and gradually bring the dilution down, than to overload the purge-and trap device and necessitate running reagent water blanks to clean the system.

8.1.2 All samples must be allowed to warm to room temperature before

analysis

8.1.3 Use all necessary methods to run the mass spectrometer under appropriate conditions.

8.1.4 BFB tuning ion abundance criteria must be met each day.

8.1.5 The Helium purge flow must be maintained at 40ml/min.


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8.1.6 Analyzing a sample: prescreen the sample by opening the vial. If

the sample is expected to have no or low concentration of analytes, the VOA vial is placed on the autosampler without opening it.

8.1.7 Measure and document sample pH (after analysis) in designated

logbook if sample is analyzed after seven days from date of collection.

8.1.8 The following procedure is appropriate for sample dilution (all

steps must be performed without delay until the sample is in a VOA vial:

8.1.8.1 If, upon initial analysis of a sample or dilution of a sample,

the concentration of an analyte is greater than the initial calibration range, the sample must be reanalyzed at a higher dilution. Fill a syringe with the proper aliquot of the sample and inject it into reagent water, making a combined volume of a full vial. Set up the data system to document the dilution. Initiate the acquisition, and start the run.

8.1.9 Matrix spike analysis: Select a sample evidently free of

contaminants and add 20ul of spiking standard to the sample. Analyze as a normal sample.

8.2 Sediment/soil and waste samples

8.2.1 For slightly contaminated or clean samples, weigh out 5.0 grams of sample directly into a VOA vial; add 10ml of reagent water.

8.2.2 Analyze the sample according to the methods described above.

8.2.3 If an analyte concentration is above the initial calibration range,

the sample must be diluted.

8.2.3.1 A soil/solid waste sample may be diluted by decreasing the mass of soil analyzed, ie. load 0.5 grams instead of 5.0 grams. The decreased mass is injected in 10ml of reagent water and analyzed the same way.

8.2.3.2 For highly contaminated samples soil/solid waste sample may be diluted in methanol (7.0g of sample in a 3-dram vial filled with methanol). An appropriate volume of methanol is injected in 10ml of reagent water and analyzed the same way. The surrogate and/or matrix spiking solution must be added to the sample before the methanol is added.


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8.3 Data interpretation

8.3.1 Qualitative analysis: An analyte of interest is identified by comparing the analytes expected retention time and reference mass spectra.

8.3.1.1 The sample relative retention time (RRT) must be within

+0.08 RRT units of the RRT of the standard component. For reference, the daily calibration run RRT is used.

8.3.1.2 All ions present in the standard mass spectra at a relative

intensity greater than 10% of the base peak for that component must be present in the sample. Also, the relative intensities of ions present in the standard mass spectra must agree to within +20% of the sample mass spectra.

8.3.1.3 Perform library searches to tentatively identify sample

components not associated with the calibration standards.

8.3.2 Quantitative analysis

8.3.2.1 When a compound has been identified, use the internal standard technique for quantification. Use the internal standard nearest the retention time of the constituent.

8.3.2.2 Using the following, calculate the concentration of each

analyte by the data system:

Concentration (ug/L)= (ax)(is) x dilution factor (ais)(rf)(vo)

Where: AX = Area of characteristic ion for compound IS =Amount of internal standard injected AIS =Area of characteristic ion for the internal standard RF =Response factor for compound VO =Volume of water purged 9.0 Quality control

9.1 Before analysis begins, reagent water blank is run to verify that interferences

from the analytical system, glassware, and reagents are below detection limits.

Each time a set of samples is run, or there is a change in reagents, a reagent

water blank must be run to evaluate contamination problems.

9.2 Each day that analyses are performed, the daily midpoint calibration standard is run to evaluate the initial


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calibration curve and to ensure that the GC/MS system is working properly. The analyst’s judgment and experience are crucial in answering the following:

Does the chromatography look correct? Is the response obtained comparable to past responses? Have the constituent retention times shifted substantially? Is there any background contamination? If changes are made to the analytical system, the system must be recalibrated. 9.3 Required instrument QC

9.3.1 In every 12 hours of operation, the mass spectrometer must meet the ion abundance criteria for BFB as set forth by the EPA.

9.3.2 The GC/MS system must be initially calibrated.

9.3.3 The reagent water blank must be run every

workday to verify that no contamination is present.

9.3.4 The initial calibration must be verified every work day by running a mid-point calibration standard.

9.3.5 A matrix spike and matrix spike duplicate must be

run on the matrix being analyzed for each analytical batch (up to 20 samples per batch sample duplication).

9.4 The analyst must consistently analyze a reagent blank, a matrix

spike, and a matrix spike duplicate for each analytical batch.

9.4.1 The QC acceptance criteria for spike/spike duplicators are 80-120% and RSD=20%

9.5 Use the following procedure to determine acceptable accuracy

and precision limits for surrogate standards:

9.5.1 Calculate the percent recovery for each surrogate in each sample being analyzed.

9.5.2 Once a minimum of 30 samples of the same matrix

type is analyzed, the average percent recovery is calculated, and the standard deviation of the percent recovery for each of the surrogates is calculated.


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9.5.3 The upper and lower control limits for method

performance for each surrogate standard for a given matrix is calculated as follow:

Upper Control Limit (UCL) = AVE + 3s Lower Control Limit (LCL) = AVE + 3s

9.5.4 For aqueous and soil matrices, compare the UCL and LCL (as Calculated above) with the control limits listed below, which should have a wider range and can be found in EPA method 8260b:

SURROGATE COMOUND LOW/MEDIUM WATER LOW MEDIUM SOIL

4-Bromofluorobenzene 80-120% 80-120%

1,2-Dichloroethane 80-120% 80-120%

Toluene (d8) 80-120% 80-120%

10.0 Each analyst is expected to keep the following instrument logs up to date: The analysis run logs for each method. The QC log book.

The section of the GC/MS maintenance log pertaining to the instrument being used. The GC/MS standards log book. 10.1.1 The analysis run logbook contains all the samples, spikes, blanks,

and standards, run on the particular instrument involved. 10.1.2 The QC logbook contains the initial calibration and the continuing

calibrations associated with the instrument involved. It also contains pertinent control charts. There is also documentation in the QC log book containing the BFB standard area log, the internal standards log, and the surrogate standards log. These logs are updated as analyses are completed.

10.1.3 The GC/MS maintenance log contains down time and services

rendered by outside service personnel (e.g., for hardware problems.)

10.1.4 The GC/MS standards logbook contains the source; date made,

and related information concerning the standards involved in ongoing analyses. This log book is maintained to facilitate locating problems with standard suppliers and standard mixes (e.g.,to recall bad batch standards).


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Standard Operating Procedure for Method 625/8270 EPA METHOD: 625/8270 ANALYTE: GC/MS for Semi-Volatiles

1.0 SCOPE AND APPLICATION 1.1 These methods are used to determine the concentration of semi-volatile

organic compounds in extracts prepared from low level waters, and soil/solid matrices.

1.2 These methods can be used to quantify most neutral, acidic, and basic

organic compounds that are soluble in methylene chloride and capable of being eluted without derivitization as sharp peaks from a gas chromatographic fused-silica capillary column coated with a slightly polar silicone. Such compounds include polynuclear aromatic hydrocarbons, chlorinated hydrocarbons, pesticides, phthalate esters, organophosphate esters, nitrosamines, haloethers, aldehydes, ethers, ketones, anilines, pyridines, quinolines, aromatic nitro compounds, and phenols.

1.3 This is a gas chromatograph/mass spectrometry (GC/MS) method

applicable to the determination of the compounds listed in Tables 1 and 2. The parameters listed in Tables 1 and 2 may be qualitatively and quantitatively determined using this method.

1.4 The following compounds may require special treatment when being

determined by one of these methods. Benzidine can be subject to oxidative losses during solvent concentration. Hexachlorocyclopentadiene is subject to thermal decomposition in the injector port, chemical reaction in an acetone solution, and photochemical degradation. N-Nitrosodimethylamine is difficult to separate from the solvent under the chromatographic conditions described. N-Nitrosodiphenylamine decomposes in the gas chromatographic inlet and cannot be separated from diphenylamine. Pentachlorophenol, 2,4-dinitrophenol, 4-nitrophenol, 4,6-dinitro-2-methylphenol, 4-chloro-3-methylphenol, benzoic acid, 2-nitroaniline, 3-nitroaniline, 4-chloroaniline, and benzyl alcohol, are all subject to erratic chromatographic behavior, especially if the GC system is contaminated with high boiling material.

1.5 The Practical Quantitation limit (PQL) of these methods varies widely

depending upon the matrix involved. The base PQL's are 2.0 ug/L for ground water samples, and 0.10 mg/kg for soil/sediment samples. The PQL's will be proportionately higher if sample contamination is present requiring the analyst to make dilutions.

1.6 These methods are restricted to use by or under the supervision of

analysts experienced in the use of gas chromatography/mass spectrometers, and skilled in the interpretation of mass spectra. Each analyst must demonstrate the ability to generate acceptable results with this method. See section 8.4.


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2.0 SUMMARY OF METHOD 2.1 Prior to analysis, the samples are prepared by our extractions department

using the appropriate sample preparation and cleanup procedures. Qualitative identification of the parameters in the extract is performed using the retention time and the relative abundance of three characteristic masses (m/z). Quantitative analysis is performed using internal standard techniques with a single characteristic m/z.

3.0 INTERFERENCES AND THEIR CORRECTIVE ACTION 3.1 Raw data from all blanks, samples, and spikes must be evaluated for

contamination interferences. The source of the contamination must be found and corrected as necessary.

3.2 Method interferences may be caused by contaminants in solvents,

reagents, glassware, and other sample processing hardware that lead to discrete artifacts and/or elevated baselines in the total ion current profiles. All of these materials must be routinely demonstrated to be free from interferences under the conditions of the analysis by running laboratory reagent blanks..

3.3 The base-neutral extraction may cause significantly reduced recovery of

phenol, 2-methylphenol, and 2,4-dimethylphenol. The analyst must recognize that

results obtained under these conditions are minimum concentrations. 3.4 Contamination by carryover can occur whenever high-level and low-level

samples are sequentially analyzed. To reduce carryover, the sample syringe must be rinsed out between samples with solvent (methylene chloride). Whenever an unusually concentrated sample is encountered, it should be followed by the analysis of a solvent blank to check for cross contamination.


4.1 All sampling and extracting equipment used for this method can be found

in their respective SOP's. The following is the apparatus used in this method.

4.1.1 Gas chromatograph/mass spectrometer system: 4.1.1.1 The GC's used are a Hewlett Packard 6890 Series with a HP 5973

mass spectrometer, equipped with a 6890 injector with an autosampler tray capable of holding 100 samples. Merlin microseal septa is installed on the GC. Hamilton syringes are to be used in the 6890 injector tower.

4.1.1.2 Column: The column used is HP-5 MS, 0.25 mm x 30 m capillary

column, 0.50 um film thickness. The guard column used is a 0.32 mm. The guard column is to be 10-15 ft. in length attached to the main column with a glass pressfit connector.


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4.1.1.3 The GC uses a 4mm ID Goosneck Splitless quartz liner, 1.2mm

Gold plated inlet seals with 0.375 OD washers. Each liner is sealed in place with an 0-ring.

4.1.1.4 Mass spectrometer: The HP 5973 is capable of scanning from 35

to 500 amu every 1 sec. or less, using 70 volts (nominal) electron energy in the electron impact ionization mode. The mass spectrometer must be capable of producing a mass spectrum for decafluorotriphenylphosphine (DFTPP) which meets all of the criteria in Table 4 when 1 U L of the GC/MS tuning standard is injected through the GC (50 ng of DFTPP).

4.1.2 Data system: The GC's are equipped with a computer system

interfaced with the mass spectrometer. The computer has a HP CD Writer Plus 7500 Series external CD writer to backup data. The HP system is a Windows 98 based MSChemstation with the enviroquant software package. The library used for identification of unknown peaks is NBS75K.

4.2 Instrument Parameters

4.2.1 General Information Inlet: GC Tune file: DFTPP Aquisition mode: SCAN 4.2.2 Scan Parameters Low Mass: 35 High Mass: 500 Threshold: 50 4.2.3 Real Time Plot Parameters Time Window: 30 min. Plot I Type: Total ion. Scale: 0 to 500000.

4.2.4 GC Inlet A Information (Pressure and Flow) Injection Mode: Splitless Ramped Flow

4.2.5 GC Temperature Ramp Information Initial column temp: 45 C. Initial column hold time: 1 min. First ramp rate: l5 C/min. Final column temp: 100 C. Second ramp rate: 20 C/min Final column temp: 240 C. Third ramp rate: 10 C/min. Final column temp: 310 Hold 6.0 min.

4.2.6 GC Zone Temperature information Injector A: 250C.


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Detector A: 280 C. Aux. Transfer line: 280 C.

4.2.7 GC Oven Parameters

Oven Equilibration time: 0.30 mm. Oven Max: 325 C. Oven: On Cryo: Off Ambient: 25 C.

4.2.8 Injector Information Injection Source: Auto Injection location: Front Sample Washes: 0 Sample Pumps: 4 Sample Volume: 1 stop Viscosity Delay: 1 sec. Solvent A Washes: 8 Solvent B Washes: 8 5.0 REAGENTS AND STANDARD SOLUTIONS 5.1 Reagents 5.1.1 Quality Control Standards (See Table 3.) 5.1.1.1 DFTPP solution 5.1.1.2 Internal Standards 5.1.1.3 Surrogate Compounds 5.1.1.4 Spike Compounds 5.1.2 NSI Standards for 625/8270. 5.1.2.1 Crescent Chemical Standards for 625/8270 Regular List (See

Table 7). 5.1.2.2 Polyscience Standard Mixtures for various 8270 compounds (

See Table 8). 5.2 Stock Solutions are purchased as certified solutions. Stock

standards are to be kept at 4 C and protected from light. The solutions should be transferred into Teflon-sealed screw cap vials. Stock standard solutions must be checked frequently for signs of degradation or evaporation, especially just prior to preparing calibration standards from them. The solutions must be replaced after 6 mo. or sooner if comparison with quality control check samples indicates a problem.

5.2.1 Internal Standard solution are purchased as certified solution. The internal standards used are1,4-dichlorobenzene-d4, naphthalene-d8, acenaphthene-d10, phenanthrene-d10, chrysene-d12, and perylene-d12. Each 1-mL sample extract undergoing analysis must be spiked with 10 uL of the internal standard solution, resulting in a concentration of 40 ug/mL of each internal standard. Store at 4 C or less when not being used. For the best results, place the solution in a mini inert microvial wrapped in aluminum foil to block out the light. Before adding any internal standard, let the solution come to room temperature.


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5.2.2 GC/MS Tuning Standard: A methylene chloride solution containing 50 ug/mL decafluorotriphenylphosphine (DFTPP) should be prepared. The standard should also contain 50 ug/mL each of 4,4'- DDT, pentachlorophenol, and benzidine to verify injection port inertness and GC column performance. Store at 4 C or less when not being used.

5.3 Working Standards: A minimum of five calibration standards should be prepared for each analyte of interest. One of the calibration standards should be at a concentration near, but above, the MDL: the others should correspond to the range of concentrations found in real samples but should not exceed the working range of the GC/MS system. Each standard should contain each analyte for detection by this method (see Table 1 and 2).

5.3.1 Five Point Curve: Table 5 and Table 7 contain the mixes used for the compounds found in Table 1. Table 6 contains the mixes used for the compounds found in Table 2. The following describes how a curve is prepared. 5.3.1.1 8270C method: Standards are prepared from solutions purchased at 2000 ug/ml for the following:

Toxic Substances Mix #1, Toxic Substances Mix #2, Base Neutral Mix #1, Base Neutral Mix #2, Phenol Mix, PAH Mix, and Benzidine & 3,3'-Dichlorobenzidine Mix. Surrogate solutions are purchased as certified solutions. The mixes (all 2000 ug/ml) are used to make the BNA stock standard by placing 200 uL of each into a 3 dram vial. The Stock standard will be 200ug/ml. The dilutions for the calibration standards are as follows:

5.0 ppm: 25 ul of stock standard to 975 ul MeCI2. 10 ppm: 50 ul of stock standard to 950 ul MeCI2. CCV: 25 ppm: 175 ul of stock standard to 750 ul MeCI2. 40 ppm: 200 ul of stock standard to 800 ul MeCI2. 50 ppm: 250 ul of stock standard to 750 ul MeCI2. Place

10 ul of 4000 ug/ml internal standard into each 1 mL calibration standard.

5.3.2 Initial Calibration Verification: ICV's are the same as the CCV's for

each appropriate curve.

5.4 Spikes: 5.4.1 Surrogate Standard: The surrogate standards used are phenol-d5,

2-fluorophenol, 2,4,6-tribromophenol, nitrobenzene-d5, 2-fluorobiphenyl, and

terphenyl-d14. All of the surrogate stock solutions are purchased as certified solutions. The working surrogate solution is 50 ug/mL. Verify the concentration of the surrogate spike before giving it to the extractions department.

5.2.4 Matrix Spike Solution: The matrix spike compounds are purchased

as certified solutions at 5000 and 7500 ug/ml concentration. The working spike solution concentration is 50.0 ug/ml. Verify the


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concentration of the spiking solution before giving it to the extractions department.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

6.1 Extraction Holding Time (from time samples are collected) is 7 days for waters and 14 days for soils. Once the samples have been extracted, analysis must be performed within 40 days.

6.2 Volume Collected: Waters requires 2 quart ambers and soils require an 8 oz. Jar, or one medium soil sleeve.

6.3 Preservation: All samples must be iced or refrigerated at 4 C from the time of collection until extraction. No preservation is needed unless residual chlorine is present. If residual chlorine is present, add 3 m1 10% sodium thiosulfate.

7.0 PROCEDURE 7.1 Sample Preparation: Samples must be prepared by one of the following

methods prior to GC/MS analysis. Matrix Methods Water 3510, 3520 Soil/Sediment 3540, 3550 Waste 3540, 3550, 3580 Methods 3510 and 3550 are most frequently used. See the appropriate

SOP for information regarding them. 7.2 Extract cleanup At this time, no cleanup procedure is in use. 7.3 Initial Calibration: The recommended operating conditions and

instruments can be found in Section 4.0. 7.3.1 Each GC/MS system must be hardware tuned to meet the criteria in

Table 4 for a 50 ng injection of DFTPP. Analyses should not begin until all these criteria are met. Background subtraction should be straightforward and designed only to eliminate column bleed or instrument background ions. The GC/MS tuning standard should also be used to access GC column performance and injection port inertness. Degradation of DDT to DDE and DDD should be less than 20%. Benzidine and Pentachlorophenol should be present at their normal responses, and no peak tailing should be visible. Peak tailing for 625's involve checking benzidine and pentachlorophenol's peak width. Benzidine must be <3 and pentachlorophenol must be <5. If degradation is excessive and/or poor chromatography is noted, the injection port may require cleaning. It may also be necessary to break off the first 6-12" of the guard column.

7.3.2 The internal standards selected in section 5.2.1 should permit most of the components of interest in a chromatogram to have retention times of 0.80-1.20 relative to one of the internal standards. Use the base peak ion from the specific internal standard as the primary ion for quantitation (see Table 1 and 2).


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7.3.3 Analyze 1 uL of each calibration standard (containing internal standards) and tabulate the area of the primary characteristic ion against concentration for each compound (as indicated in Tables I and 2). Figure 1 shows a calibration standard for the 8270C method containing base/neutral and acid analytes. Calculate response factors for each compound as follows:

RF = (AxCis)/(AisCx) where: Ax = Area of the characteristic ion for the compound being

measured Ais = Area of the characteristic ion for the specific internal standard Cx = Concentration of the compound being measured (ug/mL). Cis = Concentration of the specific internal standard (ug/mL). 7.3.4 The average RF should be calculated for each compound. The

percent relative standard deviation (%RSD = 100[SD/aveRF]) should also be calculated for each compound. The %RSD should be less than 15% for each compound. However, the %RSD for each individual Calibration Check Compound (CCC) (See Table 4) must be less than 30%. The relative retention times of each compound in each calibration run should agree within 0.06 relative retention time units (RRT).

7.3.5 A system performance check must be performed to ensure that minimum average RF's are met before the calibration curve is used. For semivolatiles, the System Performance Check Compounds (SPCC's) are located in Table 4. The minimum acceptable average RF for these compounds is 0.050. These SPCC's typically have very low RFs (0.1-0.2) and tend to decrease in response as the chromatographic system begins to deteriorate or the standard goes bad. They are usually the first to show poor performance. Therefore, they must meet the minimum requirement when the system is calibrated.

7.4 Daily GC/MS calibration: 7.4.1 Prior to analysis of samples, the GC/MS tuning standard must be analyzed. The 50 ng injection of DFTPP must result in a mass spectrum for DFTPP which meets the criteria given in Table 4. These criteria must be demonstrated during each 12-hr shift. 7.4.2 A calibration standard at the mid-level concentration containing all

semivolatile analytes, including all required surrogates, must be performed every 12-hr during analysis. Compare the response factor data from the standards every 12-hr with the average response factor from the initial calibration for a specific instrument as per the SPCC and CCC criteria.

7.4.3 System Performance Check Compounds: A system performance

check must be made during every 12-hr shift. If the SPCC criteria are met, a comparison of response factors is made for all compounds. This


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is the same check that is made during the initial calibration step. If the minimum response factors are not met, the system must be evaluated, and corrective action must be taken before sample analysis begins. The minimum RF for semivolatile SPCC's is 0.050. Some possible problem areas are standard degradation, inlet port contamination, head of column contamination, or active sites in the chromatographic system. This check must be met before analysis begins.

7.4.4 Calibration Check Compounds: After the system performance

check is met, the CCC's listed in Table 4 are used to check the validity of the initial calibration. The percent difference in RF's is calculated for each CCC. If the %D for any compound is greater than 20%, this is considered the warning limit. If the %D for each CCC is less than 30%, the initial calibration is assumed to be valid. If the criteria is not met for any CCC(>30% difference), corrective action must be taken. If no source of the problem can be determined after corrective action has been taken, a new five-point curve must be generated. This criterion MUST be met before sample analysis begins.

7.4.5 The internal standard response and retention times in the

calibration check standard must be evaluated immediately after or during data acquisition. If the retention time for any internal standard changes by more than 30 sec. from the last check calibration (12 hr), the chromatographic system must be inspected and adjustments made as necessary. If the area for any internal standard base ion has changed by more than a factor of two (-50% to +100%) from the last daily calibration standard check, the mass spectrometer must be inspected for malfunctions and corrections must be made, as appropriate.

7.5 GC/MS analysis: 7.5.1 The extract received from the extraction department must be

visually screened for high level contaminants. If contamination is apparent, the sample should be diluted accordingly. The experience of the analyst is crucial in determining dilutions. If a dilution is not made, or not made correctly, the result will be a contamination of the GC/MS system necessitating the frequent cleaning of the source and injector port.

7.5.2 Each method blank, spikes, and samples received must be spiked with 10 ul of internal standard mix before analysis.

7.5.3 The method blank, spikes, and samples are then analyzed using the GC/MS conditions previously stated in section 4. Each sample should contain 50 ug/mI on column of base/neutral and acid surrogates.

7.5.4 If the response for any quantitation ion exceeds the initial curve range of the GC/MS system, the sample must be diluted appropriately. Additional internal standard must be added to the diluted extract to maintain the required 40 ug/ml of each internal standard in the extracted volume. The diluted extract must be reanalyzed.


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7.5.5 Perform all qualitative and quantitative measurements as described in section 7.6. Store the extracts at 4 C, protected from light in screw-cap vials equipped with unpierced teflon-lined septa.

7.5.6 At every 12 hours of analyzing samples, the DFTPP solution and a CCV must follow to ensure the response factors are within required QC limits, and instrument tuning is still acceptable.

7.6 Data Interpretation: 7.6.1 Qualitative Analysis: 7.6.1.1 An analyte (e.g. those listed in Table 1 or Table 2) is

identified by comparison of the sample mass spectrum with the mass spectrum of a standard of the suspected compound. Mass spectra for standard reference must be obtained on the GC/MS within the same 12 hours as the sample analysis. These standard reference spectra may be obtained through analysis of the calibration standards. Two criteria must be satisfied to verify identification: (1) elution of sample component at the same GC relative retention time (RRT) as the standard component; and (2) correspondence of the sample component and the standard component mass spectrum.

7.6.1.1.1 The sample component RRT must compare within +or-

0.06 RRT units of the standard component. If coelution of interfering components prohibits accurate assignment of the sample component RRT from the total ion chromatogram, the RRT should be assigned by using extracted ion current profiles for ions unique to the component of interest.

7.6.1.1.2 All ions present in the standard mass spectra at a relative

intensity greater than 10% of the base peak must be present in the sample

component mass spectra. The most abundant ion in the mass spectra (equals 100%) must be present in the sample spectrum.

7.6.1.1.3 The relative intensities of the ions specified in Paragraph 7.6.1.1.2 must agree within + or - 20% between the standard and sample spectra. (Example:

For an ion with an abundance of 40% in the standard spectra, the corresponding

sample abundance must be between 20% and 60%. 7.6.1.2 For samples containing components not associated with the

calibration standards, a library search may be made for the purpose of tentative identification. The library used for such searches is NBS75K. The NBS75K settings are as follows:

+ A: 2 Flag threshold: 3% Mm. Est. Purity: 50% Low report MW: 0


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High report MW: 9999 Max hits listed: 20 Tilting: yes Cross-Correlation Sort: No Remove dup CAS #: No Only after visual comparison of sample spectra with the nearest

library searches will the mass spectral interpretation specialist assign a tentative identification (TIC). Guidelines for making tentative identification are:

(1) Relative intensities of major ions in the reference spectrum (ions >10%of the base mass) should be present in the sample spectrum.

(2) The relative intensities of the major ions should agree within + or - 20%.

(3) Ions present in the sample spectrum but not in the reference spectrum should be reviewed for possible background contamination or presence of coeluting compounds.

(4) Ions present in the reference spectrum but not in the sample spectrum should be reviewed for possible subtraction from the sample spectrum because of background contamination or coeluting peaks.

7.6.2 Quantitative Analysis: 7.6.2.1 When a compound has been identified, quantification will be based on the

integrated abundance from the extracted ion current profile (EICP) of the primary characteristic ion. Quantitation will take place using the internal standard technique. The internal standard used shall be the one nearest the retention time of that of that of a given analyte.

7.6.2.2 The concentration of each analyte is calculated by the data system. (Refer to section 9 for calculations of water and sediment/sludge samples.)

7.6.2.3 When a TIC is performed, the areas of the compound and internal standard are based on total ion chromatograms and the RF is assumed to be 1. The concentration obtained should be reported as an estimate.

8.0 QUALITY CONTROL 8.1 A formal quality control program is required to run this method. The minimum

requirements of this program consist of an initial demonstration of laboratory capability and an ongoing analysis of spiked samples to evaluate and document quality data. Before analysis begins, a method blank is run in order to ascertain that interferences from the analytical system, glassware, and reagents are under control (i.e. below detection limits). Each time a set of samples is extracted or there is a change in reagents, a method blank must be run in order to evaluate contamination problems. The blank samples should be carried through all stages of the sample preparation steps.


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8.2 Each day that analysis is performed, the DFTPP solution and the daily midpoint calibration standard (CCV) is run in order to evaluate whether the chromatographic system is functioning properly. If any major changes to the system is made (i.e. changing a column), recalibration of the system must take place.

8.3 Required instrument QC is found in the following sections: 8.3.1 The GC/MS system must be tuned to meet the DFTPP

specifications described in Sections 7.3.1 and 7.4.1. 8.3.2 There must be an initial calibration of the GC/MS system as described in

Section 7.3. 8.3.3 The GC/MS must meet the SPCC criteria specified in 7.4.3 and the CCC

criteria in 7.4.4, during each 12-hr shift. 8.4 Initial Demonstration of Capability (IDC): 8.4.1 Prepare a minimum of four replicates at a concentration of 50 ug/ml in acetone. Prepare IDC check standards at a concentration of 50 ug/mL by adding 1 ml of the IDC check standard to each of four 1-L aliquots of reagent water. 8.4.2 Analyze the four mixed IDC check standards according to the method

beginning in Section 7.1 with the extraction of the samples. 8.4.3 Calculate the average recovery in ug/L, and the standard deviation of

the recovery in ug/L, for each analyte of interest using the four results. For each analyte compare the average and standard deviation with the corresponding acceptance criteria for precision and accuracy (Table found in 40 CFR Part 136 for Method 625). If all of the analytes meet the acceptance criteria, the system performance is acceptable and analysis of actual samples can begin. If any individual standard deviation exceeds the precision limit or any average falls outside the range for accuracy, then the system performance fails for those compounds.

8.5 Determination of IDL. MDL. and PQL. 8.5.1 IDL is described as the minimum concentration of the specific analyte

which may be observed with a signal to noise ratio of three. 8.5.2 MDL is defined as the minimum concentration of a compound that can

be qualitatively and quantitatively reported with a 99% confidence that the analyte

concentration is greater than zero for a given matrix. To determine the MDL, seven identical spikes at 4.0 ug/mL (1 ml of 4.0 mg/L spike to 1 liter of reagent water) are extracted and processed in exactly the same manner as any sample.

The final results are recorded and the standard deviation for them is calculated for each analyte.

8.5.3 PQL is 3 times the MDL. This is a limit that is above the MDL, but below the MCL (Maximum Contamination Limit) for the each particular analyte. For those levels which are between the MDL and PQL, a level of "trace" will be reported. This result is an estimated value. When a change is made to the PQL, a note is added to the analytical data sheet stating its reason.

8.6 Control Charts


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8.6.1 Control charts are to be maintained to monitor the progress of 6 of the 19 spike compounds for both water and soil matrices. The following spike compounds are to be used: 2-Chlorophenol, 1-, 4-dichlorobenzene, 1,2,4-Trichlorobenzene, Acenaphthene, 2,4-Dinitrotoluene, and Pentachlorophenol. The control charts will plot % recovery versus spike date. Upper and lower limits, as well as the average, must be clearly marked. These charts are to be updated daily to monitor trends in recovery response. Long term trends may also be observed in order to identify problems in instrumentation, extraction procedure, or spike solution deterioration.

8.6.2 As part of the QC program for the laboratory, method accuracy for each matrix studied must be assessed and records must be maintained. After the control charts are completed (20 QC sets per matrix), submit to the QC department. An average percent recovery (p) and the standard deviation of the percent recovery (Sp) will be calculated. Control limits will be based on the accuracy as a percent recovery interval from p - 2sp to p + 2sp. The QC department will update control limits and calculate upper and lower control and warning limits.

8.7 QC sets- Duplicates and Spikes 8.7.1 A QC set includes a reagent blank (MB), a laboratory control sample

(LCSS or LCSW), a matrix spike (MS), a duplicate matrix spike (MSD). Each set or analytical batch must consist of 20 samples or less of the same matrix.

8.7.2 Spikes are used to determine that the sample matrix does not contain materials that adversely affect spike recoveries. The spiked compounds are listed in Table 3D. If recoveries are low or out of range due to matrix interferences, the LCSS/LCSW will be used to confirm method performance.

8.8 Log Books- Each analyst is expected to keep up to date the following: 8.8.1 625/8270 Instrument run log. The analysis run log contains all the

pertinent information related to an analytical run on a specific instrument. This log is used to keep records of when samples were run, how much sample was used for extraction, the associated QC sets involved, the final extraction volume, dilution factors, and comments related to the run.

8.8.2 The QC log book contains initial curve data, QC reports, control charts, and DFTPP tune settings. Also, a copy of the IDC and MDL/PQL study should be included.

8.8.3 A standard log book is kept in the semi-volatile GC room. Each entry into this log is given an id # beginning with the prefix "EX-". All information about the standard is found in this book, including the source, date prepared, and a description of preparation

8.8.4 A maintenance log is kept for the instrument.. This log is updated every time routine service and repairs are performed.

8.8.5 A corrective actions log is kept to document any problems associated with an analysis or an analysis set.

9.0 Calculations


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9.1 Quantitative Analysis Concentration (ug/L)= (Ax) (Is)xDilution Factor (Ais) (RF) (Vo)

where: Sx= Area of characteristic ion for compound. Is= Amount of internal standard injected Ais= Area of characteristic ion for the internal std RF= Response factor for compound. (See below Vo= Volume of water (L) or mass of solid (grams)

extracted For TIC's, the RF assumed to be 1. Response factor (RF)= (Ax) (Cis) (Ais) (Cx) where: Ax = Area of the characteristic ion for the compound being

measured Ais= Area of the characteristic ion for the specific internal standard Cx= Concentration of the compound being measured (ug/L). Cis= Concentration of the specific internal standard (ug/L). 9.2 %RSD- Initial Calibration Factor Relative Standard Deviation Percent. %RSD= (s/ave)* 100 where: s= standard deviation (sample)n-1 degrees of freedom. Ave= Average response factor. 9.3 % Difference D%=(RFi-RFc)X 100

RFi

where: RFi= Average response factor from initial calibration. RFc= Response factor from current verification 9.4 % Rec of MS/MSD % Rec. where: (A-B) xl00 T A= Sample spiked response. B= Sample concentration. T= Known true value of the spike. 9.5 RPD- Relative Percent Difference


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RPD= ([%MS - %MSD]/% Ave) * 100 where: %MS= Analyte % recovery of spike. %MSD= Analyte % recovery of duplicate spike. %Ave.= Analyte % recovery for MS and MSD. 9.6 Method Detection Limit (MDL) MDL= S* t where: s= standard deviation in %. t= Student's t-value @ 99% confidence level (tn = 3.21 for n = 7) 9.7 Practical Quantitation Limit (PQL) PQL= approximately 3-5 times the MDL. 9.8 Accuracy and Precision control limits. p = average percent recovery. Sp = standard deviation of percent recovery. Upper and Lower warning limits: p + 25p to p - 25p Upper and Lower control limits: p + 35p to p - 35p If recoveries are above are below the warning limit, corrective action must

be taken.


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Standard Operating Procedure for Method 5540C Title: Extraction and Analysis of Anionic Surfactants as Methylene Blue Active

Substances (MBAS) by SM 5540C. Scope: This method determines anionic surfactants as MBAS in drinking

water, surface water, domestic and industrial wastes, and groundwater according to Standard Method 5540C. MBAS will be measured at 652 nm using a HACH DR/2010 Spectrophotometer.


traceability of possible causes of error in analytical results. Equipment & Conditions: A Hach DR/2010 Spectrometer will be used. MBAS will be

measured at 652 nm. Sample Containers and Handling: 1. Collect samples HDPE or glass bottles. 2. Samples can be held for up to 48 hours if cooled immediately and

stored at just above freezing (≤ 6ºC). Interferences: Other methylene blue active substances will cause positive

interference. Turbidity, cationic surfactants and other cationic materials may cause negative interference.


1. Calibration standards are analyzed at no fewer than three concentrations. From these standards, a calibration curve is established for each compound. The concentrations will include:

Point #1 0.1 mg/L LAS Point #2 0.2 mg/L LAS Point #3 0.5 mg/L LAS Point #4 1.0 mg/L LAS Point #5 2.0 mg/L LAS


3. Standards shall be obtained from Fisher Scientific or equivalent. 4. A minimum of one method blank, LCS, LCSD, MS, and MSD for

every matrix and batch of twenty samples.

5. The relative percent difference (RPD) between spiked matrix duplicate determinations is to be calculated as follows:

RPD = __ |D1-D2|__ *100

[(D1 + D2)/2] D1= First sample value


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D2= Second sample value 6. A control limit of ± 10% RPD or within the documented historical

acceptance limits for each matrix shall be used for sample values greater than ten times the instrument detection limit.

7. The spiked sample or spiked duplicate sample recovery is to be within

20% of the actual value or within the documented historical acceptance limits for each matrix.

Reagents:

1. Stock LAS solution: 60 mg/L as LAS

2. Standard LAS solution: 10 mg/L as LAS

3. Phenolphthalein indicator solution, alcoholic.

4. 1N Sodium Hydroxide: Dissolve 4 g NaOH pellets in 100 ml water.

5. 1N Sulfuric Acid: Add 2.8 mL conc. H2SO4 to 50 mL of water in a 100 mL volumetric flask. Volumize with water when the solution is cool.

6. 6N Sulfuric Acid: Add 16.7 mL conc. H2SO4 to 50 mL of water in a 100 mL volumetric flask. Volumize with water when the solution is cool.

7. Chloroform ACS Grade

8. Methylene Blue Reagent: Dissolve 100 mg methylene blue in 100 mL of water. Transfer 30 mL to a 1 L volumetric flask. Add 500 mL water, 41 mL 6N H2SO4, and 50 g sodium phosphate monobasic, monohydrate to a 1 L volumetric flask. Swirl to dissolve. Dilute to 1 L with water.

9. Wash Solution: Add 41 mL 6 N H2SO4 to 500 mL water in a 1L volumetric flask. Add 50 g sodium phosphate monobasic, monohydrate and swirl to dissolve. Dilute to 1 L with water.

10. Hydrogen Peroxide 30%.

11. Water, reagent grade Procedure:

Extraction: 1. For the MB/LCS/LCSD add 100 mL of DI water to a clean separatory

funnel (sep. funnel) a. Spike both the LCS and LCSD with 5 mL of standard LAS

solution (10 mg/L as LAS solution). The LCS needs to read between 0.45-0.55 mg/L.


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b. If enough sample is provided, extract an MS/MSD for each batch using 100 mL of sample. These two samples will be spiked with 5 mL of standard solution (10 mg/L LAS solution).

2. For all samples add 100 mL of sample to a clean separatory funnel.

Use historical data to determine if less sample should be used.

3. Add a few drops of 30% H2O2 to each sample to prevent sulfide interference.

4. Add 4 drops of phenolphthalein indicator.

5. Add drops of 1N NaOH until pink color appears.

6. Add drops of 1N H2SO4 until the pink color disappears.

7. Add 5 mL CHCl3 and 12.5 mL methylene blue reagent.

8. Shake the funnel for 30 seconds with periodic venting. Let the phases

separate for 1 minute with occasional swirling. Break up emulsions by adding <10 mL isopropyl alcohol if needed. Isopropyl alcohol must be added to standards if it is added to samples. If an emulsion cannot be broken up, re-extract the sample and shake less vigorously. You can also try extracting less sample.

9. Drain the CHCl3 layer into a 250 mL Erlenmeyer flask.

10. Extract the sample 2 more times using 5 mL CHCl3. If the blue color

becomes faint or disappears from the water layer during extraction, discard the sample and re-extract with less sample.

11. Clean the sep funnels.

12. Add the CHCl3 extracts to the sep funnels.

13. Add 25 mL of wash solution and shake vigorously for 30 seconds.

14. Drain the CHCl3 layer into an Erlenmeyer flask.

15. Extract the wash solution 2 more times with 5 mL CHCl3. Drain the

CHCl3 layer into the Erlenmeyer flask.

16. Add the CHCl3 layer to a 50 mL volumetric flask. Rinse the Erlenmeyer with 2 1 mL aliquots of CHCl3. Add the rinse to the volumetric flask.

17. Bring up to volume with CHCl3.

Analysis (In the hood!!):


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1. Enter the stored program number for anionic surfactants on the spectrophotometer: PRESS: 950 ENTER

The display will show: Dial nm to 652 Rotate the wavelength dial until the small display shows 652 nm When the correct wavelength is dialed in, the display will QUICKLY

show Zero Sample then mg/L LAS. Place the Blank in the cell holder and close the light shield. Press ZERO. The display will show Zeroing… then 0.00 mg/L LAS. 2. Place the prepared sample into the cell holder. Close the light shield

and press READ. The display will show Reading… then the result as mg/L LAS will be displayed. Record the reading in the appropriate logbook and repeat for the remaining samples.

3. If the result is over-range, dilute the sample with CHCl3. Document

dilutions in the logbook.

MBAs Reagents and Standards

1. Stock LAS Solution 60 mg/L (Purchased) 2. Standard LAS Solution 10 mg/L: 16.7 mL Stock LAS Solution in a

100 mL volumetric flask to volume with reagent water. 3. Calibration Standards

a. 0.05 mg/L: 0.5 mL Standard LAS Solution in 100 mL reagent

water b. 0.1 mg/L: 1 mL Standard LAS Solution in 100 mL reagent

water c. 0.2 mg/L: 2 mL Standard LAS Solution in 100 mL reagent

water d. 0.5 mg/L: 5 mL Standard LAS Solution in 100 mL reagent

water e. 1.0 mg/L: 10 mL Standard LAS Solution in 100 mL reagent

water f. 2.0 mg/L: 20 mL Standard LAS Solution in 100 mL reagent

water

4. 1N Sodium Hydroxide: Dissolve 4 g NaOH pellets in 100 ml water. 5. 1N Sulfuric Acid: Add 2.8 mL conc. H2SO4 to 50 mL of water in a 100

mL volumetric flask. Volumize with water when the solution is cool. 6. 6N Sulfuric Acid: Add 16.7 mL conc. H2SO4 to 50 mL of water in a

100 mL volumetric flask. Volumize with water when the solution is cool.


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7. Methylene Blue Reagent: Dissolve 100 mg methylene blue in 100 mL of water. Transfer 30 mL to a 1 L volumetric flask. Add 500 mL water, 41 mL 6N H2SO4, and 50 g sodium phosphate monobasic, monohydrate to a 1 L volumetric flask. Swirl to dissolve. Dilute to 1 L with water.

8. Wash Solution: Add 41 mL 6 N H2SO4 to 500 mL water in a 1L

volumetric flask. Add 50 g sodium phosphate monobasic, monohydrate and swirl to dissolve. Dilute to 1 L with water.


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Standard Operating Procedure for Method 524.2 1.0 SCOPE AND APPLICATION

1.1 Method 524 is used to determine volatile organic compounds in drinking water, surface water, and ground water.

1.2 524 is applicable to a wide range of organic compounds including the four

trihalomethane disinfection by-products. Volatile water soluble, polar compounds can be determined using this method.

1.3 This method is based on a purge-and-trap, gas-chromatographic/mass

spectrometric (GC/MS) procedure.

2.0 SUMMARY OF METHOD

2.1 The volatile compounds are introduced to the gas-chromatograph by the purge-and –trap method or (in limited applications) by direct injection. The components are separated via the gas-chromatograph and detected using a mass spectrometer, which is used to provide both qualitative and quantitative data. The chromatographic conditions, as well as typical mass spectrometer operating parameters, will be given later.

2.2 The purge-and–trap process: Helium is bubbled through the solution at

room temperature, and the volatile components are quantitatively transferred from the aqueous phase to the vapor phase. The vapor is passed through a sorbent column, where the organic compounds are trapped. After purging is completed, the sorbent trap is heated and back-flushed with helium to desorb the components onto the gas column. The column is heated to elute the compounds, which are detected with the mass spectrometer.

3.0 SAMPLE COLLECTION, PRESERVATION, AND STORAGE

3.1 Collect all samples in duplicate. If samples are suspected to contain residual chlorine, add about 25 mg of ascorbic acid to each VOA before filling. Sodium thiosulfate (3mg) may be used if analytes that are gases at room temperature are not to be determined.

3.2 Adjust the pH <2 with two drops 1:1 HCl after dechlorination with ascorbic

acid.

3.3 THMs can be preserved with sodium thiosulfate only. 3.4 Unpreserved samples must be analyzed within 24 hours of collection for

analytes other than THMs.


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4.0 INTERFERENCES

4.1 Interferences purged from the samples will vary considerably from source to source, depending on the particular sample being analyzed. However, a method blank is analyzed to ensure that the analytical system is free from interferences under analysis conditions.

4.2 Samples may be contaminated by diffusion of volatile organics (especially

methylene choride and fluorocarbons) through the septum seal during shipment and storage. A field blank is prepared from reagent water free of contaminants and is carried through the sampling and handling to access contamination.

4.3 Cross-contamination may occur when high-level and low-level samples

are analyzed sequentially. Therefore, when highly contaminated samples are analyzed, a system blank may need to be analyzed immediately following to access and prevent cross-contamination. The purge-and–trap system may require several blanks to clean the system of contaminants.


5.1 Microsyringes: 10ul, 25ul, 100ul, 250ul, 500ul, and 1000ul are available and should only be used for VOA standard preparation and dilution.

5.2 Balance: An analytical balance (accurate to 0.10 gm) for accurate

weighing. 5.3 VOA vials are used as sample containers and dilution vials. 5.4 Volumetric flasks, spatulas, disposable pipettes, and bulbs are available

for sample preparation. 5.5 Purge –and – trap: A Tekmar lcs3100 coupled with a Varian Archon auto-

sampler. 5.5.1 Frit sparging : The purging apparatus is a fritted sparge vessel.

The nitrogen sparging gas must pass through the sample as finely divided bubbles, having diameters no greater than 3mm at inception.

5.5.2 A Supelco Vocarb 3000 trap is used.

5.6 Gas chromatograph/mass spectrometer system:

5.6.1 A Hewlett Packard, Model 6890 gas chromatograph is used.


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5.6.2 Agilent DB-VRX 60M x 0.25RTx column is used.

5.6.3 A Hewlett Packard, model 5973 mass spectrometer is used.

5.6.4 A Hewlett Packard Enviroquant Software data system is used. The GC/MS and data system are capable of meeting all EPA criteria for GC/MS volatile analytical work.

6.0 REAGENTS

6.1 Stock solutions are purchased as 2000 ppm or some other concentration in methanol. Traceable certified standard mixes or neat from various ISO 9001 approved vendors will only be used.

6.2 The surrogate standards used are dibromofluoromethane, toluene(d8)

and 4- bromofluorobenzene, which are purchased as 2500 ppm solutions from NSI or some other Iso-9001-approved vendor.

6.3 The internal standard used is fluorobenzene, which is purchased as a

2500 ppm solution from NSI or some other Iso-9001-approved vendor. 6.4 The Tuning standard used is a 25 ppm internal standard/surrogate

solution; 1 ul injection, equaling 25 nanograms.

6.5 The calibration standards are prepared as follows: the appropriate stock standard is diluted to 42ppm.

6.6 The matrix spiking standard used is the 42ppm spiking standard at the

mid-point (20.0 ppb) of the curve.

6.7 Great care must be taken to maintain all standard solution integrity. Therefore, all standards are kept below –10 C in the standards freezer. They are removed only for initial and daily calibration standard preparation and are returned to the freezer as quickly as possible. Close observation must be kept on the response factors of the gaseous compounds. These compounds are prone to degrade first and must be replaced more often than the other analytes, typically every three to four weeks.

6.8 Reagent grade water is defined as water that is free of interferences at

the method detection limit for all compounds of interest. The reagent grade water is tested every morning as a method blank. If interfering compounds are found, the cause of the contamination must be found and corrected before analysis continues.

7.0 INITIAL CALIBRATION FOR PURGE-AND-TRAP ANALYSIS

7.1 Approximate GC/MS operating conditions Electron energy: 70 volts


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Mass range: 35-300 amu A/D samples: 8 Initial column temperature 40oC Initial column hold time: 10 min. Column temperature progression: 12 C/min. Final column temperature: 190oC Final column hold time: 4 min. Injector temperature: 200oC Interface temperature: 220oC Source temperature: 200oC Carrier gas: UHP Helium

7.2 First, the GC/MS system must meet the ion-abundance criteria daily for a 25 ng injection of bromofluorobenzene (BFB). Analysis cannot begin without these criteria having been met. 1.0 ul of 25 ppm or 25 nanograms is analyzed.

7.3 Prepare a method blank using a 40-ml VOA vial, completely filled with

organic free water.

7.4 The initial calibration standard is prepared by adding 42ppm standard to a VOA vial filled with organic free water to each of 5 VOA vials and spiking them with the appropriate amount of calibration standard. Analyzing 0.5, 1.0, 20.0, 50.0, and 100ul injections of the 42ug/ml calibration standard create these calibration runs. The concentrations are 0.5, 1.0, 20.0, 50.0 and 100 ug/l. The internal/surrogate standard solution is added to every blank, spike, standard, and sample to be analyzed with this method. The Archon Auto-sampler will add the appropriate amount of IS/SS to each sample.

7.5 The average response factor (RF) is calculated by the data system for

each compound using the internal standard fluorobenzene.

7.6 Using the RFs from the initial calibration, the % RSD for a compound

should be equal to or less than 20% for each compound. This criterion must be met before the initial calibration can be used.

8.0 INITIAL DEMONSTRATION OF LABORATORY CAPABILITY

8.1 Before samples are analyzed a laboratory reagent blank must be free of contamination.

8.2 Initial demonstration of laboratory accuracy and precision


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8.2.1 Analyze 4 to 7 replicates of laboratory fortified blanks (2-5 ug/L). Use HCl or sodium thiosulfate preserved VOAs if samples are expected to be preserved.

8.2.2 Calculate the measured concentration of each analyte in each

replicate. Calculate the mean concentration, mean accuracy (as mean percentage of true value), and the precision (RSD).

8.2.3 The mean accuracy for each analyte must be 80-120%. The

precision must be <20%.

8.3 An MDL study must be performed before samples are analyzed. Analyze 7 replicates of 0.5 ug/L standard. Analyses should be run over several days.

9.0 CONTINUING CALIBRATION CHECK

9.1 Prior to analyzing a sample, 25 ng of BFB must be injected, and the mass spectra must meet the EPA requirements for ion abundances.

9.2 The initial calibration curve for each compound of interest must be

checked and verified. This is done by analyzing a calibration standard that is at the midrange concentration of the working range (20ug/l). This continuing calibration check must be within 30% of the initial calibration curve. The absolute areas of the quantitation ions of the internal standard and surrogates must not decrease more than 30% from the previous calibration check or by more than 50% from the initial calibration.

9.3 A continuing calibration check must be performed at the beginning of

every 12 hour work shift.

9.4 The CCV may be used as the LFB. An LFB is required for every twenty samples.

9.5 If THM analysis is to take place, the MRL must be verified with every

batch of samples to ensure the accuracy of the initial calibration at the MRL concentration. Analyze an MRL check standard with a concentration less than or equal to 110% of the MRL with each batch of samples. The measured concentration must be within 50% of the expected value.

10.0 GC/MS ANALYSIS

10.1 Sample analysis

10.1.1 Visually inspecting a sample helps determine the necessity of dilution before initial analysis. Use good judgment if a sample appears highly contaminated, it is better to start with a high dilution and gradually bring the dilution down, than to overload the purge-and trap device and necessitate running reagent water blanks to clean the system.


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10.1.2 All samples must be allowed to warm to room temperature before

analysis

10.1.3 BFB tuning ion abundance criteria must be met each day.

10.1.4 The nitrogen purge flow must be maintained at 40ml/min, and the sample purged for 11 minutes, followed by a four minute desorb cycle as the sample is introduced into the GC.

10.1.5 Analyzing a sample: prescreen the sample by opening the vial. If

the sample is expected to have no or low concentrations of analytes, the VOA vial is placed on the autosampler without opening it.

10.1.6 The following procedure is appropriate for sample dilution (all

steps must be performed without delay until the sample is in a VOA vial:

10.1.6.1 If, upon initial analysis of a sample or dilution of a

sample, the concentration of an analyte is greater than the initial calibration range, the sample must be reanalyzed at a higher dilution. Fill a syringe with the proper aliquot of the sample and inject it into reagent water, making a combined volume of a full vial. Set up the data system to document the dilution. Initiate the acquisition, and start the run.

10.1.7 Matrix spike analysis: Select a sample evidently free of

contaminants and add 20.0 ul (20.0 ppb) of matrix spiking standard to the sample. Analyze as a normal sample.

10.2 Data interpretation

10.2.1 Qualitative analysis: An analyte of interest is identified by comparing the analytes expected retention time and reference mass spectra.

10.2.1.1 The sample relative retention time (RRT) must be

within +0.08 RRT units of the RRT of the standard component. For reference, the daily calibration run RRT is used.

10.2.1.2 All ions present in the standard mass spectra at a

relative intensity greater than 10% of the base peak for that component must be present in the sample. Also, the relative intensities of ions present in the standard mass


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spectra must agree to within +20% of the sample mass spectra.

10.2.1.3 Perform library searches to tentatively identify

sample components not associated with the calibration standards.

10.2.2 Quantitative analysis

10.2.2.1 When a compound has been identified, use the internal standard technique for quantification.

10.2.2.2 Using the following, calculate the concentration of

each analyte by the data system:

Concentration (ug/L)= (ax)(is) x dilution factor (ais)(rf)(vo)

Where: AX = Area of characteristic ion for compound IS =Amount of internal standard injected AIS =Area of characteristic ion for the internal standard RF =Response factor for compound VO =Volume of water purged 11.0 Quality control

11.1 Before analysis begins, a reagent water blank is run to verify that interferences from the analytical system, glassware, and reagents are below

detection limits. Each time a set of samples is run, or there is a change in

reagents, a reagent water blank must be run to evaluate contamination problems.

11.2 Each day that analyses are performed, the daily midpoint calibration standard is run to evaluate the initial calibration curve and to ensure that the GC/MS system is working properly. The analyst’s judgment and experience are crucial in answering the following: Does the chromatography look correct? Is the response obtained comparable to past responses? Have the constituent retention times shifted substantially? Is there any background contamination? If changes are made to the analytical system, the system must be recalibrated.


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11.3 Required instrument QC

11.3.1 For every 12 hours of operation, the mass spectrometer must

meet the ion abundance criteria for BFB as set forth by the EPA.

11.3.2 The GC/MS system must be initially calibrated.

11.3.3 The reagent water blank must be run every workday to verify that no contamination is present.

11.3.4 The initial calibration must be verified every work day by running a

mid-point calibration standard.

11.4 Use the following procedure to determine acceptable accuracy and

precision limits for surrogate standards: 11.4.1 Calculate the percent recovery for each surrogate in each sample

being analyzed.

11.4.2 Once a minimum of 30 samples of the same matrix type is analyzed, the average percent recovery is calculated, and the standard deviation of the percent recovery for each of the surrogates is calculated.

11.4.3 The upper and lower control limits for method performance for

each surrogate standard for a given matrix is calculated as follow:

Upper Control Limit (UCL) = AVE + 3s Lower Control Limit (LCL) = AVE + 3s

11.4.4 Compare the UCL and LCL (as Calculated above) with the control limits listed below, which should have a wider range and can be found in EPA method 624:

SURROGATE COMOUND RECOVERY

4-Bromofluorobenzene 80-120%

1,2-Dichloroethane 80-120%

Toluene (d8) 80-120%

12.0 Each analyst is expected to keep the following instrument logs up to date:

12.1 The analysis run logs for each method.


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12.2 The QC log book.

12.3 The section of the GC/MS maintenance log pertaining to the instrument

being used. 12.4 The GC/MS standards log book.

12.5 The analysis run logbook contains all the samples, spikes, blanks, and

standards, run on the particular instrument involved. 12.6 The QC logbook contains the initial calibration and the continuing

calibrations associated with the instrument involved. It also contains pertinent control charts. There is also documentation in the QC log book containing the BFB standard area log, the internal standards log, and the surrogate standards log. These logs are updated as analyses are completed.

12.7 The GC/MS maintenance log contains down time and services rendered

by outside service personnel or internal staff (e.g., for hardware problems.)

12.8 The GC/MS standards logbook contains the source; date made, and

related information concerning the standards involved in ongoing analyses. This log book is maintained to facilitate locating problems with standard suppliers and standard mixes (e.g.,to recall bad batch standards).


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Appendix 13. SWAMP QAPP

http://www.waterboards.ca.gov/water_issues/programs/swamp/docs/qapp/qaprp082209.pdf


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Appendix 14. ASWA Procedure Manual

PROCEDURES MANUAL FOR WATER QUALITY MONITORING BY THE

AG AND SURFACE WATER ASSESSMENT UNIT

Updated April 2010

PREPARED BY:

CHAD DIBBLE


VICTORIA BOWLES Environmental Scientist

TJ Ditto


Lee Xiong Student Assistant


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Preface

Periodically, changes to procedures will be required. However, due to resource restraints, updates to this document will only be made every five years. To ensure the most current, approved procedure is utilized, modifications will be made following established procedure, documented in Appendix K of this document and summarized below. Summary of Revisions

Change Date of

Revision Location of

Update Procedure for updating this document added 25 March 2010 Appendix K


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TABLE OF CONTENTS

INTRODUCTION .......................................................................................................... 295 GRAB SAMPLES .......................................................................................................... 295

Monitoring Schedules ................................................................................................. 296 Preparation .................................................................................................................. 296 Sample Collection ....................................................................................................... 306

Duplicate and Split Samples ........................................................................................... 310 Sample Processing ...................................................................................................... 312

COMPOSITE SAMPLES (SIGMAS) ............................................................................ 326 Preparation .................................................................................................................. 326 Sample Collection ....................................................................................................... 328 Sigma Sample Processing ........................................................................................... 334

SEDIMENT SAMPLES ................................................................................................. 336 Preparation .................................................................................................................. 336 Sample Collection ....................................................................................................... 337 Sample Processing ...................................................................................................... 337

ADDITIONAL SAMPLING .......................................................................................... 338 ARCHIVES..................................................................................................................... 338 LABORATORY AND FIELD EQUIPMENT DECONTAMINATION/MAINTENANCE ................................................................... 339

Deionized Water ......................................................................................................... 339 Bottles ......................................................................................................................... 340 Inventory ..................................................................................................................... 340 General ........................................................................................................................ 340

SAMPLE TRACKING ................................................................................................... 340 DATA ENTRY ............................................................................................................... 341

Appendices

Appendix A. Monitoring Information Data Sheets Chain of Custody Forms Appendix B. Laboratories Maintenance South Dakota State University Sierra Foothill Laboratory CVRWQCB Laboratory Appendix C. Safety Laboratory Field Vehicle Trouble

Appendix D. Equipment Maintenance and Purchasing


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Appendix E. Parameters, Detection Levels, Holding Times and Analytical

Recoveries Appendix F. San Joaquin River Basin Bacteria Monitoring Program Appendix G. Archive and Sample Storage Procedure

Appendix H. Summary Procedure Sheets (aka “Cheat Sheets”)

Appendix I. Sample Collection Guidelines Additional Constituents

Appendix J. Methods to Develop Spiking Standards

Appendix K. Guideline for Updating this Document

List of Tables

Table 1. Grab Sample Bottle Preparation and Analysis Table 2. Travel and Lab Blank solutions Table 3. Corresponding Pole with Sample Type Table 4. Tool Box and Road Emergency Box Contents Table 5. Standard Constituent Preservation Techniques Table 6. Spiking Concentration Reference Table


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INTRODUCTION The Ag and Surface Water Assessment Unit (ASWAU) of the Central Valley Regional Water Quality Control Board (Regional Board) conducts water quality studies throughout the entire watershed and lower portions of the Sacramento-San Joaquin Delta as part of the statewide Surface Water Ambient Monitoring Program (SWAMP). This manual has been developed to address the combined efforts and serve as a reference document for monitoring by ASWAU staff. The procedures described have been revised from a 1999 document and were reviewed by the SWAMP QA Team in 2008. The QA Team comments have been incorporated into this version. Two companion manuals—San Joaquin Watershed Surface Water Sampling Field Manual (2009) and San Joaquin Watershed Laboratory Manual (2009)—summarize the basic water quality sampling and in house analytical procedures described in this document without the details specific to the SJRUW monitoring efforts (e.g. site locations, laboratories utilized and chain of custody forms). The companion documents are intended as reference material for other programs developing monitoring efforts. Since accuracy and precision are critical to ensuring validity of the data set and any actions or recommendations resulting from the data, ASWAU staff must follow the procedures presented in this program manual. The procedures have been laid out in a stepwise format under the main components of current monitoring programs: grab samples; composite samples; and sediment samples. Each section includes preparation, sampling, processing, and detailed descriptions where needed. This manual also briefly discusses sample archiving, lab and field maintenance, sample tracking, and data entry. In addition, ten appendices have been included with this report: Appendix (A) data sheets, sample tracking and chain of custody forms; (B) information on laboratories; (C) field and laboratory safety information; (D) equipment maintenance and supplies; (E) a summary of parameter, detection levels, holding times and analytical recoveries; (F) in-depth bacteria sampling and processing procedures; (G) procedures for archiving and sample storage; (H) summary sheets for each step of the procedures—aka “cheat sheets”; (I) sample collection guidelines for constituents not included in current monitoring efforts; (J) development of in-house spiking standards and (K) guidelines for updating this document. In this program, above all else, field and lab personnel safety is more important than any sample collected. Any concerns with this program or suggestions for improvement should be brought to the attention of the monitoring supervisor. GRAB SAMPLES Most samples are taken by using a grab sample method at specific site locations, which are usually determined in advance. This section has been divided into four segments: (1) monitoring schedules, (2) preparation, (3) sample collection and (4) sample processing.


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Monitoring Schedules Monitoring schedules are set in advance in order to avoid conflicts with site access and holiday schedules while still maintaining a comprehensive program. An example field sheet can be found in Appendix A. For safety reasons, two person crews are required for each sampling run. It is often part-time staff who are performing the field monitoring therefore it is imperative that the monitoring program supervisors know school and vacation schedules well in advance. Should there be conflicts with the schedule, alert the supervising staff to difficulties so other arrangements can be made. Occasionally it is necessary to schedule an overnight stay due to weather (fog) or for SWAMP studies being conducted. When an overnight trip is required, it is the sampler's responsibility to make hotel reservations and also alert designated personnel that will be setting-up the run, as it affects many aspects of the field monitoring preparation. Below is a list of hotels that are most commonly used. Check for travel restrictions before scheduling overnight trips.

Holiday Inn Express 28976 West Plaza Dr. Santa Nella, CA 95322

1/209/826-8282

Best Western 301 W. Pancheco Blvd. Los Banos, CA 93635

1/800/528-1234

Most hotels require a credit card to hold a reservation and as a security deposit. A travel expense claim form needs to be submitted at the end of the pay period for reimbursement. See your supervisor or the administrative unit for details. Preparation Safety of field personnel and the collection of quality samples rely heavily on field preparation; therefore, it is essential that field preparation be completed with care and accuracy. In addition, it is important to think ahead for any potential problems that may be met in the field such as weather conditions, road conditions, poison oak, ticks, rattlesnakes, hornets, mosquitoes and/or black widow spiders. Field preparation is generally assigned to a Scientific Aid; however, it is each sampler's responsibility to know what will be needed in the field and inspect the field equipment prior to leaving the office. If there are any special circumstances, such as leaving early or needing special equipment, ample notice must be given to those in charge of preparation so they can prioritize accordingly. All procedures must be followed in order to preserve the consistency and validity of results and information. Analytical results will only be as good as the sample collected. The following outlines the standard preparation procedures for each sampling run:


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1) Reserve the vehicle of choice several days (or weeks) in advance. A vehicle with four-wheel drive may be necessary in many instances.

2) Fill out the field sheet, chain-of-custody forms and the bacteria processing sheet

(if needed) (Appendix A). Next, count out the number of each bottle type needed for the specific run.

a. Be sure to include duplicate and/or split samples as well as travel blanks

as needed for QA/QC purposes. 3) Retrieve the sampling bottles and an appropriate sized ice chest to hold them. 4) Premark the sampling bottles according to the completed field sheet. 5) Fill travel and lab blanks if needed.

6) Assemble and check off all necessary equipment on the checklist.

7) Check the vehicle's tires, oil, gas, etc. before leaving to avoid delays out on the

road. Details for each procedure are given below: 1) Vehicle: Based on the monitoring schedule, reserve vehicles for the late afternoon prior to the monitoring date. In addition, the morning after the monitoring day may be reserved for the purpose of cleaning the vehicle. Check the vehicle log envelope to make sure the gas card and a ballpoint pen are included. 2) Field Sheets: An example field sheet can be found in Appendix A. Field sheets contain space for the sample date, samplers, sample identification, field measurements, and QA/QC samples. For consistency and to ensure non-biased laboratory analyses, samples are identified using one of the sampler's initials, date of collection, and a numbering and lettering system, as follows:

INTYYMMDD - ##A, A2, B, S, TOC, Bac, Na, Nb, or Tox INT=sampler's initials YY=year code (example: 2006=06) MM=month code (example: January=01) DD=date code (day of the month) ##=arbitrary number assigned to each site, normally 01 through 60 A=selenium A2=selenium and molybdenum B=boron


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S=total suspended solids TOC=total organic carbon Bac=bacteria Na/Nb=nutrients TOX a-b-c= acute toxicity/a-fathead/b-cerio/c-algae TOX d-e=chronic toxicity/d-fathead/e-cerio

For the same site each bottle is assigned the same site number; however, a different letter (suffix) is used to indicate sample handling and analyses. Analyses and corresponding types of containers are indicated in Table 1. Refer to this table to aid in assigning suffixes to sample ID and preparing bottles. Note that these requirements are for current contract laboratories and are also listed on field sheets for reference. Should the laboratories change, staff should contact the appropriate laboratory to confirm sample containers, preservatives, and holding times. Duplicate or split samples are used for quality assurance programs. Project Managers will determine in advance which locations will be taken as duplicate or split samples by completing the spaces provided on the bottom of the field sheet (Appendix A). The monitoring program supervisor will typically predetermine various duplicate sample locations. For all monitoring efforts, duplicates or splits must be collected at a 10% frequency, with a minimum of one QA sample per sampling run. Chain of Custody: Every collected sample must be tracked by a chain-of-custody form. Bacteria samples (total coliform and E. coli) are analyzed in-house. Fill out a CVRWQCB chain-of-custody for every applicable constituent (Appendix A). Make sure to note on the chain-of-custody whether the constituent needs to be kept cool or if it is preserved with a pH<2 (see preservation procedures). Also note who the recipient of the results and/or invoice will be and the contract number. Every contract laboratory should have its own chain-of-custody form. Should the contracted laboratory change, use the appropriate form or a standard CVRWQCB chain of custody form. COCs specific to the laboratory that the office has a contract with will be available from the Lab Director. When using the office’s lab contract a Lab Request Form must be submitted to the lab director a week prior to sample collection. Bacteria processing sheets: Bacteria samples require a pre-filled out processing sheet (Appendix A) and pre-made labels for the Quanti-trays that are used during processing. Note the bacteria processing sheet has signature spaces acting as a chain of custody form since the analyses are conducted in-house. Labels are made by copying the sample ID’s from the processing sheet onto Avery 5160 labels, which are then set aside for use on the Quanti-trays. Detailed information specific to collection and analyses of bacteria samples is available in Appendix F. 3) Bottles: Retrieve bottles from ASWAU laboratory drawers along with an ice chest(s) in which the bottles can all fit standing up. Bacteria samples are carried separately from other constituents and placed in a small cooler. For safety, verify that the TOC lids are


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tight and rinse the outside of the bottle with DI water to ensure there is no acid on the glass. Table 1 outlines the appropriate bottle type and preparation requirements required by the current contract laboratories. (See Appendix B for more details on current contract laboratories.) QA/QC split samples, are collected in containers twice the normal sample volume (e.g. if a 500 ml sample is required, collect a 1000 ml polyethylene bottle) and marked with both sample ID’s. If splits are not possible (e.g. pre-preserved glass containers), duplicates are collected.


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TABLE 1: GRAB SAMPLE BOTTLE PREPARATION AND ANALYSIS

4) Labeling: Write the sample ID on the side of the bottle with a waterproof marker. Write the sample number and suffix on the cap so both the sampler and those processing the collected samples can easily read it. Place the bottles standing up in the ice chest(s) in order (either by number or site). Include extra empty bottles for potential problems that may arise and to keep the sample bottles from tipping while in transit. 5) Blanks: Travel and lab blanks are included monthly with each field run, and with every run where bacteria samples are collected. Travel blanks are with the samples at all times in the coolers. Lab blanks are prepared at the same time that the travel blanks are, but are left in the laboratory refrigerator until sample processing and transfer. If travel or lab blanks are included in the run make sure they are triple rinsed and filled with the appropriate solution. See Table 2 for each constitutes blank solution and its source:

Suffix Anaylysis Bottle Size Cap Bottle Prep Split Preservation Holding Time Laboratatory

Se and Boron pint red no rinse quart acidify2 SFLPour off 100 mL of B into Boston Round for Se1 125 mL clear condition w/ B SDSU

Pour off into pint for Boron (see B). quart red A/A2: no rinse, condition B w/ A 2 quarts acidify2 SFLPour 100 mL of B into Boston Round (A: Se, A2: Se and Mo).1 125 mL clear condition w/ B SDSU

Na: pint Na: green no rinse Na: quartNb: quart Nb: red Nb: pre-acidified (H2SO4), no rinse Nb: 2 quarts

1 Pour off is done in the lab after the field run and after acidification.2 Acidify with 1 mL reagent grade nitric acid per 500 mL of sample w/in 24 hrs of sample collection.3 Collected in 2 quarts in the field, but composited in a 1/2 gal bottle and then split in the lab after field run.4 Holding time is 28 days, but lab must filter and acidify within 48 hours.

Bacteria QA Bottles PrepField duplicate

Lab duplicate: BacLD

Field blank

Lab blank

Total Suspended Solids (TSS)

Varies by project. See project coordinator.

quart

120 mL VOA/ amber

2 quarts 7 daysgreen

NA

NA

green

no rinse

pre-acidified (H2SO4), no rinse

no rinse

tap H2O rinse, let dry

DOC Dissolved Organic Carbon

TOC

NutrientsNab

B

S

A, A2

TOX

CVRWQCB

CVRWQCB

SC

refrigerate

refrigerateSpecific Conductivity. Performed in-house. quart

NA purchased w/ sodum thiosulfate in bottle

pint

6 mos

28 days

SFL

DFGWPCL

DFGWPCL

SFL

split performed in field

split performed in field

refrigerate

refrigerate

refrigerate

6 mos

BAC

See Bacteria chart below

one 290 ml bottle is required to go into the field, and two 125 ml bottles are required to stay in the lab

two 125 ml bottles are required to go into the field

one empty 125 ml bottle and one 125 ml bottle filled with PBS is required to go into the field

one 125 ml bottle filled with PBS is required to stay in the lab until processing

refrigerateBAC Regulatory: 6 hrs Assessment: 24 hrsBacteria 125 mL

48 hours4

Total Organic Carbon

24 hours

28 days

120 mL VOA/ amber


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TABLE 2: TRAVEL/LAB BLANK SOLUTIONS DI H20 water is created in the CVRWQCB laboratory using a NANO Pure II machine. DMW water and appropriate sampling containers are supplied by the laboratory analyzing toxicity. Type II water is available from UC Davis or through the office laboratory contract, see Appendix F page 130. (Be sure to wear nitrile gloves and a lab coat) Remember to place a note on the small bacteria cooler to remind field crew to grab the bacteria travel blank out of the lab refrigerator before leaving the laboratory. Prepare Ice Chests

Place all grab bottles into an ice chest. It is advisable to place 2-3 extra capped bottles of each type being used inside the ice chest. Always bring at least one extra of each type of pre-acidified bottles.

6) Field Equipment: Each sampler is responsible to inform the appropriate personnel of any problems relating to equipment. See equipment maintenance (Appendix D) for detailed instructions for proper use and maintenance of equipment. The following equipment is used for the field-monitoring program and is assembled in the garage the night before the field run:

Equipment Location

Ag/RB/SWAMP Field Books Calibration Room Clipboards w/field sheets Calibration Room Roadside Emergency Kit Garage ASWAU Locker Toolbox Garage ASWAU Locker First Aid Kit Garage ASWAU Locker Jumper Cables Garage ASWAU Locker pH/SC Kit Calibration Room Bucket (w/ Rope and Insect Repellant) Garage ASWAU Locker

Constituent Solution Source TSS, Boron, TOC, Nab,

Se, Mo DIH20

NANO pure II in CVRWQCB

Lab

TOX De-mineralized Water

(DMW) Sierra Foothill

Laboratory

Bacteria Type II UC Davis


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Potable Water Garage ASWAU Shelf Rain Gear (as needed) Garage ASWAU Locker Floatation Vests (1 per sampler) Garage ASWAU Locker Camera (charge battery) Calibration Room Cell Phone (charged) Calibration Room Map Books (North + South) Calibration Room Sample Poles Garage ASWAU Locker Shovel Garage ASWAU Locker SC Box Garage ASWAU Shelf Sample Coolers Calibration Room Polyethylene 5-gal Bucket Garage ASWAU Shelf YSI MDS + Sonde Calibration Room Vehicle Travel Pouch Admin office (Reserved vehicle)


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All field equipment should be calibrated prior to each field excursion (see Appendix D). In addition, the following procedures apply to selected equipment: Field monitoring books: The field monitoring books contain summarized monitoring information (e.g. site location maps, contact information, etc.), access keys and emergency information for field personnel. Should there be any changes made to the monitoring schedules, the field monitoring books should be updated as well. Field Sheets: Attach the field data sheet to the clipboard with a pencil, extra blank labels, and a photograph sheet of the monitoring sites. Multipurpose meter/sonde: Retrieve the YSI multi-meter from the ASWAU Lab calibration room shelf. Record the identification number of the meter/sonde in the space provided on the field data sheet. Make sure the battery is fully charged and the DO membrane is good (i.e. with no bubbles) for the next day’s use. Also include in the YSI bag a full service kit and a screwdriver. Included in the full service kit are:

• DO membranes • Fine sanding disks • O rings • KCL Solution • Grease • Probe installation tool • Tube brush • Q tips • Batteries

Tracking the YSI meters/sondes used in the field is important for proper maintenance. Calibration of the meter will be conducted the morning of sampling before leaving the office according to the instructions/cheat sheets (Appendix D) located in the calibration room cabinets. The YSI will also be checked or recalibrated after every fifth site and at the end of the run. These results are then recorded on the field data sheet in the space provided (Appendix A). A Myron L SC/pH meter should be included as a back-up for the field runs and stored in the pH/SC kit. Calibration of the meter should be conducted prior to use as a back-up. Calibration instructions for the Myron are on the back of the meter pH/SC kit: The pH/SC kit is an ice chest containing items used for QA/QC during field sampling runs. Staff setting up the run will organize this cooler and augment any supplies as needed. The supplies include:

• SC calibration solution (3900µmhos) (1000 ml bottle) • pH calibration solutions (4, 7, and 10) (1000 ml bottles) • DI water (1000 ml bottle) • Tap water (1000 ml bottle) • Disposable nitrile gloves (small, medium, large, & extra large)


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• Waterproof marker, ball-point pen, pencil, safety glasses, paper towels • Myron L SC/pH meter • Liquid soap • Alcohol spray bottle w/extra alcohol • Stainless steel cup • Ammonia Test Strips

Sampling poles: Sampling poles are used to retrieve a sample up to six feet from the bank. Extensions are available and should be used as necessary. There are both standard surface grab and depth integrated 500 ml/1000 ml sampling poles, PVC toxicity poles, and combination clamp/stainless steel cup sampling poles. See Table 3 below for what pole coordinates with each constitute. TABLE 3: CORRESPONDING POLE WITH SAMPLE

Pole Type Sample PVC TOX (a-b-c-d-e)

Standard and depth integrated 500 ml /1000 ml stainless steel poles Selenium, TSS, Boron, Nab

Clamp/ stainless steel cup metal pole Bacteria,TOC Bucket and rope: A stainless steel bucket (triple rinse) and rope can be used for sampling off a bridge when there is no safe access to the bank or the distance is too great for the extensions. Additionally, the bucket can be used to carry sampling bottles to and from the site. Cellular telephone: The ASWAU retains one cellular phone in the calibration room. While in the field, each sampling team must have a phone for emergencies. Life vests: Even the best swimmers can succumb to hypothermia. The ASWAU has three life vests and additional life vests are available in the office. Life vests should be worn when sampling from bridges, boats, unstable banks, or during periods of extremely high flow. Toolbox (blue) and road emergency box (red): Periodically inspect the toolbox and road emergency box to ensure that the appropriate contents are present and in working order (Table 4).


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TABLE 4: TOOL BOX AND ROAD EMERGENCY BOX CONTENTS

Shovel/spades: Carry a shovel or spade in the truck in case the truck gets stuck and must be dug out. Boots: Each sampler is responsible for being fit for their own rubber boots. If no boots fit the sampler, it will be necessary to have boots ordered. Hip waders can also be ordered as needed. Ice: Prepare bags of ice the day prior to sampling and leave these bags inside the ice machine to be pulled by the sampling crew. Water and food: Drinking water is necessary to maintain normal bodily functions. Bring plenty of water for a day. During the summer, double the amount of water you bring to avoid dehydration. While in the field, convenience food stores are not always available, therefore, pack a lunch and some snacks for the day. Wash your hands prior to eating as we are sampling waterways that may contain unknown contaminants. There are extra water coolers available to carry water for washing hands. Personal protective gear: It is the responsibility of each sampler to think ahead and watch the weather forecast in order to dress appropriately for field monitoring. Rain gear is available in the ASWAU locker located in the garage area. Items that you may want to consider bringing from home are:

• Hiking boots • Heavy coat/sweater/sweatshirt • Hat • Warm gloves • Sunglasses • Sunscreen • An extra change of clothes

Tool Box Road Emergency Box Screwdriver, pliers Flares

Flashlight Reflector triangles Graduated cylinder Fire extinguisher

Duct tape First aid kit Utility knife

Chain w/ locks W-D 40

Sigma tubing Toilet paper

Spare field keys Spare C Batteries w/ YSI Cover

Utility Saw Desiccant


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Other personal items: All field personnel will need a CRWQCB identification card that can be obtained from Scott Mills, 916/464-4688. Carry this card in case you are asked to identify yourself by other agencies or the local growers. Money is also helpful for those unexpected necessities. Double Check: After coolers with samples are placed out in the garage with the appropriate equipment, check all equipment off the checklist. The checklist is located in the garage on the ASWAU shelf. 7) Sign out: Field personnel must sign out on the ASWAU sign out board located in the ASWAU section. Note your time of departure, time expected to return, and the mobile phone number. 8) Vehicle check: Complete the vehicle travel log and check the vehicle's tire pressure, oil, coolant, lights, etc. in order to avoid problems and/or delays while in the field. Report any major maintenance needed to the appropriate personnel and if needed retrieve an alternate truck. Should the vehicle break down when in the field, refer to Appendix C for the proper repair procedure. Sample Collection While in the field you must depend on your own instincts and remember that no sample is worth injury. Therefore, the best rule of thumb is:

WHEN IN DOUBT, GET OUT!!! Be aware of your surroundings at every site

and remember that safety comes first.

For more field safety information see Appendix C.

All procedures must be followed in order to preserve the consistency and validity of results and information. Analytical results will only be as good as the sample collected.

Always verify procedures with the laboratory analyzing the samples. DO NOT FORGET TO WEAR YOUR SAFETY BELT - THEY ARE REQUIRED. The following outlines the standard sampling procedures for each sampling run:

1) Meet at the designated time at laboratory, load all supplies and calibrate the YSI. (Remember bacteria travel blank and ice.)

2) Locate sampling site location.


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3) Collect all appropriate samples at each site including YSI information.

4) Upon returning from the field unload, acidify, and refrigerate appropriate samples. Details for each procedure are given below: 1) Loading: On the morning of the field run, two scheduled samplers will meet in the garage at the designated time. For safety, there should always be two samplers on a field run. One person will load the truck and complete the check sheet, while the other will calibrate the YSI (for calibration instructions see instructions/cheat sheets located in the calibration room cabinets). Do not forget ice and the bacteria travel blank (if needed). 2) Site location: Most sites are located off the road, but be sure to park in an area that is safe from passing cars. Before stepping out of the vehicle, look down as snakes can be waiting under foot. Wear nitrile gloves at all times while handling sample bottles and during sampling. Obtain all sample bottles for the site out of the cooler. Double-check with the field sheet to ensure all sample bottles are accounted for and sample numbers match for that site. Carry the sample bottles, poles, YSI, and field sheet to the collection site. Buckets are useful to carry the sample bottles safely to the collection site and to keep the bottles from blowing away in heavy winds. If sample collection sites remain constant from week to week, remember optimal access may change with the seasons. Assess the site for the best sampling location. What you are looking for:

1. A safe sampling location. 2. A good mixing zone. (Avoid eddies, stagnate water and laminar flow.)

If the site has no flow, record as such on the field data sheet and photograph the site. If a sample location becomes inaccessible record the time on the field sheet with an explanation (take a picture if applicable) and proceed to the next site. 3) Sample collection: The sampling procedure described below is for each constituent currently sampled: TSS, boron, nutrients, TOC, bacteria and TOX. This section also covers duplicate vs. split sample collection, YSI deployment, and the concluding procedure at a site. (Note that selenium and molybdenum samples are poured off from the boron 500 ml polyethylene bottles in the laboratory at a later time.) There are two types of grab sampling methods commonly used in the ASWAU monitoring program: stream bank and mid-channel depth integrated sample collection. Stream bank and depth-integrated sampling are discussed below in the TSS and boron section. TSS/Boron: Using the standard metal pole place the 500 ml /1000 ml bottle onto the end of the pole. Try not to squeeze the bottle too tight so that it will not displace too much water.


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Rinsing Technique and Sample Collection: When rinsing, rinse and discard sample water down-stream of where the sample is to be taken. Try not to disturb sediment or any other debris that could alter the sample. Avoid floating impurities, sediment disturbed by sampling, and organic material. Do not collect sample below the point where the YSI is deployed.

Stream Bank Grab Sample Collection

1. Remove lid.

2. Submerse bottle into sample water area filling about ¼ of the way.

3. Lift sample out of water and move away/downstream from sampling spot.

4. Agitate sample thoroughly, to rinse the inside of the container, and

pour out.

5. Repeat Steps 2-4 two more times.

6. Collect the sample by submerging the bottle below the surface of the water and facing it up stream. Be sure to collect a full bottle and not disturb the bottom sediment.

7. Pour a small amount of the sample into the cap for rinsing, discard

rinse water, and cap the sample.

Repeat this procedure with all 500 ml and 1000 ml polyethylene bottles with exception of the nutrient samples or any other bottle that contains a preservative.

At specific sites a different technique, mid-channel depth-integrated is used to obtain a sample from the entire water column; therefore use the standard metal pole with the depth-integrated extension.

Mid-Channel Depth Integrated Sample Collection

1. Determine the depth of the middle of the channel.

a. Dip the sampling pole (without the bottle, but with the extension) until the bottom of the channel is reached.

b. Note depth of channel by length of pole submerged.


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c. Sampling depth is just above the bottom of the channel, so as not to disturb the bottom sediment. (The length of the sampling pole limits maximum sampling depth.)

2. Remove lid.

3. Immerse sampling bottle into the channel to the maximum

sampling depth. Note how long it takes to fill the bottle by counting (1001, 1002, etc.). The bottle is full when bubbles disappear from the stream surface.

4. Rinse sample bottles as indicated in stream bank grab procedures

steps 2-5.

5. Collect samples by immersing the sampling pole through the water column (without disturbing the stream bottom), and back to the surface in the time that was calculated to fill the bottle. The immersion and removal of the sampling pole should be done in one fairly smooth, even motion.

6. Pour a small amount of the sample into the cap for rinsing, discard

rinse water, and cap sample.

7. Indicate on the field sheet whether a Grab sample or a Depth-Integrated sample was collected.

Nutrients (Nab): Nutrient “a” (green cap) bottle is treated just like a TSS or Boron sample (Refer to TSS/Boron section for procedure) Nutrient “b” (red cap) bottle has H2S04 inside, so DO NOT rinse the Nb bottle. Fill the Na sample bottle after rinsing the bottle three times. Then fill the Nb bottle with the Na sample water and rinse cap with Na sample water. Then collect the Na sample, and cap. TOC: TOC bottles contain H2S04, so be careful not to spill when uncapping and filling (DO NOT rinse the TOC bottle). Using the stainless steel cup and metal pole, rinse and fill the cup using sample collection steps 2-5, stream bank grab (above). Then pour the sample water into the TOC bottle being careful not to overfill it. Bacteria Collection: Specific bacteria collection procedures can be found in the San Joaquin River Basin Bacteria Monitoring Program document (Appendix F).

TOX a-b-c-d-e: Using the PVC pole secure 2 TOX bottles in the pole cups with the latex rubber tubing. If it’s not a duplicate site, put sample letters together: i.e. 55 A1 and A2. (If duplicate see below) Next, follow the rinsing technique and sample collection procedures, steps 1-7 of stream bank grabs.


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Note there are two glass bottles for each Acute TOX a, b and c sample, and there are four glass bottles for each Chronic TOX d and e sample.

Duplicate and Split Samples Duplicate and split samples can be used to either evaluate the precision of the analyses or determine the heterogeneity of the sampling site—depending on the analyte’s tendency to “clump” (e.g. bacteria) and/or move in tandem with flow patterns (e.g. suspended solids). Splits tend to be more effective at determining analytical precision, while duplicates more effectively evaluate sampling precision and/or heterogeneity. Field duplicate and/or split samples are generally collected at 10% of the total samples collected. The samples are submitted blindly along with other samples collected during a monitoring run. Each constituent is collected in the following way:

1. TSS is collected in two 1000 ml bottles and later composited then split in the laboratory. See splitting procedure in processing section below.

2. Boron is collected in one 1000 ml bottle and later split in the laboratory. See splitting procedure in processing section below.

3. TOC samples are split in the field. Split the sample water between the two TOC bottles making sure to stir the cup frequently to prevent any sediment from settling. It is ok to grab more sample water to finish filling both TOC bottles.

4. Bacteria split samples are collected in 250 ml sterile polyethylene bottles that contain sodium thiosulfate and split in the laboratory during processing. See bacteria processing for splitting procedure (Appendix F).

5. TOX duplicate samples are taken simultaneously on the same PVC pole: i.e. If 55 and 16 are duplicates, put 55 A1 and 16 A1 together on the pole, etc.

YSI: Field parameters are measured using a YSI 650 MDS with either a 600 XLM sonde or 6920 sonde attached to it. The full manufacturer’s instructions for the YSI equipment are located in the calibration room cabinets.

The steps to take field measurements are as follows: 1. Remove the YSI from canvas carrying bag and exchange the calibration cup with the

weighted strainer.

2. Turn on the YSI and select the run mode prior to deploying sonde into the sample environment.

3. Place the sonde at a point where there will be flow past the probes when taking readings. When there is no flow, move the sonde up and down in the water if possible, without disturbing the sediment.

4. After stabilization has occurred, record the appropriate parameters on the field data sheet (e.g. time, dissolved oxygen, specific conductivity, pH, and temperature).


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5. After collecting parameters, return the calibration cup to the sonde and store the data-logger/sonde assembly in the canvas storage bag.

Check /or calibrate the YSI anytime during the run if values seem “abnormal” and before and after Kesterson Wildlife Refuge.

At the end of the run, rinse the probes and calibration cup with tap water. Perform a final calibration check and record values on the field data sheet. Return the calibration cup to the sonde by threading moderately tight to retain a slight moisture level inside the cup (this will prevent the probes from drying).

Before leaving site: The following information should be recorded on the field data sheet before leaving each site:

1. Time (in military format), temperature, SC, DO, and pH of the sample site.

2. Any relative factors that may influence results such as change in flow (low, medium, or

high), diversions or other uses being made of the water, weather, or overland flow.

3. Photographs should also be utilized when significant changes have occurred and once a month when indicated on the field sheet. Be sure to document the picture number on the field sheet at each site. Photos should generally be taken at the same location each time the site is photographed and in a manner that gives reference to the change in the water body (e.g. upstream and downstream of a noticeable discharge or with a bridge or some sort of size reference in the picture.

Double check the area for any equipment that may have been left or is not properly secured for the remaining trip. Keep all samples on ice until they can be preserved in the laboratory. Extremely saline samples (SCs > 20,000 µmhos/cm) should NOT be chilled since the salts will precipitate out of solution. 4) Returning from the Field: Contact: Contact the processing personnel to inform them of your estimated time of arrival. At that time they will prepare to assist the field crew in the unloading, bacteria processing, acidification, and clean up. For anticipated late arrivals, ask ASWAU personnel to extend the truck reservation until the following workday if necessary. Gas and Wash: Gas up and wash the vehicle before finalizing the travel log and returning the vehicle to the pen. It is the responsibility of the sampler to return the truck with a full tank of gas and clean inside and out. Many gas stations have discounted car washes with a fill up of gasoline. The following gas station provides discounted car washes and is located within a mile of the Rancho Cordova office.


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Flyers Shell #65 3096 Sunrise Blvd.

Rancho Cordova, CA 95670 [credit card accepted (discounted car wash with fill-up)]

To clean the interior of the truck use a hand brush and damp paper towels to clean the floor and dash areas.

As noted previously, it is possible to clean the truck the following workday as long as the truck is reserved by unit staff for the following workday. Sample preservation, splitting and storage: Keep samples on ice or in the Ag Laboratory refrigerator until preservation/process occurs. Unload samples from cooler. Preserve boron samples within 24 hours of collection to a pH<2 with reagent grade nitric acid (see sample processing). Once preserved keep samples in the fume hood for later processing. Split TSS samples (see splitting procedure) and place all samples required to stay cool in the laboratory refrigerator (see Table 5). Sign in the samples to the refrigerator on the sign in sheet next to the refrigerator. The person that meets the crew will process the bacteria samples (see Appendix F). Sign Chain of Custody forms: Complete the appropriate chain-of-custody forms for the samples that were collected (Appendix A). The field preparation personnel will have previously completed these forms for the sampler's ease. Mark through samples that were not collected and/or add samples that are not included. Sign the completed form to relinquish samples to the Ag Lab or Refrigerator. Put the COC’s next to the appropriate samples, i.e., if samples are in the refrigerator put the COC’s in a zip lock bag and place in refrigerator or if samples are in fume hood place next to samples. Cleanup: Dry out the ice chests with paper towels before returning them to the shelf in the calibration room; prop open the lid to aerate and prevent mildew. Clean all of the equipment that was used and return to proper storage locations. Report any equipment maintenance to the appropriate personnel. Sample Processing To maintain sample integrity and ensure viable laboratory results, appropriate handling of samples after collection is essential. It is necessary to commence sample processing promptly after the collection of samples in case there are any unusual developments or questions in regards to the samples collected, such as excessive amounts of sediment or pungent odors. Note any abnormalities of samples on the data sheet in addition to alerting ASWAU staff, as there may be a need for immediate action. All personnel must wear nitrile gloves while handling samples. Wearing safety glasses is recommended and required when handling samples with pH<2 or during processing and pulling bacteria. For more laboratory safety information see Appendix C.


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As deadlines change frequently and unexpected emergencies arise, it is the responsibility of the laboratory personnel to prioritize the order in which samples are processed while ensuring sample integrity. Therefore, laboratory personnel in charge of sample processing must advise ASWAU staff of the need for assistance. As part of the SJR Water Quality Monitoring Program, the following procedures have been developed for processing samples collected:

1) Preservation 2) Measurement of Specific Conductivity (SC) 3) Splitting Samples 4) Spiking Samples (usually once a month) 5) Sample Transfer/Shipment to Contract Laboratories

6) Bacteria Processing

Details for each procedure are given below: 1) Preservation: The preservation techniques for the various constituents commonly analyzed in the different programs vary, see Table 5. Always verify with the laboratory analyzing the samples. TABLE 5 : STANDARD CONSTITUENT PRESERVATION TECHNIQUES

Temperature: All samples are immediately cooled with ice upon collection. Depending on analyses required, selected samples are acidified within 24 hours. For other constituents it is

Constituent Standard Preservation Selenium, Molybdenum, and Boron

pH<2 within 24 hours using ACS grade nitric acid (for trace element analysis)

TSS and Minerals temperature (4 °C)

TOC pH<2 with H2SO4, temperature (4 °C)

Nutrients temperature (4 °C), store in dark, Ammonia add 2mL of H2SO4, (deliver to laboratory w/in 24 hrs for processing),

Toxicity Temperature (4 °C), store in dark (deliver to laboratory w/in 24 hours)

Bacteria Sodium thiosulfate (keep at 4 °C until time of process)

Specific Conductivity Keep at 4 °C and store in dark until time of process)


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common to continue temperature preservation in the ASWAU laboratory by transferring the sample to the laboratory refrigerator. Acidification: It is common for most trace elements, as well as Boron (depending on analytical technique), to be preserved with nitric acid to a pH<2. Acidify the appropriate samples upon arrival from the field. If time does not permit immediate acidification, refrigerate the samples and acidify within 24 hours. ALL ACIDIFICATION IS TO BE CONDUCTED UNDER THE HOOD WITH THE FAN ON. PROTECTIVE GEAR (LAB COAT, APRON, NITRILE GLOVES, AND GOGGLES/SAFETY GLASSES) MUST BE WORN. TWO PEOPLE MUST BE PRESENT AT ALL TIMES DURING THE ACIDIFICATION PROCESS. The standard amount of reagent grade nitric acid needed to preserve to a pH<2 is 1.0 mL per 500 ml. Therefore, 500 ml and 575 mL samples require 1.0 mL of acid while 1000 ml samples require 2.0 mL of acid, and 125 mL samples are preserved with 0.25 mL of acid. Check the pH of all samples following acidification to ensure the pH is less than 2. For samples with higher buffering capacities, such as evaporation pond water, additional acid may be needed in order to bring the pH<2. Record the amount of acid added to each sample on the COC’s. Lab blank samples are submitted monthly which allows for evaluation of contamination from the ACS grade acid on low level samples. Follow the steps below for sample acidification. Remember another person has to be present while one is performing the following procedure:

1. Turn on the laboratory ventilation system. 2. Put on protective gear (lab coat, apron, gloves, and goggles/safety glasses).

Protective gear is required. 3. Assemble samples to be preserved in hood and loosen caps. 4. Obtain the Acid Wash Bucket and fill with 1 quart of tap water and 2 to 3 tablespoons of

baking soda. This will be kept under the hood with you as you acidify. 5. Obtain the acidification only labeled clean glass beaker and pour the approximate amount

of 70% nitric acid to be used. (See Appendix D for cleaning laboratory glassware.) 6. Obtain the appropriate Eppendorf automatic pipette (adjustable or fixed) labeled "FOR

ACIDIFICATION ONLY" and a bag of pipette tips. 7.. If necessary, adjust the volume setting to 1000 µL (250 µL for samples in 125ml Nalgene

polyethylene bottles) as follows: a. Push in the side button located next to the control button.


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b. Turn the control button to select the volume (When changing the volume to a higher setting, turn the display past the desired volume and then back to the designated volume.)

c. Lock the setting in place by releasing the side button.

8. Attach a pipette tip as follows: (Pipette tips are easily contaminated, so DO NOT

TOUCH THEM WITH YOUR FINGERS OR TO ANYTHING ELSE.)

a. Insert the Eppendorf automatic pipette into the pipette tip bag. b. Attach a pipette tip securely by pushing on the sides of the tip while still in the

bag.

Precautions: Do not let acid inadvertently enter the pipette by extracting too quickly or tipping the instrument upside down to avoid drips (the suction within the pipette will be adequate). The acid will destroy the internal mechanisms as well as the reliability of the device. Should the acid enter the pipette itself, refer to equipment maintenance for seal replacement. Make a conscious effort of always handling the pipette with the tip pointing downward even when there is nothing in the tip. Doing this will demonstrate good laboratory practice and alleviate potential contamination errors when using the Eppendorf pipettes.

9. Rinse the tip one time with nitric acid prior to preserving samples as follows:

a. Press the control button down to the first stop (measuring stroke). b. Hold the pipette almost vertical. c. Immerse the pipette tip approximately 1 cm into the nitric acid to be used. d. Allow the control button to glide back slowly, never let it snap back. e. Dispense the first filling (rinse) into the nitric acid wash bottle located in the hood

by pressing the control button slowly down to the first stop (measuring stroke) and waiting 1-3 seconds, until continuing to press the control button down to the second stop (blow-out), which will deliver any remaining liquid in the pipette tip.

f. Refill the pipette tip with acid. g. Position the pipette almost vertical to the bottle in which the filling is to be

dispensed without touching bottle or sample. h. Dispense the acid into the sample bottle.


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i. Tighten the cap after preserving each sample as a reminder that the sample has been preserved. Additionally, avoid distractions while preserving samples, as it is easy to forget which samples have been preserved. If any confusion should arise, use pH paper to help identify preserved samples before continuing.

10. Follow steps outlined in 8 (a-i) to dispense appropriate amount of acid to each sample for preservation.

11. When all samples are preserved, rinse the pipette tip with water by recreating the tip

filling procedure. Dispose of the pipette tip in the garbage by holding the pipette over the container and depressing the control button all the way down until tip falls off.

12. Pour remaining acid into the nitric acid wash bottle located in the hood.

13. Rinse the glass beaker with DI water. Then put it into the “needs to be acid washed”

box, which is stored under the lab carts, to be acid washed later (Appendix D).

14. Return pipette and tips back to the acidification/spiking drawer located in the ASWAU laboratory.

15. After preservation of samples mix each sample thoroughly to obtain a homogeneous

mixture. Check the pH of all samples following acidification to ensure the pH is less than 2. Verify the pH by pouring small amount of sample into cap and then dip pH paper into sample in cap to read pH level. Dump contents of the cap into the Acid Wash Bucket so as not to introduce any outside substance to the sample.

16. Record the amount of acid added to each sample in the COC.

17. See Appendix D for appropriate neutralization procedures.

2) Measurement of Specific Conductivity (SC): The YSI 3200 Conductivity Instrument is used for reading in-house SC measurements and is kept in the ASWAU laboratory area. The following procedures were developed for consistency in measurements. Calibration solutions are available for water from varying matrices.

1. Set Up

1. Place paper towels in front of the YSI meter.

2. Fill two 600mL beakers with DI water and place them in front of the meter.

3. Retrieve the temperature probe from the box next to the YSI meter and plug it into the meter. The SC probe should already be plugged in and is sitting in an Erlenmeyer flask filled with DI water next to the YSI meter.


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4. Place the probes in the first beaker, swirl them around without touching the sides or bottom of the beaker. Do the same in the second beaker. This will be done after each sample to rinse off the probes.

2. Calibration

Note that all quality control SC readings should be noted on the appropriate field sheet with the current date, time, SC standard reading (start-, mid-, and ending- sample-set measurement), and the initials of the staff conducting the readings. A mid sample set measurement of the SC standard is necessary on larger sample sets (10 or more).

1. Fill a 100mL beaker with calibration solution.

2. Place both probes in the solution, swirl them around to get an accurate reading. Again, do not touch the sides or the bottom of the beaker. If it reads within ±20 of standard when using standards of 1417 or greater, log this number on the field sheet as “Start SC” and skip to “operation”. Program directors are allowed to specify the allowable drift for when designing their monitoring programs when using calibration standards with lower specificities; however the allowable drift for each program must be within the requirements for SWAMP. SWAMP QAPP states that the specific conductivity allowable drift is within 10%. If the SC measurement is out of range, keep the probes in the calibration solution and proceed as follows:

i. Press “cell” and verify the following numbers are in place:

[Single] Cell Cal [1.000] K [Linear] Comp [1.91] %C Comp val [0.68] T.D.S. mult [25.0] C Comp Temp

ii. If the above configuration does not match what is on the screen, press

“configure” and enter the correct values. a) Press “enter” to accept the revised values. b) Press “mode” to get back to “cell.”

iii. Press “CAL K.”

iv. Press “SINGLE PT.”

Note that before proceeding, make certain the temperature and K are stabilized.

V. Enter the value of the standard solution at the current temperature. Use the following equation to determine the above.

N25 (1 + α (T – 25 ) = NT

Where T =temperature of sample


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N25 = conductivity of the standard solution at 25ºC NT = conductivity at measurement temperature T α = temperature coefficient of the conductivity solution (1.91%/ºC = 0.0191ºC)

Note different solutions temperature coefficient can be determined manually (pg 48 of YSI Model 3200 Manual) or the YSI 3200 can calculate it (pg 17 of the YSI Model 3200 Manual)

vi. Enter the calculated NT number (round when needed)

vii. Then press “enter” to set K.

viii. Press “mode” until you get back to the “operation” screen.

ix. Check the SC reading of the calibration solution. If not in range, go back to “a”. If ok, proceed as follows. Log the above as “Start SC” on the field sheet.

3. Operation

a. To rinse, place the probes in the first DI water beaker, swirl them around without touching each other or the sides/ bottom of the beaker. Do the same in the second DI water beaker. Carefully wipe the excess water from the probes onto the paper towels.

b. Shake sample and remove cap.

c. Place the probes in the sample to be measured.

d. Swirl the probes around for about 3 seconds, without touching the sides, the

bottom of the container, or each other.

e. Let the meter stabilize and then record the SC measurement to at least 3 digits (more if the number is stable).

f. Repeat steps a-e until all samples are tested. Put the probes back in the calibration

solution to take and record the “End SC” reading. If there are more than 10 samples, a “Mid SC” reading is also required after processing half the samples being analyzed.

4. Cleaning and Storage


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a. Place the SC and temperature probes in a small beaker with Scrubbing Bubbles and water. Let the probes soak for a few minutes.

b. Rinse out the 600mL beakers and wipe down the counter.

c. Thoroughly rinse off the SC probe. Return probe in the Erlenmeyer flask with

fresh DI water.

d. Thoroughly rinse the temperature probe, dry it off and put it back in the box. 3) Splitting Samples: Collecting duplicate samples is done in compliance with QA/QC programs as explained above in Sample Collection. The 1000-ml samples for TSS, Boron and Nutrients are later split in the laboratory. TSS duplicate 1000 ml bottles are first composited into an acid washed ½ gallon container (triple rinse). Note these containers are labeled “Bottle split. Do not discard. Rinse 5%.” The following is the sample splitting procedure:

1. Obtain the appropriate sample bottles. 2. Mark the bottles with the sample identification, site numbers, and suffix, in the same

manner that they were prepared for the run. It is helpful to prepare these bottles during sample preparation.

3. Thoroughly shake the sample to ensure a homogenous mixture. 4. Rinse the 500 ml /1000 ml bottles three times with the sample as follows:

a. Pour a small amount of the sample in each bottle. Note that if there is a visual difference in the sample, i.e. one has more sediment than the other, make sure to rinse with equal sample volume from each bottle.

b. Cap the bottles and shake vigorously in order to coat all sides of the bottle with the sample.

c. Pour out the rinse water, note acidified sample water needs to be poured into a

bucket with tap water for later disposal (Appendix D).

5. Repeat 3 and 4 a-c twice. 6. Thoroughly shake sample.

7. Pour equal amounts of sample water, about a quarter at a time, into the rinsed 500 ml

bottles going back and forth between each bottle. Be sure to shake the sample between each pour. Rinse the caps and cap the sample.


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4) Spiking Samples: Analytical accuracy of contract laboratories is determined by submitting blind, spiked samples at least once per month. ONLY TRAINED PERSONNEL HAVE AUTHORIZATION TO CREATE THE BLIND SPIKES. The following steps are to be used as a guideline and may require adjustment to fit the specific needs of a project or the constituent being tested. The procedure below is for spiking one split field sample and one DI lab blank. You will need the following items to perform this procedure:

• 4 - 500 ml Volumetric flasks • Spiking Standards • Eppendorf pipette labeled “For spiking only” • Pipette tips • 1 - 25ml beaker (acid washed) • 2 1000 ml; one field sample and one duplicate field sample that has been

previously split • 2 1000 ml of DI H20 (triple rinsed) • ~3ml of HNO3 • Paper Towels • Blank Spike data sheet • Spike flow chart

Choosing a field sample: To choose the most representative sample to be spiked follow the criteria below:

1. Choose a duplicate sample that will be analyzed for all constituents of concern (selenium, molybdenum, and boron etc.)

2. Choose a duplicate sample with adequate amounts of water collected to allow for spiking

and analysis of the unspiked sample (~2 1000 ml). Spiking procedures: If you are in doubt about any part of the process, ask other qualified ASWAU personnel for clarification. Filling out the flow chart in Appendix A can help in clarification and can be used as a cheat sheet if needed. SAFETY GEAR MUST BE WORN FOR THIS PROCESS, AS YOU WILL BE DEALING WITH NITRIC ACID AND HIGH CONCENTRATIONS OF TRACE ELEMENTS. Select a time when there will be no distractions, as this process requires your full attention.

1. Verify pipette calibration by measuring 1 mL of water on analytical scale. 1 mL of water weighs 1 gram.

2. Obtain a blank spike data sheet. (see Appendix A).

3. Complete the sections "spiked by," "project," and "date."


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4. Determine the samples to be spiked (see Choosing a field sample above for criteria) and fill in the sample identification for each section (selenium, molybdenum, trace metals, minerals). Three new sample numbers will be made; one for the spiked field sample and two for the lab blank samples. For the lab spike follow the field run numbers, initials and date. For the lab blanks follow normal labeling procedures (see Grab Sample Section).

5. Indicate the site code of the field sample or put DIH20 for the lab spike and blank

samples in the space provided on the right side of the field sheet. 6. Determine the amount of spike needed and amount of standards to be used and enter the

appropriate amounts on the spike sheet. (The goal is to double the expected constituent concentration. So if the sample historically contains 10 μg/L of selenium, the spike should be 10 μg/L to give a final concentration of 20 μg/L.)

7. Fill out a spike flow chart (this will help with organization)(Appendix A).

8. Label the DI water 1000 ml with the given sample ID number on the spike data sheet. 9. Line up the field sample 1000 ml (Note that the duplicate sample is the one to be spiked)

and the DI water 1000 ml in the fume hood. 10. Obtain four 500 mL volumetric flask stored with a 1% nitric acid solution in the ASWAU

supplies cupboard and place in front of each 1000 ml. Carefully dispose of the acid solution bath into a bucket half full of tap water (see disposal procedures in Appendix D).

11. Lay a clean laboratory paper towel down for each flask and state on the paper towel

whether it is a spike, normal, DI spike, or a blank sample. 12. Rinse 3 times with the appropriate 1000 ml sample water. Shake each 1000 ml and fill

the appropriate volumetric flask half full of the sample water.

13. For the DI samples only, add 2ml of 70% HNO3 to preserve the sample (the field samples are already preserved). Follow the preservation procedure.

14. Pull standard out of the refrigerator and place in fume hood. 15. Obtain the Eppendorf pipette labeled "For Spiking Only" and a bag of clean pipette tips

from the supplies drawer.

16. Spike as follows:

a. Obtain standard spiking solution and uncap the lid


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b. Adjust the pipette to the measurement indicated on the spike sheet. Use a clean disposable tip. Remember to not touch the pipette tips with fingers, sample, or anything else that may cause contamination.

c. Pour standard solution into standard solution bottle lid. To rinse pipette tip, extract

from the standard bottle lid the specific amount of standard and dispose of it into the acid wash bucket.

d. Extract the specified amount again and dispense into one of the flasks labeled to

spike. Dispense directly into the sample and not down the sides of the flask.

e. Repeat step 14d for additional flasks to be spiked.

17. Shake the remaining 1000 ml sample and pour the sample into the flask until the meniscus is just below the etched line.

18. Using the pipette, a clean pipette tip, and the given sample, fill the flask until the bottom

of the meniscus is even with the etched line on the flask. Do this for each flask, using a new pipette tip for each sample.

19. Cap all flasks and shake thoroughly.

20. Pour each sample into the appropriate 500 ml bottles as shown in the pre made spike flow

chart (make sure to triple rinse first).

21. With the left over sample (if enough) from the duplicate 1000 ml bottle pour the remaining sample into the now empty normal 1000 ml bottles flask (Do not rinse flask again). Note look at the spike flow chart for clarification. Follow steps 16-19.

Final spiking cleanup:

1. Return spiking solution, the pipette, and pipette tips to the appropriate location.

2. Discard any remaining sample from the volumetric flask

(Appendix D). Clean the volumetric flasks as follows:

a. Rinse flask with a small amount of DI water. b. Dispense a small amount of 5% nitric acid into the volumetric flask, cap, and

shake in order to coat all sides of the flask. Discard liquid into acid wash bucket half full of tap water (see Appendix D).

c. Rinse three times with DI water. d. Fill the flask with DI water to approximately the etched marking.


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e. Add approximately 8 mL of 70% reagent grade nitric acid to make a slightly stronger than 1% storage solution (see preservation procedures in the Grab Sample Section).

f. Cap the volumetric flask and return it to the fume hood cupboard.

3. Discard contents in acid wash bucket (see Appendix D). Clean the

waste bucket by rinsing with tap water.

4. Wipe down the fume hood.

5. Add samples to COC that contains the grab samples to previous days run.

5) Sample Transfer/Shipment to Contract Laboratories: All samples are stored in the RWQCB laboratory area or refrigerator as this area is considered secure from Regional Board visitors and locked during non-business hours. Once samples have undergone preservation, splitting, and spiking, the samples must be prepared for shipment or transfer to the contract laboratories. See Appendix B for details on current contract laboratories and maintenance. Shipping bottles: Samples to be analyzed for selenium and molybdenum are sent in 125 mL Nalgene polyethylene bottles. The labels created below are used for sample identification on the 125ml Nalgene polyethylene shipping bottles. The labeling procedure is as follows:

1. Line up the sample 500 ml bottles (for boron) in order along the counter and place an empty 125ml Nalgene polyethylene bottle in front of each sample.

2. Place the corresponding label on the 125ml Nalgene polyethylene bottle horizontally.

Pour-off: Although the transfer of samples from a 500 ml bottle to a 125ml Nalgene polyethylene bottle may seem simple it is important to follow the instructions below:

1. Double check that the sample ID on the 500 ml bottle matches the sample ID on the 125ml Nalgene polyethylene bottle.

2. Shake the sample to be poured-off to ensure a homogenous mixture. 3. Pour a small amount (~10 mL) into 125ml Nalgene polyethylene bottle. 4. Cap 125ml Nalgene polyethylene bottle and shake to thoroughly rinse the inner walls of

the bottle and cap. 5. Dispose of rinse water into bucket half filled with tap water for later disposal (Appendix

D).


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6. Repeat steps 3-5 two more times.

Note If not enough samples volume, e.g. 500ml sample very low, single rinse for the boston round has been found adequate and can be performed if needed. Record on COC if single rinse was performed.

7. Reshake the 500 ml bottle prior to final pour-off.

8. Pour sample a cm below the neck of the 125ml Nalgene polyethylene bottle. It is

necessary to send the laboratory a sample at least 3/4 full of water for selenium and/or molybdenum analyses—but not so full that should the sample freeze during shipment, the top might pop off.

9. Cap both samples tightly. 10. Repeat steps 1 through 7 until all samples are poured-off. 11. Place the samples in laboratory ID order in a 10x8x8 sized box lined with a garbage bag.

Each box can hold 40 samples. Shipment preparation: Samples needing priority analyses are normally sent separately but can be sent with the other samples if the timing coincides. Instructions for mailing are listed below.

1. Review the shipping sheet copies by checking that all information is complete (i.e. analyses required, sample identification, and expected ranges; site codes and names are blocked out).

2. Seal garbage bags around samples, place the shipping sheet copies in each box, use

packing material in boxes that are not full, and tape each box closed. 3. Shipment of boxes is conducted by:

FedExStaffed Federal Express 11140 Suncenter Dr

Rancho Cordova, CA 95670 1/800/463-3339

Our office has an account set up with this company. Original shipping sheet(s) and tracking label(s) are to be placed into the “in box” of the contract manager. Pick up schedules: Some laboratories may pick up samples at the CVRWQCB Laboratory for analyses. Sample pick up schedules are generated by ASWAU laboratory personnel through a review of monitoring schedules, analyses holding time limits, and personnel schedules.


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Chain of custody review: Upon the arrival of the laboratory representative, review the chain of custody forms for completeness. The main areas to review are to compare sample identification to the actual samples, analyses necessary, and appropriate signatures. Sample transfer: The laboratory representative will arrive before 12:00 pm on the arranged pick up day with empty coolers and ice for sample transport. ASWAU personnel must be present at all times while the laboratory representative reviews the chain of custody forms to ensure all samples are present. Once the review is complete, ASWAU personnel sign the chain of custody to release the samples over to the laboratory representative. The laboratory representative will then sign the chain of custody form to receive the samples. Retain the yellow copy of the chain of custody forms as a receipt and place in the “in box” of the contract manager. To ensure the integrity of the samples, make sure the samples stand upright in the transfer coolers and are not stacked. In addition, samples that are temperature preserved must continue to be chilled with blue ice or ice. Bacteria Processing (In-House) Bacteria processing is completed at the CVRWQCB laboratory (in-house). Procedures for processing bacteria samples, pulling sample trays and QA/QC can be found in Appendix F.


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COMPOSITE SAMPLES (SIGMAS) Composites are collected using American Sigma 800 SL, 900, and 900 MAX--Streamline Portable Wastewater samplers (Sigmas). Sigma automated sampling machines are designed to collect samples from a liquid source, including surface water, wastewater, light sludges, industrial wastewater, etc. They can be programmed to collect water samples on an hourly, daily, or composite basis. Currently the 900 MAX units are primary used with the 800 SL and 900 units being used as backup samplers. Each sampling unit consists of three main parts; a top cover, central control section, and the bottle/base section, all of which are made of ABS plastic. Each Sigma sampler is completely self-contained, and may be completely exposed to the elements without need for shelter. A rechargeable gel battery powers each unit. Batteries are normally rotated every two weeks. Sigma samplers collect water samples on a timed basis. The frequency and the volume of samples collected are programmable to accommodate a wide variety of desired monitoring programs. This chapter has been divided into three sections: (1) preparation (2) sample collection and (3) sample processing. In addition, Appendix D further details equipment maintenance and troubleshooting. Preparation Scientific Aids generally perform sigma preparation along with the grab sample preparation. Remember that the safety of field personnel and the collection of quality samples rely heavily on field preparation as explained in grab sample preparation. All procedures must be followed in order to preserve the consistency and validity of results and information. Analytical results will only be as good as the sample collected. The following outlines the standard preparation procedures for servicing a sigma:

1) Fill out the sigma field sheets following the labeling instructions. 2) Set up equipment.

3) Prepare QA/QC samples.

4) Set out equipment.

5) Review key terms for collecting samples.

Details for each procedure are given below: 1) Sigma Field Sheets: A copy of an example sigma field sheet can be found in Appendix A. Sigma field sheets contain space for the sample date, sampler’s initials, sample identification,


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and QA/QC samples. A copy of the past weeks sigma field sheet is necessary to fill out the QA/QC sample info. Follow the labeling procedure below to identify samples: Labeling: It is critical for the validity of our sampling program that each sample be labeled correctly. The following standard procedures will be used for this program. In general, the sample ID is similar to the identifications used for grab samples except that a three-letter site code is used rather that the sampler’s initials and the date stands for the date that the last increment for the composite sample was collected as follows:

XXXYYMMDD where:

XXX = site ID code YY = the year

MM = the month DD = the date the last part of the composite sample was collected

All samples collected by the Sigma program are labeled with the suffix –01, except for quality assurance/quality control samples. Quality assurance/quality control samples will be randomly labeled with the suffixes -02, -03, -04, -05, -06, –07, -08 and –09. 2) Equipment: Below lists most of the items needed to service each Sigma Sampler during the standard, biweekly servicing:

• Sigma base(s) w/acid washed/labeled (see sigma field sheet)/capped wedge bottles (one bottle filled with DI H2O)

• Extra wedge caped bottle and SC bottle (500 ml) for G1 (details below) • Charged Battery (24 hour charge) • Sigma field sheets (Appendix A) • Gallon of DI H2O • Pad lock keys to access sampler • Gate access keys (If needed) • Toolbox (screw driver, scissors, graduated cylinder, duct tape) • May or may not be needed:

o Desiccant o Extra intake tubing o Extra bottles

In addition to the above items, you will also need to bring a completely functional sigma unit, including all appropriate components to allow field Sigmas to be serviced on a rotational basis. In the event that a unit in the field is damaged, missing, or stolen, the extra Sigma can be deployed. Sigmas are located in the ASWAU area of the garage. Sigma components are located in the ASWAU calibration room within the laboratory. 3) QA/QC samples: The QA/QC samples include a DI blank to be placed in position 23 and remain until the following servicing, a Sigma grab sample (G2) to be placed in position 24 and


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remain until the following servicing and a Sigma grab sample (G1) returned to the office to be submitted for laboratory analysis. 4) Set out: The above equipment is put out in the garage the night before the field run along with the grab sample equipment. Make sure to check off all appropriate equipment on the check-list that is located in the garage area. 5) Key Terms: It is essential to know the various programming terms displayed by the Sigmas and what they mean in order to correctly program and troubleshoot the equipment. The most common terms are listed below: Time-Proportional Sample Collection: The sigma will collect samples based on time intervals under this mode. Enter the number of hours and minutes between sample collection. The most commonly used intervals are 4 hours for six samples per day frequency and 12 hours for two samples per day frequency. Samples/Bottle: An ENABLE response to this message allows the programmer to select the number of samples collected in each bottle. This is the appropriate selection for our needs because the machines are programmed to composite samples; six samples/bottle/day or two samples/bottle/day. Bottles/Sample: An ENABLE response to this message allows the programmer to select the number of bottles liquid is discharged into per sample. For example: the Sigmas can be programmed to collect a single sample in 3 bottles if a large amount of water is needed for analysis. This function is not commonly used in ASWAU’s standard monitoring procedures. Start/Stop Times: This feature allows the programmer to start and stop a program at pre-arranged times. Program stop times are generally set for twenty days after program start date. This allows for continued sampling in case the Sigma cannot be serviced on the normal two week schedule, but will not allow the QA samples to be over-topped. Sample Volume: If selected, this function allows the operator/programmer to increase or decrease the volume of liquid collected per sample. Volume Calibration: This function is sometimes used in the field if the expected volume of sample has not been collected in the container. It allows the operator/programmer to manually calibrate the volume using a graduated cylinder. Intake Rinse: This function allows the programmer to select the number of times the Sigma will pump water into the line in order to flush out the tubing, and clear it of any debris prior to sample collection. The current monitoring program requires two rinses. Intake Retries: This function allows the programmer to select the number of times the Sigma will attempt to collect a sample, even if the first or second attempts result in failure. The current monitoring program allows two faults. Sample Collection


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The following instructions are intended to provide enough information to service and collect samples from the Sigmas. The instructions are not written in a site specific format because there may be differences in set up at each site. The instructions focus on the standard collection procedure of six samples composited in each 575-ml bottle. The following outlines the procedure for sample collection:

1) Safety precautions 2) Collection

3) Field maintenance 4) Trouble shooting

1) Safety Precautions: After a few trips servicing the Sigmas, the procedure may seem routine and uneventful. Unfortunately, accidents can happen any time, to anyone, regardless of experience. Individuals who service the Sigmas need to be aware of potential hazardous conditions. Following a few simple rules and being aware of, and acting accordingly to, the potential hazardous conditions may help avoid serious injury.

GOLDEN RULE: WHEN IN DOUBT, GET OUT. If you suspect that you may be putting yourself in danger in order to collect a sample, don’t

do it. No monitoring program is worth serious bodily injury to the sampler. Many potential hazards are unique to each Sigma location, while other hazards are common to all sites. The following below is intended to bring about awareness of the major hazards at all sites. Since the Sigmas are compositing samples over a period of time, the composition of the samples may contain potentially toxic constituents such as sewage and pesticides. Therefore, disposable nitrile gloves must be worn when servicing the samplers. The disposable nitrile gloves are located in the SC/pH kit. Sigmas are located next to surface water, the presence of snakes is always a potential problem. Most snakebites occur on the legs of the victim, so use over-the-ankle field boots or rubber boots as added protection against unwelcome attacks. By the same token, when walking through tall grasses and vegetation, be on the look out for ticks and other insects landing on your body. It is advisable to wear light colored long pants and long sleeve shirts when field sampling. The light colors allow the sampler to easily identify any unwanted hitchhikers such as ticks. When opening the doors of the locked cabinets or sigma lids, watch for insects (e.g. wasps, spiders, and other biting insects). When reaching around or handling the Sigmas, never place you hand into dark or blind places without looking first. Otherwise, you may be the recipient of a nasty sting. For more information on field safety see Appendix C.


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2) Collection: Samples collected using the auto-samplers are not preserved in the field. The containers are not specially insulated to maintain a constant temperature. Acid cannot be added to the bottles to lower the pH since volatilization will cause the condensation of the acid on the inside surfaces of the samplers and may also impact the electronic components of the machinery. Samples remain at ambient conditions until removed from the unit every two weeks. Therefore, when servicing each Sigma, two grab samples (G1, G2) are collected using the unit as the collection device to verify that there are no potential losses/contamination due to samples being unpreserved while in the sigma. The intake line is rinsed twice, prior to sample collection. One grab sample (G2) is left in the sampler, then collected and analyzed two weeks later. The other grab sample (G1) is taken back to the lab for standard processing. These two grab samples are then treated similar to duplicate samples and must pass QA/QC (see Appendix B) for unqualified use of the associated sample data. In addition to the grab sample left in the Sigma unit, a blank composed of deionized water is placed in the Sigma and analyzed after it is removed at the next servicing. Although the Sigmas are not programmed identically, the following procedures can be used with minor adjustments. These procedures are primarily for the use with the Sigma 900 MAX units because of the frequency of their use in the field, however, the 800SL and 900 units are similar. The following is the setup procedure for the 900 MAX Sigma unit: Note if the sigma is left untouched for over 2 minutes, the screen will automatically turn off. Touch any key to turn it back on. Sigma data entry sheets are necessary for sigma sample collection (Appendix A). Review Sample History:

1. Remove cover. 2. Press the RUN/STOP key twice to halt the program. 3. Press the MAIN MENU key and then select STATUS. 4. Scroll through data and record the information required by the datasheet. When done,

press the MAIN MENU key. 5. Select the SETUP option and then select REVIEW ALL ITEMS. 6. Record the remaining information required by the datasheet. 7. The CURRENT TIME is located in the upper left hand corner of the screen at all times. 8. Press MAIN MENU when done.

Replace Base: 1. Remove the Sigma from the base and cap all bottles using caps from replacement base. 2. Note sample volume collected. If too little collected or apparent overflow, go to the

calibration section and calibrate. 3. If the last bottle needs to be topped off, use sigma grab sample procedure. DO NOT fill

from distributor arm with the Sigma still attached to the base. Grab Samples:


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1. Collect three grab samples (G1, G1 SC, and G2). 2. Disconnect the pump tubing from the Sigma. 3. Press the MANUAL MODE key. 4. Select PUMP OPERATION. 5. Press PURGE until bubbles appear in the water, and then press any key to stop. 6. Press PUMP until the water has circulated to the top of the hose, and then press any key to

stop. Repeat these last two steps followed by one last PURGE to ensure that the line is adequately conditioned.

7. Fill the G1, G1 SC, and G2 bottles by inserting the pump tubing into each bottle and pressing PUMP.

8. Record the time of grab sample collection on the Sigma Field Sheet. 9. Put the G1 and G1 SC bottles in the ice chest with the other grabs for processing. 10. Put the G2 bottle in slot #23 of the replacement base. Sigma Rotation: 1. Have two half-gallon jugs of DI water available (wide mouth bottles preferable). 2. Disconnect the pump tubing from the Sigma. 3. Press the MANUAL MODE key. 4. Select PUMP OPERATION. 5. Remove the intake tubing from the water and access the strainer. 6. Press PURGE again to remove all water from the line. 7. Place strainer in the “RINSE” DI container. 8. Press PUMP until DI water exits pump tubing. 9. Remove strainer from DI water and PURGE until tubing is clear. 10. Repeat the purge and pump steps one more time. 11. Using the “FOR SAMPLE” DI container, PUMP DI water into collection bottle labeled

equipment rinse. 12. Rotate old Sigma with the new unit and attach the new battery and hose. 13. Sign and date the new and old batteries in the proper location. Volume Calibration:

To allow complete drainage of the intake line and proper calibration, install the sampler above the sample source, with the intake tubing sloping downward to the sample and make sure that the intake tubing is free of kinks or loops. 1. Within the MAIN MENU select OPTIONS. 2. Locate and select VOLUME CALIBARATION. 3. Select MANUAL CALIBRATION.

a. Remove the pump tubing from the Sigma at the point where it enters the base. Direct the tubing into a large graduated cylinder to collect the sample.

4. Select START PUMPING. a. Collect the sample and measure the volume delivered within the graduated

cylinder. 5. Select DONE.


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6. Enter the actual volume of sample collected into the space provided. 7. Select ACCEPT. 8. To return, press the MAIN MENU key. 9. Re-attach the pump tubing.

Checking the volume calibration:

It is important to check the final calibration after the program setup is complete. This sample is collected from the distributor arm under the Sigma to mimic an actual sample collection as closely as possible.

1. This sample is collected from the distributor arm under the Sigma to mimic an actual

sample collection as closely as possible. (Said twice on purpose ) 2. Remove the sampler from the base containing the bottles. 3. Prop the sampler on a flat surface exposing the distributor arm for sample collection.

Double check the pump tubing to be sure that it is attached. 4. Press the MANUAL MODE key on the keyboard. 5. Select GRAB SAMPLE. 6. Confirm that the grab sample volume is that which is desired and place the graduated

cylinder or collection bottle at the end of the distributor arm and press ACCEPT. 7. If the proper volume is pumped, press the MAIN MENU key and proceed to creating the

new program. If the volume is incorrect, recalibrate and repeat process. 8. Place the new sigma on the base. Be sure bottle #1 is in the correct position for the

control unit in use (different starting positions for the 800 vs. 900 sigma units). Creating a new program:

1. Press the MAIN MENU key and select the SETUP option. 2. From this menu, select MODIFY SELECTED ITEMS. 3. Scroll down to:

a. ADVANCED SAMPLING -SELECT

b. START/STOP TIMES -SELECT

c. START/STOP TIMES PROGRAM BY TIME: i. ENABLED.

-ACCEPT d. METHOD OF ENTERING START STOP TIMES:

i. TIME/DATE. -ACCEPT

e. BEGIN WITH BOTTLE #1 ON EACH NEW START: i. DISABLED.

-ACCEPT f. PROGRAM START #1:

i. 12:00 AM Day-Month-Year. -ACCEPT


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(1) Start date should correspond to the day after servicing. g. PROGRAM STOP #1:

i. 12:00 PM Day-Month-Year. -ACCEPT

(1) Stop date should correspond to three-weeks (21 days) after start date. h. PROGRAM START #2:

i. Press CLEAR ENTRY and then ACCEPT. ii. This will void out multiple starts and stop times.

4. Press MAIN MENU on the keypad to return to the main menu. 5. To start the new program, press the RUN/STOP key on the keypad and then any key.

The bottom left hand corner of the screen should say “running”. 6. Make sure that the distributor arm is in the #1 position, and the pump tubing is connected

before assembling the Sigma. Verification Checks: On the Sigma field sheet in the bottom left corner initial the following after verification:

1. Recheck bottle placement and labels. 2. Distributor arm in number 1 position (800Sigma’s and 900max positions are different and

marked on the inside of the base). 3. Program is running. 4. Pump tubing is connected. 5. Hand tight housing bolts.

Completion:

1. Replace top cover, lock up and secure the site. 2. Make sure sigma data sheet is completely filled out, make note of any partially full

samples or anything out of the ordinary. 3. Put the G1 sample with the G1 SC sample into the cooler with ice.

3) Field Maintenance: Often times, things happen in the field that the staff cannot control such as damaged tubing, clogged strainers, and fluctuating water levels. Therefore, standard maintenance is performed during each sample collection and during sigma rotations. Performed every Sigma servicing:

1. Replace the old battery with a freshly charged battery. 2. Check the condition of strainer by removing it from the stream, visual inspection is

usually adequate, free the strainer of any unwanted debris, clear off and away any debris that may clog the strainer with the brush in the field kit.


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3. After removing the strainer, inspect the clear intake tubing for any cuts, cracks, holes, or gashes that may be a result of age, improper placement, or other forces at work. Replace tubing if needed. (Be sure to check length against original.)

4. Visually inspect the condition of the interior wall of the intake tubing, the tubing should

be free of any algae, scum, or foreign material. If it is not clear, replace. 5. Check the condition of the desiccant (humidity indicator), replace if needed. (The

relative humidity inside the electronics housing is determined by the color of the indicator. The desired dry condition exists if the humidity indicator is blue. If the indicator is pink or white, the desiccant bag should be replaced and the electronics housing should be inspected for seal failure.)

6. Replace intake tubing as needed.

Performed every sixty days: Sigmas are removed from the field and swapped with a newly serviced unit every sixty days. Once removed from the field, the Sigmas are then cleaned (in-house) and all tubing and desiccants are replaced. The Sigmas are then inspected for any necessary repairs; calibrated; programmed; and stored in the garage for future use. 4) Trouble Shooting: The most common problems encountered in the field include: clogged intake tubing; incorrect sample volume; incorrect programming; and no response from the control unit when activated. For these and other problems encountered, refer to Appendix D under "Sigma Trouble Shooting." Sigma Sample Processing There are several steps involved in processing Sigma samples. These steps include measuring specific conductivity, preserving the samples to a pH<2, pouring the sample into separate containers for shipment to various analytical laboratories, and the actual transfer to analyzing laboratories. Sigma samples require specific conductivity measurements prior to acidification; therefore, it is necessary to delay the preservation with nitric acid. In addition, laboratory SC measurements are typically taken when the sample is at room temperature, since the samples were un-refrigerated when they were in the field. If sample processing will commence the day after sample collection, the Sigma samples may remain at ambient temperature. Should there be any delays in sample processing, refrigerate the Sigma samples until processing is initiated. Preservation to a pH<2 should take place within 24 hours of sample collection. Therefore, Sigma laboratory SC measurements are considered high priority in order to expedite sample preservation. The following sections detail:

1) Specific conductivity measurements

2) Preservation of samples


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3) Pouring off sigma samples

4) Transfer to analyzing laboratories 1) Specific Conductivity Measurements: Since the SC measurements are taken directly from the sample to be analyzed the potential for cross contamination is increased with the insertion of the probe and thermometer. Therefore, SC measurements must be conducted following the special instructions below.

1. Calibrate and process samples on the YSI 3200 Conductivity Meter as detailed in the

Grab Sample Section of this report, with the following additions: a. Separate the Sigma samples into sets according to site.

b. After every 10-measurements and/or each set, rotate out the rinse beaker with a beaker of

clean DI water. *Note a mid sample set measurement of the SC standard is necessary on larger sample sets (10 or more) such as those associated with Sigmas. 2) Preservation of Samples: Preservation of samples is conducted in the same manner as that describe in the Grab Sample Section of this report (page 21). All preservation is done using reagent grade nitric acid to a pH<2. Safety clothing must be worn at all times and the preservation must take place in the fume hood with the fan on. Refer to sample preservation for specific procedures. 3) Pouring Off Sigma Samples: Since the samples are initially collected in specialized containers designed for the Sigmas, the water must be transferred to containers that will be submitted to the analyzing laboratory. This transfer only takes place after the SC is measured and the sample acidified. The procedure is outlined below:

1. Label the appropriate bottle with the sample ID for each sigma sample collected. 2. Place all sigma samples in a row along the laboratory counter top. 3. Place the corresponding, labeled new bottle in front of the sigma samples. 4. Have a small bucket half full with tap water to dump excess liquid (Appendix D). 5. For each sample:

a. Shake the sigma container to thoroughly mix the contents.


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b. Uncap the new bottle and pour in a small amount (approx. 10 to 20 ml) of sample.

c. Cap the new bottle and shake container. d. Discard rinse from the new bottle into bucket.

e. Repeat rinse 5a-d two more times

Note If not enough samples volume, e.g. sigma sample very low, a single rinse has been found adequate and can be performed if needed. Record on COC if single rinse was performed.

f. Fill the new bottle with remaining water from sigma container.

g. Recap the new bottle.

6. Place Sigma wedge container and cap into sink to be rinsed (Appendix D).

4) Transfer to Analyzing Laboratory: Once the Sigma sample has been transferred to the appropriate laboratory container, follow the normal sample transfer procedures outlined in Grab Sample Section. SEDIMENT SAMPLES Sediment samples are collected using scoops or core tubes that are provided from the contracted laboratory and are typically analyzed for toxicity, TOC, and grain size analysis. Occasionally samples are taken in conjunction with bioassessment monitoring so care must be taken regarding substrate disturbance. Preparation The laboratories will need at least three weeks notice that a sediment sampling run is going to occur so that bottles can be prepared and shipped, test animals can be ordered and the laboratory can prepare the space to run the samples. The first step is to conduct an inventory of shoulder length gloves (see next page) and then contact the Moss Landing Marine Laboratory (MLML) coordinator, which is currently:

Marco Sigala 7544 Sandholdt Rd.

Moss Landing, Ca 95039 (831) 771-4173

Marco will send an excel spreadsheet where you will fill in the sites to be sampled and the analysis that will be performed at each site. Marco will then ship coolers with all the necessary


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bottles, bottle labels, COC’s, sampling scoops or core tubes, shipping labels, and a cooler contents sheet that details the number of each type of bottle included in the cooler. Upon receiving the cooler from Moss Landing it must be inspected to ensure all the necessary bottles, labels, COC’s, and sample scoops or core tubes are included. The number of bottles for each analysis and instructions for the sample handling is included in the contents sheet. The next step will be placing the labels on the bottles and filling out the field sheet for the run. Sediment samples do not go to the laboratory “blind”. This means that the field sheet will be labeled with the SWAMP site code including the hydrologic unit number and site code. The bottle labels are preprinted by MLML and include the following:

1. Station ID: This will be the SWAMP station ID including the hydrologic unit number. For example 541STC516

2. Sample Code: This is an internal SWAMP code and will be filled out by MLML 3. Matrix: This indicates that the samples are Sediment and will say SEDAnalysis 4. Type: This indicates what analysis will be run on the sample. 5. Project ID: This is assigned by MLML 6. Date/Time: To be filled in by the sampler on the day of collection.

Field sheets will be filled out exactly like a normal water sampling run with the exception of the sample numbers. After the inventory of equipment and all bottles are labeled it will be necessary to collect the special gear needed for sediment sampling. Note that this equipment is in addition to the normal sampling and safety gear outlined elsewhere in this manual. Sediment sampling equipment needed includes: All the above that came in the coolers from MLML, Chest waders of the appropriate size, shoulder length gloves (these are supplied by MLML and stored in the ASWAU section of the garage. Do an inventory check before contacting MLML for the sample bottles etc.), and a write in the rain pen. Sample Collection Sample collection procedures follow those outlined in the SWAMP Sampling Document: http://www.waterboards.ca.gov/water_issues/programs/swamp/docs/reports/sopfieldmeasures_sedimentcollection.pdf Sample Processing Upon returning to the office the samples will be handled differently according to the analysis being performed and the laboratory they will be shipped to. All samples are first checked into in the CVRWQCB laboratory refrigerator with the appropriately filled out COC forms prior to any shipment to the contracted laboratories. Shipping: Toxicity samples must be wrapped well in bubble wrap, then packed in the coolers supplied by MLML with double bagged wet ice (note that the cooler will not be shipped, even if in mid transit, if it is leaking in anyway. Triple bag the ice if you feel it is necessary to avoid


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leaks) and the COC’s (COC’s should be placed in a sealed Ziploc bag and taped to the lid of the cooler). Also include the used scoops or core tubes in coolers. They will be acid washed and reused. Place the Cal Overnight shipping tag supplied by MLML on the cooler, fill in the service options: Sunrise – By 10:30am. Billing information: Bill Shipper’s Account. Estimate the cooler weight (note that the cooler must be kept under 100 lbs or it will not be picked up by Cal Overnight. Put the samples into two coolers if necessary) and then call for a pick up. The shipping tag should be pre labeled with the Granite Canyon Laboratory information. Grain size and TOC samples are shipped to Applied Marine Sciences, Inc. and must be wrapped in bubble wrap and placed in a small cooler with double bagged wet ice (again shipment will cease if the cooler is leaking). The COC and a cooler return request letter must be placed in a sealed Ziploc bag and taped to the lid. Fill out an office FedEx shipping tag to ship the samples.

Pesticide samples are normally bagged with their COC’s and placed in the large freezer in the CVRWQCB laboratory until confirmation of toxicity. Should confirmation of toxicity of a sample come, remove the frozen samples that will go out for analysis, fill out the COC, then place in a cooler with bagged wet ice. The samples are to be hand delivered to the Department of Fish and Game, Water Pollution Control Lab. Call ahead of time to make sure that there will be someone there to meet you and check in the samples. ADDITIONAL SAMPLING Past sampling efforts have included collecting water from wells, filtering samples in the field, and acidifying samples in the field. Summary procedures for these efforts have been documented in Appendix I. For any additional sampling refer to the SWAMP sampling document and QAPP: SWAMP Sampling Document: http://www.waterboards.ca.gov/water_issues/programs/swamp/docs/reports/sopfieldmeasures_sedimentcollection.pdf SWAMP QAPP: http://www.waterboards.ca.gov/water_issues/programs/swamp/docs/swamp_qapp.pdf ARCHIVES The extensive Grassland sampling program has remained relatively continuous for over 25-years and therefore provided a unique opportunity to archive surface water from key sites throughout various seasons, water year types, and man-made adjustments to the valley’s hydrology. Since 1983, water has been archived on a monthly basis from:

• The San Joaquin River at Lander Ave. (MER522)


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• Salt Slough (MER531) • Mud Slough (north) upstream of the San Luis Drain (MER536) • Mud Slough (north) downstream of the San Luis Drain (MER542) • The San Joaquin River at Hills Ferry (STC512--discontinued in 2000) • The San Joaquin River at Crows Landing (STC504); and • The San Joaquin River at Airport (SJC501)

Samples to be archived are culled from the samples returned every six months from South Dakota State University. Once the required samples (which includes spike, equipment blank, trip blank and lab blank samples) have been pulled and recorded in the archive log (located at T:\R5S Sections\Irrigated Lands Assessment Planning\Units\AG Surface Water Assessment\Sampling\Archive Logs), the 125ml boston round Nalgene bottles are topped off with remaining sample which has been kept in house. The remaining samples are the 1000 ml (A bottles) containers on the ASWAU shelves in the garage in boxes marked with the month and year. The 125ml bottles are filled to within one half inch from the top in order to allow expansion during freezing. These samples are then stored in the ASWAU freezer. Once the archive samples are frozen, the remaining sample is discarded (Appendix D) and the remaining 1000 ml and 125ml sample bottles are rinsed with tap water and taken to a recycling facility. A detailed procedure of the above is located in Appendix G. LABORATORY AND FIELD EQUIPMENT DECONTAMINATION/MAINTENANCE Throughout the sample collection and processing procedures there is a limited amount of clean up required to maintain the integrity of the samples. However, to prevent cross contamination and ensure equipment accuracy, periodic decontamination and maintenance of the laboratory and equipment is required. Below is a list of some basic areas of importance. Deionized Water The bottle washing process and other procedures use large amounts of deionized (DI) water. To produce DI water by using the NANOpure II equipment, follow the steps below:

1. Place the hose leading from the NANOpure II system (held by a burette clamp when not in use) into the sink.

2. Simultaneously, push the red power button on while turning the final filter switch open

(down). (The red power button is located on the left side of the four filters under the LCD display window. The final filter switch is located above and to the right of the four filters.)

3. The LCD display should begin flashing numbers. Once the reading on the LCD display

stabilizes (around 17.9-18.0), place the hose from the sink into the DI containers. Be careful not to overfill!


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4. Once finished, simultaneously push the red power button off and turn the final filter switch closed (left).

5. Record the date, amount of DI produced, and user's initials on the record sheet in the

drawer to the right of the system to aid in timely filter replacement and maintenance of the NANOpure II equipment. Note that when the LCD displays 16 or less, filters will need to be changed (Appendix D).

Bottles Depending on sample collection protocol, certain bottles are reused so require acid washing decontamination. The bottles used in the Sigma samplers must be reused. Consequently, periodic washing is necessary. Table 1 provides a summary of the types of bottles used for the monitoring program. See Appendix D for detailed instructions on bottle preparation/cleaning. Inventory

Review laboratory and field supplies needed based on the monitoring schedule. A minimum of a three month supply of necessary equipment and supplies should always be on hand. An inventory of supplies is conducted in the months of March and September. At that time, a six-month supply of necessary items is ordered. A major inventory of all the ASWAU equipment is conducted annually in July. At this time, every piece of equipment should be accounted for and the condition noted. Arrange equipment servicing at this time if needed. General Fume Hood: Any laboratory glassware should be removed, cleaned and put in the appropriate drawer. Non-labeled glassware and solutions under the fume hood should be brought to the attention of the laboratory coordinator. Countertops: Reorganize items normally left on the countertops (pH/SC solutions, paperwork, etc.) to gain optimal countertop work space. Wipe down the countertops with water. Field: Field equipment is maintained on a regular basis. See Appendix D for maintenance schedules and procedures for various field equipment. Field Safety Equipment: The safety equipment requires frequent checks as equipment may break, batteries die, and first aid supplies expire. If you use any safety supplies, alert supervisor so that proper actions can be taken and supplies can be replenished. For more laboratory and field equipment maintenance see Appendix D. SAMPLE TRACKING


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Detailed sample tracking is covered under laboratory contract maintenance, however, a less formal method is used to track sample progress during data entry to verification. Tracking logs are located: T:\R5S Sections\Irrigated Lands Assessment Planning\Units\AG Surface Water Assessment\SWAMP Database\Tracking logs. Information on the above tracking log procedure is located in the T:\R5UNITS/R5S Sections/Irrigated Lands Assessment Planning/Units/AG Surface Water Assessment/SWAMP Database/Tracking logs. DATA ENTRY Data entry occurs in five stages:

1) Field Data 2) QA/QC Results 3) Data Entered 4) Data Verification 5) Data Validation

The actual process for entering the data is outlined in the SWAMP Database training document (T:\R5S Sections\Irrigated Lands Assessment Planning\Units\AG Surface Water Assessment\SWAMP Database\SWAMP Binder_ASWAU) , which has the appropriate methods for entering, verifying and finally validating all entered results. Before the information is added to the database, it must first pass acceptable analytical recovery criteria outlined in each programs QAPP. The following briefly summarizes the data entry stages.

1) Field Data:

1. Once laboratory SCs are complete, the original field sheets are copied. 2. Originals are filed chronologically by sample date in the field data binder (Sigma sheets

are filed chronologically by site).

3. Copies are placed in the “Data to be Entered” basket. 2) QA/QC results: After the analytical results pass the quality assurance criteria outlined in each

programs QAPP, copies of the results are placed in the “Data to be Entered” basket.

3) Data Entered: Field data is entered directly into the database, as per the SWAMP Database training document. Lab Data is entered into an excel spreadsheet corresponding with the run number.


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4) Data Verification: Field Data:

1. After a data entry session, printouts are made of the field entered data. 2. The printouts are clipped to the appropriate copies of the field sheets and/or results and

placed in the “Data to be Verified” basket in the data entered cubical.

3. A separate person reviews the printouts, verifies the entries, and if:

a. Correct, put “data ok” with dated initials and record in the tracking log. Then place the verified data, sorted by analyte and date, in a box labeled by water year.

b. Incorrect then put data not ok with dated initials and place in the “Amends” basket to be corrected and verified again.

Lab Results Data

1. After the lab report is entered into an excel spreadsheet, a separate person reviews the excel sheet directly. Any mistakes are fixed and the excel sheets progress is tracked using the tracking logs.

2. The lab results are reviewed again by a test loader and then again by the person who

will actually load the results into the SWAMP Database. This whole process is tracked using the tracking logs.

4. Data will be synchronized with the master database at Moss Landing Marine Labs on a weekly basis.

5) Data Validation: On a quarterly basis, verified SC, selenium, and boron data are plotted for each site to determine potential outliers (e.g. unusually high or low values). Any outliers found should be brought to the attention of the project manager immediately.


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Appendix 15. References

American Public Health Association, et al. 2006. Standard Methods for the Examination of Water and Waste Water, 19th edition, or later. Available at: http://www.standardmethods.org/

Central Valley Regional Water Quality Control Board (Central Valley Water Board). 2010. Procedures Manual for the San Joaquin River Water Quality Monitoring Program.

Central Valley Water Board. 2016. The Water Quality Control Plan for the Sacramento River and the San Joaquin River Basins (Basin Plan). 4th Edition.

Federal Register Volume 49, No. 209, Friday, October 26, 1984, EPA, 40 Code of Federal Regulations, Part 136.

Hach Company, Hach. 2008. Portable Turbidimeter Model 2100P Instrument and Procedure Manual. Available at: http://www.hach.com/fmmimghach?/CODE%3A4650088-2008-0416048%7C1

State Water Resources Control Board (State Water Board). 2008. SWAMP Quality Assurance Program Plan. Available at: http://www.waterboards.ca.gov/water_issues/programs/swamp/docs/qapp/qaprp082209.pdf

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Yellow Springs International, YSI. 2012. EXO Water Quality Sonde User Manual—Advanced Water Quality Monitoring Platform. Available at: http://www.ysi.com/productsdetail.php?EXO1-Water-Quality-Sonde-89


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http://www.ysi.com/productsdetail.php?EXO1-Water-Quality-Sonde-89