Guidance Manual for Environmental Site Characterizationin ...

1 Guidance Manual FOR Environmental SITE CHARACTERIZATION IN SUPPORT OF Environmental AND HUMAN HEALTH RISK ASSESSMENT VOLUME 4 ANALYTICAL METHODS PN 1557 ISBN 978-1-77202-032-8 PDF Canadian Council of Ministers of the Environment, 2016 Volume 4: Analytical Methods i TABLE OF CONTENTS TABLE OF CONTENTS .. I ACKNOWLEDGEMENTS .. V ABBREVIATIONS AND ACRONYMS .. VI X 1 2 PARAMETER GROUP DESCRIPTIONS ..3 Organic Parameters Group ..4 Acid/Base/Neutral Extractable Organic Compounds (ABNs)* ..4 Chlorophenols (CPs) and Non-Chlorinated Phenols (NCPs)* ..4 1,4-Dioxane* ..4 Glycols ..4 Organochlorine Pesticides (OCs) ..5 Organotin Compounds ..5 Perfluorinated Sulphonic Acids, Perfluorinated Carboxylic Acids and their Salts* ..5 Pesticides and Herbicides (P&H)*..6 Petroleum Hydrocarbons (PHCs) ..7 Polychlorinated Biphenyls (PCBs) ..7 Polychlorinated Dibenzo-p- Dioxins/Dibenzofurans (PCDDs/PCDFs).

2 7 Polycyclic Aromatic Hydrocarbons (PAHs) ..8 Trihalomethanes (THMs)* ..8 Volatile Organic Compounds I (VOCs) ..8 Volatile Organic Compounds II: Benzene, Ethybenzene, Toluene, Xylenes (BTEX) ..9 Organics Single Analysis Parameters (ORPs) ..10 Inorganics Parameters Group ..10 Metals ..10 Inorganic Single Analysis Parameters (ORPs) ..11 Coliforms ..11 Cyanobacteria ..11 3 SAMPLE HANDLING AND STORAGE REQUIREMENTS ..12 Table 3A: Soil and Sediment Sample Handling and Storage Requirements ..14 Volume 4: Analytical Methods ii Table 3B: Water Sample Handling and Storage Requirements ..15 Subsampling ..18 Procedure: Soils and Sediment Inorganic/Other Regulated Parameters ..18 Procedure: Soils and Sediment Organic Parameters ..18 Procedure: Water Samples Inorganic/Other Regulated Parameters ..19 Water Samples Organic Biotic Samples ..21 4 ANALYTICAL METHODS ..22 Organic Parameters Group.

3 24 Acid/Base/Neutral Extractable Organic Compounds (ABNs) ..24 Chlorophenols (CPs) and Non-Chlorinated Phenols (NCPs) ..25 1,4-Dioxane ..26 Glycols ..27 Organochlorine Pesticides (OCs) ..28 Organotin Compounds ..30 Perfluorinated Sulphonic Acids, Perfluorinated Carboxylic Acids and their Salts ..30 Pesticides and Herbicides (P&H)..31 Petroleum Hydrocarbons (PHCs) ..36 Polychlorinated Biphenyls (PCBs) ..39 Polychlorinated Dibenzo-p- Dioxins/Dibenzofurans (PCDDs/PCDFs) ..41 Polycyclic Aromatic Hydrocarbons (PAHs) ..44 Trihalomethanes (THMs) ..45 Volatile Organic Compounds I (VOCs) ..46 Volatile Organic Compounds II: Benzene, Ethylbenzene, Toluene, Xylenes (BTEX) ..48 Organics Single Analysis Parameters ..49 Inorganic Parameters Group ..53 Metals ..53 Inorganic Single Analysis Parameters ..55 Coliforms ..81 Cyanobacteria ..82 5 REPORTING ..84 Laboratory Reporting Limits (LRLs).

4 84 Volume 4: Analytical Methods iii Table Laboratory Reporting Limits Water and Soil/Sediment ..85 Reporting Requirements ..118 Sample Dilution ..119 Elevated Non-target Analyte or Matrix Interferences Resulting in LRLs above the Standard ..120 6 REQUIRED QUALITY ASSURANCE/QUALITY CONTROL (QA/QC) ..121 Accreditation ..121 Initial Method Validation ..121 Initial Demonstration of Acceptable Precision, Accuracy, Selectivity and Specificity ..121 Initial Assessment of Method Detection Limits ..122 Determination of MDL for Summed Parameters ..124 Determination of MDL or LRL for Subtracted Parameters ..124 Calculation of Toxic Equivalence MDL ..125 Measurement Uncertainty ..126 Periodic Re- evaluation of Performance ..127 Quality Control Samples ..128 Table 6-1: Performance Criteria Acid/Base Neutral Extractable Organic Compounds (ABNs), Chlorophenols (CPs), Perfluorooctanesulphonate (PFOS), Polycyclic Aromatic Hydrocarbons (PAHs).

5 131 Table 6-2: Performance Criteria 1,4-Dioxane ..133 Table 6-3: Performance Criteria Diisopropanolamine; Glycols; Nonylphenol and its Ethoxylates; Organochlorine (OC) Pesticides; Organotin Compounds; Pesticides and Herbicides Carbamates, Glyphosate, Phenoxy Herbicides; Polychlorinated Biphenyls; Sulfolane ..134 Table 6-4: Performance Criteria Petroleum Hydrocarbons F1-F4 (PHCs)..135 Table 6-5: Performance Criteria Polychlorinated Dibenzo-p-Dioxins/Dibenzofurans ..136 Table 6-6: Performance Criteria Volatile Organic Compounds (VOCs), Trihalomethanes (THMs), BTEX ..137 Table 6-7: Performance Criteria Fraction Organic Carbon (FOC) ..139 Table 6-8: Performance Criteria Methyl Mercury ..140 Table 6-9: Performance Criteria Ammonia (Total and Un-ionised); Chromium, Hexavalent Cr(VI); Cyanide (CN ) ..141 Volume 4: Analytical Methods iv Table 6-10: Performance Criteria Boron, Hot Water Soluble (HWS); Chloride; Fluoride; Mercury; Metals; Nitrate; Nitrate + Nitrite; Nitrite; Nutrients (TN Phosphorus; Sulphate.)

6 142 Table 6-11: Performance Criteria Dissolved Oxygen (DO) ..143 Table 6-12: Performance Criteria Conductivity (EC), Salinity ..144 Table 6-13: Performance Criteria pH ..145 Table 6-14: Performance Criteria Colour (True); Reactive Chlorine Species*; Suspended Sediments (Total Suspended Solids); Turbidity; Total Dissolved Solids ..146 Table 6-15: Performance Criteria Sulphur (elemental) ..147 Table 6-16: Performance Criteria Coliforms Total, Coliforms Fecal (Escherichia coli)* ..148 7 REFERENCES ..149 APPENDICES ..152 Appendix 1. Alphabetical List of Compounds / Regulatory Criteria / Laboratory Reporting Limits ..152 Appendix 2. Participants and Affiliations ..180 Volume 4: Analytical Methods v ACKNOWLEDGEMENTS This compendium was prepared for CCME by Maxxam Analytics, Mississauga, Ontario, Canada, with Dr. Barry Loescher acting as Project Lead and Elizabeth Walsh as Technical Editor.

7 The compendium was developed through a series of twelve webinars held in 2012 with technical analytical methods experts from provincial, territorial and federal environment agencies, as well as private Environmental laboratories across Canada, and was extensively reviewed by CCME s Soil Quality Guidelines Task Group. The contribution of time and expertise of all participants is gratefully acknowledged. A list of participating experts and their affiliations is available in Appendix 2. Volume 4: Analytical Methods vi ABBREVIATIONS AND ACRONYMS A Area AAS Atomic absorption spectrophotometry ABN Acid base neutral extractable AES Atomic emission spectroscopy AFFF Aqueous film forming foam AFS Atomic fluorescence spectroscopy aka Also known as AMPA 2-Amino-3 -(5-methyl-3 -oxo-1,2- oxazol-4 -yl) propanoic acid AOAC Association of Analytical Chemists APHA American Public Health Association ASTM ASTM International (formerly the American Society for Testing and Materials) AWWA American Water Works Association B[a]P Benzo[a]pyrene BTEX Benzene/toluene/ethylbenzene/xylenes C of A Certificate of Analysis CALA Canadian Association for Laboratory Accreditation (formerly the Canadian Association for Environmental Analytical Laboratories, CAEAL)

8 CAN-P-1585 Standards Council of Canada Requirements for the Accreditation of Environmental Testing Laboratories CAS RN Chemical Abstract Service of the American Chemical Society Registration Number CCME Canadian Council of Ministers of the Environment CCV Continuing calibration verification CEQG Canadian Environmental Quality Guidelines Ci Concentration of compound i in g/L CITAC Cooperation on International Traceability in Analytical Chemistry CP Chlorophenols CRM Certified Reference Material CU Colour units CVAAS Cold vapour atomic absorption spectrophotometry CVAFS Cold vapour atomic fluorescence spectrophotometry CWS-PHC Canada-Wide Standards for Petroleum Hydrocarbons d Distance DC Differential coliform DF Dilution factor DL Detection limit DNP 2,4-Dinitrophenol DO Dissolved oxygen DPC 1,5-Diphenylcarbazide Volume 4: Analytical Methods vii DPD N,N-Diethyl-p -phenylenediamine DQO Data quality objectives ECD Electron capture detector EDL Estimated detection limit EPA Environmental Protection Act, 1990, c.

9 F4 Gsg F4G, silica gel clean-up FID Flame ionization detector FOC Fraction organic carbon GC Gas chromatography (or GLC, gas liquid chromatography) GCxGC Two-dimensional gas chromatography GC-ECD Gas chromatography electron capture detector GC-FID Gas chromatography flame ionization detector GC-HRMS Gas chromatography high resolution mass spectrometry GC-MS Gas chromatography mass spectrometry GC-MS/MS Gas chromatography tandem mass spectrometry HDPE High density polyethylene HPLC High performance liquid chromatography HPLC-UV High performance liquid chromatography with ultraviolet detection HPLC- FLU High performance liquid chromatography with fluorescence detection HRGC-HRMS High resolution gas chromatography high resolution mass spectrometry HRMS High resolution mass spectrometry HS GC-FID Head space gas chromatography flame ionization detector HWSB Hot water soluble boron IACR Index of additive cancer risk IC Ion chromatography ICP inductively coupled plasma spectroscopy ICP-MS inductively coupled plasma mass spectrometry ICP-OES inductively

10 coupled plasma optical emission spectroscopy IS Internal standard ISE Ion selective electrode ISO/IEC International Organisation for Standardisation/International Electrotechnical Commission IUPAC International Union of Pure and Applied Chemistry LC Liquid chromatography LC-MS Liquid chromatography mass spectrometry LC-MS/MS Liquid chromatography tandem mass spectrometry LCS Laboratory control sample LRL Laboratory reporting limit, reporting limit, (aka reporting detection limit) LRLd Laboratory reporting limit for diluted sample LaSB Laboratory Services Branch, Ontario Ministry of the Environment and Climate Change Volume 4: Analytical Methods viii MDDEP Minist re du D veloppement durable, de l Environnement, de la Faune et des Parcs MDL Method detection limit MEQ Milliequivalents MRM Multiple reaction monitoring MS Mass spectrometry N/A Not applicable or not available N/V No value listed for standard ND Not detected NCPs Non-chlorinated phenolic compounds NP Nonylphenol NPEC Nonylphenol ethyl carboxylate NPEO Nonylphenol ethoxylate NTU Nephelometric turbidity units O.