Atmospherically Deposited PBDEs, Pesticides, PCBs, and PAHs in Western US National Park Fish: Concentrations and Consumption Guidelines

Similar documents
Multi-residue Analysis for PAHs, PCBs and OCPs on Agilent J&W FactorFour VF-Xms

Accelerated Solvent Extraction GC-MS Analysis and Detection of Polycyclic Aromatic Hydrocarbons in Soil

DETERMINATION OF OCs, PCBs AND SYNTHETIC PYRETHROIDS IN ANIMAL FAT

Katherine K. Stenerson, Michael Ye, Michael Halpenny, Olga Shimelis, and Leonard M. Sidisky. Supelco, Div. of Sigma-Aldrich Bellefonte, PA USA

Determination of Polycyclic Aromatic Hydrocarbons (PAHs) in Seafood Using GC/MS

METHOD 8100 POLYNUCLEAR AROMATIC HYDROCARBONS

Gas Chromatography Mass Spectrometry (GCMS)

Yokogawa Analytical Systems Inc., Nakacho, Musashino-shi, Tokyo , Japan.

Organochlorine Pesticides by GCxGC-ECD

Certificate of Analysis

Polycyclic Aromatic Hydrocarbons in Water by GC/MS PBM

appendix C QUALITY ASSURANCE/ QUALITY CONTROL

Sample Prep Solutions for Environmental Contaminants

Extraction of Residual Chlorinated Pesticides from Cotton Matrix As a part from certification method of cotton reference material

Quantification of Pesticides in Food without Calibration using GC/FID with the Polyarc Reactor

Analysis of Pesticides and Contaminants using HS-SPME-GC/MS and DRS Detection. Blair Surridge, Tyler Dyer, Rene Bilideau, Paloma Bertolin Presoti

Application Note. Abstract. Introduction. Determination of Polycyclic Aromatic Hydrocarbons in Seafood by an Automated QuEChERS Solution

Determination of Organochlorine Pesticides and Polychlorinated Biphenyls Using GC/MS/MS Operated in the MRM Mode

ENVIRONMENTAL analysis

Developing Large Volume Injection (LVI) in Split / Splitless Inlets. Philip J. Koerner Phenomenex Inc. NEMC 2014

Facility: Mansfield Revision 3. Title: PAHs by SPME Page 1 of 11

Sensitive and rapid determination of polycyclic aromatic hydrocarbons in tap water

Evaluation of Several Columns and Solvents for Post-Extraction Gel Permeation Chromatography (GPC) Clean-up of Fish Tissue Prior to PCB Analysis

Rely on Rxi -PAH Columns

STANDARD OPERATING PROCEDURES SOP: 1828 PAGE: 1 of 14 REV: 0.0 DATE: 05/12/95 ANALYSIS OF METHYL PARATHION IN CARPET SAMPLES BY GC/MS

Spectra Library Electron Capture Negative Ion (ECNI) Mass Spectra of Selected Polybrominated Diphenyl Ethers (PBDEs)

Determination of 24 PAHs in Drinking Water

Analysis of Total PCBs and PCB Congeners and Trans-nonachlor in Fish by Gas Chromatography/ Negative Chemical Ionization Single Ion Mass Spectrometry

U.S. EPA Method 8270 for multicomponent analyte determination

High Throughput Multi-Residue Screening of Drinking Water using the SPE-DEX~ and Pegasus GC-TOF-MS

STANDARD OPERATING PROCEDURES

Pesticides Analysis Using the Agilent 5977A Series GC/MSD

METHOD DETERMINATION OF CHLORINATED PESTICIDES, HERBICIDES, AND ORGANOHALIDES BY LIQUID-SOLID EXTRACTION AND ELECTRON CAPTURE GAS CHROMATOGRAPHY

18/05/2010 Soil. 18/05/2010 Soil

STANDARD OPERATING PROCEDURES SOP: 1826 PAGE: 1 of 18 REV: 0.0 DATE: 03/30/95 ANALYSIS OF METHYL PARATHION IN WIPE SAMPLES BY GC/MS

APPENDIX A TO PART 136 METHODS FOR ORGANIC CHEMICAL ANALYSIS OF MUNICIPAL AND INDUSTRIAL WASTEWATER METHOD 610 POLYNUCLEAR AROMATIC HYDROCARBONS

Selection of a Capillary

Challenging Pesticide Analysis Using an Agilent J&W DB-35ms Ultra Inert GC Column

VALIDATION OF A UPLC METHOD FOR A BENZOCAINE, BUTAMBEN, AND TETRACAINE HYDROCHLORIDE TOPICAL SOLUTION

STANDARD OPERATING PROCEDURES SOP: 1810 PAGE: 1 of 31 REV: 0.0 DATE:03/14/05 ANALYSIS OF POLYNUCLEAR AROMATIC HYDROCARBONS (PAHs) IN DUST BY GC/MS-SIM

METHOD 3600C CLEANUP

Application of gas chromatography atmospheric pressure chemical ionization mass spectrometry for analysis of contaminants in environmental samples

SUPELCO. Improved Performance for Cyanopropylphenyldimethylpolysiloxane (SPB-1701, SPB-1301) Capillary Columns

Introduction to Gas Chromatography

SUPPORTING INFORMATION

PAH Analyses with High Efficiency GC Columns: Column Selection and Best Practices

STANDARD OPERATING PROCEDURES

Certificate of Analysis

METHOD July J.W. Hodgeson. W.J. Bashe (Technology Applications Inc.) T.V. Baker (Technology Applications Inc.)

Trim Time Not Columns Multiresidue Pesticides Analysis with an Intuvo GC/TQ

Semivolatile Organics Analysis Using an Agilent J&W HP-5ms Ultra Inert Capillary GC Column

METHOD 3665 SULFURIC ACID/PERMANGANATE CLEANUP

Low Bleed Stationary Phases for Gas Chromatography

Proposed Inventory of Emissions, Discharges and Losses of Substances, and Chemical Analysis Information

CALIBRATION OF GC/MS METHOD AND VALIDATION OF THE MODIFIED SAMPLE PREPARATION FOR DETERMINATION OF POLYCYCLIC AROMATIC HYDROCARBONS

Selection of a Capillary GC Column

Application Note # Performance of Method 8270 Using Hydrogen Carrier Gas on SCION Bruker SCION GC-MS

Method 680. Determination of Pesticides and PCBs in Water and Soil/Sediment by Gas Chromatography/Mass Spectrometry. November 1985

Method 8270C PAH. FD- Field Duplicate Samples

APPENDIX G. Data Management Rules. Dioxin Data Report Appendix G. Lower Duwamish Waterway Superfund Site: T-117 Early Action Area

anthracene Figure 1: Structures of Selected Polyaromatic Hydrocarbons (PAHs)

MULTIRESIDUE ANALYSIS OF PRIORITY POLLUTANTS IN SURFACE WATERS USING EXACT MASS GC-TOF MS

Determination of Pesticides in Aqueous Samples by On-Line Coupling Solid-Phase Extraction to Gas Chromatography with At-Column Concentrating Interface

Food analysis. Solutions for Your Analytical Business Markets and Applications Programs

Meeting Challenging Laboratory Requirements for USEPA Method 8270 Using a Highly Sensitive, Robust, and Easy-to-Use GC/MS

KSA Environmental Laboratory Inc.

Simultaneous determination of 74 kinds of pesticides in Chinese herbal medicine listed in Chinese pharmacopoeia (2015) by GPC-GC-MS/MS

METHOD 3510B SEPARATORY FUNNEL LIQUID-LIQUID EXTRACTION

TETRA TECH, INC. December 8, Lynn Nakashima Berkeley Regional Office 700 Heinz Avenue, Suite 200C Berkeley, California 94710

Solid Phase Extraction of Pesticides with Determination by Gas Chromatography

EPA Method 535: Detection of Degradates of Chloroacetanilides and other Acetamide Herbicides in Water by LC/MS/MS

Application Note No Introduction. DMI Instrumentation. DMI Method. DMI for Lettuce and Pea Extracts. Lettuce results

EPA Method 535: Detection of Degradates of Chloroacetanilides and other Acetamide Herbicides in Water by LC/MS/MS

Analysis of Trace (mg/kg) Thiophene in Benzene Using Two-Dimensional Gas Chromatography and Flame Ionization Detection Application

METHOD SUPERCRITICAL FLUID EXTRACTION OF POLYCHLORINATED BIPHENYLS (PCBs) AND ORGANOCHLORINE PESTICIDES

Sample Pre-Treatment : Introduction to Commonly Used Techniques for Gas

Analysis of Biomarkers in Crude Oil Using the Agilent 7200 GC/Q-TOF

A biphasic oxidation of alcohols to aldehydes and ketones using a simplified packed-bed microreactor

Sensitive Detection of Pyrethroids in Surface Water and Sediment

STANDARD OPERATING PROCEDURES SOP: 1824 PAGE: 1 of 22 REV: 0.0 DATE: 04/21/95 ANALYSIS OF METHYL PARATHION IN SOIL SAMPLES BY GC/MS

The Use of Tandem Quadrupole GC/MS/MS for the Determination of Polycyclic Aromatics Hydrocarbons (PAHs) in Food Products

This project has been funded with support from the European Commission. This publication reflects the views only of the authors, and the Commission

Application Note. Gas Chromatography/Mass Spectrometry/Food Safety. Abstract. Authors

Non-Potable Water A2LA Certificate

Shaker Table Extraction

METHOD 3520B CONTINUOUS LIQUID-LIQUID EXTRACTION

Optimizing GC Parameters for Faster Separations with Conventional Instrumentation

Fast USEPA 8270 Semivolatiles Analysis Using the 6890/5973 inert GC/MSD with Performance Electronics Application

METHOD 8081B ORGANOCHLORINE PESTICIDES BY GAS CHROMATOGRAPHY

Mass Spectrometry. Ionizer Mass Analyzer Detector

OREGON Environmental Laboratory Accreditation Program ORELAP Fields of Accreditation ALS Environmental - Simi Valley

Fast and Accurate Analysis of PBDEs in a Single Run, Including

Analytical Method for the Determination of Selected PACs in Ambient Air Samples

Sensitive and Repeatable Analysis of Pesticides in QuEChERS Extracts with APGC-MS/MS

Standard Operating Procedure for the Analysis of PCB Congeners by GC/ECD and Trans-Nonachlor by GC/MS/ECNI

METHOD 8033 ACETONITRILE BY GAS CHROMATOGRAPHY WITH NITROGEN-PHOSPHORUS DETECTION

METHOD 8032A ACRYLAMIDE BY GAS CHROMATOGRAPHY

Sulfotepp impurities in Chlorpyrifos EC formulations

ALLOWAY STANDARD OPERATING PROCEDURES FOR METHOD 525.2

Application Note. Agilent Application Solution Analysis of PAHs in soil according to EPA 8310 method with UV and fluorescence detection.

Transcription:

6 7 8 9 10 11 1 1 1 16 17 18 19 0 1 6 7 8 9 0 1 6 7 8 9 0 1 6 Supporting Information For: Atmospherically Deposited PBDEs, Pesticides, PCBs, and PAHs in Western US National Park Fish: Concentrations and Consumption Guidelines Luke K. Ackerman, Adam R. Schwindt, Staci L. Simonich*, Dan C. Koch, Tamara F. Blett, Carl B. Schreck, Michael L. Kent, Dixon H. Landers Number of Pages: Number of Tables: Number of Figures: - 1 -

6 7 8 9 10 11 1 1 1 16 17 18 19 0 1 6 7 8 9 0 1 6 7 8 9 0 1 6 Experimental Chemicals All solvents were Optima grade from Fisher Scientific (Fairlawn, NJ). Anhydrous sodium sulfate was Mallinckrodt Baker (Phillipsburg, NJ) pesticide grade. Isotopically NONlabeled chemical standards (natives) in mixes and individually were purchased from, the EPA repository, Chem Services Inc. (West Chester, PA), Restek (Bellefonte, PA), Sigma- Aldrich Corp. (St. Louis, MO), AccuStandard (New Haven, CT), or Cambridge Isotope Labs (Andover, MA). Isotopically labeled standards were purchased from CDN Isotopes (Pointe-Claire, Quebec, Canada) or Cambridge Isotope Labs (Andover, MA). The isotopically-labeled recovery surrogates were d 10 -fluorene, d 10 -phenanthrene, d 10 -pyrene, d 1 -triphenylene, d 1 -benzo[a]pyrene, d 1 -benzo[ghi]perylene, d 1 -EPTC, d -atrazine, d 10 - diazinon, d 7 -malathion, d 10 -parathion, d 8 -p,p -DDE, d 8 -p,p -DDT, d 6 -methyl parathion, d - alachlor, d 11 -acetochlor, C 1 -PCB 101 (,,,, -pentachlorobiphenyl), C 1 -PCB 180 (,,,,,, -heptachlorobiphenyl), d 10 - chlorpyrifos, C 6 -HCB, d 6 --HCH, d - endosulfan I, d -endosulfan II, d 1 -trifluralin, C 1 -BDE 8 (,, -tribromodiphenyl ether), C 1 -BDE 7 (,,, -tetrabromodiphenyl ether), C 1 -BDE 99 (,,,,- tetrabromodiphenyl ether), C 1 -BDE 100 (,,,,6-tetrabromodiphenyl ether), C 1 - BDE 118 (,,,,-tetrabromodiphenyl ether), C 1 -BDE 8 (,,,,, - tetrabromodiphenyl ether), C 1 -BDE 1 (,,,,, -tetrabromodiphenyl ether), and C 1 -BDE 18 (,,,,,,6-tetrabromodiphenyl ether). The isotopically-labeled internal standards were d 10 -acenaphthene, d 1 -benzo[k]fluoranthene, d 10 -fluoranthene, and C 1 -PCB 8 (,,,,, -hexachlorobiphenyl). All standards were stored at C and remade as needed, or at least once a year to insure stability. The organophosphate standards were stored separately from other chemical classes in ethyl acetate (EA) to minimize degradation. All lab ware was washed, rinsed, covered in foil, baked at C for 1hrs, and solvent-rinsed prior to use. Samples Standard Reference Material (SRM) #196 Lake Superior Lake Trout was purchased from the National Institute of standards and Technology (NIST) (Gaithersburg, MD). Representative fish samples for method detection limit and recovery studies were collected from remote lakes of US National Parks, specifically Wonder Lake, Denali NP, AK, Emerald Lake, Sequoia NP, CA, and Mills Lake, Rocky Mountain NP, CO. Most fish were caught with hook and line, stored in 8 gall buckets with lake water for less than 0 min prior to euthanasia and field dissection. Gill-nets and set lines were employed for the collection of some fish from Denali National Park. Upon capture ~100uL of blood was removed from the caudal vein for hormone, biomarker, and hematological analysis, and the fish was euthanized, weighed, and fork length measured. A quick field dissection to obtain pathological slices of kidney, spleen, liver, gills, and gonads was performed on solvent rinsed and baked foil with solvent rinsed scalpels and forceps. Gut contents were evacuated, and the carcass was wrapped in foil or aluminized poly-bags, double-bagged, and shipped to the laboratory on dry ice. Field blanks of the collection procedure without a fish were also obtained. When received at the lab the samples were logged into a - C freezer until analysis. - -

6 7 8 9 10 11 1 1 1 16 17 18 19 0 1 6 7 8 9 0 1 6 7 8 9 0 1 6 Sample Preparation Whole fish carcasses were homogenized in liquid nitrogen inside a Blixer BX-6 HP stainless steel food processor with polycarbonate lid until a fine, frozen slurry of nitrogen and fish homogenate was obtained. Personal protective equipment included face shields and cold gloves. Frozen homogenate was transferred to cleaned jars, sealed, weighed, and stored at - C, until extraction. Method blanks were obtained by grinding 10 g clean sodium sulfate with the liquid nitrogen and processing samples through the method. A 1- g subsample of the fish homogenate was gravimetrically analyzed for moisture content by baking for hrs at 10 C and re-weighing (until stable). Sample Extraction Samples and method blanks (~0g fish, 1.8g SRM) were weighed out onto a clean tarred glass mortar with a bed of clean sodium sulfate, sodium sulfate was added and the mixture ground until free flowing (<10min). The fish sodium sulfate mixture was transferred into 100mL stainless steel Accelerated Solvent Extractor (ASE) cells (Dionex, Sunnyvale, CA) with each cell containing ~10 g of the fish/sodium sulfate mixture. Once in the ASE cells, 1.-10ng of isotopically labeled recovery surrogates in 1.-10 ng/ul solutions were distributed equally among the tops of the cells containing sample or blank. The cells were capped. The sample or blank was extracted using dichloromethane (DCM) (100 C, 100 psi, cycles of minutes, 10 % flush volume). The extract was dried with clean sodium sulfate, decanted and filtered with glass wool into a 00mL volumetric flask, which was filled to the mark. Gravimetric lipid analysis was performed on % of the sample by heating the evaporated 10ml extract sub-sample at 10 C for one hour and weighing the extracted lipid that remained (until stable). The remainder of the extract was concentrated to 0. ml in the TurboVap II (Zymark, Hopkinton, MA) with nitrogen, and solvent exchanged to hexane. Polar matrix interferences were removed by loading the hexane extract on a 0 g silica solid phase extraction (SPE) cartridge (Mega Bond Elut Varian). Analytes were eluted from the silica SPE using ml hexane, ml 60:0 hexane:dcm, and 7 ml 70:0DCM:hexane. The combined eluate was then concentrated and solvent exchanged to DCM. Elemental sulfur and the high molecular weight interferences were removed using a Waters Gel Permeation Chromatography (GPC) Cleanup System (Milford, MA). The target fraction was concentrated to 0. ml with ethyl acetate rinses under a gentle stream of nitrogen and spiked with 1 µl of a 10 ng/µl isotopically labeled internal standard solution. Blank extracts were carried through the entire method together with batches of to samples. GC/MS Analysis In general extracts were analyzed by gas chromatographic mass spectrometry (GC/MS) on an Agilent 6890 GC coupled with an Agilent 97N MSD, using both electron impact (EI) ionization and electron capture negative ionization (ECNI) modes. The ECNI compounds monitored, their SIM windows, and characteristic ions are listed in Table S. Analysis was attempted for a larger list of compounds than that for which the method was subsequently validated. One microliter of the 0. ml extract was injected in pulsed splitless mode with a HP 768 auto-sampler. The inlet was a mm id glass gooseneck with wool, at 00 C (pulse of 0 psi until 0.6 min). Chromatographic separations were achieved on a DB-MS column (J&W Scientific, 0m x 0. mm id.; 0. Rm film thickness) with helium carrier gas flowing at 0.9 ml/min. The GC oven temperature program used for the GC/EI-MS was - -

6 7 8 9 10 11 1 1 1 16 17 18 19 0 1 6 7 8 9 0 1 6 7 8 reported previously and the program for the ECNI/MS was modified as follows to permit quantitation of the PBDEs: 10 C for 1 min, ramped at C/min to 7 C, ramp 6 C to 0, held 6.7 min for a total runtime of minutes. QA/QC Internal standard calibration curves were prepared from standard solutions, ranging. fg/ul to ng/ul. A minimum of calibration points (S per order of magnitude) were included in every curve and the curve was required to yield an r >0.98, or less than 1% deviation at every point. Calibration accuracy was checked with a low level calibration solution at a frequency of at least 18%, and the instrument re-calibrated as needed. Calibration solutions were re-prepared at least once a year or as needed. Duplicate injections were performed at a frequency of 10% and duplicates with > % relative deviation were flaged and re-run as needed. Standard reference material was analyzed at a frequency of 10%. Target compounds were identified only when the following criteria were met: a peak of greater than :1 S:N was observed for all three characteristic ions within 0.01 min or one scan of each other, the quantitation ion peak matched standard RT within 0.0 min, and the relative response of the three ions was within 0% of standards relative responses. Sample values were flagged if the lab blank was greater than % of the sample analyte mass, the field blank greater than 0%, the calibration check >0% deviation, or if the recovery surrogate yielded >0% or <0% recovery. Quantitation values were later censored according to method detection and quantitation limits. The method quantitation limit was set as the mass of the lowest concentration calibration solution used for each curve, normalized to each sample s mass extracted. If the mass in any blank was greater than % of the corresponding sample s mass, the sample value was deleted and flaged. All reported values have been blank subtracted and recovery corrected. Results The following compounds were detected in less than 0% of the samples and less than 0% of the samples from any single lake: b-hch, d-hch, heptachlor, aldrin, endrin, endrinaldehyde, PCB 7, BDEs #10, 7, 8, 1,, 1, 0,, 17,,, 7, 7, 71, 66, 77, 119, 116, 16, 118, 8, 166, 181, 190, triallate, chlorpyrifos oxon, etridiazole, parathion, ethion, and all PAHs. - -

Table S1. Average Fish Sample and Site Characteristics Lake US National Park Latitude (dd) Longitude (dd) Elevation (m) Fish Species Length (mm) mass (g) Age (yr) Growth Rate (g/yr) Condition Factor (cg/cm ) Sex Ratio (M:F) Date Sampled 1) Emerald Sequoia-Kings Canyon 6.8 118.67 810 brooktrout 199 7. 16 0.91 1. 08//0 10 ) Pear Sequoia-Kings Canyon 6.60 118.67 908 brooktrout 01 7. 17 0.9.0 08//0 10 ) LonePine Rocky Mountain 0. 10.7 018 brooktrout 11.7 0.9 1. 09//0 10 ) Mills Rocky Mountain 0.9 10.6 00 rainbow trout 1 1.9 7 1.19 0.7 09/08/0 10 ) LP19 Mt. Rainier 6.8 11.89 7 brooktrout 7 1.0 9 0.9 1.0 08/08/0 10 6) Golden Mt. Rainier 6.89 11.90 69 brooktrout 110. 7 0.97. 08//0 10 7) Hoh Olympic 7.90.79 79 brooktrout 06 8 8.1 0.9 1.0 09/08/0 10 8) PJ Olympic 7.9. 8 brooktrout 197 67. 1 0.90 1.0 09//0 10 9) Oldman Glacier 8.0 1.6 06 cutthroat trout 8 96.6 167 1.0 1. 08/19/0 10 10) Snyder Glacier 8.6 1.79 197 cutthroat trout 179 7.6 0.97 1.0 08//0 10 11) McLeod Denali 6.8 11.07 6 burbot, whitefish 7 110. 0.6.0 08/10/0, 1) Wonder Denali 6.8 10.88 60 lake trout 7 100 19. 7 1.09 1. 08/1/0 10 ) Matcharak Gates of the Arctic 67.7 16.1 0 lake trout 08 110 19. 7 1.0 1.0 08/01/0 10 1) Burial Noatak National Preserve 68. 19.18 0 lake trout 11 768 16.9 0.96 1.0 08/0/0 10 Total 6 n

Figure S1 Map of National Parks/Preserves Sampled 1

Table S. ECNI Target Analytes, Surrogates, Internal Standards, & SIM Windows Analytes, Surrogate for Internal Standard Retention Time Quantiation Confirmation nd Confirmation & Surrogates Quantitation for Quantitation (min) Ion m/z Ion m/z Ion m/z SIM Window 1 d 1 Trifluralin C 1 PCB 8.69 9. 0. 19. Trifluralin d 1 Trifluralin.90.1 6.1 0.1 SIM Window HCH, alpha d 6 gamma-hch 1.61 71.0 7.0 70.0 C 6 -HCB HCB C 1 PCB 8 1.69 91.8 9.8 89.9 C 6 HCB 1.70 8.8 8.8 81.8 SIM Window HCH, beta d 6 gamma-hch 1.9 71.0 7.0 70.0 d 6 gamma-hch C 1 PCB 8 16.01 7.0 7.0 6.0 HCH, gamma d 6 gamma-hch 16.19 71.0 7.0 70.0 SIM Window HCH, delta d 6 gamma-hch 17.70 71.0.9.9 Triallate d 6 gamma-hch 17.7 160.0 161.1 10.1 SIM Window PBDE #10 C 1 PBDE 8 19.0 167.1 80.9 78.9 Metribuzin d 6 gamma-hch 19.1 198.1 199.1 18.1 Heptachlor d 6 gamma-hch 19.61 6.9 67.9 99.9 PBDE 7 C 1 PBDE 8 0.1 167.1 80.9 78.9 SIM Window 6 Chlorpyrifos oxon d 10 Chlorpyrifos 1.1 97.0 98.0 99.0 d 10 Chlorpyrifos C 1 PCB 8 1.19.0.0 1.0 Aldrin d 6 gamma-hch 1. 167.1 78.9 80.9 PBDE #8 C 1 PBDE 8 1.8 7.0 9.0 9.9 Chlorpyrifos d 10 Chlorpyrifos 1.7.0 1.0 1.0 SIM Window 7 Dacthal d 6 gamma-hch 1..0 0.0.0 PBDE 1 C 1 PBDE 8 1.6 167.1 80.9 78.9 PBDE C 1 PBDE 8 1.79 167.1 80.9 78.9 PBDE 1 C 1 PBDE 8. 167.1 80.9 78.9 SIM Window 8 Chlordane, oxy d Endosulfan I.1.9.9 1.9 Heptachlor epoxide d Endosulfan I. 89.8 87.8 91.8 PCB 7 C 1 PCB 101.8 91.9 9.9 89.9 SIM Window 9 Chlordane, trans d Endosulfan I.6 09.9 07.9 11.8 PBDE 0 C 1 PCB 101 SIM Window 10 C 1 PBDE 8.67 6.9 80.9 78.9 C 1 PCB 8.68 7.9.9 9.9 1 PCB 101 C 1 PCB 101.69.9 7.9.9 d Endosulfan I C 1 PCB 8.7 77.9 7.9 7.9 Endosulfan I d Endosulfan I.8 0.9 71.9 69.9 Chlordane, cis d Endosulfan I.8 6.9 6.9 67.9 SIM Window 11 Nonachlor, trans d Endosulfan I.98.8.8 1.8 SIM Window 1 Dieldrin d Endosulfan I 6.07.9 7.9 79.9 PBDE C 1 PBDE 8 6.6 6.9 80.9 78.9 SIM Window Endrin d Endosulfan II 7.0.9 7.9 79.9 PBDE 17 C 1 PBDE 8 7.1 6.9 80.9 78.9 PBDE C 1 PBDE 8 7.0 6.9 80.9 78.9

Table S. ECNI SIM Windows continued. SIM Window 1 d Endosulfan II C 1 PCB 8 7.1 11.9.9 09.9 PCB 118 C 1 PCB 101 7..9 7.9.9 Endosulfan II d Endosulfan II 7.6 0.9 07.9 71.9 SIM Window 1 Nonachlor, cis d Endosulfan II 7.79.8.8 1.8 C 1 PBDE 8 C 1 PCB 8 7.90 8.8 78.9 80.9 PBDE 8 C 1 PBDE 8 7.90 6.9 78.9 80.9 SIM Window 16 Endrin aldehyde d Endosulfan II 8. 79.9 81.9.9 PBDE C 1 PBDE #8 8. 6.9 78.9 80.9 PCB 1 C 1 PCB 180 8.8 9.9 61.9 7.9 PBDE 7 C 1 PBDE 8 9.0 6.9 78.9 80.9 SIM Window 17 Endosulfan sulfate d Endosulfan II 9. 8.9 87.9 1.8 PCB 8 C 1 PCB 180 9.6 60.0 6.0 8.0 C 1 PCB 8 Internal Standard 9.6 71.9 69.9 7.9 SIM Window 18 PCB 187 C 1 PCB 180 0.9 9.9 9.9 97.9 PCB 18 C 1 PCB 180 0. 9.9 9.9 97.9 PBDE 7 C 1 PBDE 7 1.7.9 78.9 80.9 PBDE 9 C 1 PCB 180 SIM Window 19 C 1 PBDE 7..9 78.9 80.9 C 1 PCB 8.60 0.9 07.9 09.9 PBDE 7 C 1 PBDE 7 C 1 PBDE 7.9.9 78.9 80.9 C 1 PCB 8.9 6.7 78.9 80.9 SIM Window 0 PBDE 66 C 1 PBDE 7.76 0.8 78.9 80.9 Mirex C 1 PCB 180.10 67.8 69.8 0.8 PBDE 66 C 1 PBDE 7.10.9 78.9 80.9 SIM Window 1 PBDE 100 L C 1 PBDE 100 6.61 0.8 78.9 80.9 C 1 PBDE 100 C 1 PCB 8 6.61 16.7 78.9 80.9 PBDE 119 7.10 0.8 78.9 80.9 PBDE 99 L C 1 PBDE 99 7.78 0.8 78.9 80.9 C 1 PBDE 99 C 1 PCB 8 7.79 16.7 78.9 80.9 1 PBDE 116 PBDE 118 L C 1 PBDE 118 PBDE 8/1 PBDE 1 PBDE 16 PBDE 1 PBDE 1 L C 1 PBDE 1 PBDE 8 PBDE 166 PBDE 18 L C 1 PBDE 18 PBDE 181 PBDE 190 C 1 PBDE 99 8.1 0.8 78.9 80.9 SIM Window C 1 PBDE 118 8.78 0.8 78.9 80.9 C 1 PCB 8 8.78 17.7 78.9 80.9 SIM Window C 1 PBDE 99 9.79 0.8 78.9 80.9 C 1 PBDE 1 9.80 6. 78.9 80.9 C 1 PBDE 1 0.1 0.8 78.9 80.9 SIM Window C 1 PBDE 1 0.6 8.7 78.9 80.9 C 1 PBDE 1.08 0.8 78.9 80.9 C 1 PCB 8.08 1.6 78.9 80.9 C 1 PBDE 1.77 01.8 78.9 80.9 C 1 PBDE 1.9 01.8 78.9 80.9 SIM Window C 1 PBDE 18.1 81.7 78.9 80.9 C 1 PCB 8.1 9.6 78.9 80.9 C 1 PBDE 18 7.0 81.7 78.9 80.9 C 1 PBDE 18 7.1 81.7 78.9 80.9

Figure S. Representative Final Fish Extract Selected Ion Chromatograms

Table S.Fish analytical method recovery, estimated method detection limits, accuracy, and precision Compounds Log K ow Method Recovery 1 (%) Estimated Method Detection Limit (pg/g ww) Determined Values for NIST SRM 196 (ng/g ww) Deviation from Certified Values (%) Avg. SD Avg. RSD Avg. RSD % Diff % % Method Averages Median 6.1 9.. 18. 7. 9.7 0.0 Average 6.1 61..1 79 11 0 1 7.1 Min.6 1. 0. 0. 0.8 0.10 0. 0 Max 9. 98. 1 90 86 0 66 0 Organochlorines Pesticides & Metabolites HCH, gamma.8 8. 1.6 17 7. 1.0 6 0 HCH, alpha.8 7.6 1.6 0. 8.1. 6. 0 HCH, beta.0. 1.7 7.8 1.7 0.6 HCH, delta.1. 1.7 0.6.0 Methoxychlor. 6.1 1.8 99 7 Heptachlor epoxide.6.6.0 1.. 1.1 0 Endrin. 89.1. 170 6.7 0. Heptachlor. 8. 1. 1.6 1. 0.8 7 Hexachlorobenzene. 7.8 1.9.0 1.9 6.6.7 0 o,p'-dde..8.1 8 0.91 1 0 Chlordane, oxy..1 1.9. 1.9 16 7.9 1 Dieldrin. 9..6 8. 1.8 0 Chlordane, cis.9.6 1.0 16 6.8 1 8.9 0 p,p'-ddd.9 67.8 1.0 99 9 1 9.0 0 Nonachlor, trans 6.1.0 1.0.9 1. 90 7.1 9. o,p'-ddd 6.1..1 68 16 1.8 17 Chlordane, trans 6.1 1. 1.0 1.6 0.96 9.7 66 16 Nonachlor, cis 6. 0. 1..0 1.0 9.9 16 Aldrin 6. 9. 1.6 1. o,p'-ddt 6.8 61.1.8 97 6 16 0 8 p,p'-dde 6.9 6.7.7 98 1 0 9. 0 Mirex 6.9.0. 6.8 1. 6.1. 0 p,p'-ddt 6.9 68.1.1 9 0 6.1 0 OrganochlorineSulfide Pesticides & Metabolites Endosulfan sulfate.7 6..0.7 0.8 0. 1 Endosulfan I.7 6.0..9.6 0.10 10 Endosulfan II.8 9.0. 8.9.8 Phosphorothioate Pesticides Parathion.8. 9.6 9.1 1.0 Ethion.1 8.8 10. 1.9.9 Chlorpyrifos.1. 8.9. 0.88 Miscellaneous Pesticides Etridiazole.6.8 1.8 1. Dacthal. 6...6 1.6.6 11 Triallate.6 88.0. 11 1.80 Trifluralin..9. 7. 0.89 1 PolyChlorinated Biphenyls PCB 7 6. 78.9 1. 8 1.1 0 1 PCB 101 6. 66.. 1.1.6 8 9 0 PCB 8 6.7 77..7.6.9 1 PCB 1 6.9 6.0.6. 0.87 110 0 0 PCB 118 7.0 7. 6.1. 0.96 1 6. 0 PCB 18 8. 7.9. 0.8.7 8.6 0 PCB 187 7. 77..0 1.. 0 1 - @8ng/g spike, n=; - n=; - Values within NIST confidence intervals = 0% diff

Table S.Fish analytical method performance, continued Compounds Log K ow Method Recovery 1 (%) Estimated Method Detection Limit (pg/g ww) Determined Values for NIST SRM 196 (ng/g ww) Deviation from Certified Values (%) Avg. SD Avg. RSD Avg. RSD % Diff % % Polycyclic Aromatic Hydrocarbons Acenaphthylene.9 6.0. 8.1 Acenaphthene.0.. 0. Fluorene. 1.7 1.6 16 1.7 Anthracene. 1.8. 9 6.8 Phenanthrene. 6..8 6 10 Pyrene.1 6.7. 6.7. Fluoranthene. 8..0 7.6 1.8 Chrysene /Triphenylene.7 9. 0.9 0 1 Benzo(a)anthracene.9 9.. 6 0.96 Retene 6...8 1 Benzo(k)fluoranthene 6. 6.6 0. 0.9 Benzo(a)pyrene 6... 17 1.7 Benzo(b)fluoranthene 6.6 6. 0.9 0 1.6 Indeno(1,,-cd)pyrene 6.7 60. 0. 18. Dibenz(a,h)anthracene 6.8 8.0 1.6 19 8.9 Benzo(e)pyrene 6.9 7.8 0.7 100 Benzo(ghi)perylene 7.0 60.1 0.7 6. 1. 1 PolyBrominated Diphenyl Ethers BDE 10.0 6. 6. 90 6 BDE 7.0 9.7. 10 BDE 8.0.0. 710 BDE 1.8.. 880 18 BDE.8 0..7 910 1 BDE 1.8 8. 6. 860 1 BDE 0.9 7. 6.6 0 7 BDE.9 6.9. 8 7.6 BDE 17.8.7. 8. BDE.9.9. 7.1 BDE 8.9 1.1.1.8 0.9 1.9 6 BDE 6.7.6.0 7.8 BDE 7 6.7..1 0 8.1 BDE 7 6.8 86.9 6.7. BDE 9 6.8 9.1 7.1 0.6 BDE 71 6.8 8.8. 1.9 BDE 7 6.8 91.1 7. 1 1.1 9 10 0 BDE 66 6.8 8.6 8. 10 6 n/a BDE 77 7.6 9.6 8.0 8 BDE 100 7.7 79.0 8. 6.7 1.1 8..7 0 BDE 119 7.7 78.9 7. 19 1 BDE 99 7.7 8.7 6. 1.9 18. 0 BDE 116 7.7 7.6 7.9 91 8 BDE 8/1 7.7 / 8.6 91.8 8. 7 10 BDE 16 8. 88.6 9. 6 9. BDE 118 7.7 7.0 11.9 00 86 BDE 1 8.6 80.8 7.0. 1.0 0.68 11 BDE 1 8.6 79.7 7. 8..7 6. 18 0 BDE 1 8.6 78.6 6.7 6..1.9 9. 0 BDE 8 8.6 81.6 7.1 1.1 1.1 BDE 166 8.6 98. 7.8 1.9 1.7 BDE 18 9. 81..8 1.6 0.9 0. 1 BDE 181 9. 76.8.1..1 BDE 190 9. 7..0.0. 1 - @8ng/g spike, n=; - n=; - Values within NIST confidence intervals = 0% diff 6

Figure S - Concentrations of select current (A,B) and historic use contaminants (C,D) in average (bars) & individual fish (symbols) from western US national park lakes compared to estimated non-cancer (A,B) and cancer (C,D) health thresholds for recreational fishing. * - nd>0% of lake fish. 7

8

2024 © sciencedocbox.com Privacy Policy | Terms of Service | Feedback