USGS-NWQL: O-5504-03: Organochlorine Pesticides and Polychlorinated Biphenyls in Bottom and Suspended Sediment by Gas Chromatography with Electron Capture Detection

Summary
Analytes
Revision
Data and Sites

Official Method Name

Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory-Determination of Organochlorine Pesticides and Polychlorinated Biphenyls in Bottom and Suspended Sediment by Gas Chr

Current Revision

2003

Media

SOILS/SEDIMENT

Instrumentation

Gas Chromatography with Electron Capture Detection

Method Subcategory

Organic

Method Source

USGS-NWQL

Citation

Noriega, M.C., Wydoski, D.S., and Foreman, W.T., 2004, Methods of Analysis of the U.S. Geological Survey National Water Quality Laboratory - Determination of Organochlorine Pesticides and Polychlorinated Biphenyls in Bottom and Suspended Sediment by Gas Chromatography with Electron-Capture Detection, U.S. Geological Survey Water-Resources Investigations Report 03-4293, 54 p.

Brief Method Summary

A bottom-sediment sample is centrifuged to remove excess water. A sample size of 25-g equivalent dry weight is extracted overnight with dichloromethane (93%) and methanol (7%). The sample extract is concentrated and first filtered through a 1.0-um polytetrafluoroethylene syringe filter then through a 0.2-um polytetrafluoroethylene syringe filter connected in series. For the determination of organochlorine (OC) pesticides and PCBs, a 1,100-uL aliquot of the sample extract is injected quantitatively onto two serial polystyrene-divinylbenzene GPC columns. Compounds are eluted with dichloromethane at a flow rate of 1 mL/min and are collected in a distinct fraction time window. Interferences elute first from the GPC columns and are not collected. The method compounds then are collected in a GPC fraction for about 8.9 minutes. Sulfur elutes immediately after this GPC fraction and is not collected. The collected GPC fraction of OCs is concentrated and solvent exchanged, then undergoes cleanup using alumina/silica combined column adsorption chromatography and further split into two OC fractions. The second OC fraction undergoes additional cleanup using a Florisil column. Both OC fractions are analyzed by dual capillary-column gas chromatography with electron-capture detection (GC/ECD). The GC/ECD is calibrated for both capillary columns by the external standard method using multipoint calibration standards. The OCs subsequently are quantitated against the calibration curve processed for each column.

Scope and Application

This method is suitable for the determination of 19 individual organochlorine (OC) pesticides, including total toxaphene as a complex OC pesticide mixture, and 3 PCB mixtures as Aroclor equivalents -- Aroclor 016/1242, 1254, and 1260 -- in soil, bed sediment, suspended sediment, and dry sludge. This method is applicable to samples with OC compounds that are (1) efficiently extracted from the solid matrix by methanol or dichloromethane, (2) adequately separated from natural co-extracted compounds by gel permeation chromatography (GPC), (3) efficiently recovered from the alumina-over-silica adsorption chromatography clean-up/fractionation step and the Florisil adsorption chromatography clean-up step, (4) sufficiently volatile and thermally stable for gas chromatographic analysis, and (5) responsive to electron-capture detection. This method is applicable to a 25-g equivalent dry-weight sample size for extraction. A minimum of 0.1-g dry-weight sample size can be used, with reporting levels raised accordingly. This method also is applicable to suspended-sediment samples collected on glass-fiber filters, with concentrations reported in micrograms per liter for known sample-volume filtered.

Applicable Concentration Range

Interferences

This method is designed to minimize false positives through dual-column confirmation. However, nonmethod organohalogen, oxygenated, and other ECD-sensitive compounds that are co-extracted, collected in the GPC fraction and adsorption chromatography fractions, and have GC retention times identical to those of the selected OCs of interest potentially can interfere with the analytical method. Hydrocarbon contamination from oils on the analytical instrument or in sediments, polychlorinated napthalenes, phthalates, and inorganic sulfur that is incompletely removed during the GPC step can interfere with qualification and quantification of method compounds. Follow-up analysis by mass-spectral confirmation also may be used to confirm identification, if uncertain. For some samples, reliable detection might not be possible because of the levels of interferences in the matrix, and interim reporting levels might have to be raised. Furthermore, the shorter GC oven temperature program in contrast with that described by Foreman and others (1995) causes some recognizable coelutions, for example, dieldrin and p,p'-DDE on the Rtx-5 primary column (5.10.1.1), and p,p'-DDE and a PCB congener on the Rtx-1701 secondary column (5.10.1.2). Consequently, high PCB concentrations might interfere with p,p'-DDE determination.

Quality Control Requirements

Laboratory extraction samples are prepared in sample sets, each consisting of a laboratory reagent blank, a laboratory reagent spike, a standard reference material, and 13 field samples, which may include a laboratory duplicate. The aspects of the analytical process that the QA/QC samples monitor are described within the method report.

Sample Handling

Use sampling methods that will collect bottom-sediment and suspended-sediment samples that accurately represent organic contaminant compositions and concentrations at a given location and time. Use sample collection equipment that is free of plastic tubing, gaskets, and other parts that might leach interferences, sorb contaminants, or abrade and thus contaminate sediment samples.
Ship samples, contained in either 500- or 1,000-mL wide-mouth glass jars (precleaned by baking at 450^oC for at least 2 hours) with PTFE-lined lids or other NWQL-approved containers, on ice by overnight carrier to the laboratory as soon as possible following collection. Decant excess water to allow space in the jars for expansion from freezing.
At the laboratory, the samples are stored at -15^oC in freezers dedicated to organochlorine sediment samples until time of analysis. Foil may be wrapped around the glass jars to prevent breakage and possible contamination. After analysis, the remaining sample materials are stored at -15^oC for a minimum of 3 years; however, the sample extracts are stored indefinitely at -15^oC.

Maximum Holding Time

>6 months expected

Relative Cost

Greater than $400

Sample Preparation Methods

This method has 25 analytes associated with it.

Analyte	Detection Level	Bias	Precision	Spiking Level
4,4'-DDD(72-54-8) 1,1-Dichloro-2,2-bis(p-chlorophenyl)ethane 4,4'-DDD Benzene, 1,1'-(2,2-dichloroethylidene)bis[4-ch Benzene, 1,1'-(2,2-dichloroethylidene)bis[4-chloro- Dichloro-2,2-bis(p-chlorophenyl)ethane,1,1- Dichlorodiphenyldichloroethane Ethane, 1,1-dichloro-2,2-bis(p-chlorophenyl)- Rhothane TDE Tetrachlorodiphenylethane p,p'-DDD p,p'-Dichlorodiphenyl dichloroethane p,p'-TDE	1.030 ug/kg	82% Rec (SL)	19.95 % RSD (SL)	2.00 ug/kg
4,4'-DDE(72-55-9) 1,1'-(-Dichloroethenylidene)bis(4-chlorobenzene) 4,4'-DDE 4,4'-DDE, DDT, DDD Benzene, 1,1'-(dichloroethenylidene)bis[4-chlo Benzene, 1,1'-(dichloroethenylidene)bis[4-chloro- Ethylene, 1,1-dichloro-2,2-bis(p-chlorophenyl)- bis(p-Chlorophenyl)-1,1-dichloroethylene,2,2- p,p'-DDE p,p'-Dichlorodiphenyldichloroethylene	0.688 ug/kg	136% Rec (SL)	16.86 % RSD (SL)	1.00 ug/kg
Aldrin(309-00-2) Aldrex Aldrin Aldrin-R Aldrite Aldrosol HHDN Hexachlorohexahydro-endo-exo-dimethanonaphthalene Octalene Seedrin liquid	0.859 ug/kg	74% Rec (SL)	18.43 % RSD (SL)	2.00 ug/kg
Dieldrin(60-57-1) 1,2,3,4,10,10-Hexachloro-6,7-epoxy-1,4,4a,5, 6 1,2,3,4,10,10-Hexachloro-6,7-epoxy-1,4,4a,5, 6,7,8, ... 2,7:3,6-Dimethanonaphth(2,3-b)oxirene, 3,4,5,6 2,7:3,6-Dimethanonaphth(2,3-b)oxirene, 3,4,5,6,9,9- ... Alvit Dieldrin Dieldrin (hexachloroepoxyoctahydro-endo,exo- ... Dieldrin/aldrin Dimethanonaphthalene, 1,2,3,4,10,10-hexachloro-6,7- ... Heod Octalox	0.215 ug/kg	91% Rec (SL)	7.55 % RSD (SL)	1.00 ug/kg
Endosulfan-I(959-98-8) 6,9-Methano-2,4,3-benzodioxathiepin, 6,7,8,9,10,10- ... Endosulfan-I Endosulfan-alpha Thiodan I alpha-Endosulfan	0.234 ug/kg	48% Rec (SL)	7.81 % RSD (SL)	2.00 ug/kg
Endrin(72-20-8) 2,7:3,6-Dimethanonaphth[2,3-b]oxirene, 3,4,5,6,9,9- ... 3,4,5,6,9,9-Hexachloro-1a,2,2a,3,6,6a,7,7a-oct 3,4,5,6,9,9-Hexachloro-1a,2,2a,3,6,6a,7,7a-octahydro ... Compound 269 Endrin Hexachloroepoxyoctahydro-endo,endo-dimethanonaphthalene Hexadrin Mendrin Nendrin	0.336 ug/kg	115% Rec (SL)	9.32 % RSD (SL)	1.00 ug/kg
Heptachlor(76-44-8) 1,4,5,6,7,8,8-Heptachlorotetrahydro-4,7-methanoindene Drinox Heptachlor Heptachlor [1,4,5,6,7,8,8-heptachloro-3a,4,7,7a- ... Heptachlor/Heptachlor epoxide (SARA 110) Heptachlorodicyclopentadiene Heptagran Heptamul Velsicol-104	0.309 ug/kg	66% Rec (SL)	15.54 % RSD (SL)	1.00 ug/kg
Heptachlor epoxide(1024-57-3) Heptachlor epoxide Velsicol 53-CS-17 Vesicol 53-CS-17	0.601 ug/kg	77% Rec (SL)	12.44 % RSD (SL)	2.00 ug/kg
Hexachlorobenzene(118-74-1) Anticarie Benzene, hexachloro- Bunt-cure HCB Hexachlorobenzene Perchlorobenzene	1.430 ug/kg	62% Rec (SL)	5.92 % RSD (SL)	13.00 ug/kg
Lindane(58-89-9) Cyclohexane, 1,2,3,4,5,6-hexachloro-, (1-alpha Cyclohexane, 1,2,3,4,5,6-hexachloro-, (1-alpha, 2- ... HCH-gamma Hexachlorocyclohexane (gamma) Lindane Lindane ( gamma isomer of benzene hexachloride ) (99 ... gamma-BHC gamma-Benzenehexachloride gamma-HCH gamma-Hcch gamma-Hexachlorocyclohexane	0.200 ug/kg	55% Rec (SL)	11.60 % RSD (SL)	1.00 ug/kg
Methoxychlor(72-43-5) 1,1'-(2,2,2-Trichloroethylidene)bis[4-methoxybenzene] 1,1,1-Trichloro-2,2-bis(4-methoxyphenyl)ethane Benzene, 1,1'-(2,2,2-trichloroethylidene)bis[4-methoxy- Dimethoxy DDT Ethane, 1,1,1-trichloro-2,2-bis(p-methoxypheny Ethane, 1,1,1-trichloro-2,2-bis(p-methoxyphenyl)- Marlate Methoxcide Methoxychlor Metox p,p'-Methoxychlor p,p'DMDT	1.560 ug/kg	608% Rec (SL)	N/A	1.00 ug/kg
Mirex(2385-85-5) Bichlorendo Cyclopentadiene,hexachloro-, dimer Dechlorane Ferriamicide Hexachloropentadiene dimer Mirex	0.589 ug/kg	74% Rec (SL)	12.75 % RSD (SL)	2.00 ug/kg
Organics, semivolatile(E-12884) Organics, semivolatile Semi-volatile organics Semivolatile organics	N/A	N/A	N/A
Organochlorine pesticides(E-12851) Organochlorine pesticides Pesticides, organochlorine	N/A	N/A	N/A
PCB-1016(12674-11-2) Aroclor 1016 PCB-1016	2.020 ug/kg	87% Rec (SL)	14.82 % RSD (SL)	5.00 ug/kg
PCB-1242(53469-21-9) Arochlor 1242 Aroclor 1242 PCB-1242	2.020 ug/kg	87% Rec (SL)	14.82 % RSD (SL)	5.00 ug/kg
PCB-1254(11097-69-1) Arochlor 1254 Aroclor 1254 PCB-1254	2.090 ug/kg	180% Rec (SL)	7.38 % RSD (SL)	5.00 ug/kg
PCB-1260(11096-82-5) Arochlor 1260 Aroclor 1260 PCB-1260	2.340 ug/kg	139% Rec (SL)	10.77 % RSD (SL)	5.00 ug/kg
Toxaphene(8001-35-2) Alltox Camphechlor Camphechlor, Camphene, octachloro- Camphochlor Estonox Geniphene Phenacide Phenatox Polychlorocamphene Toxaphene Toxaphene ( Technical chlorinated camphene (67-69% ...	57.300 ug/kg	67% Rec (SL)	14.25 % RSD (SL)	201.00 ug/kg
alpha-BHC(319-84-6) .alpha.-Benzenehexachloride Cyclohexane, 1,2,3,4,5,6-hexachloro-, alpha-isomer HCH-alpha alpha-BHC alpha-HCH alpha-Hexachlorocyclohexane alpha-Lindane	0.550 ug/kg	58% Rec (SL)	15.08 % RSD (SL)	2.00 ug/kg
alpha-Chlordane(5103-71-9) 4,7-Methano-1H-indene 1,2,4,5,6,7,8,8-octachlo Methanoindan, 1-alpha,2-alpha,4-beta,5,6,7-beta,8,8- ... Methanoindan,alpha-1,2,4,5,6,7,8,8-octachloro-3a- ... alpha-Chlordane cis-4,7-Methano-1H-indene 1,2,4,5,6,7,8,8-octachloro ... cis-Chlordane	0.415 ug/kg	63% Rec (SL)	0.13 % RSD (SL)	2.00 ug/kg
beta-BHC(319-85-7) Cyclohexane, 1,2,3,4,5,6-hexachloro-, beta-isomer HCH-beta beta-BHC beta-Benzenehexachloride beta-HCH beta-Hexachlorocyclohexane beta-Lindane	0.221 ug/kg	73% Rec (SL)	9.68 % RSD (SL)	1.00 ug/kg
p,p'-DDT(50-29-3) 1,1,1-Trichloro-2,2-bis(p-chlorophenyl)ethane 4,4'-DDT Benzene, 1,1'-(2,2,2-trichloroethylidene)bis[4-chloro- Chlorophenothane DDT Dichlorodiphenyltrichloroethane Ethane, 1,1,1-trichloro-2,2-bis(p-chlorophenyl)- bis(p-Chlorophenyl)-2,2,2-trichloroethane,1,1- p,p'-DDT p,p'-Dichlorodiphenyltrichloroethane	0.442 ug/kg	71% Rec (SL)	19.78 % RSD (SL)	1.00 ug/kg
trans-Chlordane(5103-74-2) AI3-16398 EINECS 225-826-0 Methanoindan, 1,2,3,5,6,7,8,8-octachlor-3a,4,7,7a- ... Methanoindan,1,2,4,5,6,7,8,8-octachloro-3a,4,7,7a- ... trans-4,7-Methano-1H-indene 1,2,4,5,6,7,8,8- ... trans-Chlordan trans-Chlordane	0.207 ug/kg	70% Rec (SL)	9.42 % RSD (SL)	1.00 ug/kg
trans-Nonachlor(39765-80-5) trans-Nonachlor	0.385 ug/kg	57% Rec (SL)	21.58 % RSD (SL)	1.00 ug/kg

Precision Descriptor Notes:	The matrices used to test method performance included a reagent (sodium sulfate); a sediment sample collected from Evergreen Lake, Evergreen, Colorado; and a sediment sample collected from Clear Creek near Central City, Colorado.
Detection Level Note:	The estimated MDLs were determined by fortifying eight sodium sulfate reagent replicates with method compounds and were calculated using methods outlined in USEPA Appendix B, Part 136.

Revision	PDF/Link
2003

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USGS-NWQL: O-5504-03: Organochlorine Pesticides and Polychlorinated Biphenyls in Bottom and Suspended Sediment by Gas Chromatography with Electron Capture Detection

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