USGS-NWQL: O-5505-03: Polycyclic aromatic hydrocarbons, sediment, capillary-column gas chromatography/mass spectrometry

Summary
Analytes
Revision
Data and Sites

Official Method Name

Polycyclic aromatic hydrocarbons, sediment, high-performance gel permeation chromatography, capillary-column gas chromatography/mass spectrometry

Current Revision

2003

Media

SOILS/SEDIMENT

Instrumentation

Gas Chromatography with Mass Spectrometry Detection

Method Subcategory

Organic

Method Source

USGS-NWQL

Citation

Olson, M.C., Iverson, J.L., Furlong, E.T., and Schroeder, M.P., 2004, Methods of Analysis of the U.S. Geological Survey National Water Quality Laboratory - Determination of Polycyclic Aromatic Hydrocarbon Compounds in Sediment by Gas Chromatography/Mass Spectrometry, U.S. Geological Survey Water-Resources Investigations Report 03-4318, 53 p.

Brief Method Summary

Wet-sediment samples are homogenized and centrifuged, if necessary, to remove water, and water content is determined. Each sample is mixed with anhydrous sodium sulfate and placed into a glass Soxhlet thimble. After adding the method surrogate compounds and 25 mL of methanol to remove water not bound by sodium sulfate, wait 30 minutes. Extract the sample with 350 mL of dichloromethane plus the methanol in a Soxhlet apparatus for at least 12 hours, typically overnight. The extract is dried with sodium sulfate and reduced to 3 mL by Kudema-Danish concentration and filtered with a polytetrafluoroethylene membrane. A method gel permeation chromatography (GPC) surrogate compound is added and the volume is increased to 4 mL. A 1,400-uL aliquot of the sample extract is injected quantitatively onto two polystyrene-divinylbenzene GPC columns, connected in series and eluted with dichloromethane. The PAH compounds are isolated from coextracted chemical interferences and collected in an 8.6-mL fraction. This GPC fraction is exchanged into ethyl acetate and reduced to 0.5 mL. A perdeuterated polycyclic aromatic hydrocarbon internal standard (dPAHIS) solution is added to each extract. The extract-containing vial then is sealed and held at <5^oC until analysis for PAHs. Organophophate pesticides (OP) also can be determined using this extract. A second aliquot (1,100 uL) of the sample extract is injected onto the GPC if OCs are requested and taken through separate steps.
The instrumental analysis consists of a gas chromatographic (GC) separation of the compounds followed by mass spectrometric (MS) identification and quantification in full-scan mode. The compounds are separated within the GC using a fused-silica capillary column with temperature programming to optimize compound separation. The compounds are identified by comparison to a library of reference mass spectra. The internal standard method is used to quantitate the compounds using a multiple-p

Scope and Application

This method is suitable for the determination of polycyclic aromatic hydrocarbons in soil and sediment samples containing at least 10 ug/kg of each PAH compound. This method is applicable to compounds that are efficiently extracted from sediment by a dichloromethane/methanol azeotrope, adequately separated from natural coextracted compounds by gel permeation chromatography, and sufficiently volatile and thermally stable for determination by gas chromatography/mass spectrometry.

Applicable Concentration Range

<10-1,000 g/kg

Interferences

Organic compounds that are coextracted, collected in the GPC fraction, and have GC retention times and characteristic ions with masses identical to those of the selected PAHs of interest might interfere. In particular, hydrocarbons and hydrocarbon degradation products can cause substantial interferences. Diluting the sample extract before analysis can minimize the interferences.
Analyses of laboratory reagent blanks provide information about the presence of contaminants and are used to determine if an interference exists. If interferences are identified, cleaning or replacement of parts may be required to remove the interference(s).
Contaminants might interfere when a sample containing low (ug/kg) concentrations of compounds is analyzed immediately after a sample containing a high (mg/kg) concentrations of compounds. Syringes and splitless injection port liners need to be cleaned carefully or replaced as needed. The GPC system needs to be monitored continuously to ensure that it is not a source of sample cross-contamination.

Quality Control Requirements

Laboratory reagent blanks and spikes, surrogate standards, and CCVs are used by the analyst to control data quality. The method report provides detailed instructions for preparing these controls. Calibrate instrument using calibration standards (CAL); quality control samples (QCS); and laboratory blanks (LB) analyzed at a minimum of 1 for every 10 samples.

Sample Handling

1 L Glass jar, wide-mouth baked at 450^oC. DO NOT RINSE BOTTLE. Chill and maintain at 4^oC, ship immediately.

Maximum Holding Time

None noted in method

Relative Cost

Greater than $400

Sample Preparation Methods

This method has 30 analytes associated with it.

Analyte	Detection Level	Bias	Precision	Spiking Level
1,2-Dimethylnaphthalene(573-98-8) 1,2-Dimethylnaphthalene NSC 59832 Naphthalene, 1,2-dimethyl- (8CI,9CI)	2.600 ug/kg	76% Rec (SL)	8.90 % RSD (SL)	12.00 ug/kg
1,6-Dimethylnaphthalene(575-43-9) 1,6-Dimethylnaphthalene NSC 52966 Naphthalene, 1,6-dimethyl- (8CI,9CI)	1.500 ug/kg	78% Rec (SL)	5.20 % RSD (SL)	12.00 ug/kg
1-Methyl-9H-fluorene(1730-37-6) 1-Methyl-9H-fluorene 1-Methylfluorene 9H-Fluorene, 1-methyl-	2.000 ug/kg	77% Rec (SL)	6.90 % RSD (SL)	12.00 ug/kg
1-Methylphenanthrene(832-69-9) 1-Methylphenanthrene Phenanthrene, 1-methyl-	2.100 ug/kg	80% Rec (SL)	6.80 % RSD (SL)	12.00 ug/kg
1-Methylpyrene(2381-21-7) 1-Methylpyrene 3-Methylpyrene Methylpyrene NSC 90776 Pyrene, 1-methyl- (6CI,7CI,8CI,9CI)	3.700 ug/kg	86% Rec (SL)	11.00 % RSD (SL)	12.00 ug/kg
2,3,6-Trimethylnaphthalene(829-26-5) 2,3,6-Trimethylnaphthalene NSC 11848 Naphthalene, 2,3,6-trimethyl- (6CI,7CI,8CI,9CI)	5.100 ug/kg	75% Rec (SL)	3.70 % RSD (SL)	12.00 ug/kg
2,6-Dimethylnaphthalene(581-42-0) 2,6-Dimethylnaphthalene	3.100 ug/kg	78% Rec (SL)	10.00 % RSD (SL)	12.00 ug/kg
2-Ethylnaphthalene(939-27-5) 2-Ethylnaphthalene 3-Ethylnaphthalene NSC 59389 Naphthalene, 2-ethyl- (6CI,8CI,9CI) beta-Ethylnaphthalene	3.100 ug/kg	78% Rec (SL)	9.20 % RSD (SL)	12.00 ug/kg
2-Methylanthracene(613-12-7) 2-Methylanthracene Anthracene, 2-methyl- (8CI,9CI) NSC 87376	1.700 ug/kg	72% Rec (SL)	6.10 % RSD (SL)	12.00 ug/kg
4H-Cyclopenta[def]phenanthrene(203-64-5) 4,5-Methylenephenanthrene 4H-Cyclopenta[def]phenanthrene Benzo[def]fluorene Phenanthrene, 4,5-methylene	2.700 ug/kg	79% Rec (SL)	9.00 % RSD (SL)	12.00 ug/kg
Acenaphthene(83-32-9) 1,2-Dihydroacenaphthylene 1,8-Ethylenenaphthalene Acenaphthene Acenaphthene,1,2-dihydro- Acenaphthylene, 1,2-dihydro- Periethylenenaphthalene	2.400 ug/kg	76% Rec (SL)	8.30 % RSD (SL)	12.00 ug/kg
Acenaphthylene(208-96-8) Acenaphthalene Acenaphthylene Cyclopenta(de)naphthalene	2.700 ug/kg	76% Rec (SL)	9.60 % RSD (SL)	12.00 ug/kg
Anthracene(120-12-7) Anthracene Anthracin Green oil Paranaphthalene Tetra olive n2g	2.800 ug/kg	73% Rec (SL)	10.00 % RSD (SL)	12.00 ug/kg
Benz[a]anthracene(56-55-3) 1,2-Benzanthracene 2,3-Benzphenanthrene Benz[a]anthracene Benzanthrene Benzo(a)anthracene Benzoanthracene Naphthanthracene Tetraphene	2.200 ug/kg	90% Rec (SL)	6.40 % RSD (SL)	12.00 ug/kg
Benzo(a)pyrene(50-32-8) 3,4-Benzopyrene 3,4-Benzpyrene BP BaP Benzo(a)pyrene Benzo[a]pyrene	1.800 ug/kg	78% Rec (SL)	6.30 % RSD (SL)	12.00 ug/kg
Benzo(b)fluoranthene(205-99-2) 2,3-Benzofluoranthene 3,4-Benzfluoranthene 3,4-Benzofluoranthene B(b)F Benz[e]acephenanthrylene Benzo(b)fluoranthene Benzo(e)fluoranthene Benzo[b]fluoranthene	1.600 ug/kg	76% Rec (SL)	5.70 % RSD (SL)	12.00 ug/kg
Benzo(g,h,i)perylene(191-24-2) 1,12-Benzoperylene 1,12-Benzperylene B(ghi)P Benzo(g,h,i)perylene Benzo(ghi)perylene	3.300 ug/kg	52% Rec (SL)	17.00 % RSD (SL)	12.00 ug/kg
Benzo(k)fluoranthene(207-08-9) 11,12-Benzofluoranthene B(k)F Benz(k)fluoranthene Benzo(k)fluoranthene	3.200 ug/kg	90% Rec (SL)	9.40 % RSD (SL)	12.00 ug/kg
Benzo[e]pyrene(192-97-2) 2,3-Benzofluoranthene 3,4-Benzfluoranthene 4,5-Benzopyrene B[E]P Benzo[e]pyrene	2.400 ug/kg	75% Rec (SL)	6.40 % RSD (SL)	12.00 ug/kg
Chrysene(218-01-9) 1,2,5,6-Dibenzonaphthalene 1,2-Benzophenanthrene 1,2-Benzphenanthrene Benz(a)phenanthrene Benzo(a)phenanthrene Chrysene	1.700 ug/kg	94% Rec (SL)	4.80 % RSD (SL)	12.00 ug/kg
Dibenzo(a,h)anthracene(53-70-3) 1,2:5,6-Dibenzanthracene DB(a,h)A Dibenz(a,h)anthracene Dibenzo(a,h)anthracene	2.500 ug/kg	88% Rec (SL)	7.60 % RSD (SL)	12.00 ug/kg
Fluoranthene(206-44-0) 1,2-Benzacenaphthene Benzo(j,k)fluorene Fluoranthene Idryl	1.300 ug/kg	87% Rec (SL)	4.00 % RSD (SL)	12.00 ug/kg
Fluorene(86-73-7) 2,2'-Methylenebiphenyl 9H-Fluorene Diphenylenemethane Fluorene o-Biphenylenemethane	3.400 ug/kg	75% Rec (SL)	12.00 % RSD (SL)	12.00 ug/kg
Indeno(1,2,3-cd)pyrene(193-39-5) 1,10-(1,2-Phenylene)pyrene 2,3-Phenylenepyrene Indeno(1,2,3-cd)pyrene o-Phenylenepyrene	3.800 ug/kg	89% Rec (SL)	11.00 % RSD (SL)	12.00 ug/kg
Naphthalene(91-20-3) Moth balls Naphthalene Naphthalin Naphthene Tar camphor White tar	4.000 ug/kg	77% Rec (SL)	14.00 % RSD (SL)	12.00 ug/kg
Organics, semivolatile(E-12884) Organics, semivolatile Semi-volatile organics Semivolatile organics	N/A	N/A	N/A
Perylene(198-55-0) Dibenz(de,k)anthracene Dibenz(de,kl)anthracene Perylene peri-Dinaphthalene	3.100 ug/kg	78% Rec (SL)	11.00 % RSD (SL)	12.00 ug/kg
Phenanthrene(85-01-8) Phenanthrene Phenathrin	3.000 ug/kg	82% Rec (SL)	9.60 % RSD (SL)	12.00 ug/kg
Pyrene(129-00-0) Benzo[def]phenanthrene Pyrene Pyrene[def]phenanthrene	2.800 ug/kg	88% Rec (SL)	8.30 % RSD (SL)	12.00 ug/kg
Volatile organic compounds(E-12419) Organic compounds, volatile VOCs Volatile organic compounds	N/A	N/A	N/A

Precision Descriptor Notes:	Matrices chosen to test method performance were: reagent-sodium sulfate (matrix-free); bottom sediment collected from Evergreen Lake, Evergreen, Colorado; and bottom sediment collected near Clear Creek, Colorado. The performance of this method for the extraction isolation, and determination of the PAHs was evaluated by adding aliquots of standard solutions to seven 25-g dry-weight subsamples of each matrix and processing the fortified samples through the entire method. The bias and precision data summarized in NEMI consists of the analysis results of reagent-sodium sulfate at the 12.0 ug/kg spiking concentration. Method surrogates nitrobenzene-d₅, 2-fluorobiphenyl, and terphenyl-d₁₄ were included in the bias, accuracy, and MDL table; however, no MDL data was provided with these compounds. Twenty-five groups of alkylated PAHs are included. These groups are homologs of five groups of isomeric parent PAHs and are reported semi-quantitatively using a response factor from a parent PAH or a specific alkylated PAH. Precision data are presented using two different standard reference materials produced by the National Institute of Standards and Technology.
Detection Level Note:	The MDL was determined using the methodology described in USEPA report Part 136, Appendix B.

Precision Descriptor Notes:

Matrices chosen to test method performance were: reagent-sodium sulfate (matrix-free); bottom sediment collected from Evergreen Lake, Evergreen, Colorado; and bottom sediment collected near Clear Creek, Colorado. The performance of this method for the extraction isolation, and determination of the PAHs was evaluated by adding aliquots of standard solutions to seven 25-g dry-weight subsamples of each matrix and processing the fortified samples through the entire method.
The bias and precision data summarized in NEMI consists of the analysis results of reagent-sodium sulfate at the 12.0 ug/kg spiking concentration.
Method surrogates nitrobenzene-d₅, 2-fluorobiphenyl, and terphenyl-d₁₄ were included in the bias, accuracy, and MDL table; however, no MDL data was provided with these compounds.
Twenty-five groups of alkylated PAHs are included. These groups are homologs of five groups of isomeric parent PAHs and are reported semi-quantitatively using a response factor from a parent PAH or a specific alkylated PAH. Precision data are presented using two different standard reference materials produced by the National Institute of Standards and Technology.

Detection Level Note:

The MDL was determined using the methodology described in USEPA report Part 136, Appendix B.

Revision	PDF/Link
2003

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USGS-NWQL: O-5505-03: Polycyclic aromatic hydrocarbons, sediment, capillary-column gas chromatography/mass spectrometry

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