USGS-NWQL: O-5506-06: PAHs in Soils, Bottom Sediment, and Solids by GC-MS

Summary
Analytes
Revision
Data and Sites

Official Method Name

Determination of Semivolatile Organic Compounds and Polycyclic Aromatic Hydrocarbons in Solids by Gas Chromatography/Mass Spectrometry

Current Revision

2006

Media

SOILS/SEDIMENT

Instrumentation

Gas Chromatography with Mass Spectrometry Detection

Method Subcategory

Organic

Method Source

USGS-NWQL

Citation

Zaugg, S.D., Burkhardt, M.R., Burbank, T.L., Olson, M.C., Iverson, J.L., and Schroeder, M.P., 2006, Determination of semivolatile organic compounds and polycyclic aromatic hydrocarbons in solids by gas chromatography/mass spectrometry: U.S. Geological Survey Techniques and Methods, book 5, chap. B3, 44 p.

Brief Method Summary

A method for the determination of 38 polycyclic aromatic hydrocarbons (PAHs) and semivolatile organic compounds in solid samples is described. Samples are extracted using a pressurized solvent extraction system. The compounds of interest are extracted from the solid sample twice at 13,800 kilopascals; first at 120 degrees Celsius using a water/isopropyl alcohol mixture (50:50, volume-to-volume ratio), and then the sample is extracted at 200 degrees Celsius using a water/isopropyl alcohol mixture (80:20, volume-to-volume ratio). The compounds are isolated using disposable solid-phase extraction (SPE) cartridges containing divinylbenzene-vinylpyrrolidone copolymer resin. The cartridges are dried with nitrogen gas, and then sorbed compounds are eluted from the SPE material using a dichloromethane/diethyl ether mixture (80:20, volume-to-volume ratio) and through a sodium sulfate/Florisil SPE cartridge to remove residual water and to further clean up the extract. The concentrated extract is solvent exchanged into ethyl acetate and the solvent volume reduced to 0.5 milliliter. Internal standard compounds are added prior to analysis by capillary-column gas chromatography/mass spectrometry.

Scope and Application

This method is suitable for the determination of 38 semivolatile organic compounds and polycyclic aromatic hydrocarbons and 25 alkylated PAH homolog groups in solids by GC/MS. The method extracts 25 g of bed sediment (stream and lakebeds), soil, or aqueous suspended sediment (minimum of 0.5-g material) to determine the method compounds in microgram-per-kilogram concentrations. The method is applicable to compounds that are (1) efficiently extracted from sediment samples using high-pressure water/isopropyl alcohol, (2) partitioned from the resulting water/isopropyl alcohol extract onto the divinylbenzene-vinylpyrrolidone copolymer organic phase, (3) volatile and thermally stable for gas chromatography (GC), (4) sufficiently stable to chemical and thermal degradation, and (5) are amenable to electron impact (EI) mass spectrometry (MS) analysis.

Applicable Concentration Range

Variable and dependant upon analyte

Interferences

Samples, collection equipment, ASE extraction cells, or SPE cartridges must be cleaned with phosphate-free detergent, followed by copious amounts of tap water, and then deionized water. Compounds that compete with or displace the compounds of interest from the SPE cartridge materials (divinylbenzene-vinylpyrrolidone copolymer phase and Florisil) might cause interferences or low method recovery, or both. In addition, coextracted dissolved organic material, such as humic and fulvic acids, might reduce the SPE extraction efficiency and recoveries of the compounds of interest. Phthalates and preservatives [butylated hydroxy toluene (BHT) and related compounds] in the SPE cartridge material and housing can potentially contribute to low-concentration contamination. Compounds that have gas-chromatographic retention times and characteristic ions with mass-to-charge ratios identical to, or similar to, the compounds of interest might interfere.

Quality Control Requirements

Laboratory quality-control data includes reagent blank and spike samples, surrogate standards, and continuous calibration verifications to determine if corrective actions are necessary. Standard reference material and instrumental checks provide external verification of method performance and are considered quality-assurance samples. Refer to section 10 of the report for information about: 10.1 Laboratory Blank 10.2 Laboratory Spike 10.3 Surrogate Compounds 10.4 Continuous Calibration Verification (CCV) 10.5 Decafluorotriphenylphosphine (DFTPP) Tuning 10.6 Instrument Detection Limit (IDL) 10.7 Third-party Check Solution 10.8 Internal Standard Compounds 10.9 Standard Reference Material (SRM) 10.10 Matrix Spikes

Sample Handling

Dependant on form (ie. core sample, suspended sediment, soil); refer to method report for technique references for sample collection. For organic sediment, samples are collected in 500 mL baked, amber glass bottles. The samples can be preserved by freezing at −20^oC with a 1-year sample-holding time limit (prior to sample extraction) from the date of sample collection.

Maximum Holding Time

Up to 1 year if frozen at -20^oC; The sample-holding time limit is provisional until a validated method can be used to determine the effectiveness of the sample-freezing procedure.

Relative Cost

Greater than $400

Sample Preparation Methods

This method has 38 analytes associated with it.

Analyte	Detection Level	Bias	Precision	Spiking Level
1,2,4-Trichlorobenzene(120-82-1) 1,2,4-Trichlorobenzene 1,2,5-Trichlorobenzene 1,3,4-Trichlorobenzene Benzene, 1,2,4-trichloro- TCB Trichlorobenzene, 1,2,4- unsym-Trichlorobenzene	11.400 ug/kg	50% Rec	13.20 % RSD	1.50 ug/kg
1,2-Dimethylnaphthalene(573-98-8) 1,2-Dimethylnaphthalene NSC 59832 Naphthalene, 1,2-dimethyl- (8CI,9CI)	9.200 ug/kg	91% Rec	5.90 % RSD	1.50 ug/kg
1,6-Dimethylnaphthalene(575-43-9) 1,6-Dimethylnaphthalene NSC 52966 Naphthalene, 1,6-dimethyl- (8CI,9CI)	7.200 ug/kg	86% Rec	4.80 % RSD	1.50 ug/kg
1-Methyl-9H-fluorene(1730-37-6) 1-Methyl-9H-fluorene 1-Methylfluorene 9H-Fluorene, 1-methyl-	17.300 ug/kg	100% Rec	9.90 % RSD	1.50 ug/kg
1-Methylphenanthrene(832-69-9) 1-Methylphenanthrene Phenanthrene, 1-methyl-	13.700 ug/kg	111% Rec	7.10 % RSD	1.50 ug/kg
1-Methylpyrene(2381-21-7) 1-Methylpyrene 3-Methylpyrene Methylpyrene NSC 90776 Pyrene, 1-methyl- (6CI,7CI,8CI,9CI)	13.100 ug/kg	113% Rec	6.70 % RSD	1.50 ug/kg
2,3,6-Trimethylnaphthalene(829-26-5) 2,3,6-Trimethylnaphthalene NSC 11848 Naphthalene, 2,3,6-trimethyl- (6CI,7CI,8CI,9CI)	10.800 ug/kg	92% Rec	6.70 % RSD	1.50 ug/kg
2,6-Dimethylnaphthalene(581-42-0) 2,6-Dimethylnaphthalene	8.500 ug/kg	87% Rec	5.70 % RSD	1.50 ug/kg
2-Ethylnaphthalene(939-27-5) 2-Ethylnaphthalene 3-Ethylnaphthalene NSC 59389 Naphthalene, 2-ethyl- (6CI,8CI,9CI) beta-Ethylnaphthalene	7.700 ug/kg	84% Rec	5.30 % RSD	1.50 ug/kg
2-Methylanthracene(613-12-7) 2-Methylanthracene Anthracene, 2-methyl- (8CI,9CI) NSC 87376	13.000 ug/kg	103% Rec	7.30 % RSD	1.50 ug/kg
4H-Cyclopenta[def]phenanthrene(203-64-5) 4,5-Methylenephenanthrene 4H-Cyclopenta[def]phenanthrene Benzo[def]fluorene Phenanthrene, 4,5-methylene	12.500 ug/kg	106% Rec	6.80 % RSD	1.50 ug/kg
Acenaphthene(83-32-9) 1,2-Dihydroacenaphthylene 1,8-Ethylenenaphthalene Acenaphthene Acenaphthene,1,2-dihydro- Acenaphthylene, 1,2-dihydro- Periethylenenaphthalene	8.900 ug/kg	90% Rec	5.70 % RSD	1.50 ug/kg
Acenaphthylene(208-96-8) Acenaphthalene Acenaphthylene Cyclopenta(de)naphthalene	8.900 ug/kg	84% Rec	6.10 % RSD	1.50 ug/kg
Anthracene(120-12-7) Anthracene Anthracin Green oil Paranaphthalene Tetra olive n2g	11.900 ug/kg	103% Rec	6.60 % RSD	1.50 ug/kg
Anthraquinone (8CI)(84-65-1) 9,10-Anthracenedione (9CI) 9,10-Anthraquinone Anthracene-9,10-quinone Anthradione Anthraquinone (8CI) DAQ-N Flight Control Flight Control Plus Hoelite Morkit NSC 7957	14.000 ug/kg	117% Rec	6.90 % RSD	1.50 ug/kg
Benz[a]anthracene(56-55-3) 1,2-Benzanthracene 2,3-Benzphenanthrene Benz[a]anthracene Benzanthrene Benzo(a)anthracene Benzoanthracene Naphthanthracene Tetraphene	13.400 ug/kg	102% Rec	7.60 % RSD	1.50 ug/kg
Benzo(a)pyrene(50-32-8) 3,4-Benzopyrene 3,4-Benzpyrene BP BaP Benzo(a)pyrene Benzo[a]pyrene	13.900 ug/kg	98% Rec	8.20 % RSD	1.50 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	13.300 ug/kg	96% Rec	8.00 % RSD	1.50 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	13.500 ug/kg	99% Rec	7.90 % RSD	1.50 ug/kg
Benzo(k)fluoranthene(207-08-9) 11,12-Benzofluoranthene B(k)F Benz(k)fluoranthene Benzo(k)fluoranthene	11.600 ug/kg	96% Rec	7.00 % RSD	1.50 ug/kg
Benzo[e]pyrene(192-97-2) 2,3-Benzofluoranthene 3,4-Benzfluoranthene 4,5-Benzopyrene B[E]P Benzo[e]pyrene	12.000 ug/kg	99% Rec	7.00 % RSD	1.50 ug/kg
Carbazole(86-74-8) 9H-Carbazole Carbazole Dibenzopyrrole	13.900 ug/kg	102% Rec	7.80 % RSD	1.50 ug/kg
Chrysene(218-01-9) 1,2,5,6-Dibenzonaphthalene 1,2-Benzophenanthrene 1,2-Benzphenanthrene Benz(a)phenanthrene Benzo(a)phenanthrene Chrysene	13.500 ug/kg	102% Rec	7.60 % RSD	1.50 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	14.400 ug/kg	97% Rec	8.50 % RSD	1.50 ug/kg
Dibenzothiophene(132-65-0) Dibenzo(b,d)thiophene Dibenzothiophene Diphenylene sulfide	16.000 ug/kg	105% Rec	8.80 % RSD	1.50 ug/kg
Diethyl phthalate(84-66-2) 1,2-Benzenedicarboxylic acid, diethyl ester Benzenedicarboxylic acid,1,2-, diethyl ester DEP Diethyl phthalate Phthalic acid, diethyl ester o-Diethyl phthalate	26.400 ug/kg	86% Rec	17.60 % RSD	1.50 ug/kg
Fluoranthene(206-44-0) 1,2-Benzacenaphthene Benzo(j,k)fluorene Fluoranthene Idryl	13.000 ug/kg	111% Rec	6.80 % RSD	1.50 ug/kg
Fluorene(86-73-7) 2,2'-Methylenebiphenyl 9H-Fluorene Diphenylenemethane Fluorene o-Biphenylenemethane	9.800 ug/kg	94% Rec	6.00 % RSD	1.50 ug/kg
Hexachlorobenzene(118-74-1) Anticarie Benzene, hexachloro- Bunt-cure HCB Hexachlorobenzene Perchlorobenzene	14.300 ug/kg	97% Rec	8.50 % RSD	1.50 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	12.900 ug/kg	102% Rec	7.30 % RSD	1.50 ug/kg
Naphthalene(91-20-3) Moth balls Naphthalene Naphthalin Naphthene Tar camphor White tar	7.700 ug/kg	67% Rec	6.60 % RSD	1.50 ug/kg
Pentachloroanisole(1825-21-4) Pentachloroanisole	15.500 ug/kg	97% Rec	9.30 % RSD	1.50 ug/kg
Pentachloronitrobenzene(82-68-8) Benzene, pentachloronitro- Brassicol PCNB Pentachloronitrobenzene Quintozene Terrachlor Terraclor Terracur	12.900 ug/kg	91% Rec	8.10 % RSD	1.50 ug/kg
Perylene(198-55-0) Dibenz(de,k)anthracene Dibenz(de,kl)anthracene Perylene peri-Dinaphthalene	9.800 ug/kg	87% Rec	6.40 % RSD	1.50 ug/kg
Phenanthrene(85-01-8) Phenanthrene Phenathrin	12.900 ug/kg	102% Rec	7.30 % RSD	1.50 ug/kg
Phentanthridine(229-87-8) 3,4-Benzoisoquinoline 3,4-Benzoquinoline 5-Azaphenanthrene 9-Azaphenanthrene Benzo[c]quinoline NSC 338473 NSC 73482 NSC 93336 Phentanthridine	17.300 ug/kg	99% Rec	10.10 % RSD	1.50 ug/kg
Pyrene(129-00-0) Benzo[def]phenanthrene Pyrene Pyrene[def]phenanthrene	13.200 ug/kg	113% Rec	6.80 % RSD	1.50 ug/kg
bis(2-Ethylhexyl) phthalate(117-81-7) 1,2-Benzenedicarboxylic acid, bis(2-ethylhexyl 1,2-Benzenedicarboxylic acid, bis(2-ethylhexyl)ester BEHP BEHP, DEHP DEHP Di(2-ethylhexyl) phthalate Di(2-ethylhexyl)orthophthalate Di(sec-octyl) phthalate Di-(2-ethylhexyl)phthalate Di-sec-octyl phthalate Diethylhexyl phthalate Phthalic acid dioctyl ester Phthalic acid, bis(2-ethylhexyl) ester bis(2-Ethylhexyl) phthalate bis(2-Ethylhexyl)-1,2-benzenedicarboxylate bis(2-Ethylhexyl)-o-phthalate	27.900 ug/kg	128% Rec	12.60 % RSD	1.50 ug/kg

Precision Descriptor Notes:	This report describes method performance for the quantitative determination of 38 semivolatile compounds (most of which are PAHs). The semiquantitation of 25 alkylated PAH homolog groups associated with five parent PAHs also is described, but results must be obtained by means of a separate request to the NWQL. Method performance (mean bias and variability) was determined using Ottawa sand, a commercially available topsoil, and an environmental stream sediment, fortified at 1.5 and 15 micrograms per compound. NOTE: The performance data provided in NEMI represent nine replicate samples with compounds spiked at 1.5 ug per sample in reagent sand. The reproducibility of the method was evaluated by using 10 environmental sediment samples. Results for this method also were compared to the existing Soxhlet method at the NWQL using 28 environmental sediment samples. This new ASE method is more efficient and cost effective for extracting PAH compounds from solids than the NWQL Soxhlet method (Olson and others, 2004). For more specific information, see Section 11 (Results and Discussion of Method Validation).
Detection Level Note:	The MDL was determined from nine replicate reagent sand samples fortified at 60 ug/kg per compound. The calculated MDL for each compound assumes a 25-g sample size in the analysis. No method performance data are presented for the 25 alkylated PAH homolog groups because of the lack of reference standards, reproducibility data using standard reference material are provided.

Precision Descriptor Notes:

This report describes method performance for the quantitative determination of 38 semivolatile compounds (most of which are PAHs). The semiquantitation of 25 alkylated PAH homolog groups associated with five parent PAHs also is described, but results must be obtained by means of a separate request to the NWQL. Method performance (mean bias and variability) was determined using Ottawa sand, a commercially available topsoil, and an environmental stream sediment, fortified at 1.5 and 15 micrograms per compound. NOTE: The performance data provided in NEMI represent nine replicate samples with compounds spiked at 1.5 ug per sample in reagent sand. The reproducibility of the method was evaluated by using 10 environmental sediment samples. Results for this method also were compared to the existing Soxhlet method at the NWQL using 28 environmental sediment samples. This new ASE method is more efficient and cost effective for extracting PAH compounds from solids than the NWQL Soxhlet method (Olson and others, 2004). For more specific information, see Section 11 (Results and Discussion of Method Validation).

Detection Level Note:

The MDL was determined from nine replicate reagent sand samples fortified at 60 ug/kg per compound. The calculated MDL for each compound assumes a 25-g sample size in the analysis. No method performance data are presented for the 25 alkylated PAH homolog groups because of the lack of reference standards, reproducibility data using standard reference material are provided.

Revision	PDF/Link
2006

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USGS-NWQL: O-5506-06: PAHs in Soils, Bottom Sediment, and Solids by GC-MS

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