USGS-OWQ: O-2143-09 (water): Pyrethroid Insecticides in Water Using GC/MS

Summary
Analytes
Revision
Data and Sites

Official Method Name

Determination of Pyrethroid Insecticides in Water and Sediment Using Gas Chromatography/Mass Spectrometry (GC/MS) or Gas Chromatography/Tandem Mass Spectrometry (GC/MS/MS).

Current Revision

2009

Media

WATER

Instrumentation

Gas Chromatography with Mass Spectrometry Detection

Method Subcategory

Organic

Method Source

USGS-OWQ

Citation

Methods of Analysis—Determination of Pyrethroid Insecticides in Water and Sediment Using Gas Chromatography/Mass Spectrometry

Brief Method Summary

Samples are filtered either in the field or in the laboratory using a GF/F-grade glass-fiber filter (GF/F). The water samples are spiked with surrogate standards and passed through an HLB SPE cartridge. Adsorbed compounds are eluted from the cartridge with ethyl acetate (EtOAc). The empty sample bottle is rinsed with dichloromethane (DCM). Both the eluent and the bottle rinsate are evaporated in a hood using a gentle stream of nitrogen to 0.2 mL; internal standards are then added. The concentrations of the pyrethroids in the extracts are determined by gas chromatography/mass spectrometry (GC/MS) or gas chromatography/tandem mass spectrometry (GC/MS/MS).

Scope and Application

This method covers 14 pyrethroid insecticides in environmental water at nanograms-per-liter concentrations.

Applicable Concentration Range

0.5 to 500

Interferences

(A) Compounds that compete with, displace, or influence extraction efficiency (e.g., humic and fulvic acids) during SPE: Addressed with matrix-spiked samples and surrogate compounds. (B) Contamination from exposure to household pesticide products: Limit exposure to these products prior to sample collection or sample handling and monitor with field and lab blanks.

Quality Control Requirements

Internal standard solution (ISTD), Surrogate standard solution, Primary standard solutions, Pyrethroid standard solution, Calibration solutions, Matrix-spike solution, Surrogate spike solution, Continuous calibration verification (CCV) solutions, laboratory blank, laboratory matrix spike, laboratory matrix spike duplicate, laboratory replicate, surrogate standards, solvent blank.

Sample Handling

Samples are chilled immediately, shipped to the PFRG, and refrigerated at 4 °C until analysis (within 48 hours of collection).

Maximum Holding Time

Samples are to be analyzed within 48 hrs of collection.

Relative Cost

Unknown

Sample Preparation Methods

Samples are filtered either in the field or in the laboratory using a GF/F-grade glass-fiber filter.

This method has 14 analytes associated with it.

Analyte	Detection Level	Bias	Precision	Spiking Level
Allethrin(584-79-2) 3-Allyl-2-methyl-4-oxo-2-cyclopenten-1-yl chrysanthemate Allethrin Allethrin [BSI:ISO] Bioallethrin [BAN] Esbiothrin HSDB 1511 NSC 11782	6.000 ng/L	N/A	7.00 % RSD	10.00 ng/L
Bifenthrin(82657-04-3) Bifenthrin	4.700 ng/L	N/A	6.00 % RSD	10.00 ng/L
Cyfluthrin(68359-37-5) Cyfluthrin	5.200 ng/L	N/A	9.00 % RSD	10.00 ng/L
Cypermethrin(52315-07-8) Cypermethrin	5.600 ng/L	N/A	8.00 % RSD	10.00 ng/L
Deltamethrin(52918-63-5) (S)-alpha-Cyano-3-phenoxybenzyl (1R,3R)-3-(2,2-dibromovinyl)-2,2- dimethyl-cyclopropan-1-carboxylate Butox Cyclopropanecarboxylic acid, 3-(2,2-dibromoethenyl)-2,2-dimethyl-, (S)-cyano(3-phenoxyphenyl)methyl ester, (1R,3R)- Decamethrin Deltamethrin Deltamethrin [BSI:ISO] HSDB 6604	3.500 ng/L	N/A	9.00 % RSD	10.00 ng/L
Esfenvalerate(66230-04-4) Benzeneacetic acid, 4-chloro-alpha-(1-methylethyl)-, (S)-cyano(3-phenoxyphenyl)methyl ester, (alphaS)- (9CI) Esfenvalerate	3.900 ng/L	N/A	8.00 % RSD	10.00 ng/L
Fenpropathrin(39515-41-8) Cyano-3-phenoxybenzyl-2,2,3,3-tetramethylcyclopropanecarboxylate Danitol EINECS 254-485-0 EPA Pesticide Chemical Code 127901 Fenpropathrin Fenpropathrin [ISO] Meothrin	4.100 ng/L	N/A	9.00 % RSD	10.00 ng/L
Permethrin(52645-53-1) 3-(2,2-Dichloroethenyl)-2,2-dimethylcyclopropanecarboxylic acid (3-phenoxyphenyl)methyl ester 3-phenoxy benzyl (1RS)-cis,trans-3-(2,2 dichlorovinyl)-2,2 dimethyl-cyclopropane carboxylate Dragnet Permethrin	3.400 ng/L	N/A	8.00 % RSD	10.00 ng/L
Phenothrin(26002-80-2) 3-Phenoxybenzyl 2-dimethyl-3-(methylpropenyl)cyclopropanecarboxylate 3-Phenoxybenzyl chrysanthemate Anchimanaito 20S EINECS 247-404-5 EPA Pesticide Chemical Code 069005 HSDB 3922 Phenothrin Phenothrin [BSI:ISO] Phenothrin [INN:BAN] Phenoxythrin Sumitrin	5.100 ng/L	N/A	8.00 % RSD	10.00 ng/L
Resmethrin(10453-86-8) Benzofuroline Chryson Cyclopropanecarboxylic acid, 2,2-dimethyl-3-(2-methyl-1-propenyl)-, (5-(phenylmethyl)-3-furanyl)methyl ester EINECS 233-940-7 EPA Pesticide Chemical Code 097801 HSDB 1516 NRDC 104 Resmethrin Synthrin	5.700 ng/L	N/A	8.00 % RSD	10.00 ng/L
Tefluthrin(79538-32-2) Tefluthrin	4.800 ng/L	N/A	7.00 % RSD	10.00 ng/L
Tetramethrin(7696-12-0) Cyclopropanecarboxylic acid, 2,2-dimethyl-3-(2-methyl-1-propenyl)-, (1,3,4,5,6,7-hexahydro-1,3-dioxo-2H-isoindol-2-yl)methyl ester EINECS 231-711-6 EPA Pesticide Chemical Code 069003 HSDB 6738 Neo-pynamin SP-1103 Tetramethrin Tetramethrin [ANSI:BSI:ISO] Tetramethrin [INN] d-Phthalthrin	2.900 ng/L	N/A	5.00 % RSD	10.00 ng/L
t-fluvalinate(102851-06-9) D-Valine, N-(2-chloro-4-(trifluoromethyl)phenyl)-, cyano(3- phenoxyphenyl)methyl ester Fluvarol Fluwarol Klartan Tau-fluvalinate Tau-fluvalinate [ISO] t-fluvalinate	5.300 ng/L	N/A	9.00 % RSD	10.00 ng/L
λ-Cyhalothrin(91465-08-6) Cyclopropanecarboxylic acid, 3-[(1Z)-2-chloro-3,3,3-trifluoro-1-propenyl]-2,2-dimethyl-, (R)-cyano(3-phenoxyphenyl)methyl ester, (1S,3S)-rel- λ-Cyhalothrin λ-Cyhalothrin	2.000 ng/L	N/A	9.00 % RSD	10.00 ng/L

Precision Descriptor Notes:	Pyrethroid recoveries were determined using seven samples spiked at 10 and 100 ng per 1 L in three matrixes, American River water (reagent), a surface drain, and an agricultural drain. The American River water was used in place of reagent water as this better represents clean real-world conditions. Method variability, determined as relative percent difference, was evaluated by the use of laboratory replicates and matrix-spike/matrix spike duplicate pairs.
Detection Level Note:	MDLs were determined using seven samples spiked at 10 ng/L according to the procedure outlined by the U.S. Environmental Protection Agency in 40 CFR 136, Appendix B, assuming a 1-L sample size. The MDL was calculated according to the equation stated in the method. Seven replicate samples are fortified with compounds at concentrations two to five times the estimated MDL. This concentration range was used to calculate initial MDLs for the pyrethroids. All samples are first run via GC/MS for verification of pyrethroids and quantification. If the pyrethroid concentrations are lower than the GC/MS MDLs, the sample extracts are run on the GC/MS/MS to decrease background noise. In samples with high background matrix, the pyrethroid may not undergo complete dissociation by GC/MS/ MS, confounding the calculation of analyte concentrations. Samples that are run in both modes will have their concentrations compared as described in section 11.1; if the sample run by GC/MS/MS has spectra where the parent ion has not undergone complete dissociation, there may be background interferences, and the GC/MS data (and associated MDLs) will be reported. The MDLs for the tandem mass spectrometry analyzed samples are lower (0.5 to 1.0 ng/L for water) than those for the single mass spectrometry samples (2.0 to 6.0 ng/L for water). The MDLs were also compared with the theoretical limits of detection (LOD). The LOD was calculated as the concentration of analyte in the spiked sample that produced a signal greater than three times the background signal. For GC/MS, the LODs were 2 to 5 ng/L for water. The MDLs are higher than the LODs because MDLs take into account sample recovery and variability rather than the theoretical lowest concentration that can be measured.

Precision Descriptor Notes:

Pyrethroid recoveries were determined using seven samples spiked at 10 and 100 ng per 1 L in three matrixes, American River water (reagent), a surface drain, and an agricultural drain. The American River water was used in place of reagent water as this better represents clean real-world conditions. Method variability, determined as relative percent difference, was evaluated by the use of laboratory replicates and matrix-spike/matrix spike duplicate pairs.

Detection Level Note:

MDLs were determined using seven samples spiked at 10 ng/L according to the procedure outlined by the U.S. Environmental Protection Agency in 40 CFR 136, Appendix B, assuming a 1-L sample size. The MDL was calculated according to the equation stated in the method. Seven replicate samples are fortified with compounds at concentrations two to five times the estimated MDL. This concentration range was used to calculate initial MDLs for the pyrethroids. All samples are first run via GC/MS for verification of pyrethroids and quantification. If the pyrethroid concentrations are lower than the GC/MS MDLs, the sample extracts are run on the GC/MS/MS to decrease background noise. In samples with high background matrix, the pyrethroid may not undergo complete dissociation by GC/MS/ MS, confounding the calculation of analyte concentrations. Samples that are run in both modes will have their concentrations compared as described in section 11.1; if the sample run by GC/MS/MS has spectra where the parent ion has not undergone complete dissociation, there may be background interferences, and the GC/MS data (and associated MDLs) will be reported. The MDLs for the tandem mass spectrometry analyzed samples are lower (0.5 to 1.0 ng/L for water) than those for the single mass spectrometry samples (2.0 to 6.0 ng/L for water). The MDLs were also compared with the theoretical limits of detection (LOD). The LOD was calculated as the concentration of analyte in the spiked sample that produced a signal greater than three times the background signal. For GC/MS, the LODs were 2 to 5 ng/L for water. The MDLs are higher than the LODs because MDLs take into account sample recovery and variability rather than the theoretical lowest concentration that can be measured.

Revision	PDF/Link
2009

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USGS-OWQ: O-2143-09 (water): Pyrethroid Insecticides in Water Using GC/MS

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