USGS-NWQL: O-6143-09: Pyrethroid Insecticides in Sediment Using GC/MS

Summary
Analytes
Revision
Data and Sites

Official Method Name

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

Current Revision

2009

Media

SOILS/SEDIMENT

Instrumentation

Gas Chromatography with Mass Spectrometry Detection

Method Subcategory

Organic

Method Source

USGS-NWQL

Citation

Determination of pyrethroid insecticides in water and sediment using gas chromatography/mass spectrometry

Brief Method Summary

For extraction, the samples are thawed, and the percentage moisture is adjusted to 50 percent. The samples are extracted with microwave-assisted extraction two times using DCM:methanol. The extract is reduced to 0.5 mL and co-extracted matrix interferences are removed using stacked graphitized carbon and alumina SPE cartridges. The pyrethroids are eluted from the SPE cartridge with DCM and then exchanged into EtOAc. Further removal of sulfur and matrix is achieved by high-performance liquid chromatography with gel-permeation chromatography (HPLC-GPC) of the EtOAc fraction. The GPC eluent is evaporated in a hood using a gentle stream of nitrogen to a final volume of 0.2 mL. The concentrations of the pyrethroids in the extracts are determined by gas chromatography/mass spectrometry (GC/MS) or gas chromatography with tandem mass spectrometry (GC/MS/MS).

Scope and Application

This method covers 14 pyrethroids in sediment samples at microgram-per-kilogram concentrations.

Applicable Concentration Range

Pyrethroids are reported in concentrations from 0.2 to 100 µg/kg. If the concentration is greater than 500 ng/L or 100 µg/kg, a portion of the original sample extract is diluted appropriately with EtOAc, prepared with internal standard, and reanalyzed.

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

Sediment or soil samples are collected in the field using the methods such as those outlined by Radtke (2005), typically into 500-mL amber glass jars. Samples are chilled immediately, shipped to the PFRG, and frozen at –20 °C until analysis (within 6 months).

Maximum Holding Time

Six months at –20 °C prior to extraction.

Relative Cost

Unknown

Sample Preparation Methods

MAE (DCM:MeOH), SPE (C/Al), HPLC-GPC

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	1.500 ug/kg	82% Rec (SL)	7.00 % RSD (SL)	2.00 ug/kg
Bifenthrin(82657-04-3) Bifenthrin	2.200 ug/kg	97% Rec (SL)	7.00 % RSD (SL)	2.00 ug/kg
Cyfluthrin(68359-37-5) Cyfluthrin	2.000 ug/kg	82% Rec (SL)	6.00 % RSD (SL)	2.00 ug/kg
Cypermethrin(52315-07-8) Cypermethrin	2.600 ug/kg	87% Rec (SL)	8.00 % RSD (SL)	2.00 ug/kg
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	2.500 ug/kg	82% Rec (SL)	8.00 % RSD (SL)	2.00 ug/kg
Esfenvalerate(66230-04-4) Benzeneacetic acid, 4-chloro-alpha-(1-methylethyl)-, (S)-cyano(3-phenoxyphenyl)methyl ester, (alphaS)- (9CI) Esfenvalerate	2.100 ug/kg	83% Rec (SL)	8.00 % RSD (SL)	2.00 ug/kg
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	2.100 ug/kg	90% Rec (SL)	6.00 % RSD (SL)	2.00 ug/kg
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	1.000 ug/kg	93% Rec (SL)	3.00 % RSD (SL)	2.00 ug/kg
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	1.300 ug/kg	101% Rec (SL)	3.00 % RSD (SL)	2.00 ug/kg
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	1.900 ug/kg	89% Rec (SL)	6.00 % RSD (SL)	2.00 ug/kg
Tefluthrin(79538-32-2) Tefluthrin	1.100 ug/kg	91% Rec (SL)	4.00 % RSD (SL)	2.00 ug/kg
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	1.400 ug/kg	83% Rec (SL)	4.00 % RSD (SL)	2.00 ug/kg
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	2.600 ug/kg	99% Rec (SL)	9.00 % RSD (SL)	2.00 ug/kg
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	2.400 ug/kg	89% Rec (SL)	9.00 % RSD (SL)	2.00 ug/kg

Precision Descriptor Notes:	Pyrethroid recoveries were determined using seven samples spiked at 5 g (dry weight) of sediment in two sediment matrixes (bed sediment and suspended sediment), and one soil matrix.
Detection Level Note:	Initial method performance was evaluated for recovery using sediment collected from a Northern California agricultural drain with undetectable pyrethroid levels prior to spiking. MDLs were determined using seven samples spiked at 10 µg/kg according to the procedure outlined by the U.S. Environmental Protection Agency in 40 CFR 136, Appendix B, assuming a 5-g 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 (0.2 to 0.5 µg/kg) than those for the single mass spectrometry samples (1.0 to 2.6 µg/kg). 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 each method using GC/MS, the LODs was 1 to 2 µg/kg. The MDLs are higher than the LODs because MDLs account for sample recovery and variability rather than the theoretical lowest concentration that can be measured. MDLs noted are for GC/MS; see method paper for MDLs for GC/MS/MS.

Precision Descriptor Notes:

Pyrethroid recoveries were determined using seven samples spiked at 5 g (dry weight) of sediment in two sediment matrixes (bed sediment and suspended sediment), and one soil matrix.

Detection Level Note:

Initial method performance was evaluated for recovery using sediment collected from a Northern California agricultural drain with undetectable pyrethroid levels prior to spiking. MDLs were determined using seven samples spiked at 10 µg/kg according to the procedure outlined by the U.S. Environmental Protection Agency in 40 CFR 136, Appendix B, assuming a 5-g 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 (0.2 to 0.5 µg/kg) than those for the single mass spectrometry samples (1.0 to 2.6 µg/kg). 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 each method using GC/MS, the LODs was 1 to 2 µg/kg. The MDLs are higher than the LODs because MDLs account for sample recovery and variability rather than the theoretical lowest concentration that can be measured. MDLs noted are for GC/MS; see method paper for MDLs for GC/MS/MS.

Revision	PDF/Link
2009

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USGS-NWQL: O-6143-09: Pyrethroid Insecticides in Sediment Using GC/MS

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