USGS-NWQL: O-1121-91: Organonitrogen Herbicides in Water by Solid Phase Extraction, GC/MS

Summary
Analytes
Revision
Data and Sites

Official Method Name

Methods of analysis by the U.S. Geological Survey National Water Quality Laboratory -Determination of organonitrogen herbicides in water by C-18 SPE and capillary-column GC-MS with selected-ion monito

Current Revision

1994

Media

WATER

Instrumentation

Gas Chromatography with Mass Spectrometry Detection

Method Subcategory

Organic

Method Source

USGS-NWQL

Citation

M.W. Sandstrom, D.S. Wydoski, M.P. Schroeder, J.L. Zamboni and W.T. Foreman, 1992, Methods of analysis by the U.S. Geological Survey National Water Quality Laboratory--Determination of organonitrogen herbicides in water by solid-phase extraction and capillary-column gas chromatography/mass spectrometry with selected-ion monitoring: U.S. Geological Survey Open-File Report 91-519

Brief Method Summary

Water samples (100 mL) are filtered to remove suspended particulate matter. Glass-fiber filters with a nominal 0.7-um pore diameter or disposable, in-line filter units, containing a nylon membrane with a nominal 0.45-um pore diameter depending on the concentration of the suspended particulate matter in the water samples, are used. Filtered water samples are pumped through disposable, polypropylene SPE cartridges containing 0.5 g of porous silica coated with a C-18 organic phase that is chemically bonded to the surface of the silica. The SPE cartridges are dried using a gentle stream of carbon dioxide to remove interstitial water. The adsorbed herbicides and metabolites are removed from the SPE cartridges by elution with 1.8 mL of hexane-isopropanol (3:1). The eluant is further evaporated using a gentle stream of nitrogen to a final volume of 100 uL. Extracts of the eluant are analyzed by a capillary-column GC/MS operated in the SIM mode.

Scope and Application

This method is suitable for the determination of selected organonitrogen herbicides and metabolites in natural-water samples containing at least 0.05 ug/L of each herbicide or metabolite. The method is applicable to herbicides and metabolites that are: (1) efficiently partitioned from the water phase onto an octadecyl (C-18) organic phase that is chemically bonded to a solid inorganic matrix; and (2) sufficiently volatile and thermally stable for gas chromatogrphy. Suspended particulate matter is removed from the samples by filtration, so this method is suitable only for dissolved-phase herbicides and metabolites. The method was used to determine the concentrations of the 23 herbicides and the 2 metabolites of atrazine-desethylatrazine and desisopropylatrazone.
Previously completed development of the method (Sandstrom, 1989), as well as other comparable methods (Thurman and others, 1990) served as background for this report. Testing of the method included adjustment of sample volume and final extract volume to optimize recovery of the herbicides, especially the metabolites of atrazine-destylatrazine and desisopropylatrazine.

Applicable Concentration Range

>0.05

Interferences

Organic compounds having gas-chromatographic retention times and characteristic ions with a mass identical to those of the herbicides and metabolites of interest may interfere.

Quality Control Requirements

Quality-control samples area analyzed at a minimum of one in every ten samples. These QC samples include at least one of each of the following: blanks, quality control samples, third party check solutions, replicates, and spikes. Correlation coefficients for calibration curves must be at least 0.99. QC samples must fall within 1.5 standard deviations of the mean value. If all of the data-acceptance criteria in the SOPs are met, then the analytical data are acceptable.

Sample Handling

This schedule consumes the entire sample. Description: 1-L, 125-mL, or 60-mL (see schedule for size) glass amber bottle baked at 450^oC by laboratory. Some GCC's should be filtered. CHECK METHOD REFERENCE OR E-MAIL LABHELP@USGS.GOV FOR FILTERING REQUIREMENTS. DO NOT RINSE BOTTLE. Do not fill bottle beyond shoulder. Reagents must be added to the sample at the NWQL before analyses. Chill sample and maintain at 4^oC and ship immediately.

Maximum Holding Time

Relative Cost

$201 to $400

Sample Preparation Methods

USGS-WRIR 95-4105

This method has 26 analytes associated with it.

Analyte	Detection Level	Bias	Precision	Spiking Level
Alachlor(15972-60-8) 2-Chloro-N-(2,6-diethylphenyl)-N-(methoxymethy Acetanilide,2-chloro-2',6'-diethyl-n-(methoxymethyl)- Alachlor Alanex Lasso Metachlor Methachlor	0.067 ug/L	101% Rec (SL)	0.09 % RSD (SL)	0.20 ug/L
Ametryn(834-12-8) 2-Ethylamino-4-isopropylamino-6-methylthio-s-t 2-Ethylamino-4-isopropylamino-6-methylthio-s-triazine 2-Ethylamino-4-isopropylamino-6-methylthio-s-trizaine Ametryn Ametryn (ANSI) Ametryn (N-Ethyl-N'-(1-methylethyl)-6-(methylthio)-1 ... Ametryne Cemerin Evik Gesapax	0.060 ug/L	87% Rec (SL)	0.09 % RSD (SL)	0.20 ug/L
Atrazine(1912-24-9) 1,3,5-Triazine-2,4-diamine, 6-chloro-N-ethyl-N'-(1- ... 2-Chloro-4-(ethylamino)-6-(isopropylamino)-S-triazine 2-Chloro-4-(ethylamino)-6-(isopropylamino)-s-t 2-Chloro-4-ethylamino-6-isopropylamine-sym-triazine AAtrex Atratol 8P Atrazine Atrazine (ANSI) Bicep	0.088 ug/L	67% Rec (SL)	0.18 % RSD (SL)	0.20 ug/L
Bromacil(314-40-9) 5-Bromo-3-sec-butyl-6-methyluracil Borea Bromacil Bromacil (ANSI) Bromax Hyvar Uragon Urox "B" Urox 'B'	0.213 ug/L	150% Rec (SL)	0.19 % RSD (SL)	0.20 ug/L
Butachlor(23184-66-9) 2-Chloro-2',6'-diethyl-N-(butoxymethyl)acetanilide Acetamide, N-(butoxymethyl)-2-chloro-N-(2,6-di Acetanilide,2-chloro-2',6'-diethyl-n-(butoxymethyl)- Butachlor Butachlor (ANSI) Butanox Hiltachlor Machete N-(Butoxymethyl)-2-chloro-N-(2,6-diethylphenyl)acetamide N-(butoxymethyl)-2-chloro-2',6'-diethyl acetan N-(butoxymethyl)-2-chloro-2',6'-diethyl acetanilide	0.084 ug/L	95% Rec (SL)	0.12 % RSD (SL)	0.20 ug/L
Butylate(2008-41-5) Anelda Butylate Carbamic acid, diisobutylthio-, S-ethyl ester Carbamothioic acid, bis(2-methylpropyl)-, S-et Carbamothioic acid, bis(2-methylpropyl)-, S-ethyl ester Diisocarb S-Ethyl diisobutylthiocarbamate S-Ethyldiisobutyl thiocarbamate Sutan bis(2-Methylpropyl)carbamothioate-S-ethyl n,n-Diisobutylthiocarbamate-Ethyl	0.052 ug/L	41% Rec (SL)	0.17 % RSD (SL)	0.20 ug/L
Carboxin(5234-68-4) 2,3-Dihydro-6-methyl-1,4-oxathiin-5-carboxanil 2,3-Dihydro-6-methyl-1,4-oxathiin-5-carboxanilide 5,6-Dihydro-2-methyl-1,4-oxathiin-3-carboxanalide Carbathiin Carboxin Carboxin (5,6-Dihydro-2-methyl-N-phenyl-1,4-oxathiin ... Fenoxan Vitavax	0.064 ug/L	120% Rec (SL)	0.07 % RSD (SL)	0.20 ug/L
Cyanazine(21725-46-2) 2-((4-Chloro-6-(ethylamino)-1,3,5-triazin-2-yl)amino)-2-methylpropanenitrile 2-((4-Chloro-6-(ethylamino)-s-triazin-2-yl)amino)-2-methylpropionitrile Bladex Cyanazine Fortrol Payze	0.063 ug/L	109% Rec (SL)	0.08 % RSD (SL)	0.20 ug/L
Cycloate(1134-23-2) Carbamothioic acid, cyclohexylethyl-, S-ethyl Carbamothioic acid, cyclohexylethyl-, S-ethyl ester Cycloate Cyclohexanecarbamic acid,n-ethylthio-, s-ethyl ester Etsan Etsan, Eurex Eurex Hexylthiocarbam N-ethylthiocyclohexanecarbamic acid, s-ethyl ester Ro-Neet S-Ethyl N-cyclohexyl-N-ethylthiocarbamate S-Ethyl cyclohexylethylthiocarbamate S-Ethyl-N-cyclohexyl-N-ethylthiocarbamate Sabet	0.096 ug/L	71% Rec (SL)	0.18 % RSD (SL)	0.20 ug/L
Desethylatrazine(6190-65-4) 1,3,5-Triazine-2,4-diamine, 6-chloro-N-(1-methylethyl)- (9CI) 2-Amino-4-chloro-6-(isopropylamino)-s-triazine 2-Chloro-4-amino-6-isopropylamino-1,3,5-triazine 2-Chloro-4-amino-6-isopropylamino-s-triazine 2-Chloro-4-isopropylamino-6-amino-s-triazine Atrazine-desethyl Chloroaminoisopropylaminotriazine DEA Deethylatratone Desethylatrazine s-Triazine, 2-amino-4-chloro-6-(isopropylamino)- (6CI,7CI,8CI)	0.096 ug/L	82% Rec (SL)	0.16 % RSD (SL)	0.20 ug/L
Desisopropylatrazine(1007-28-9) 2-Amino-4-chloro-6-(ethylamino)-s-triazine 2-Chloro-4-amino-6-(ethylamino)-s-triazine 2-Chloro-4-ethylamino-6-amino-1,3,5-triazine 2-Chloro-4-ethylamino-6-amino-s-triazine 4-Amino-2-chloro-6-(ethylamino)-s-triazine 4-Amino-2-chloro-6-ethylamino-1,3,5-triazine Atrazine-desisopropyl DIA Deethylsimazine Deisopropylatrazine Desisopropylatrazine F703 G 28279 NSC 13909 s-Triazine, 2-amino-4-chloro-6-(ethylamino)- (6CI,7CI,8CI)	0.037 ug/L	72% Rec (SL)	0.07 % RSD (SL)	0.20 ug/L
Diphenamid(957-51-7) 2,2-Diphenyl-N,N-dimethylacetamide Acetamide,n,n-dimethyl-2,2-diphenyl Benzeneacetamide, N,N-dimethyl-.alpha.-phenyl- Diherbid Dimid, Dymid Diphenamid Diphenamid (ANSI) Dymid Enide N,N-Dimethyl-2,2-diphenylacetamide N,N-Dimethyldiphenylacetamide Rideon	0.083 ug/L	115% Rec (SL)	0.10 % RSD (SL)	0.20 ug/L
Herbicides(E-12839) Herbicide formulations Herbicides	N/A	N/A	N/A
Hexazinone(51235-04-2) 1,3,5-Triazine-2,4(1H,3H)-dione, 3-cyclohexyl- 1,3,5-Triazine-2,4(1H,3H)-dione, 3-cyclohexyl-6-(di ... 3-Cyclohexyl-6-(dimethylamino)-1-methyl-1,3,5- ... 3-Cyclohexyl-6-(dimethylamino)-1-methyl-s-tria 3-Cyclohexyl-6-(dimethylamino)-1-methyl-s-triazine-2 ... Cyclohexyl-6-(dimethylamino)-1-methyl-1,3,5-triazine ... Cyclohexyl-6-(dimethylamino)-1-methyl-s-triazine-2,4 ... Hexazinone Velpar	0.132 ug/L	124% Rec (SL)	0.14 % RSD (SL)	0.20 ug/L
Metolachlor(51218-45-2) 2-Chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-4- ... 2-Chloro-N-(6-ethyl-o-tolyl)-N-(2-methoxy-1- ... 2-chloro-6'-ethyl-N-(2-methoxy-1-methylethyl)-o- ... Acetamide, 2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2- ... Codal Cycle Dual Metelilachlor Metolachlor Metolachlor (ANSI)	0.097 ug/L	114% Rec (SL)	0.11 % RSD (SL)	0.20 ug/L
Metribuzin(21087-64-9) 4-Amino-6-(1,1-dimethylethyl)-3-(methylthio)-1 Bay 94337 Lexone Metribuzin Sencoral Sencorer	0.052 ug/L	89% Rec (SL)	0.08 % RSD (SL)	0.20 ug/L
Prometon(1610-18-0) 2,4-bis(Isopropylamino)-6-methoxy-S-triazine 2,4-bis(Isopropylamino)-6-methoxy-sym-triazine 2,6-Diisopropylamino-4-methoxytriazine Gesafram 50 Methoxypropazine Pramitol Prometon Prometon (ANSI) Prometon(pramitol) Prometone	0.069 ug/L	101% Rec (SL)	0.09 % RSD (SL)	0.20 ug/L
Prometryn(7287-19-6) 1,3,5-Triazine-2,4-diamine, N,N'-bis(1-methyle 1,3,5-Triazine-2,4-diamine, N,N'-bis(1-methylethyl)- ... 2,4-bis(Isopropylamino)-6-(methylthio)-S-triazine 2,4-bis(Isopropylamino)-6-methylthio-sym-triazine Caparol Gesagard Gesagard, Gesagaro Primatol Q Prometrin, Prometryn (ANSI), Prometryne Prometryn Prometryn (N,N'-Bis(1-methylethyl)-6-methylthio-1,3, ... Selectin Uvon	0.070 ug/L	89% Rec (SL)	0.11 % RSD (SL)	0.20 ug/L
Propachlor(1918-16-7) 2-Chloro-N-isopropylacetanilide 2-Chloro-n-isopropyl-n-phenylacetamide Acetamide, 2-chloro-N-(1-methylethyl)-N-phenyl Acetamide, 2-chloro-N-(1-methylethyl)-N-phenyl- Bexton Propachlor Propachlore Ramrod	0.080 ug/L	82% Rec (SL)	0.13 % RSD (SL)	0.20 ug/L
Propazine(139-40-2) 1,3,5-Triazine-2,4-diamine, 6-chloro-N,N'-bis( 2-Chloro-4,6-bis(isopropylamino)-S-triazine Chloro-4,6-bis(isopropylamino)-sym-triazine,2- Gesamil Milocep Milogard Primatol P Propasin Propazine Propazine (ANSI)	0.059 ug/L	67% Rec (SL)	0.12 % RSD (SL)	0.20 ug/L
Simazine(122-34-9) 1,3,5-Triazine-2,4-diamine, 6-chloro-N,N'-diethyl- 2,4-bis(Ethylamino)-6-chloro-s-triazine 2-Chloro-4,6-bis(ethylamino)-1,3,5-triazine 2-Chloro-4,6-bis(ethylamino)-S-triazine 6-Chloro-N,N'-diethyl-1,3,5-triazine-2,4-diami 6-Chloro-N,N'-diethyl-1,3,5-triazine-2,4-diamine Aquazine Princep Radocon S-Triazine,2-chloro-4,6-bis(ethylamino)- Simadex, Simanex, Simazine (ANSI) Simazine	0.109 ug/L	81% Rec (SL)	0.18 % RSD (SL)	0.20 ug/L
Simetryn(1014-70-6) 1,3,5-Triazine-2,4-diamine, N,N'-diethyl-6-(me 1,3,5-Triazine-2,4-diamine, N,N'-diethyl-6-(methylthio)- 2,4-Bis(ethylamino)-6-(methylthio)-s-triazine 2,4-bis(Ethylamino)-6-methylmercapto-s-triazine Simetryn	0.050 ug/L	84% Rec (SL)	0.08 % RSD (SL)	0.20 ug/L
Terbacil(5902-51-2) 2,4(1H,3H)-Pyrimidinedione, 5-chloro-3-(1,1-di 2,4(1H,3H)-Pyrimidinedione, 5-chloro-3-(1,1-dimethyl ... 3-tert-Butyl-5-chloro-6-methyluracil 3-tert-Butyl-s-chloro-6-methyluracil 5-Chloro-3-(1,1-dimethylethyl)-6-methyl- 2 ... Geonter Sinbar Terbacil Turbacil	0.092 ug/L	107% Rec (SL)	0.11 % RSD (SL)	0.20 ug/L
Terbuthylazine(5915-41-3) GS 13529 Gardoprim Primatol M Terbuthylazine Terbuthylazine (ANSI) Terbutylethylazine	0.054 ug/L	68% Rec (SL)	0.11 % RSD (SL)	0.20 ug/L
Trifluralin(1582-09-8) Commence Dinitro-n,n-dipropyl-4-(trimethylfluoro)benzenamine,2,6- Treflan Trifluoralin, Trifluraline Trifluralin Triflurex p-Toluidine, alpha, alpha, alpha-trifluoro-2,6	0.015 ug/L	52% Rec (SL)	0.04 % RSD (SL)	0.20 ug/L
Vernolate(1929-77-7) Carbamothioic acid, dipropyl-, S-propyl ester PPTC Propyl-n,n-dipropylthiocarbamate S-Propyl dipropylthiocarbamate S-Propyldipropylthiocarbamate Vernam Vernolate	0.090 ug/L	53% Rec (SL)	0.23 % RSD (SL)	0.20 ug/L

Precision Descriptor Notes:	A reagent-water sample, a surface-water sample collected from the South Platte River in Colorado, and a ground-water sample collected from Jefferson County, Colorado (Arvada Well No. 14) were used to test the method performance. One set of three subsamples was fortified with 0.2 ug/L of each analyte and the other set of three subsamples was fortified with 2.0 ug/L of each analyte. Seven 100-mL aliquots of each of the six subsamples were analyzed in one laboratory using one GC/MS.
Detection Level Note:	Method detection limits (MDLs) were determined for this method using the procedures of the U.S. Environmental Protection Agency (1997).

Precision Descriptor Notes:

A reagent-water sample, a surface-water sample collected from the South Platte River in Colorado, and a ground-water sample collected from Jefferson County, Colorado (Arvada Well No. 14) were used to test the method performance. One set of three subsamples was fortified with 0.2 ug/L of each analyte and the other set of three subsamples was fortified with 2.0 ug/L of each analyte. Seven 100-mL aliquots of each of the six subsamples were analyzed in one laboratory using one GC/MS.

Detection Level Note:

Method detection limits (MDLs) were determined for this method using the procedures of the U.S. Environmental Protection Agency (1997).

Revision	PDF/Link
1994

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USGS-NWQL: O-1121-91: Organonitrogen Herbicides in Water by Solid Phase Extraction, GC/MS

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