USGS-NWQL: O-1131-95: Pesticides in Water by Solid Phase Extraction and High Performance Liquid Chromatography (HPLC)

Summary
Analytes
Revision
Data and Sites

Official Method Name

Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory - Determination of Pesticides in Water by CarboPak-B Solid-Phase Extraction and HPLC

Current Revision

1996

Media

WATER

Instrumentation

High Performance Liquid Chromatography with Ultraviolet Detection

Method Subcategory

Organic

Method Source

USGS-NWQL

Citation

Werner, S.L., Burkhardt, M.R., and DeRusseau, S.N., 1996, Methods of analysis by the U.S. Geological Survey National Water Quality Laboratory -- Determination of pesticides in water by Carbopak-B solid-phase extraction and high-performance liquid chromatography: U.S. Geological Survey Open-File Report 96-216.

Brief Method Summary

One liter of prefiltered water is pumped through the SPE cartridge at 25 mL/min. After extraction the adsorbed base and neutral compounds are eluted from the SPE cartridge using 6 mL of an 80:20 (v:v) mixture of methylene chloride and methanol. The acidic compounds are eluted from the same cartridge into a second collection container using 8 mL of the 80:20 solution that has been acidified with trifluoroacetic acid (TFAA) at 0.2 percent. The methylene chloride is removed from both fractions and is replaced with a water-methanol mixture; the final volume is 800 uL. The water-methanol solutions minimizes methylene chloride interference on the HPLC. Compounds are determined in each fraction by HPLC using ultraviolet spectrometry for detection, indentification and quantification.

Scope and Application

This method is designed for the determination of 41 pesticides and pesticide metabolites in filtered natural-water samples. The method is applicable to pesticides that are efficiently partitioned into a graphitized carbon-based solid-phase extraction (SPE) material and are chromatographically resolved and identified using an HPLC equipped with a diode array detector.

Applicable Concentration Range

0.006 - 1.6 (undiluted)

Interferences

Interferences may be caused by compounds recovered from a sample matrix that have similar chemical and physical properties and are not chromatographically resolved from the compounds of interest.

Quality Control Requirements

Laboratory extraction samples are formed into sets of 10 environmental samples plus a blank and a spike for a total set number of 12 samples. In addition, the following QA/QC samples are analyzed with each set of environmental samples: laboratory control spike (LCS), laboratory reagent blank (LRB), continuous calibration verification (CCV), continuing calibration blank (CCB), surrogate, field equipment blank (FEB) and field matrix spike (FMS). See USGS OFR 96-216 for definitions for each QA/QC sample.

Sample Handling

This schedule consumes the entire sample. Description: 1 L Glass bottle, amber bottle baked at 450 deg C by laboratory. Filter sample through a burned glass fiber filter. Treatment and Preservation: 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 deg C, ship immediately.

Maximum Holding Time

7 days from arrival at the NWQL

Relative Cost

$201 to $400

Sample Preparation Methods

This method has 43 analytes associated with it.

Analyte	Detection Level	Bias	Precision	Spiking Level
1-Napthol(90-15-3) 1-Hydroxynaphthalene 1-Naphthalenol 1-Napthol Alpha-naphthol	0.007 ug/L	N/A	3.00 % RSD (SL)
2,4,5-T(93-76-5) 2,4,5-T 2,4,5-T Acid 2,4,5-Trichlorophenoxyacetic acid 2,4,5-trichloro-Acetic acid Acetic acid, (2,4,5-trichlorophenoxy)- Dacamine 4D Weedone	0.010 ug/L	77% Rec (SL)	8.00 % RSD (SL)	0.50 ug/L
2,4-D(94-75-7) 2,4-D 2,4-D Acid 2,4-D [acetic acid, (2,4-dichlorophenoxy)-1] 2,4-Dichlorophenoxyacetic acid, salts and este 2,4-Dichlorophenoxyacetic acid, salts and esters Acetic acid, (2,4-dichlorophenoxy)- Hedonal Trinoxol Weed-b-gone	0.013 ug/L	71% Rec (SL)	9.00 % RSD (SL)	0.50 ug/L
2,4-DB(94-82-6) 2,4-DB 2,4-Dichlorophenoxybutyric acid 4-(2,4-Dichlorophenoxy)butyric acid Butanoic acid, 4-(2,4-dichlorophenoxy)- Butoxone Butyrac Butyric acid, 4-(2,4-dichlorophenoxy)- Embutone Legumex Venceweed	0.013 ug/L	44% Rec (SL)	8.00 % RSD (SL)	0.50 ug/L
2-Methyl-4,6-dinitrophenol(534-52-1) 2,4-Dinitro-6-methyl-phenol 2,4-Dinitro-o-cresol 2-Methyl-4,6-dinitrophenol 4,6-Dinitro-o-cresol DNOC Dinitrocresol Methyl-4,6-dinitrophenol,2- Phenol, 2-methyl-4,6-dinitro-	0.006 ug/L	N/A	5.00 % RSD (SL)
3-Hydroxycarbofuran(16655-82-6) 3,7-Benzofurandiol, 2,3-dihydro-2,2-dimethyl-, 3-Hydroxycarbofuran	0.014 ug/L	64% Rec (SL)	7.00 % RSD (SL)	0.50 ug/L
Acifluorfen sodium(62476-59-9) Acifluorfen sodium Benzoic acid, 5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitro-, sodium salt (9CI)	0.008 ug/L	N/A	5.00 % RSD (SL)
Aldicarb(116-06-3) 2-Methyl-2-(methylthio)propanal, O-((methylamino)carbonyl)oxime Aldicarb Carbanolate Temik UC-21149	0.016 ug/L	61% Rec (SL)	7.00 % RSD (SL)	0.50 ug/L
Aldicarb sulfone(1646-88-4) Aldicarb sulfone Aldicarb sulfone, wh Aldoxycarb Aldoxycarb (ANSI) Standak Sulfocarb Temik sulfone	0.016 ug/L	53% Rec (SL)	9.00 % RSD (SL)	0.50 ug/L
Bentazon(25057-89-0) 3-(1-methylethyl)-1H-2,1,3-benzothiadiazin-4(3 Basagran Bendioxide Bentazon Bentazon (ANSI) Bentazone	0.014 ug/L	N/A	8.00 % RSD (SL)
Bromacil(314-40-9) 5-Bromo-3-sec-butyl-6-methyluracil Borea Bromacil Bromacil (ANSI) Bromax Hyvar Uragon Urox "B" Urox 'B'	0.011 ug/L	N/A	5.00 % RSD (SL)
Bromoxynil(1689-84-5) 3,5-Dibromo-4-hydroxybenzonitrile Benzonitrile, 3,5-dibromo-4-hydroxy- Bromoxynil Bromoxynil (3,5-Dibromo-4-hydroxybenzonitrile)	0.012 ug/L	N/A	8.00 % RSD (SL)
Carbamate pesticides(E-12895) Carbamate pesticides Carbamate pesticides, N-methyl- N-methyl carbamate pesticides	N/A	N/A	N/A
Carbaryl(63-25-2) 1-Naphthyl methylcarbamate 1-Naphthyl-N-methylcarbamate Carbamic acid, methyl-, 1-naphthyl ester Carbaril Carbaryl Carbaryl (ANSI) Carbaryl [1-naphthalenol, methylcarbamate] Sevimol Sevin	0.008 ug/L	61% Rec (SL)	3.00 % RSD (SL)	0.50 ug/L
Carbofuran(1563-66-2) 2,3-Dihydro-2,2-dimethyl-7-benzofuranyl methylcarbamate Carbofuran Carbofuran (ANSI) Dihydro-2,2-dimethyl-7-benzofuranyl methylcarbamate,2,3- Euradan Furadan	0.028 ug/L	80% Rec (SL)	11.00 % RSD (SL)	0.50 ug/L
Chloramben(133-90-4) 3-Amino-2,5-dichlorobenzoic acid Amiben Chloramben Chloramben (ANSI) Chloramben [benzoic acid, 3-amino-2,5-dichloro] Vegiben	0.011 ug/L	N/A	5.00 % RSD (SL)
Chlorothalonil(1897-45-6) 1,3-Benzenedicarbonitrile, 2,4,5,6-tetrachloro 1,3-Benzenedicarbonitrile, 2,4,5,6-tetrachloro- 2,4,5,6-Tetrachloro-1,3-dicyanobenzene 2,4,5,6-Tetrachloroisophthalonitrile Bravo Chloroalonil Chlorothalonil Daconil 2787 Isophthalonitrile, tetrachloro- Sweep Vanox	0.007 ug/L	N/A	4.00 % RSD (SL)
Clopyralid(1702-17-6) 2-Pyridinecarboxylic acid, 3,6-dichloro- (9CI) Clopyralid	0.018 ug/L	N/A	13.00 % RSD (SL)
DCPA mono-acid degradate(887-54-7) DCPA mono-acid degradate Dacthal mono-acid degradate	0.017 ug/L	N/A	12.00 % RSD (SL)
Dicamba(1918-00-9) 3,6-Dichloro-2-methoxybenzoic acid 3,6-Dichloro-o-anisic acid Banex Banlen, Banvel Benzoic acid, 3,6-dichloro-2-methoxy- Dianate Dicamba Dicamba ( 3,6-dichloro-o-anisic acid ) Dicamba (3,6-Dichloro-2-methoxybenzoic acid) Mediban Methoxy-3,6-dichlorobenzoic acid,2-	0.110 ug/L	64% Rec (SL)	8.00 % RSD (SL)	0.50 ug/L
Dichlobenil(1194-65-6) Benzonitrile, 2,6-dichloro- (6CI,8CI,9CI) Dichlobenil	0.012 ug/L	N/A	5.00 % RSD (SL)
Dichlorprop(120-36-5) 2,4-DP 2-(2,4-Dichlorophenoxy)propionic acid 2[2,4-(Dichlorophenoxy)]-propanoic acid Cornox RK Dichloroprop Dichlorprop Hedonal DP Polytox Propanoic acid, 2-(2,4-dichlorophenoxy)- Propionic acid,2-(2,4-dichlorophenoxy)-	0.032 ug/L	73% Rec (SL)	15.00 % RSD (SL)	0.50 ug/L
Dinoseb(88-85-7) 2,4-Dinitro-6-sec-butylphenol 2-sec-Butyl-4,6-dinitrophenol Butaphene Dinitrobutyl phenol Dinoseb Dinoseb (ANSI) Phenol, 2-(1-methylpropyl)-4,6-dinitro- Phenol,2-sec-butyl-4,6-dinitro-	0.010 ug/L	69% Rec (SL)	8.00 % RSD (SL)	0.50 ug/L
Diuron(330-54-1) Diuron Urea, N'-(3,4-dichlorophenyl)-N,N-dimethyl- (9CI)	0.012 ug/L	N/A	5.00 % RSD (SL)
Esfenvalerate(66230-04-4) Benzeneacetic acid, 4-chloro-alpha-(1-methylethyl)-, (S)-cyano(3-phenoxyphenyl)methyl ester, (alphaS)- (9CI) Esfenvalerate	0.019 ug/L	N/A	16.00 % RSD (SL)
Fenuron(101-42-8) Fenuron Urea, N,N-dimethyl-N'-phenyl- (9CI)	0.013 ug/L	N/A	6.00 % RSD (SL)
Fluometuron(2164-17-2) Fluometuron	0.010 ug/L	N/A	7.00 % RSD (SL)
Herbicides(E-12839) Herbicide formulations Herbicides	N/A	N/A	N/A
Linuron(330-55-2) Linuron	0.006 ug/L	N/A	3.00 % RSD (SL)
MCPA(94-74-6) ((4-Chloro-o-tolyl)oxy)acetic acid 2,4-MCPA 2-Methyl-4-chlorophenoxyacetic acid 4-Chloro-o-toloxyacetic acid Acetic acid, (4-chloro-2-methylphenoxy)- Agroxon MCPA Mephanac Mephanac, Metaxon Metaxon Methoxone (4-Chloro-2-methylphenoxy) acetic acid Netazol Rhonox	0.014 ug/L	66% Rec (SL)	10.00 % RSD (SL)	0.50 ug/L
MCPB(94-81-5) Butanoic acid, 4-(4-chloro-2-methylphenoxy)- (9CI) MCPB	0.010 ug/L	N/A	7.00 % RSD (SL)
Methiocarb(2032-65-7) 3,5-Dimethyl-4-(methylthio)phenol methylcarbamate 4-(Methylthio)-3,5-xylyl methylcarbamate Carbamic acid, methyl-, 4-(methylthio)-3,5-xyl Carbamic acid, methyl-, 4-(methylthio)-3,5-xylyl ester Mercaptodimethur Mesurol Methiocarb Phenol, 3,5-dimethyl-4-(methylthio)-, methylca Phenol, 3,5-dimethyl-4-(methylthio)-, methylcarbamate	0.026 ug/L	59% Rec (SL)	13.00 % RSD (SL)	0.50 ug/L
Methomyl(16752-77-5) Acetamidic acid, thio-N-[(methyl-carbamoyl)oxy Acetamidic acid, thio-N-[(methyl-carbamoyl)oxy]-, ... Dupont 1179 Insecticide 1179 Lannate Methomyl S-methyl-n-((methylcarbamoyl)oxy)thioacetimidate	0.017 ug/L	79% Rec (SL)	9.00 % RSD (SL)	0.50 ug/L
Neburon(555-37-3) Neburon Urea, N-butyl-N'-(3,4-dichlorophenyl)-N-methyl- (9CI)	0.015 ug/L	N/A	7.00 % RSD (SL)
Norflurazon(27314-13-2) 3(2H)-Pyridazinone, 4-chloro-5-(methylamino)-2 Norflurazon Telok	0.024 ug/L	N/A	11.00 % RSD (SL)
Organochlorine pesticides(E-12851) Organochlorine pesticides Pesticides, organochlorine	N/A	N/A	N/A
Oryzalin(19044-88-3) Benzenesulfonamide, 4-(dipropylamino)-3,5-dinitro- (9CI) Oryzalin	0.019 ug/L	N/A	13.00 % RSD (SL)
Oxamyl(23135-22-0) 2-o-Methylcarbamoyl monoxime DPX 1410 Oxamyl Thioxamyl Vydate Vydate L	0.018 ug/L	N/A	14.00 % RSD (SL)
Picloram(1918-02-1) 2-Pyridinecarboxylic acid, 4-amino-3,5,6-trichloro- 4-Amino-3,5,6-trichloro-2-pyridinecarboxylic a 4-Amino-3,5,6-trichloro-2-pyridinecarboxylic acid 4-Amino-3,5,6-trichloropicolinic acid Amdon Borolin Picloram Picolinic acid,4-amino-3,5,6-trichloro- Tordon	0.004 ug/L	N/A	3.00 % RSD (SL)
Piperonyl sulfoxide(120-62-7) 1,2-Methylenedioxy-4-(2-(octylsulfidnyl)propyl)benzene 1,2-Methylenedioxy-4-(2-(octylsulfinyl)propyl) benzene 1,3-Benzodioxole, 5-[2-(octylsulfinyl)propyl]- Isosafrole-n-octylsulfoxide Piperonyl sulfoxide Sulfox-cide Sulfoxyl Sulphoxide	0.021 ug/L	N/A	12.00 % RSD (SL)
Propoxur(114-26-1) 2-Isopropoxyphenyl-n-methylcarbamate Aprocarb Baygon Blattenex Isocarb N-methyl-2-isopropoxyphenylcarbamate Phenol, 2-(1-methylethoxy)-, methylcarbamate Propoxur Propoxur [phenol, 2-(1-methylethoxy)-, methylcarbamate] Sendran, Suncide Unden o-Isopropoxyphenyl methylcarbamate	0.008 ug/L	N/A	3.00 % RSD (SL)
Silvex(93-72-1) 2,4,5-TP 2,4,5-TP Acid 2,4,5-Trichlorophenoxypropionic acid 2-(2,4,5-Trichlorophenoxy)propionic acid Fenoprop Propanoic acid, 2-(2,4,5-trichlorophenoxy)- Propionic acid, 2-(2,4,5-trichlorophenoxy)- Silvex Silvex (ANSI)	0.021 ug/L	73% Rec (SL)	14.00 % RSD (SL)	0.50 ug/L
Trichlopyr(55335-06-3) Trichlopyr	0.010 ug/L	N/A	7.00 % RSD (SL)

Precision Descriptor Notes:	Single-operator method detection limits in organic-free water samples ranged from 0.006 - 0.032 ug/L. Recoveries in organic-free water samples ranged from 37 to 88 percent. Recoveries in ground- and surface-water samples ranged from 29 to 94 percent. The single-operator average standard deviation at a spike level of 0.1 ug/L in organic-free water is 8 percent. The multiple operator (5) and multiple instrument (7) average relative standard deviation for a 0.05 ug/L spike in organic-free water for the two year period April 1993 to April 1995 is 25 percent. Recoveries in organic-free water spiked at the 0.05 ug/L ranged from 22 to 100 percent.
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:

Single-operator method detection limits in organic-free water samples ranged from 0.006 - 0.032 ug/L. Recoveries in organic-free water samples ranged from 37 to 88 percent. Recoveries in ground- and surface-water samples ranged from 29 to 94 percent. The single-operator average standard deviation at a spike level of 0.1 ug/L in organic-free water is 8 percent. The multiple operator (5) and multiple instrument (7) average relative standard deviation for a 0.05 ug/L spike in organic-free water for the two year period April 1993 to April 1995 is 25 percent. Recoveries in organic-free water spiked at the 0.05 ug/L ranged from 22 to 100 percent.

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
1996

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USGS-NWQL: O-1131-95: Pesticides in Water by Solid Phase Extraction and High Performance Liquid Chromatography (HPLC)

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