Methods of Analysis by the U.S. Geological Survey Organic Geochemistry Research Group—Determination of Acetamide Herbicides and Their Degradation Products in Water Using Online Solid-Phase Extraction and Liquid Chromatography/Mass Spectrometry

An analytical method for the determination of 6 acetamide herbicides (acetochlor, alachlor, dimethenamid, flufenacet, metolachlor, and propachlor) and 16 of their degradation products in natural water samples using solid-phase extraction and liquid chromatography/mass spectrometry is described in this report. Special consideration was given during the development of the method to prevent the formation of degradation products during the analysis. Filtered water samples were analyzed using octadecylsilane as the solid-phase extraction media on online automated equipment followed by liquid chromatography/mass spectrometry. The method uses only 10 milliliters of sample per injection. Three different water-sample matrices, a reagent-water, a ground-water, and a surface-water sample spiked at 0.10 and 1.0 microgram per liter, were analyzed to determine method performance.

Method detection limits ranged from 0.004 to 0.051 microgram per liter for the parent acetamide herbicides and their degradation products. Mean recoveries for the acetamide compounds in the ground- and surface-water samples ranged from 62.3 to 117.4 percent. The secondary amide of acetochlor/metolachlor ethanesulfonic acid (ESA) was recovered at an average rate of 43.5 percent. The mean recoveries for propachlor and propachlor oxanilic acid (OXA) were next lowest, ranging from 62.3 to 95.5 percent. Mean recoveries from reagent-water samples ranged from 90.3 to 118.3 percent for all compounds. Overall the mean of the mean recoveries of all compounds in the three matrices spiked at 0.10 and 1.0 microgram per liter ranged from 89.9 to 100.7 percent, including the secondary amide of acetochlor/metolachlor ESA and the propachlor compounds. The acetamide herbicides and their degradation products are reported in concentrations ranging from 0.05 to 2.0 micrograms per liter. The upper concentration limit is 2.0 micrograms per liter for all compounds without dilution.

With the exception of the secondary amide of acetochlor/metolachlor ESA, good precision and accuracy for the chloroacetanalide herbicides and their degradation compounds were demonstrated for the method in buffered reagent water, ground water, and surface water. The extraction method as used did not optimize the recovery of the secondary amide of acetochlor/metolachlor ESA.

CONTENTS

Abstract
Introduction
Determination of Acetamide Herbicides and Their Degradation Products in Water

Method of Analysis

Application
Summary of Method
Interferences
Apparatus and Instrumentation
Reagents and Consumable Materials
Sampling Methods
Standards
Safety Precautions
Evaluation of Instrument Performance

High-Performance Liquid Chromatograph and Diode Array Detector Performance
Mass Spectrometer Performance
Calibration
Alternate Calibration
Extraction Efficiency
Analytical Procedure
Calculation of Results

Qualitative Identification
Quantitation
Alternate Quantitation
Reporting of Results
Method Performance

Corrections for Background Concentrations
Method Detection Limits
Mean Recovery
Discussion
Conclusions
References Cited

Lee, E.A. and Strahan, A.P., 2003, Methods of Analysis by the U.S. Geological Survey Organic Geochemistry Research Group•Determination of acetamide herbicides and their degradation products in water using online solid-phase extraction and liquid chromatography/mass spectrometry: U.S. Geological Survey Open-File Report 03-173, 17 p.

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