Multiresidue analysis of pesticides in water from rice cultures by on-line solid phase extraction followed by LC-DAD

An automated on-line solid phase extraction procedure followed by liquid chromatography with diode array detection was investigated for the determination of different classes of pesticides in water samples containing varied amount of humic substances. The different pesticides used were: carbendazin, carbofuran, atrazine, diuron, propanil, molinate, alachlor, parathion-ethyl, diazinon, trifluralin and the degradation products deisopropylatrazine and deethylatrazine. Humic substances extracted from a Brazilian sediment were used from 5 to 80 mg/l and their influence on recoveries was evaluated in neutral and acidic media. Recoveries higher than 70% were obtained for all the pesticides, from the preconcentration of 75 mi of aqueous sample fortified at 2 ng/ml using precolumns packed with PLRP-S. Good recoveries were obtained at neutral pH for most of the analytes up to 40 mg/l of humic acid. Only at 80 mg/l the recoveries were significantly affected, both at acidic and neutral pH. The method was applied to the determination of pesticides in river water spiked at 0.1 to 1 ng/ml. Detection limits obtained for water containing 10 mg/l of humic acid were between 0.05 and 0.3 ng/ml

Determination of rice herbicides, their transformation products and clofibric acid using on-line solid-phase extraction followed by liquid chromatography with diode array and atmospheric pressure chemical ionization mass spectrometric detection

A simultaneous method for the trace determination of acidic, neutral herbicides and their transformation products in estuarine waters has been developed through an on-line solid-phase extraction method followed by liquid chromatography with diode array and mass spectrometric detection. An atmospheric pressure chemical ionization (APCI) interface was used in the negative ionization mode after optimization of the main APCI parameters. Limits of detection ranged from 0.1 to 0.02 ng/ml for 50 mi of acidified estuarine waters preconcentrated into polymeric precolumns and using time-scheduled selected ion monitoring mode. Two degradation products of the acidic herbicides (4-chloro-2-methylphenol and 2,4-dichlorophenol) did not show good signal response using APCI-MS at the concentration studied due to the higher fragmentor voltage needed for their determination For molinate and the major degradation product of propanil, 3,4-dichloroaniline, positive ion mode was needed for APCI-MS detection. The proposed method was applied to the determination of herbicides in drainage waters from rice fields of the Delta del Ebro (Spain). During the S-month monitoring of the herbicides, 8-hydroxybentazone and 4-chloro-2-methylphenoxyacetic acid were successively found in those samples. (C) 2000 Elsevier B.V. B.V. All rights reserved

Rapid degradation of propanil in rice crop fields

Propanil and its major degradation product, 3,4-dichloroaniline (DCA), were monitored in surface water and soil samples from two rice fields of the Ebre Delta area (Tarragona, Spain) following agricultural application. On-line solid-phase extraction (SPE) (water) and Soxhlet extraction (soil) followed by liquid chromatography/diode array detection (LC/DAD) were used for the trace determination of both compounds. Unequivocal confirmation/identification was conducted by using liquid chromatography/atmospheric pressure chemical ionization-mass spectrometry, LC/APCI/MS (using negative and positive ionization modes). Concentrations of the herbicide propanil in water samples varied from 1.9 to 55.9 mu g/L. Propanil degraded very rapidly to DCA, and high concentrations of this product were found, varying from 16.5 to 470 mu g/L in water and 119 +/- 22 mu g/kg in soil samples. No detectable DCA (<0.001%) was found in the applied pesticide formulation, indicating that DCA formation took place after propanil application. These field results compared favorably with laboratory experiments showing that humic interactions had a strong influence on the pesticide degradation. The half-lifes under real conditions for propanil and DCA, calculated using a first-order decay, were 1.2 and 1.6 days, respectively