Fábio F. Gonçalves

Poluição das águas por herbicidas utilizados no cultivo do arroz irrigado na região central do estado do Rio Grande do Sul, Brasil: predição teórica e monitoramento

This article presents an evaluation of the pollution of river water by herbicides used in the culture of irrigated rice in Rio Grande do Sul State, Brazil. Firstly, a theoretical evaluation was made using the approaches suggested by EPA-USA, the Groundwater Ubiquity Score index and the Goss method to estimate the pollution possibilities. Afterwards, a monitoring program was established for the rivers of the area from 2001 to 2003 to investigate the presence of herbicide residues. The results indicate that the herbicides clomazone and propanil are the ones with larger presence and frequency in the analyzed samples. The theoretical forecast was confirmed by the results of the monitoring program.

Monitoring of the herbicide clomazone in environmental water samples by solid-phase extraction and high-performance liquid chromatography with ultraviolet detection

SummaryEvaluation of a simple and rapid method for determination of clomazone in environmental water samples, by high-performance liquid chromatography with ultraviolet detection, is described. After solid-phase extraction with C18 extraction cartridges clomazone was separated on a C18 column with 65∶35 (v/v) methanol-water, pH 4.0, as mobile phase at a flow-rate of 1.0 mL min−1. After optimization of the extraction and separation conditions, the method was used for determination of clomazone residues in rivers and agricultural waters of the central region of the Rio Grande do Sul province. The results revealed that clomazone persists in agricultural water at least for 130 days, and was present in 90% of the river water samples analyzed.

Development and validation of a high-performance liquid chromatographic method for the determination of clomazone residues in surface water.

A method is described for the determination of clomazone residues in surface water by high-performance liquid chromatography with UV detection. The method involves solid-phase extraction with C18 extraction tubes. Clomazone was separated on a C18 column with a mobile phase of methanol-water (65:35, v/v) at pH 4.0 and a flow-rate of 1.0 ml/min. After optimization of the extraction and separation conditions, the method was validated. The method developed can be used for determination of clomazone in surface water, at the limit of 0.1 mcirog/l set by the European Union drinking water directive, with a 400-fold preconcentration.

Risk assessment of surface water contamination by herbicide residues: monitoring of propanil degradation in irrigated rice field waters using HPLC-UV and confirmation by GC-MS

This study evaluates the degradation of the herbicide propanil and of its major degradation product, 3,4-dichloroaniline (3,4-DCA) in water from irrigated rice farming in the State of Rio Grande do Sul, Brazil. It also assesses the contamination risk of surrounding surface waters. After a solid phase extraction step, the concentration of both compounds was determined by high performance liquid chromatography with ultraviolet detection. Confirmation was conducted by gas chromatography-mass spectrometry. Concentrations of propanil in water samples varied from 0.1 to 3600 µg L-1. Propanil was degraded very rapidly to 3,4-DCA and high concentrations of this product were found, varying from 1.0 to 567.5 µg L-1 in water. The obtained half-life times for propanil in water under real conditions for the 2001, 2002 and 2003 harvests were 18.2, 12.5 and 12.2 h, respectively.

Persistência dos herbicidas imazethapyr e clomazone em lâmina de água do arroz irrigado

Herbicides can persist in soil and be transported from the application site to the environment. An experiment was conducted to estimate imazethapyr and clomazone persistence in rice paddy water. The treatments included application of the formulated herbicide mixture (imazethapyr 75xa0gxa0a.i.xa0L-1 + imazapic 25xa0gxa0a.i.xa0L-1) and clomazone (500xa0gxa0a.i.xa0L-1). Imazethapyr and clomazone concentrations in water were evaluated from the 1st to the 62nd day after flooding. The period of herbicide detection in water was longer for imazethapyr. Imazethapyr half-life in paddy water varied between 1.6 and 6.2 days and clomazone half-life was 5xa0days.

Study of the Degradation of the Herbicide Clomazone in Distilled and in Irrigated Rice Field Waters using HPLC-DAD and GC-MS

This study evaluated the degradation of the herbicide clomazone in distilled water and from irrigated rice fields, through UV irradiation and under natural conditions. After a solid phase extraction (SPE) as preconcentration step, the remained concentration of clomazone was determined by high performance liquid chromatography with diode array detection (HPLC-DAD) and the identification of the degradation products was achieved by gas chromatography-mass spectrometry (GC-MS). Under UV irradiation, the clomazone was degraded faster in distilled water than in surface water. In irrigated rice water, under sunlight irradiation, clomazone presented a half-life time average of 3.2 days in three consecutive harvests, and after application the concentration in water remained higher than 0.1 μg L-1 for 20 days. Several by-products, like 2-chlorobenzaldehyde and 2-chlorobenzene methanol, were identified by GC-MS, which evidenced that the concentration of intermediates at the begining increase and then they also undergo degradation.

A gas chromatographic method for the determination of the fungicide chlorothalonil in tomatoes and cucumbers and its application to dissipation studies in experimental greenhouses

A new method to evaluate the levels of residue and the dissipation of chlorothalonil fungicide in tomatoes and cucumbers grown in experimental greenhouses was developed and validated. The vegetables were submitted to a single spraying with chlorothalonil at half, equal to and double of the recommended dose. Chlorothalonil residues were extracted in Ultra-Turrax system using ethyl acetate in the presence of anhydrous sodium sulphate and determined by gas chromatography with electron capture detection. The analytical curves were linear from 0.005 to 5.0 mg L-1, with coefficient of determination higher then 0.995. The assays provide acceptable results with RSD values below 10.5% and recoveries were between 92.2 and 114.5% for tomatoes, and between 86.2 and 103.3% for cucumbers, both obtained from spiked samples at 0.028, 0.28, 2.8 and 5.0 mg kg-1 levels. Statistical interpretation of residue levels fitted to a first-order model for the dissipation behavior of chlorothalonil. The mean half-life after treatments at the recommended dose, in the two experimental years, was 8.8 days for tomatoes and 1.6 days for cucumbers. The higher decrease rate of chlorothalonil residues in cucumbers is mainly due to the higher growth rate of this vegetable relative to tomato. The developed method has proven to be efficient for the determination of chlorothalonil residues in tomatoes and cucumbers with a limit of quantification of 0.02 mg kg-1 level, permitting to evaluate the risk of consumer exposure to these residues.

Rapid and accurate hplc-dad method for the determination of the herbicide bispyribac-sodium in surface water, and its validation

A new method is described for the determination of the herbicide bispyribac-sodium in surface water, especially from river and irrigated rice water samples. The method involves extraction in solid phase and quantification by high performance liquid chromatography with diode array detection (HPLC-DAD). After optimization of the extraction and separation parameters, the method was validated. The method presented average recoveries of 101.3 and 97.7%, under repeatability and intermediate precision conditions, respectively, with adequate precision (RSD from 0.9 to 7.5%). The method was applied for the determination of bispyribac-sodium in surface water samples with a limit of detection of 0.1 μg L-1.

FLOW INJECTION SPECTROPHOTOMETRIC DETERMINATION OF PROPOXUR WITH DIAZOTIZED 4-AMINOBENZOIC ACID

ABSTRACT A flow injection spectrophotometric method for the determination of propoxur with diazotized 4-aminobenzoic acid as the coupling agent was developed. The determination involves on-line hydrolysis at room temperature of the propoxur with sodium hydroxide. The resulting 2-isopropoxyphenol is coupled with diazotized 4-aminobenzoic acid in order to achieve an appropriate selectivity and sensitivity to the spectrophotometric measurements. The calibration curve is linear over the range 1–10 mg L−1 of propoxur. The proposed method has provided a detection limit of 0.15 mg L−1 of propoxur and a sample frequency of 120 injections per hour. The relative standard deviation of six independent determinations of a sample containing 5 mg L−1 propoxur was 0.74%. The suitability of the proposed procedure for the determination of propoxur in commercial pesticide formulations was studied. The procedure provides results comparable to those obtained by the liquid chromatography analysis.

Desenvolvimento de procedimento de extração para análise de sedativos e B-bloqueadores em rim suíno

A procedure was developed for determination of 5 sedatives and 14 β-blockers in swine kidney and subsequent analysis by liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS). Three different procedures for extraction were tested, evaluated through recovery studies. The procedure using acetonitrile for extraction and cleanup with freezing at low temperature and dispersive solid phase extraction using 500 mg celite® 545 before the concentration step presented the better results. The dried samples were redissolved with methanol and analyzed using a LC-MS/MS system with electrospray ionization (ESI) operating in positive MRM mode. The recovery values for this procedure were in the 75-88% range. The robustness of the method was tested against small variations. The method was used to analyze carazolol, azaperone and azaperol in collaborative assay, obtaining results close to designed value.