Renato Zanella

QuEChERS: a modern sample preparation method for pesticide multiresidue determination in food by chromatographic methods coupled to mass spectrometry

This review attempts to provide an updated overview of the Quick, Easy, Cheap, Effective, Ruged and Safe (QuEChERS) multiresidue extraction method, that involves initial extraction in acetonitrile, an extraction/partition step after the addition of salt, and a cleanup step utilizing dispersive solid phase extraction. QuEChERS method is nowadays the most applied extraction method for the determination of pesticide residues in food samples, providing acceptable recoveries for acidic, neutral and basic pesticides. Several applications for various food matrices (fruits, vegetables, cereals and others) in combination with chromatographic mass spectrometry analysis were presented.

Rice herbicide monitoring in two Brazilian rivers during the rice growing season

Irrigated rice production can involve environmental contamination with pesticides due to the proximity of the fields to rivers and to management problems. During three years (2000 to 2003) the rice herbicides clomazone, propanil and quinclorac were quantified in water during the rice growing season, in the Vacacai and Vacacai-Mirim Rivers, located in Rio Grande do Sul (RS) State, Brazil. Water samples were taken at several locations in each river, selected by their importance in terms of rice drainage area. The samples were analyzed by HPLC-UV. At least one herbicide was detected in 41% of the samples from the Vacacai River and 33% from the Vacacai-Mirim River. The most frequent herbicide in both rivers and in each year was clomazone. The amount of herbicides in the river water was dependent on the rainfall regime. River water contamination by rice herbicides is probably caused by the rice water management used in the fields. The maintenance of flooded areas makes herbicides prone to contaminate the environment. To reduce the environmental contamination risk it is necessary to adopt measures to avoid overflow of flooded rice fields, keeping paddy water in the field for time enough to reduce the herbicide concentration before its release and enhancing the quality of the levees to reduce the probability of paddy rice overflow.

Optimization of a QuEChERS based method by means of central composite design for pesticide multiresidue determination in orange juice by UHPLC-MS/MS.

In this study, different extraction procedures based on the QuEChERS method were compared for the multiresidue determination of pesticides in orange juice by ultra high performance liquid chromatography coupled to tandem mass spectrometry (UHPLC-MS/MS). After choosing preliminary conditions, an experimental design was carried out with the variables C18, PSA, NaOH and CH3COONa to optimize the sample preparation step. The validation results of the validation were satisfactory, since the method presented recoveries between 70% and 118%, with RSD lower than 19% for spike levels between 10 and 100 μg L(-1). The method limit of detection (LOD) and limit of quantification (LOQ) ranged from 3.0 to 7.6 μg L(-1) and from 4.9 to 26 μg L(-1), respectively. The method developed was adequate for the determination of 74 pesticide residues in orange juice.

Monitoramento de agrotóxicos em dois mananciais hídricos no sul do Brasil

The objective of this study was to evaluate and to monitor the presence of pesticides in the waters of the Sao Goncalo channel and the Piratini river located in the southern region of the State of Rio Grande do Sul. During the rice growing season, water samples were collected five times, three samples from the river Piratini and four from the Sao Goncalo canal. The methodology used for the analysis of residues of quinclorac, carbofuran and clomazone was the High Performance Liquid Chromatography with Diode Array Detection (HPLC-DAD) and for residues of the pesticides fipronil and betacyfluthrin, the Gas Chromatography with Electron Capture Detection (GC-ECD) was used. Results show that from sowing to harvesting the quantity of pesticide residues in water decreased. It was also observed that, at the lowest point (Laranjal), a greater number of analyses contaminated with residues was detected (11 samples with some type of pesticide). Insecticide carbofuran and herbicide quinclorac were pesticides that presented residues more frequently (16 and 15 times, respectively). Clomazone and fipronil were present in each of the 7 samples with residues and betacyfluthrin was not detected at any site.

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.

Evaluation of the QuEChERS method for the extraction of pharmaceuticals and personal care products from drinking-water treatment sludge with determination by UPLC-ESI-MS/MS

A modified version of the QuEChERS method has been evaluated for the determination of 21 pharmaceuticals and 6 personal care products (PPCPs) in drinking-water sludge samples by employing ultra high liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). The performance of the method was evaluated through linearity, recovery, precision (intra-day), method detection and quantification limits (MDL and MQL) and matrix effect. The calibration curves prepared in acetonitrile and in the matrix extract showed a correlation coefficient ranging from 0.98 to 0.99. MQLs values were on the ng g(-1) order of magnitude for most compounds. Recoveries between 50% and 93% were reached with RSDs lower than 10% for most compounds. Matrix effect was almost absent with values lower than 16% for 93% of the compounds. By coupling a quick and simple extraction called QuEChERS with the UPLC-MS/MS analysis, a method that is both selective and sensitive was obtained. This methodology was successfully applied to real samples and caffeine and benzophenone-3 were detected in ng g(-1) levels.

Effects of the commercial formulation containing fipronil on the non-target organism Cyprinus carpio: implications for rice-fish cultivation.

The aim of this research was to evaluate possible toxic effects of commercial formulation containing fipronil on Cyprinus carpio tissues under rice field conditions. Antioxidant profile (SOD, catalase, glutathione S-transferase), oxidative stress parameters (thiobarbituric acid-reactive substances, protein carbonyl), and growth were investigated in carp exposed to fipronil under rice field conditions for 7, 30, and 90 days. Waterborne insecticide concentrations were measured and the detectable concentration of fipronil was observed up to 45 day after application. Common carp survival and growth was not affected by fipronil. Liver superoxide dismutase activity was enhanced while liver catalase activity was inhibited at 7, 30, and 90 days. Alterations were not observed in the glutathione S-transferase activity in any experimental periods. Protein carbonyl increased only after 30 and 90 days of exposure. The thiobarbituric acid-reactive substances levels were enhanced in all analyzed tissues (liver, muscle, and brain) and periods of exposure. This study demonstrates that fipronil insecticides cause alterations in the biochemical parameters in different tissues of carp without affecting the growth or the survival of the fish.

Toxicological responses of Cyprinus carpio after exposure to a commercial herbicide containing imazethapyr and imazapic

Cyprinus carpio was exposed to imazethapyr and imazapic at laboratory and at field conditions. The laboratory experiment was carried out for 7 days and at rice field for 7, 30 and 90 days. Oxidative stress parameters and antioxidant profile were studied as well as metabolic parameters. After 7 days, brain AChE activity increases in laboratory and field, but in muscle, reduction was observed only in laboratory. At the same period, brain and muscle TBARS and liver CAT increase in the laboratory. Metabolic parameters showed changes in both conditions and exposure periods. After 30 days in rice field, brain AChE activity decreases and in muscle it was enhanced. After 90 days in field, only muscle AChE activity was reduced. The disorders in oxidative stress parameters and metabolism remained, indicating mainly a protein catabolism. This study pointed out short- and long-term effects of rice herbicides at environmentally relevant concentrations on toxicological parameters in tissues of C. carpio.

Investigation of the occurrence of pesticide residues in rural wells and surface water following application to tobacco

In this work the exposure of wells and surface water to pesticides, commonly used for tobacco cropping, was assessed. Water consumption wells and surface water flows were sampled at different times. After a preconcentration step with solid phase extraction (SPE), the selected pesticides were determined by gas chromatography with electron capture detection (GC-ECD) or high performance liquid chromatography with diode array detection (HPLC-DAD). No pesticides were detected in the well water samples and surface water flow in the winter season. However, in the spring and summer higher concentrations of chlorpyrifos and imidacloprid were found in the water source samples. Atrazine, simazine and clomazone were also found. The occurrence of pesticides in collected water samples was related with the application to tobacco.

Contaminação de águas superficiais por agrotóxicos em função do uso do solo numa microbacia hidrográfica de Agudo, RS

This work was accomplished with the intention of quantifying the presence of pesticide molecules in surface waters of three landscape units (LU) with different usage configurations in the Agudo watershed of the State of Rio Grande do Sul, Brazil. Two semiautomatic water collectors were installed at the stream of each LU, from which samples were collected during rain over three stages of the tobacco growing season: seedling transplant, tobacco plants with 6-10 expanded leaves, and at harvest. Imidacloprid, atrazine, simazine, and clomazone compounds were quantified by High Performance Liquid Chromatography with Ultraviolet Detector (HPLC-UV). Chlorpyrifos, flumetralin and iprodione were analyzed by Gas Chromatography with Electron Capture Detector (GC-ECD), but these compounds were not detected in the samples. The sampling points where the LU was configured with both the presence of tobacco crops and reduced gallery forest, showed at least one pesticide compound in a sampling time. No pesticide was detected in the LU, which is completely covered with permanent vegetation or with gallery forest protecting the water courses.