Eliana Freire Gaspar de Carvalho Dores

CONTAMINAÇÃO DO AMBIENTE AQUÁTICO POR PESTICIDAS. ESTUDO DE CASO: ÁGUAS USADAS PARA CONSUMO HUMANO EM PRIMAVERA DO LESTE, MATO GROSSO - ANÁLISE PRELIMINAR

A preliminary analyses of the possible contamination of superficial and underground water by the active ingredients of the pesticide products used in the surroundings of the urban area of Primavera do Leste, Mato Grosso, Brazil, was carried out. A description of the study region and of its environmental characteristics, which can favor the contamination of the local aquatic environment, was presented. The EPA screening criteria, the groundwater ubiquity score (GUS) and the criteria proposed by Goss were used to evaluate which pesticides might contaminate the local waters. Among the active ingredients studied, several present risks to the local aquatic environment.

Acetamiprid, carbendazim, diuron and thiamethoxam sorption in two Brazilian tropical soils

Sorption of acetamiprid ((E)-N1-[(6-chloro-3-pyridyl)methyl]-N2-cyano-N1-methylacetamidine), carbendazim (methyl benzimidazol-2-ylcarbamate), diuron (N-(3,4-dichlorophenyl)-N, N-dimethyl urea) and thiamethoxam (3-(2-chloro-thiazol-5-ylmethyl)-5-methyl-[1,3,5]oxadiazinan-4-ylidene-N-nitroamine) was evaluated in two Brazilian tropical soils, Oxisol and Entisol, from Primavera do Leste region, Mato Grosso State, Brazil. To describe the sorption process, batch experiments were carried out. Linear and Freundlich isotherm models were used to calculate the K d and K f coefficients from experimental data. The K d values were utilized to calculate the partition coefficient normalized to soil organic carbon (K oc ). For the pesticides acetamiprid, carbendazim, diuron and thiamenthoxan the K oc (mL g− 1) values ranged in both soils from 98 – 3235, 1024 – 2644, 145 – 2631 and 104 – 2877, respectively. From the studied pesticides, only carbendazim presented correlation (r2 = 0.82 and p < 0.01) with soil organic carbon (OC) content. Acetamiprid and thiamethoxam showed low sorption coefficients, representing a high risk of surface and ground water contamination.

Biosensor based on atemoya peroxidase immobilised on modified nanoclay for glyphosate biomonitoring.

A biosensor based on atemoya peroxidase immobilised on modified nanoclay was developed for the determination of glyphosate by the enzyme inhibition method. The inhibitor effect of the biocide results in a decrease in the current response of the hydroquinone that was used as a phenolic substrate to obtain the base signal. The biosensor was constructed using graphite powder, multiwalled carbon nanotubes, peroxidase immobilised on nanoclay and mineral oil. Square-wave voltammetry was utilised for the optimisation and application of the biosensor, and several parameters were investigated to determine the optimum experimental conditions. The best performance was obtained using a 0.1 mol L(-1) phosphate buffer solution (pH 7.0), 1.9×10(-4) mol L(-1) hydrogen peroxide, a frequency of 30 Hz, a pulse amplitude of 50 mV and a scan increment of 4 mV. The glyphosate concentration response was linear between 0.10 and 4.55 mg L(-1) with a detection limit of 30 μg L(-1). The average recovery of glyphosate from spiked water samples ranged from 94.9 to 108.9%. The biosensor remained stable for a period of eight weeks.

Currently used pesticides in water matrices in Central-Western Brazil

This study provides data on the presence of the pesticides atrazine, chlorpyrifos, α-endosulfan, β-endosulfan, flutriafol, malathion and metolachlor in water matrices in urban and rural areas of Campo Verde and Lucas do Rio Verde Cities, Mato Grosso State, Brazil. Surface, rain, and groundwater samples were collected in the rainy and dry seasons during 2007 and 2008 in these important grain-producing areas. The findings revealed a higher diversity of compounds and frequency of detection in the rain water than in surface and groundwater samples. Concentrations of atrazine, endosulfan and malathion above those permitted by Brazilian regulations were found in some surface and groundwater samples, and the degradation products DIA (deisopropylatrazine) and endosulfan sulfate, rather than their parental compounds, were found at higher levels in some samples. Our findings show the vulnerability of water systems in these areas and point to the risk of pesticide contamination in important headwater streams.

Pesticide residues in river sediments from the Pantanal Wetland, Brazil.

Sediment samples from 25 sites in 17 rivers of the Pantanal (Brazil) were analyzed with the objective of evaluating pesticide contamination in sediments. Samples were extracted with an acetone, ethylacetate, and water mixture 2:2:1 (v/v/v). The extract was purified by flash chromatography with aluminum oxide and florisil. A multiresidue gas chromatography-mass spectrometry method was applied to monitor 23 pesticides of different chemical classes (organochlorine, organophosphorus, triazines, anilides and pyrethroids) with some of their degradation products. Compounds identified in sediment samples included λ -cyhalothrin (1.0 to 5.0 μ g kg− 1), p,p′-DDT (3.6 μ g kg− 1), deltamethrin (20.0 μ g kg− 1) and permethrin (1.0 to 7.0 μ g kg− 1).

Uso de agrotóxicos na produção de soja do estado do Mato Grosso: um estudo preliminar de riscos ocupacionais e ambientais

Objective: To identify and to discuss some of the major risks associated to pesticide use in the soybean production in Mato Grosso State, Midwestern Brazil. Method: It is a descriptive exploratory pilot-study that was carried out between 2008 and 2009, using methodological triangulation, comprising the following: analysis of an agricultural database, analysis of biological indicators of pesticide exposure, and analysis of rainwater contamination by these chemicals. Results: Analysis of pesticides consumption data showed a high and growing use of pesticides in soybean production, particularly glyphosate. Rainwater analysis evidenced the occurrence of different pesticide residues, indicating the amplification of the risks beyond workplace. This environmental exposure was also detected by biological indicator analysis among workers and residents of the plantation neighboring areas. Conclusion: The study data indicate the need for permanent environmental and human health monitoring in soybean production areas as part of workers’ health and environmental surveillance strategies.

Environmental dynamics of pesticides in the drainage area of the São Lourenço River headwaters, Mato Grosso State, Brazil

This study assessed the environmental dynamics of pesticides in the Sao Lourenco River headwaters, Mato Grosso State, Brazil. The pesticides atrazine, flutriafol, metolachlor, α- and β-endosulfan and the metabolites endosulfan sulfate, desethylatrazine and desisopropylatrazine were determined in water (rain, surface, ground and runoff) and in sediment (runoff and bottom) samples, collected from August 2009 to July 2010, by SPE-GC/MS-SIM (solid phase extraction-gas chromatography/mass detector with selected ion monitoring). Runoff and rain atmospheric deposition showed to be important pathways for surface water contamination mainly by highly sorbed pesticides found in sediment with maximum concentration of 2218 μg kg-1 for β-endosulfan, and in water with maximum concentration of 28.3 μg L-1 for atrazine. Endosulfan sulfate, atrazine and metolachlor were the compounds with the highest frequency of detection. Leaching was an important process of off-site transport mainly due to the hydric behavior of soil and the low depth of water table, leading to contamination of groundwater as well as surface water via subsurface flow.

RESÍDUOS DE PESTICIDAS EM ÁGUAS SUPERFICIAIS DE ÁREA DE NASCENTE DO RIO SÃO LOURENÇO- MT: VALIDAÇÃO DE MÉTODO POR EXTRAÇÃO EM FASE SÓLIDA E CROMATOGRAFIA LÍQUIDA

A multiresidue method using HPLC/DAD for the determination of fourteen pesticides in water based on SPE, using SDVB (styrene divynilbenzene copolymer) as adsorbent was validated. Recoveries from 61 to 120%, relative standard deviation between 2 and 15% and detection limits from 0.07 to 0.75 µg L-1 were obtained. It was applied to 66 surface water samples collected in a degraded area at the headwaters of Sao Lourenco river, Mato Grosso, Brazil. Eight pesticides were detected in concentrations ranging from 0.15 to 35.25 µg L-1. Considering ecotoxicological data, carbendazim and carbofuran may represent a risk to aquatic organisms. These results draw attention to the contamination of this vulnerable degraded area.

Validation and application of an analytical method for determining pesticides in the gas phase of ambient air

A method for determining atmospheric concentrations of eight pesticides applied to corn and soybean crops in Mato Grosso state, Brazil is presented. The method involved a XAD-2 resin cartridge coupled to a low volume air pump at 2 L min−1 over 8 hours. Pesticides were recovered from the resin using sonication with n-hexane:ethyl acetate and determined by GC-MS. Good accuracy (76–128%) and precision (CV < 20%) were obtained for atrazine, chlorpyrifos, alpha- and beta-endosulfan, endosulfan sulfate, flutriafol, malathion, metolachlor and permethrin. Method detection ranged from 9.0 to 17.9 ng m−3. This method was applied to 61 gas phase samples collected between December 2008 and June 2009. Atrazine and endosulfan were detected both in urban and rural areas indicating the importance of atmospheric dispersion of pesticides in tropical areas. The simple and efficient extraction method and sampling system employed was considered suitable for identifying pesticides in areas of intense agricultural production.

Environmental Behavior of Chlorpyrifos and Endosulfan in a Tropical Soil in Central Brazil

The environmental behavior of chlorpyrifos and endosulfan in soil was studied in the central-western region of Brazil by means of a field experiment. Sorption was evaluated in laboratory batch experiments. Chlorpyrifos and endosulfan were applied to experimental plots on uncultivated soil and the following processes were studied: leaching, runoff, and dissipation in top soil. Field dissipation of chlorpyrifos and endosulfan was more rapid than reported in temperate climates. Despite the high Koc of the studied pesticides, the two endosulfan isomers and endosulfan sulfate as well as chlorpyrifos were detected in percolated water. In runoff water and sediment, both endosulfan isomers and endosulfan sulfate were detected throughout the period of study. Observed losses of endosulfan by leaching (below a depth of 50 cm) and runoff were 0.0013 and 1.04% of the applied amount, whereas chlorpyrifos losses were 0.003 and 0.032%, respectively. Leaching of these highly adsorbed pesticides was attributed to preferential flow.