Grab and passive sampling applied to pesticide analysis in the São Lourenço river headwater in Campo Verde - MT, Brazil.

In this study, the quality of surface water in the headwaters of São Lourenço River in Mato Grosso, Brazil, was evaluated in relation to contamination by pesticides. For this purpose, samples were collected between December 2015 and June 2016 by grab sampling and by passive sampling using an integrative polar organic compound sampler installed in the field during four 14-day cycles between March and June 2016. The analyses were performed by gas chromatography (CG/MS) and by liquid chromatography (UPLC-MS/MS). The results showed the detection of two pesticides (atrazine and pyraclostrobin) of the five analyzed by passive sampling and eight active principles among the 20 analyzed (malathion, diuron, carbofuran, carbendazim, trifluralin, imidacloprid, metolachlor, and acetamiprid) by grab sampling. The detection of 10 pesticides, even almost a decade after the beginning of a recovery process of the ciliary forest, confirms the headwaters' vulnerability to these contaminants and passive sampling proved to be an important tool in capturing small concentrations of pesticides constituting an interesting complement to grab sampling.

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.

Assessment of metolachlor and diuron leaching in a tropical soil using undisturbed soil columns under laboratory conditions.

In the present study, diuron [3-(3,4-dichlorophenyl)-1,1-dimethylurea] and metolachlor [2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-metoxi-1-methylethyl)acetamide] leaching was studied in undisturbed soil columns collected in a cotton crop area in Mato Grosso State, Brazil. The pesticides were applied to the soil surface in dosages similar to those used in a cotton plantation. To assess the leaching process, soil columns were submitted to simulated rain under laboratory conditions at 25 ± 3°C, in the absence of wind and direct solar radiation. During the rain simulations, leachate solutions were collected and herbicide concentrations were determined. At the end of the experiment, the soil columns were cut into 10 cm sections to determine the remaining herbicide concentrations through the soil profile. Metolachlor was detected in all soil sections, and approximately 4% of the applied mass was leached. Diuron was detected only in the upper two soil sections and was not detected in the leachate. A linear correlation (r > 0.94) between the metolachlor soil concentrations and the organic contents of the soil sections was observed. Mass balance suggests that around 56% of diuron and 40% of metolachlor were degraded during the experiments. Measurements of the water table depth in the area where the samples were collected showed that it varied from 2 to 6 m and is therefore vulnerable to contamination by the studied herbicides, particularly metolachlor, which demonstrated a higher leaching potential.

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.

Método analítico para identificar plaguicidas en el aire atmosférico / Analytical method to identify pesticides in the atmosphere

La volatilización puede ser una importante ruta de distribución de plaguicidas en el medio ambiente y la toma de muestras de aire para la cuantificación de plaguicidas es crítica para el proceso analítico.

Método analítico para identificar plaguicidas en el aire atmosférico / Analytical method to identify pesticides in the atmosphere

La volatilización puede ser una importante ruta de distribución de plaguicidas en el medio ambiente y la toma de muestras de aire para la cuantificación de plaguicidas es crítica para el proceso analítico.

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.

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 lambda -cyhalothrin (1.0 to 5.0 micro g kg(- 1)), p,p'-DDT (3.6 micro g kg(- 1)), deltamethrin (20.0 micro g kg(- 1)) and permethrin (1.0 to 7.0 micro g kg(- 1)).

Pesticide levels in ground and surface waters of Primavera do Leste Region, Mato Grosso, Brazil.

Residues of the herbicides simazine, metribuzin, metolachlor, trifluralin, atrazine, and two metabolites of atrazine, deisopropylatrazine (DIA) and deethylatrazine (DEA), are surveyed in the surface and groundwater of the Primavera do Leste region, Mato Grosso, Brazil during September and December 1998 and April 1999. Different water source sampling stations of groundwater (irrigation water well, drinking water well, and water hole) and surface water (dam and river) are set up based on agricultural land use. A solid-phase extraction procedure followed by gas chromatography-nitrogen-phosphorus detection is used for the determination of these compounds. All compounds are detected at least once in water samples. A temporal trend of pesticide contamination is observed, with the highest contamination frequency occurring in December during the main application season. Metribuzin shows the highest individual detection frequencies throughout the monitoring period, followed by metolachlor, simazine, and DEA. The maximum mean concentrations of pesticides in this study are in the range from 0.14 to 1.7 microg/L. We deduct that the contamination of water resources is predominantly caused by non-point pollution of pesticides used in intensive cash-crop cultures of the Cerrado area. Therefore, a continuous monitoring of pesticide concentrations in water resources of this tropical region is necessary to detect the longer term contamination trends and developing health risks.

Leaching of seven pesticides currently used in cotton crop in Mato Grosso State-Brazil.

This study aimed to evaluate the leaching of pesticides and the applicability of the Attenuation Factor (AF) Model to predict their leaching. The leaching of carbofuran, carbendazim, diuron, metolachlor, alpha and beta endosulfan and chlorpyrifos was studied in an Oxisol using a field experiment lysimeter located in Dom Aquino-Mato Grosso. The samples of percolated water were collected by rain event and analyzed. Chemical and physical soil attributes were determined before pesticide application to the plots. The results showed that carbofuran was the pesticide that presented a higher leaching rate in the studied soil, so was the one representing the highest contamination potential. From the total carbofuran applied in the soil surface, around 6% leached below 50 cm. The other pesticides showed lower mobility in the studied soil. The calculated values to AF were 7.06E-12 (carbendazim), 5.08E-03 (carbofuran), 3.12E-17 (diuron), 6.66E-345 (alpha-endosulfan), 1.47E-162 (beta-endosulfan), 1.50E-06 (metolachlor), 3.51E-155 (chlorpyrifos). AF Model was useful to classify the pesticides' potential for contamination; however, that model underestimated pesticide leaching.

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 (r(2) = 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.