Alicio A. Pinto

Leaching and degradation of corn and soybean pesticides in an Oxisol of the Brazilian Cerrados

Pesticide pollution of ground and surface water is of growing concern in tropical countries. The objective of this pilot study was to evaluate the leaching potential of eight pesticides in a Brazilian Oxisol. In a field experiment near Cuiabá, Mato Grosso, atrazine, chlorpyrifos, lambda-cyhalothrin, endosulfane alpha, metolachlor, monocrotofos, simazine, and trifluraline were applied onto a Typic Haplustox. Dissipation in the topsoil, mobility within the soil profile and leaching of pesticides were studied for a period of 28 days after application. The dissipation half-life of pesticides in the topsoil ranged from 0.9 to 14 d for trifluraline and metolachlor, respectively. Dissipation curves were described by exponential functions for polar pesticides (atrazine, metolachlor, monocrotofos, simazine) and bi-exponential ones for apolar substances (chlorpyrifos, lambda-cyhalothrin, endosulfane alpha, trifluraline). Atrazine, simazine and metolachlor were moderately leached beyond 15 cm soil depth, whereas all other compounds remained within the top 15 cm of the soil. In lysimeter percolates (at 35 cm soil depth), 0.8-2.0% of the applied amounts of atrazine, simazine, and metolachlor were measured within 28 days after application. Of the other compounds less than 0.03% of the applied amounts was detected in the soil water percolates. The relative contamination potentials of pesticides, according to the lysimeter study, were ranked as follows: metolachlor > atrazine = simazine >> monocrotofos > endsulfane alpha > chlorpyrifos > trifluraline > lambda-cyhalothrin. This order of the pesticides was also achieved by ranking them according to their effective sorption coefficient Ke, which is the ratio of Koc to field-dissipation half-life.

Pesticide displacement along preferential flow pathways in a Brazilian Oxisol

Abstract Previous studies conducted in tropical soils showed that pesticides of different polarity reached subsoil lysimeters within the same time intervals. This cannot be explained by pesticide transport under matrix flow conditions. The objective of this study was to elucidate pesticide transport in an Oxisol under preferential flow conditions. In a field experiment near Cuiaba, Brazil, alachlor, atrazine, chlorpyrifos, λ-cyhalothrin, deltamethrin, endosulfan-α, metolachlor, monocrotophos, simazine, and trifluralin were applied onto a Typic Haplustox. Afterwards, 40 mm day−1 of tracer solution (containing 5 g l−1 of the dye Brilliant Blue FCF and 0.015 M KBr) were applied in duplicate experiments over a period of 3 days, using either a tension infiltrometer (3.3 cm tension) or manual irrigation with a watering can. Soil monoliths were laid open, and the soil layers of 0–5, 5–10, 10–20, 20–30, and 30–40 cm were quantitatively removed. The soil of each depth interval was separated into a “blue”, a “nonblue”, and, if necessary, into a “nonseparable” fraction. Pesticide concentrations in 10–30 cm soil depth were 2.0–3.5 times higher at the dye front than in the entirely blue fraction. In the Oxisol under study, transport along preferential flow pathways contributed a major part to total pesticide displacement. This relative contribution was two to five times higher for the nonpolar than for the polar pesticides. The measured pesticide displacement reached deeper soil layers than that simulated for these compounds with the leaching model PEARL. Can irrigation, causing an occasional ponding, enhanced leaching of the corn herbicides (simazine, atrazine, alachlor, metolachlor) from the top 5 cm by a factor of 2.8–4.2, compared with strictly unsaturated infiltrometer irrigation. For the other compounds, differences in leaching behaviour between plots exceeded those between the different infiltration regimes.

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.

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.

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.

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.