Desenvolvimento e validação de métodos para a determinação de agrotóxicos em água e solo das áreas de recarga de Aquífero Guarani, na região das nascentes do Rio Araguaia, MT/GO.

Abstract: The area near the Araguaia River, between Goiás and Mato Grosso States, is the location of a portion of the recharging of the Guarani Aquifer, which is one of the world¿s largest aquifer systems and an important source of drinking water. This reservoir could be threatened by the widespread use of pesticides in maize and soybean cultivation in this area. Thus, this work developed analytical methods for the determination of imazethapyr, nicosulfuron, imazaquin, carbofuran, atrazine, linuron, clorimuronethyl and diflubenzuron, pesticides used in maize and soybean cultivation. Pesticide separation, identification and quantification were performed using High-Performance Liquid Chromatography with Diode Array Detection (HPLC-DAD) and Liquid Chromatography-Electrospray Ionization Tandem Mass Spectrometry (LC-ESI-MS/MS). Solid Phase Extraction (SPE) with C18 sorbents was optimized for sample extraction from water. Soil samples were extracted by mechanical shaking, sonication or microwave-assisted extraction with industrial and home microwave ovens. Methods were validated resulting in limits of quantification (LOQ) for the pesticides in water in the range of 0.015-0.1 ng mL, using SPE-HPLC-DAD, and 0.01 ng mL using LC-ESI-MS/MS. LOQ of 1 ng mL for all pesticides in soil were achieved using the home microwave oven and LC-ESI-MS/MS. Recoveries for pesticides with all methods were in the range 70-120 %. Relative standard deviations for repeatability and intermediate precision were less than 15 %. SPEHPLC- DAD and LC-ESI-MS/MS were employed for the analysis of samples of water from the recharge area and most of the pesticides were detected at concentrations below the minimum residue limit (MRL) of 0.1 ng mL established by the European Community. The home microwave oven and LC-ESI-MS/MS were used for the analysis of soil samples from two other regions of Brazil and the pesticides were not detected in these samples. Adsorption and desorption parameters were determined for imazethapyr, imazaquin, nicosulfuron and chlorimuron-ethyl, indicating that these pesticides have little affinity for the soil of the region of the Guarani Aquifer recharge, and show significant leaching potential, according to the ground water ubiquity score (GUS index) for these pesticides.

Water risk contamination trends by yellow-passion fruit pesticides in a small catchment in the eastern Amazon.

2009

Multiresidue determination of pesticides in surface water by SPE-HPLC-ESI and SPE-UPLC-ESI tandem mass spectrometry (MS/MS- triple quadrupole analyser).

2009

Biotechnology and crop protection in Brazil.

The process of modernization of Brazilian agriculture aimed at increasing the productivity in response to the high demand for agricultural products in the world market and it was based on the intensive use of inputs such as agrochemicals, intense mechanisation and breeding of new varieties. Among these, pesticides were incorporated in almost all production systems. Over reliance on pesticide use has produced many negative effects on both biotic and abiotic components of the environment, generating chemical contamination of soil and water, decrease in biological diversity of agroecosystems, disruption of natural cycles, pest resistance, intoxication of growers, among others. The consumption of pesticides in Brazil was 151.8 thousand tonnes in 1989, and today the country is the fifth world market of these products. The use of pesticides increased from 16 thousand tonnes (a.i.) in 1964 to 60.2 thousand tonnes in 1991, while the area planted to crops grew from 28.4 to 50.0 million ha in the same period. This means an increase of 276.2% in consumption of pesticides compared to an increase of 76% in planted area. Even with this large increase in the use of pesticides, the losses caused by pests have not been significantly reduced, and the net gain in crop productivity has been low. On the other hand, problems with food contamination, environmental degradation of growers have considerably mounted. It is possible to define two classes of crops regarding intense use of pesticides. One is represented by those crops that occupy large areas, and therefore contribute to a large amont of pesticides used for pest control in a country basis. The other class comprises crops that require large amounts of pesticides per unit of area, but not necessarily represent large amounts of pesticides used coutry-wide. Based on the classes proposed, citrus, soybean and sugarcane stand as crops with a nationally great consumption of pesticides, while tomato, potato and citrus are important as intensive users of pesticides. In this paper the biotechnologies in use, the biotechnologies in advanced stages of development, the main constraints to the development and use of biotechnlology and the impact of pesticed on the environment are discussed.

Numeric model to estimate pesticide deposition and losses from aerial spraying.

Pesticides applications have been described by many researches as a very inefficient process. In some cases, there are reports that only 0.02% of the applied products are used for the effective control of the problem. The main factor that influences pesticides applications is the droplet size formed on spraying nozzles. Many parameters affects the dynamic of the droplets, like wind, temperature, relative humidity, and others. Small droplets are biologically more active, but they are affected by evaporation and drift. On the other hand, the great droplets do not promote a good distribution of the product on the target. In this sense, associated with the risk of non target areas contamination and with the high costs involved in applications, the knowledge of the droplet size is of fundamental importance in the application technology. When sophisticated technology for droplets analysis is unavailable, is common the use of artificial targets like water-sensitive paper to sample droplets. On field sampling, water-sensitive papers are placed on the trials where product will be applied. When droplets impinging on it, the yellow surface of this paper will be stained dark blue, making easy their recognition. Collected droplets on this papers have different kinds of sizes. In this sense, the determination of the droplet size distribution gives a mass distribution of the material and so, the efficience of the application of the product. The stains produced by droplets shows a spread factor proportional to their respectives initial sizes. One of methodologies to analyse the droplets is a counting and measure of the droplets made in microscope. The Porton N-G12 graticule, that shows equaly spaces class intervals on geometric progression of square 2, are coulpled to the lens of the microscope. The droplet size parameters frequently used are the Volumetric Median Diameter (VMD) and the Numeric Median Diameter. On VMD value, a representative droplets sample is divided in two equal parts of volume, in such away one part contains droplets of sizes smaller than VMD and the other part contains droplets of sizes greater that VMD. The same process is done to obtaining the NMD, which divide the sample in two equal parts in relation to the droplets size. The ratio between VMD and NMD allows the droplets uniformity evaluation. After that, the graphics of accumulated probability of the volume and size droplets are plotted on log scale paper (accumulated probability versus median diameter of each size class). The graphics provides the NMD on the x-axes point corresponding to the value of 50% founded on the y-axes. All this process is very slow and subjected to operator error. So, in order to decrease the difficulty envolved with droplets measuring it was developed a numeric model, implemented on easy and accessfull computational language, which allows approximate VMD and NMD values, with good precision. The inputs to this model are the frequences of the droplets sizes colected on the water-sensitive paper, observed on the Porton N-G12 graticule fitted on microscope. With these data, the accumulated distribution of the droplet medium volumes and sizes are evaluated. The graphics obtained by plotting this distributions allow to obtain the VMD and NMD using linear interpolation, seen that on the middle of the distributions the shape of the curves are linear. These values are essential to evaluate the uniformity of droplets and to estimate the volume deposited on the observed paper by the density (droplets/cm2). This methodology to estimate the droplets volume was developed by 11.0.94.224 Project of the CNPMA/EMBRAPA. Observed data of herbicides aerial spraying samples, realized by Project on Pelotas/RS county, were used to compare values obtained manual graphic method and with those obtained by model has shown, with great precision, the values of VMD and NMD on each sampled collector, allowing to estimate a quantities of deposited product and, by consequence, the quantities losses by drifty. The graphics of variability of VMD and NMD showed that the quantity of droplets that reachs the collectors had a short dispersion, while the deposited volume shows a great interval of variation, probably because the strong action of air turbulence on the droplets distribution, enfasizing the necessity of a deeper study to verify this influences on drift.