Evaluation of soil temperature effect on herbicide leaching potential into groundwater in the Brazilian Cerrado

The effect of annual variations in the daily average soil temperatures, at different depths, on the calculation of pesticide leaching potential indices is presented. This index can be applied to assess the risk of groundwater contamination by a pesticide. It considers the effects of water table depth, daily recharge net rate, pesticide sorption coefficient, and degradation rate of the pesticide in the soil. The leaching potential index is frequently used as a screening indicator in pesticide groundwater contamination studies, and the temperature effect involved in its calculation is usually not considered. It is well known that soil temperature affects pesticide degradation rates, air-water partition coefficient, and water-soil partition coefficient. These three parameters are components of the attenuation and retardation factors, as well as the leaching potential index, and contribute to determine pesticide behavior in the environment. The Arrhenius, van't Hoff, and Clausius-Clapeyron equations were used in this work to estimate the soil temperature effect on pesticide degradation rate, air-water partition coefficient, and water-soil partition coefficient, respectively. The relationship between leaching potential index and soil temperature at different depths is presented and aids in the understanding of how potential pesticide groundwater contamination varies on different climatic conditions. Numerical results will be presented for 31 herbicides known to be used in corn and soybean crops grown on the municipality of S?o Gabriel do Oeste, Mato Grosso do Sul State, Brazil.     

Assessing the effect of climate oscillations and land-use changes on streamflow in the central Spanish Pyrenees

Plans to increase the amount of irrigated land in Mediterranean countries should consider how changes in climate and land-use affect water resources. In this study, both precipitation and temperature were used to analyze regional trends in discharge in the basins of the Central Spanish Pyrenees since the mid-20th century. Annual variations in the relationship between precipitation and discharge suggested that discharge was relatively lower in the second half of the study period, coinciding with major changes in land use. On a monthly scale, precipitation increased significantly in October, April, and July, and decreased in March, and temperature increased in January and February and decreased in April. Nevertheless, discharge has decreased significantly in most months in the past 50 years. Land-use and plant-cover changes are the only nonclimatic factor that can explain the loss of around 30% of the average annual discharge.     

Styrene dimers and trimers affect reproduction of daphnid (Ceriodaphnia dubia)

The endocrine disruptor activity of styrene in humans and other vertebrates appears to be negligible. However, offspring numbers were reduced in Ceriodaphnia dubia bred in polystyrene cups. Styrene dimers and trimers were found to be eluted from the polystyrene cups by hexane and methanol with gas chromatography-mass spectrometry. Styrene dimers and trimers at concentrations of 0.04-1.7 microg/l affected C. dubia fertility (25% reduction after seven days), suggesting that styrenes have the potential to impair crustacean populations in the aquatic environment.     

Cobalt-based alumina pillared zirconium phosphate catalysts for the selective catalytic reduction of NO by propane

A series of cobalt containing alumina pillared zirconium phosphate materials have been prepared by ion exchange or by impregnation, and fully characterised. The catalytic behaviour of these materials in the selective catalytic reduction of NO by propane, in excess of oxygen, at temperatures ranging between 350 and 550 degrees C, has been also evaluated. A maximum NO conversion close to 14% is obtained on Co-impregnated catalysts heated at 600 degrees C. The NO reduction seems to be related to the presence of Co3+, thus the calcination temperature of samples influences the resulting activity much more than the cobalt content.     

Methodologies for estimating disaggregated anthropogenic emissions--application to a coastal Mediterranean region of Spain

Regional estimates of both anthropogenic and biogenic emissions are important inputs for models of atmospheric chemistry. A disaggregated emissions inventory of all relevant pollutants for an area of 100 x 100 km2 centered in Burriana (Castellon, Spain) has been worked out. Time and spatial resolutions were hourly and 1 x 1 km2, respectively. Estimates were made for all relevant sources of anthropogenic emissions. The pollutants considered were SO2, NOx, NMVOCs (nonmethane volatile organic compounds), CH4, CO, CO2, N2O, and NH3. Thus, the emissions inventory includes up to 18 different NMVOCs. Emissions were computed for a typical sunny workday in June when strong photochemical activity could be expected. A "top-down" methodology was applied, taking as a starting point official annual and provincial estimates based on CORINAIR emission factors. This procedure is a very useful tool, particularly for those cases where a lack of sufficient local detailed information about the main emission-generating activities, such as road traffic, makes the use of a "bottom-up" approximation inadvisable. Moreover, updating these emission inventories is easier and they could be used to evaluate the impact of possible abatement strategies.     

Effect of methyl tertiary butyl ether concentrations on exhaust emissions from gasoline used in the metropolitan area of Mexico City

In this work, the primary objective was to assess the impact of oxygenated fuel on the exhaust emissions from an important fraction of vehicles in the Metropolitan Area of Mexico City (MAMC). The results aim to provide information on the actual effect of MTBE on a fleet that represents more than 60% of the in-use vehicles in the MAMC. Ten vehicles were tested with a low-octane base gasoline, and 10 more with a regular-grade unleaded base gasoline. Three MTBE concentrations, 5, 10, and 15 vol %, were tested following the U.S. Federal Test Procedure (FTP). CO, total HC, and NOx from the exhaust gases were quantitatively evaluated and also characterized for FTP speciated organic emissions. From this data, the O3-forming potential of the fuels was calculated. Results show that for the fleet using low-octane gasoline, the addition of 10% MTBE substantially reduced CO emissions, but total HC concentration in the exhaust showed a modest decrease. For the regular gasoline, the 10% MTBE blend seemed to be the best choice, but there was not a significant decrease in emissions. The specific reactivity of each fuel, expressed in grams of O3 per gram of nonmethane organic gases, increased with MTBE concentration in both cases. This result is important to consider, especially for a region like Mexico City, which has high atmospheric O3 concentrations.     

The use of mosses and pine needles to detect persistent organic pollutants at local and regional scales

Polycyclic aromatic hydrocarbons (PAHs) were analysed in mosses (Hypnum cupressiforme) and pine needles (Pinus sylvestris) collected in the Czech Republic between 1988-94 at a regional background site in Kosetice, south Bohemia (1988-94) and two industrial sources. One industrial site (sampled 1989-91) in middle Moravia, was near a factory producing PAHs, carbon black and phthalates, the other (sampled 1991-93) near a coal and gas fuel production plant in western Bohemia. Selected chlorinated pesticides and polychlorinated biphenyl congeners were also analysed in samples at the regional background site. This study clearly shows that vegetation sampling can be used to show spatial differences in the atmospheric burden of a range of persistent organic pollutants with differences in the mixtures of compounds reflecting differences in their regional or local use/atmospheric emission.     

A voltammetric screening method to determine ronidazole in bovine meat

Abstract

An original voltammetric screening method, employing glassy carbon electrode (GCE) with the differential-pulse voltammetry technique (DPV), has been developed to determine residues of the anti-parasitic agent Ronidazole (RNZ) in bovine meat. By using cyclic voltammetry (CV), it has been demonstrated that an irreversible cathodic process occurs at approximately ?0.740?V (vs. Ag|AgCl, KCl 3?mol L^?1) in a 0.100?mol L^?1 phosphate buffer at pH 6.5 as supporting electrolyte. Furthermore, the behavior of RNZ in CV indicates the occurrence of a diffusion mass transfer process to the working electrode surface. The RNZ reduction mechanism was proposed as a 6-electron transfer, similar to Metronidazole under the same pH range. Quantification of RNZ and method validation were then carried out by DPV. The relative standard deviation (RSD) were 3.21% for intraday precision of 10 consecutive repetitions and 6.78% for interday precision after five analysis. Limits of detection and quantification were also obtained, and the values were 0.107 and 0.358?mg kg^?1, respectively. The recovery percentage for three different concentrations of RNZ in the bovine meat matrix ranged between 98.1% and 100.3%. The method proved to be efficient for screening RNZ in bovine meat.     

Natural phillipsite as a matrix for a slow-release formulation of oxamyl

The performance of phillipsite as a matrix for slow-release formulation of oxamyl [N,N-dimethyl-2-methylcarbamoyl-oxymino-2-(methylthio)acetamide] was tested. The adsorption kinetics followed a first-order law, and the adsorption isotherm fitted well in a two-surface Langmuir model, suggesting a double mechanism of interaction between oxamyl and the sorbent. The sorption mechanism, studied by FTIR, provided two fractions of oxamyl. The first one is sorbed on the mineral surface, linked by H-bonding, and the second one is constituted by a multilayer of oxamyl molecules linked by a water bridge between them. The release kinetics of oxamyl from a substratum zeolite-oxamyl also follows a first-order law, with two stages that correspond to both fractions of oxamyl previously detected.     

Distribution of endocrine disruptors in the Llobregat River basin (Catalonia, NE Spain)

The Llobregat basin is a Mediterranean fluvial system with major agricultural, urban and industrial impacts. We combined chemical quantification by liquid chromatography–mass spectrometry with electrospray interface (LC-ESI-MS) and the recombinant yeast assay (RYA) assays to estimate the loads of endocrine disrupting compounds (EDCs) along the basin. Chemical analysis revealed maximum concentrations (at μg l⁻¹ level) of alkylphenols at the lower course of the Llobregat River, which correlated with high levels of estrogenic activity detected by RYA. Analysis by RYA and LC-ESI-MS of influent and effluent waters from four sewage treatment plants (STP) discharging into the basin showed the removal of 80–95% of EDCs by STP treatment. Chemical analysis data and RYA data showed a quasi-linear correlation, demonstrating the complementariness of both methods. Our data suggest that the concentrations of the analysed compounds were enough to explain the total estrogenicity of water and STP samples from the Llobregat basin.