Simulation of pesticide runoff at Rosemaund Farm (UK) using the SoilFug model

A validation exercise of the SoilFug model using field runoff data from Rosemaund Farm (UK) is described. A comparison has been made of modelled and measured concentrations of several pesticides in surface water and soil during and after specific rain events following application. The field experiments were designed to obtain data on rainfall, outflows of water, pesticide application rates and concentrations in soil and water. The results were satisfactory for the undissociated pesticides (atrazine, carbofuran, dimethoate, isoproturon, lindane, simazine and trifluralin), whose concentrations in water were mostly predicted within an order of magnitude of measured data. The results for the dissociated pesticides (dichlorprop, MCPA, mecoprop) were less satisfactory, giving generally much higher predicted concentrations in water. The use of the SoilFug model is suggested for the calculation of predicted environmental concentrations (PECs) in water, since it generally produces acceptable results from a relatively small set of input data, most of which is generally available.     

Estimation of PCDD/F distribution and fluxes in the Venice Lagoon,Italy: combining measurement and modelling approaches

The available experimental information on the occurrence of PCDD/Fs in the Venice Lagoon, Italy, was compiled and used to calculate fugacities for the environmental compartments of sediment, suspended particulate matter (SPM), water and air and then used to estimate fugacity ratios and assess the likely net direction of flux between media. The bottom sediment: SPM fugacity ratios for different PCDD/Fs indicate conditions close to equilibrium, suggestive of the close coupling of SPM with re-suspended sediment. Sediment/water and the sediment/air fugacity ratios suggest that net flux directions vary depending on the congener and the location within the lagoon. Net sediment-water-air movement (i.e. re-mobilisation/volatilisation) is suggested for the lighter congeners from the industrial canals, where the highest PCDD/F concentrations in the lagoon occur. The tendency to volatilise increases with decreasing congener molecular weight. In contrast, net deposition (air-water-sediment) appears to be occurring for the heaviest (hepta- and octa-) substituted PCDD/Fs. OCDF represents a marker of the industrial district of the lagoon, decreasing in concentration and as a fraction of total PCDD/Fs with increasing distance. The fugacity-based quantitative water air sediment interaction (QWASI) mass-balance model was applied to the central part of the lagoon. The key parameters for the determination of the model output, identified by a sensitivity analysis, were: the sediment active depth, the sediment re-suspension and deposition rates, and the total input of PCDD/Fs to the system. The QWASI model also indicates the tendency for the lighter PCDD/Fs to be released from surface sediment to the water column.     

Bioaccumulation and elimination of 14C-lindane by Enchytraeus albidus in artificial (OECD) and a natural soil

Bioaccumulation and elimination of 14C-lindane in Enchytraeus albidus was studied in artificial OECD soil and a silty loam from an agricultural field in Central West Portugal. Results showed that enchytraeids were able to bioaccumulate the chemical with a kinetic pattern similar to that of earthworms: fast uptake within a few days and a biphasic elimination pattern. A 10 day period to study uptake was sufficient, but a few more days were probably necessary for elimination. Bioaccumulation was influenced by soil type. The authors suggest that higher organic matter (OM) content and also the higher content on sand particles in the OECD soil may have led to a faster elimination: hydrophobic chemicals tend to adsorb to OM being in this way less bioavailable and therefore less bioaccumulated having bioaccumulation factor value around 6 while in natural soil is 10; the sand could act as abrasive particles (helpers) in the elimination process leading to an elimination of 90% of the chemical in two days while in natural soil 67% was eliminated in the same period of time.     

Lead levels of feral pigeons (Columba livia) from Madrid (Spain)

Tissue lead data are presented for populations of feral pigeons (Columba livia) from three locations in Madrid (Spain). The lead present in the lungs and digestive tract of pigeons increased progressively with traffic density and in parallel with atmospheric and ground lead values. The contribution of the respiratory route of Pb intake to the pigeons was about three times greater than the digestive route. The highest Pb values were found in bones. It is suggested that the pigeons gave a greatly magnified picture of lead pollution in cities than indicated by atmospheric lead concentrations.     

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.     

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.     

Electrochemical degradation of chlorophenoxy and chlorobenzoic herbicides in acidic aqueous medium by the peroxi-coagulation method

The degradation of 4-chlorophenoxyacetic acid (4-CPA), 4-chloro-2-methylphenoxyacetic acid (MCPA), 2,4-dichlorophenoxyacetic acid (2,4-D) and 2,4,5-trichlorophenoxyacetic acid (2,4,5-T) as chlorophenoxy herbicides, as well as of 3,6-dichloro-2-methoxybenzoic acid (dicamba) as chlorobenzoic herbicide, has been studied by peroxi-coagulation. This electrochemical method yields a very effective depollution of all compounds in acidic aqueous medium of pH 3.0 working under pH regulation, since they are oxidized with hydroxyl radicals produced from Fenton's reaction between Fe(2+) and H(2)O(2) generated by the corresponding Fe anode and O(2)-diffusion cathode. Their products can then be removed by mineralization or coagulation with the Fe(OH)(3) precipitate formed. Both degradative paths compete at low currents, but coagulation predominates at high currents. The peroxi-coagulation process of dicamba at I>or=300 mA leads to more than 90% of coagulation, being much more efficient than its comparative electro-Fenton treatment with a Pt anode and 1 mM Fe(2+), where only mineralization takes place. For the chlorophenoxy compounds, electro-Fenton gives a slightly lower depollution than peroxi-coagulation, because more easily oxidable products are produced. Oxidation of chlorinated products during peroxi-coagulation is accompanied by the release of chloride ion to the solution. The efficiency of this method decreases with increasing electrolysis time and current. The decay of all herbicides follows a pseudo-first-order reaction, with a similar constant rate for 4-CPA, MCPA, 2,4-D and 2,4,5-T, and a higher value for dicamba.     

Retention of arsenic on hydrous ferric oxides generated by electrochemical peroxidation

Electrochemical peroxidation (ECP), an emerging remediation technology, with direct electric current applied to steel electrode and small addition of H2O2, was used to remove As(III) from contaminated aqueous solutions. Bench scale experiments were conducted to evaluate the sorption and distribution of arsenic between the soluble and solid state hydrous ferric oxides (HFO) formed as part of the ECP process. ECP was effective in removing arsenic from the aqueous solution, with >98% of the applied As(III) adsorbed on HFO. Removal was complete within 3 min of ECP treatment and apparently independent of the initial pH of the water (3.5-9.5). In the absence of H2O2 more As(III) was adsorbed by solid state iron at pH 9.5 than at 3.5 (2600 vs. 1750 microg l(-1)). Thus H2O2 was crucial to oxidize As(III) to As(V) which is more strongly retained by HFO. Removal of As was not significantly affected by the concentration of H2O2 or by current processing time. The optimal operating conditions were pH < 6.5, H2O2 concentration of 10 mg l(-1) and current process time not exceeding 3 min. X-ray diffraction (XRD), diffuse-reflectance infrared Fourier transform (DRIFT) spectroscopy and transmission electron microscopy (TEM) were applied to study the HFO deposits. The XRD data indicated the prevalence of poorly ordered Fe minerals in the suspended ECP solids with a dominance of 5 line ferrihydrite in the absence of H2O2. At pH 3.5 and with 100 mg H2O2 l(-1), akaganeite was formed, whereas an incipient hematitic phase, reflection at 0.39 nm, occurred at pH 6.5. DRIFT data indicate that both As(III) and As(V) were specifically adsorbed onto HFO at acid and neutral pH. TEM observations indicated the presence of spherical shape ferrihydrite and provided evidence for possible formation of subrounded hematite and acicular shape goethite.     

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.     

Soil moisture determines the effectiveness of two urease inhibitors to decrease N<Subscript>2</Subscript>O emission

Among the mitigation strategies to prevent nitrogen (N) losses from ureic fertilizers, urease inhibitors (UIs) have been demonstrated to promote high N use efficiency by reducing ammonia (NH₃) volatilization. In the last few years, some field experiments have also shown its effectiveness in reducing nitrous oxide (N₂O) losses from fertilized soils under conditions of low soil moisture. An incubation experiment was carried out with the aim of assessing the main biotic mechanisms behind N₂O emissions once that the UIs N-(n-butyl) thiophosphoric triamid (NBPT) and phenil phosphorodiamidate (PPDA) were applied with Urea (U) under different soil moisture conditions (40, 60 and 80 % water-filled pore space, WFPS). In the same study we tried to analyze to what extent soil WFPS regulates the effect of these inhibitors on N₂O emissions. The use of PPDA in our study allowed us to compare the effect of NBPT with that of another commercially available urease inhibitor, aiming to see if the results were inhibitor-specific or not. Based on the results from this experiment, a WFPS (i.e. 60 %) was chosen for a second study (i.e. mesocosm experiment) aiming to assess the efficiency of the UIs to indirectly affect N₂O emissions through influencing the pool of soil mineral N. The N₂O emissions at 40 % WFPS were almost negligible, being significantly lower from all fertilized treatments than that produced at 60 and 80 % WFPS. When compared to U alone, NBPT+U reduced the N₂O emissions at 60 % WFPS but had no effect at 80 % WFPS. The application of PPDA significantly increased the emissions with respect to U at 80 % WFPS whereas no significant effect was found at 60 %. At 80 % WFPS, denitrification was the main source of N₂O emissions for all treatments. In the mesocosm study, the application of NBPT+U was an effective strategy to reduce N₂O emissions (75 % reduction compared to U alone), due to a lower soil ammonium (NH₄ ⁺) content induced by the inhibitor. These results suggest that adequate management of the UI NBPT could provide, under certain soil conditions, an opportunity for mitigation of N₂O emissions from fertilized soils.