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A modeling study on fertilizer by-products fate and transport was performed in an unconfined shallow aquifer equipped with a grid of 13 piezometers. The field site was located in a former agricultural field overlying a river paleochannel near Ferrara (Northern Italy), cultivated with cereals rotation until 2004 and then converted to park. Piezometers were installed in June 2007 and were monitored until June 2009 via pressure transducer data loggers to evaluate the temporal and spatial variation of groundwater heads, while an onsite meteorological station provided data for recharge rate calculations via unsaturated zone modeling. The groundwater composition in June 2007 exhibited elevated nitrate (NO 3 ? ) and chloride (Cl?) concentrations due to fertilizer leaching from the top soil. The spatial distribution of NO 3 ? and Cl? was heterogeneous and the concentration decreased during the monitoring period, with NO 3 ? attenuation (below 10?mg/l) after 650?days. A transient groundwater flow and contaminant transport model was calibrated versus observed heads and NO 3 ? and Cl? concentrations. Cl? was used as environmental tracer to quantify groundwater flow velocity and it was simulated as a conservative species. NO 3 ? was treated as a reactive species and denitrification was simulated with a first order degradation rate constant. Model calibration gave a low denitrification rate (2.5e?3 mg-NO 3 ? /l/d) likely because of prevailing oxic conditions and low concentration of dissolved organic carbon. Scenario modeling was implemented with steady state and variable flow time discretization to identify the mechanism of NO 3 ? attenuation. It was shown that transient piezometric conditions did not exert a strong control on NO 3 ? clean up time, while transient recharge rate did, because it is the main source of unpolluted water in the domain.  相似文献   
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Nitrogen fertilizers used in agriculture often cause nitrate leaching towards shallow groundwater, especially in lowland areas where the flat topography minimize the surface run off. In order to introduce good agricultural practices that reduce the amount of nitrate entering the groundwater system, it is important to quantify the kinetic control on nitrate attenuation capacity. With this aim, a series of anaerobic batch experiments, consisting of loamy soils and nitrate-contaminated groundwater, were carried out using acetate and natural dissolved organic matter as electron donors. Acetate was chosen because it is the main intermediate species in many biodegradation pathways of organic compounds, and it is a suitable carbon source for denitrification. Sorption of acetate was also determined, fitting a Langmuir isotherm in both natural and artificially depleted organic matter soils. Experiments were performed in quadruplicate to account for the spatial variability of soil parameters. The geochemical code PHREEQC (version 2) was used to simulate kinetic denitrification using Monod equation, equilibrium Langmuir sorption of acetate, and equilibrium reactions of gas and mineral phases (calcite). The reactive modeling results highlighted a rapid acetate and nitrate mineralization rate, suggesting that the main pathway of nitrate attenuation is through denitrification while calcite acted as a buffer for pH. However, in the absence of acetate, the natural content of organic matter did not allow to complete the denitrification process leading to nitrite accumulation. Reactive modeling is thought to be an efficient and robust tool to quantify the complex biogeochemical reactions which can take place in underground environments.  相似文献   
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This paper contributes to increase the knowledge of the contents and sources of heavy metals (Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb and Zn) to agricultural soils in Castellón province (Spain), a representative area of the European Mediterranean region. The surface horizons of 77 agricultural soils under vegetable crops were sampled and heavy metals were analysed by atomic absorption spectroscopy (AAS) after microwave extraction using the USEPA 3051A method. Mean heavy metal contents were similar to those obtained in other areas of this region. However, heavy metal contents (e.g. Cr, Pb) in some soils were above the maximum limit set in the 86/278/CEE Directive. Multivariate analysis (correlation analysis and principal component analysis – PCA) was performed so as to identify the sources of heavy metals to soils. Co, Fe and Ni were highly correlated amongst them (r?>?0.800; p?<?0.01), whereas Cr and Mn were less correlated with Co, Fe and Ni (r?>?0.500; p?<?0.01). Other relationships among heavy metals (i.e. Cu, Pb and Zn) were also identified, although correlation coefficients were not so high as those among Co, Fe and Ni (r?<?0.500; p?<?0.01). Contents of Co, Fe, Mn and Ni were interpreted to be mainly associated with parent rocks corresponding to the first principal component (PC1). On the other hand, Cd, Cu, Pb and Zn were interpreted to be mainly related to anthropogenic activities and comprised the second (Pb and Zn) and the third (Cd and Cu) principal components (PC2 and PC3, respectively), designated as anthropogenic components. Remarkably, Cr appears to be related in the study area to both the lithogenic and the anthropogenic components. Lithogenic elements were highly correlated with soil properties. Positive relationships with CEC (r?>?0.200; p?<?0.05) and clay (r?>?0.400; p?<?0.01), and negative relationships with carbonates (r?>??0.400; p?<?0.01) and sand (r?>??0.300; p?<?0.01) were observed. Anthropogenic elements were less correlated with soils properties, since these elements are generally more mobile because they form more soluble chemical species associated to anthropogenic sources. Particularly, no correlation was found between Cd and Zn and soil properties. These findings extend results achieved in other parts of the region, highlighting the need to set soil quality standards in order to declare soils affected by anthropogenic pollution, particularly in the case of anthropogenic metals such as Cd, Cu and Pb, and also Cr and Zn in some areas. Further knowledge from other areas in this region would improve the basis for proposing such standards at regional level, which is a priority objective in Europe according to the European Thematic Strategy for Soil Protection.  相似文献   
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Diffused petroleum and chlorinated hydrocarbon contamination was detected in a sandy aquifer below a chemical plant in Southern Italy. The contamination was due to underground leaking tanks and pipes. The site is located near the shore line and is bordered by canals which, in combination with pumping wells, control the groundwater flow direction toward the sea. In this study, a comprehensive three-dimensional flow model was developed and calibrated to simulate the general groundwater flow system and to individuate a flow line. On this latter, a detailed field investigation was performed in order to determine the fate of dissolved hydrocarbons. Depth profiles obtained from multi-level samplers located along the modelled flow line, including measurements of hydrocarbons, all major ions and dissolved gasses, were used to constrain the conceptual model. These data were then included into a two-dimensional transport model in order to verify the efficacy of the hydraulic barrier (HB) in preventing the hydrocarbon plume to reach the shore line. Two different approaches were used in the transport simulation, one accounting for density-dependent flow and the other not. The calibrated models show that the plume length and consequently, the submarine groundwater discharge of contaminants is slightly different for the two approaches. For the simulation not accounting for the density contrast between freshwater and saltwater, the mass of contaminant discharged downstream to the HB was underestimated and also the reconstructed plume geometry was different than the observed. Moreover, the reconstruction of the saltwater intrusion interface (SWII) with the two different approaches was substantially different. This study demonstrates that at field site, variable density processes should be carefully taken into account not only when the modelling is devoted to the reconstruction of the SWII but also when the modelling is targeting the fate of hydrocarbons at sites affected by SWII, in order to provide accurate data on which soundly environmental management of the coastal zone can be based.  相似文献   
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Column laboratory experiments were employed to assess the leaching behaviour of pyroclastic glassy ash deposits collected in the central Main Ethiopian Rift, where surface and groundwater resources are affected by fluoride (F?) pollution, which is the cause of an endemic disease (fluorosis) in the local community. To elucidate the source of F? and simulate the water–rock interaction processes, as well as quantify its distribution within different grain sizes, the pyroclastic ash was analysed by XRF, XRD and SEM and separated into coarse and fine fractions. Three columns were filled with raw (unsieved), coarse (63 μm–2 mm) and fine (<63 μm) fraction, respectively, and flushed with synthetic rain water in saturated conditions. Very fast F? leaching was observed in the fine fraction column at the start of the experiment, while in the other two columns, F? was slowly released; in addition, a strong accumulation of F? was found in the fine fraction. The effect was more pronounced in the fine fraction column due to the available effective adsorbing surface area. Subsequent to elution experiments, the columns were characterised via moment analysis of tracer test. Finally, flow and transport modelling (MODFLOW-2000 and MT3DMS) was employed to compute the amount of F? adsorbed onto the solid phase, comparing the calculated conservative transport of F? and the observed concentrations. The results of this study suggest that fluoride is a fundamental constituent of the glass phase (about 0.3 wt.%) and that it is released during the incongruent dissolution of glassy particles. Dissolution of coatings on glass particles could provide an additional contribution to the geochemistry of the interacting fluids. These processes are more effective in the fine fraction due to a much higher reactive (specific) surface area.  相似文献   
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