Model-Based Analysis of Arsenic Retention by Stimulated Iron Mineral Transformation under Coastal Aquifer Conditions.

A multitude of geochemical processes control the aqueous concentration and transport properties of trace metal contaminants such as arsenic (As) in groundwater environments. Effective As remediation, especially under reducing conditions, has remained a significant challenge. Fe(II) nitrate treatments are a promising option for As immobilization but require optimization to be most effective. Here, we develop a process-based numerical modeling framework to provide an in-depth understanding of the geochemical mechanisms controlling the response of As-contaminated sediments to Fe(II) nitrate treatment. The analyzed data sets included time series from two batch experiments (control vs treatment) and effluent concentrations from a flow-through column experiment. The reaction network incorporates a mixture of homogeneous and heterogeneous reactions affecting Fe redox chemistry. Modeling revealed that the precipitation of the Fe treatment caused a rapid pH decline, which then triggered multiple heterogeneous buffering processes. The model quantifies key processes for effective remediation, including the transfer of aqueous As to adsorbed As and the transformation of Fe minerals, which act as sorption hosts, from amorphous to more stable phases. The developed model provides the basis for predictions of the remedial benefits of Fe(II) nitrate treatments under varying geochemical and hydrogeological conditions, particularly in high-As coastal environments.

Geostatistical assessment of groundwater arsenic contamination in the Padana Plain.

Arsenic (As) in groundwater from natural and anthropogenic sources is one of the most common pollutants worldwide affecting people and ecosystems. A large dataset from >3600 wells is employed to spatially simulate the depth-averaged As concentration in phreatic and confined aquifers of the Padana Plain (Northern Italy). Results of in-depth geostatistical analysis via PCA and simulations within a Monte Carlo framework allow the understanding of the variability of As concentrations within the aquifers. The most probable As contaminated zones are located along the piedmont areas in the confined aquifers and in the lowland territories in the phreatic aquifers. The distribution of the As contaminated zones has been coupled with hydrogeological, geological, and geochemical information to unravel the sources and mechanisms of As release in groundwater. The reductive dissolution of Fe oxyhydroxides and organic matter mineralization under anoxic conditions resulted to be the major drivers of As release in groundwater. This phenomenon is less evident in phreatic aquifers, due to mixed oxic and reducing conditions. This large-scale study provides a probabilistic perspective on As contamination, e.g. quantifying the spatial probability of exceeding national regulatory limits, and to outline As major sources and drivers.

Salinity origin in the coastal aquifer of the Southern Venice lowland.

Groundwater salinization can be natural and anthropogenic in origin, although it often results from a combination of both, especially in low-lying coastal regions that are hydraulically controlled. This study proposes a method to assess the origin of salinity using environmental tracers in porewater, like Cl- and Br-, combined with depositional facies associations detected in sediment cores. Such integrated approach was tested in a target area south of the Venice Lagoon (Italy), where groundwater salinization is triggered by multiple mechanisms due to the complexity of the hydro-geomorphological environment. Batch tests were performed on sediment core samples from boreholes to quantify major anions and total inorganic N. Cl- and Br- porewater concentrations coupled with sedimentary facies association provided insights into the origin of groundwater salinity from a variety of sources, including past and present seawater intrusion, agricultural leaching, and evaporites. The strengths and limitations of the integrated approach are discussed to provide a pathway for improving water resource management and planning measures to prevent groundwater salinization in coastal areas.

Modelling biogeochemical reactions triggered by graphene's addition in a fertilized calcareous sandy soil.

Graphene production has dramatically increased in the last years and new ways to recycle this engineered material need to be investigated. To this purpose, a reactive model network was developed using PHREEQC-3 code to quantify the relevant biogeochemical reactions induced by graphene scraps' incorporation in a calcareous sandy soil. The numerical model was calibrated versus a complete dataset of column experiments in water saturated conditions using two different fertilizers, a synthetic NPK fertilizer and fertigation water produced in a wastewater treatment plant. Column experiments consisted of 50 cm columns filled with a mixture of graphene scraps (0.015 % dry weight) and soil in the first 10 cm, while the remaining 40 cm had only soil. The model performance was tested using classical statistical indices (R2, Modelling Efficiency, and Index of Agreement), resulting to be satisfactory. Besides, a simple sensitivity analysis via the perturbation of relevant parameters showed a low degree of uncertainty. The main outcome of this study was the quantification of the increased denitrification rate triggered by graphene incorporation into the soil. Moreover, graphene incorporation substantially increased soil CEC and DOC sorption capacity, demonstrating a good adsorption capacity for ammonium and organic compounds, thus decreasing nutrients leaching that represents a major concern related to agricultural practice. Indeed, Graphene incorporation increased by 40 % the CEC in the first 10 cm of the CSG_NPK column (2.50e-02 mol/L) respect to the CS_NPK column (1.75e-02 mol/L) and increased it by 150 % in the first 10 cm of the CSG_FW column (2.50e-02 mol/L) in comparison with the CS_FW column 1.00e-02 (mol/L). pH fluctuations were most likely due to the precipitation of Ca5(PO4)3OH, indeed the consumption of H+ ions could have triggered the pH lowering during the experiment. These results could be relevant for future graphene applications as a soil improver or as suitable material to enhance soil bioremediation in order to include graphene in a circular economy loop.

Modeling stochastic saline groundwater occurrence in coastal aquifers.

The issue of freshwater salinization in coastal areas has grown in importance with the increase of the demand of groundwater supply and the more frequent droughts. However, the spatial patterns of salinity contamination are not easy to be understood, as well as their numerical modeling is subject to various kinds of uncertainty. This paper offers a robust, flexible, and reliable geostatistical methodology to provide a stochastic assessment of salinity distribution in alluvial coastal areas. The methodology is applied to a coastal aquifer in Campania (Italy), where 83 monitoring wells provided depth-averaged salinity data. A Monte Carlo (MC) framework was implemented to simulate depth-averaged groundwater salinity fields. Both MC stochastic fields and the mean across MC simulations enabled to the delineation of which areas are subject to high salinity. Then, a probabilistic approach was developed setting up salinity thresholds for agricultural use to delineate the areas with unsuitable groundwater for irrigation purposes. Furthermore, steady spatial patterns of saline wedge lengths were unveiled through uncertainty estimates of seawater ingression at the Volturno River mouth. The results were compared versus a calibrated numerical model with remarkable model fit (R2=0.96) and versus an analytical solution, obtaining similar wedge lengths. The results pointed out that the high groundwater salinities found inland (more than 2 km from the coastline) could be ascribed to trapped paleo-seawater rather than to actual seawater intrusion. In fact, the inland high salinities were in correspondence of thick peaty layers, which can store trapped saline waters because of their high porosity and low permeability. Furthermore, these results are consistent with the recognition of depositional environments and the position of ancient lagoon alluvial sediments, located in the same areas where are the highest (simulated) salinity fields. This robust probabilistic approach could be applied to similar alluvial coastal areas to understand spatial patterns of present salinization, to disentangle actual from paleo-seawater intrusion, and more in general to delineate zones with unsuitable salinity for irrigation purposes.

Performance of graphene and traditional soil improvers in limiting nutrients and heavy metals leaching from a sandy Calcisol.

Given the large amount of Graphene produced in the last years, there is the need to introduce this new material into a green and circular economy loop. In this study, for the first time, the fate of nutrients and heavy metals in a sandy Calcisol amended with Graphene was monitored and compared to other traditional improvers such as Compost, Zeolites, and Biochar. This was performed via saturated and unsaturated columns' experiments with two different fertilization regimes: one with NPK fertilizer and one with an innovative fertigation water (FW) produced from a pilot wastewater treatment plant. The breakthrough curves of each nutrient and heavy metal were analysed to understand the main processes occurring in saturated and unsaturated conditions, comparing the columns amended with the improvers versus the unamended Controls. Mass balances for each nutrient and heavy metal were developed to infer whether the different soil improvers were effective in minimizing leaching. Graphene, for most cases, behaved as the Control in nutrients' leaching for all the saturated and unsaturated experiments, both with NPK and FW. Biochar increased EC, K+, and pH of the leaching water, which could be an issue for the growth of some plants. Compost increased NO3- leaching in all the experiments. Zeolites showed the best N compounds retention, but great PO43- leaching in saturated conditions. Heavy metals leachates were analysed only for unsaturated columns (as more representative of field conditions) and found at concentrations well below the limits suggested by the U.S. Environmental Protection Agency. Overall, Graphene performed well in minimizing nutrients and heavy metals leaching, respect to classical improvers. This study is a starting point for field studies that will be critical to have a clear understanding of how Graphene behaves in the environment.

Assessment of intrinsic aquifer vulnerability at continental scale through a critical application of the drastic framework: The case of South America.

An assessment of the intrinsic aquifer vulnerability of South America is presented. The outcomes represent the potential sensitivity of natural aquifers to leaching of dissolved compounds from the land surface. The study, developed at continental scale but retaining regionally a high resolution, is based on a critical application of the DRASTIC method. The biggest challenge in performing such a study in South America was the scattered and irregular nature of environmental datasets. Accordingly, the most updated information on soil, land use, geology, hydrogeology, and climate at continental, national, and regional scale were selected from international and local databases. To avoid spatial discrepancy and inconsistency, data were integrated, harmonized, and accurately cross-checked, using local professional knowledge where information was missing. The method was applied in a GIS environment to allow spatial analysis of raw data along with the overlaying and rating of maps. The application of the DRASTIC method allows to classify South America into five vulnerability classes, from very low to very high, and shows an overall medium to low vulnerability at continental scale. The Amazon region, coastal aquifers, colluvial Andean valleys, and alluvial aquifers of main rivers were the areas classified as highly vulnerable. Moreover, countries with the largest areas with high aquifer vulnerability were those characterized by extended regions of rainforest. In addition, a single parameter sensitivity analysis showed depth to water table to be the most significant factor, while a cross-validation using existing vulnerability assessments and observed concentrations of compounds in groundwater confirmed the reliability of the proposed assessment, even at regional scale. Overall, although additional field surveys and detailed works at local level are needed to develop effective water management plans, the present DRASTIC map represents an essential common ground towards a more sustainable land-use and water management in the whole territory of South America.

In situ arsenic immobilisation for coastal aquifers using stimulated iron cycling: Lab-based viability assessment.

Arsenic (As) is one of the most harmful and widespread groundwater contaminants globally. Besides the occurrence of geogenic As pollution, there is also a large number of sites that have been polluted by anthropogenic activities, with many of those requiring active remediation to reduce their environmental impact. Cost-effective remedial strategies are however still sorely needed. At the laboratory-scale in situ formation of magnetite through the joint addition of nitrate and Fe(II) has shown to be a promising new technique. However, its applicability under a wider range of environmental conditions still needs to be assessed. Here we use sediment and groundwater from a severely polluted coastal aquifer and explore the efficiency of nitrate-Fe(II) treatments in mitigating dissolved As concentrations. In selected experiments >99% of dissolved As was removed, compared to unamended controls, and maintained upon addition of lactate, a labile organic carbon source. Pre- and post experimental characterisation of iron (Fe) mineral phases suggested a >90% loss of amorphous Fe oxides in favour of increased crystalline, recalcitrant oxide and sulfide phases. Magnetite formation did not occur via the nitrate-dependent oxidation of the amended Fe(II) as originally expected. Instead, magnetite is thought to have formed by the Fe(II)-catalysed transformation of pre-existing amorphous and crystalline Fe oxides. The extent of amorphous and crystalline Fe oxide transformation was then limited by the exhaustion of dissolved Fe(II). Elevated phosphate concentrations lowered the treatment efficacy indicating joint removal of phosphate is necessary for maximum impact. The remedial efficiency was not impacted by varying salinities, thus rendering the tested approach a viable remediation method for coastal aquifers.

The origin of Uranium in groundwater of the eastern Halkidiki region, northern Greece.

Uranium (U) pollution in groundwater has become a serious problem worldwide. Even in low concentrations, U has both radiological and toxicological impacts on human health. In this study an integrated hydrogeological approach was applied to conceptualize an aquifer system, and determine the origin of U detected in the aquifer of the eastern Halkidiki region in northern Greece. Data from measurements of groundwater level and hydrochemical and stable isotope analyses of groundwater samples were applied to perform geochemical modeling and multivariate statistical analysis. The modeling and statistical analysis identified three hydrogeochemical groups within the studied hydro-system, and U(VI) as the dominant U species. The first group is linked to the deeper aquifer which is characterized by water-rock interactions with weathering products of granodiorite. In this group the dominant U species is uranyl phosphate and U concentration is 3.7 µg/L. The upper aquifer corresponds to the second hydrogeochemical group where U concentrations are mainly influenced by high concentrations of nitrogen species (NO3- and NO2-). Factor analysis further discriminated the upper aquifer into a saline coastal zone and an inland zone impacted by agricultural activities. The third hydrogeochemical group presents the highest concentration of U (up to 15 µg/L) in groundwater and corresponds to the internal aquifer system. The U within this system is triggered by the presence of Mn2+, while the long residence time of the groundwater contributes synergistically to the hydrogeochemical process. Manganese triggers U oxidation in parallel with Fe2+ precipitation that acts as a regulator of U concentration. Groundwater depletion of the upper aquifers promotes the up-coning of geothermal fluids from fault zones leading to increased concentrations of U in the mid-depth aquifers.

Predictive modeling of selected trace elements in groundwater using hybrid algorithms of iterative classifier optimizer.

Trace element (TE) pollution in groundwater resources is one of the major concerns in both developing and developed countries as it can directly affect human health. Arsenic (As), Barium (Ba), and Rubidium (Rb) can be considered as TEs naturally present in groundwater due to water-rock interactions in Campania Plain (CP) aquifers, in South Italy. Their concentration could be predicted via some readily available input variables using an algorithm like the iterative classifier optimizer (ICO) for regression, and novel hybrid algorithms with additive regression (AR-ICO), attribute selected classifier (ASC-ICO) and bagging (BA-ICO). In this regard, 244 groundwater samples were collected from water wells within the CP and analyzed with respect to the electrical conductivity, pH, major ions and selected TEs. To develop the models, the available dataset was divided randomly into two subsets for model training (70% of the dataset) and evaluation (30% of the dataset), respectively. Based on the correlation coefficient (r), different input variables combinations were constructed to find the most effective one. Each model's performance was evaluated using common statistical and visual metrics. Results indicated that the prediction of As and Ba concentrations strongly depends on HCO3-, while Na+ is the most effective variable on Rb prediction. Also, the findings showed that the most powerful predictive models were those that used all the available input variables. According to models' performance evaluation metrics, the hybrid ASC-ICO outperformed other hybrid (BA- and AR-ICO) and standalone (ICO) algorithms to predict As and Ba concentrations, while both hybrid ASC- and BA-ICO models had higher accuracy and lower error than other algorithms for Rb prediction.

Evaluating SWAT model performance, considering different soils data input, to quantify actual and future runoff susceptibility in a highly urbanized basin.

The Soil and Water Assessment Tool (SWAT) is a physical model designed to predict the hydrological processes that could characterize natural and anthropized watersheds. The model can be forced using input data of climate prediction models, soil characteristics and land use scenarios to forecast their effect on hydrological processes. In this study, the SWAT model has been applied in the Aspio basin, a small watershed, highly anthropized and characterized by a short runoff generation. Three simulations setup, named SL1, SL2 and SL3, were investigated using different soil resolution to identify the best model performance. An increase of space requirement and calibration time has been registered in conjunction with the increasing soil resolution. Among all simulations, SL1 has been chosen as the best one in describing watershed streamflow, despite it was characterized by the lower soil resolution. A map of susceptibility to runoff for the entire basin was so created reclassifying the runoff amount of four years in five classes of susceptibility, from very low to very high. Eleven sub-basins, coinciding with the main urban settlements, were identified as highly susceptible to runoff generation. Considering future climate predictions, a slight increase of runoff has been forecasted during summer and autumn. The map of susceptibility successfully identified as highly prone to runoff those sub-basins where extreme flood events were yet recorded in the past, remarking the reliability of the proposed assessment and suggesting that this methodology could represent a useful tool in flood managing plan.

Soil conditioners effects on hydraulic properties, leaching processes and denitrification on a silty-clay soil.

Agricultural landscapes are often affected by groundwater quality issues due to fertilizers leaching. To address this worldwide problem several agricultural best practices have been proposed, like limiting the amount of fertilizers and increasing soil organic matter content. To evaluate if these practices may promote groundwater quality enhancement, vadose zone retention time and complex biogeochemical processes must be known in detail. In this study, sequential undisturbed column experiments were performed to determine the amount of nutrients and heavy metals leached after simulated stormwater events. The column was amended with urea then flushed for two pore volumes, then straw residuals were incorporated and flushed for two pore volumes and finally compost was incorporated and flushed for six pore volumes. Dissolved ions, major gasses and heavy metals were determined in leachate samples. Nitrate and nitrite were leached in the urea treatment producing the highest concentrations, followed by compost and straw residuals. The redox conditions were aerobic in all treatments and pH was circumneutral or slightly basic. Denitrification was low but increased with the addition of straw residuals and compost. Heavy metals were all at very low concentrations except for lead and cadmium, which slightly exceeded threshold limits (10 and 1 µg/L, respectively) in all the treatments. The compost treatment, after three pore volumes, was affected by clay swelling due to sodium dispersion, which in turn provoked a reduction of porosity and hydraulic conductivity.

A novel hybrid method of specific vulnerability to anthropogenic pollution using multivariate statistical and regression analyses.

Groundwater resources are the main supply of freshwater for human activities. However, in the last fifty years aquifers have become more susceptible to chemical pollution due to human activities. The concept of groundwater vulnerability constitutes a worldwide accepted tool for water protection and planning. However, the existing methods and modified versions do not account for all the hydrogeochemical processes that drive anthropogenic pollution. The hydrogeochemical processes occurring within an aquifer can be determined using multivariate statistical analysis. In this study a specific vulnerability method named SVAP (Specific Vulnerability to Anthropogenic Pollution) is proposed. The index is based on seven quantitative parameters: depth to groundwater, recharge, nitrate losses, hydraulic resistance of the vadose zone, aquifer thickness, hydraulic conductivity of the aquifer, and slope. Weights of anthropogenic factors were determined by factor analysis and used to validate the SVAP methodology. The parameters' classification was selected according to the highest Pearson's correlation coefficient with factor weights and then grouped via a linear combination. The new index was applied in two watersheds: the Florina basin (Greece) and the Garigliano River basin (Italy), both of which possess complex hydrogeochemical regimes. The main hydrogeochemical processes acting in the study areas were identified via factor analysis, which revealed that the anthropogenic pollution in both sites was due mainly to chemical fertilizers and manure. Verification of the SVAP method produced correlation coefficients with nitrate concentrations of 0.75 and 0.62 in Florina and Garigliano, respectively. The proposed SVAP method is more reliable and flexible than standard vulnerability assessment methods and can be easily adapted for complex aquifers.

Contrasting biogeochemical processes revealed by stable isotopes of H2O, N, C and S in shallow aquifers underlying agricultural lowlands.

Lowland coastal areas as the Po Delta (Italy) are often intensively cultivated and affected by nitrogen imbalance due to fertilizers leaching to groundwater and export via run-off. To address this issue several agricultural best practices have been proposed, like limiting the amount of fertilizers and increasing soil organic matter content. In this study, groundwater samples were analysed for major ions and stable isotopes of H2O, C, N and S using multi-level sampler (MLS) from two contrasting depositional environments, one representative of alluvial plain (AP) and the other representative of a reclaimed coastal plain (RCP). In each site, controlled plots with different agriculture practice including fertilizers and tillage and compost amendment and no tillage were considered in the study. Tracer test results highlight that recharge water infiltrated at the start of the controlled study has not yet reached the saturated zone, thus current groundwater concentrations are representative of former agricultural practices. Stable isotopes show a clear distinction between different sources of nitrogen in both sites, from synthetic fertilizers to sedimentary nitrogen pool and atmospheric input. The main source of sulphate in groundwater is pyrite and fertilizers. Denitrification, sulphate reduction and methanogenesis were involved in the C, N and S cycle in the RCP site characterized by low hydraulic conductivity sediments and high SOM. These processes were not relevant in the AP site characterized by oxic condition and low SOM, but some evidence of denitrification was found in one of the AP sites. High resolution monitoring was a key tool to identify the different redox zones responsible for N, C and S cycling in these aquifers. This study shows that a clear understanding of transit times in the vadose zone is a key prerequisite to evaluate the effect of controlled agriculture practice on the quality of shallow groundwater.

Effect of ebullition and groundwater temperature on estimated dinitrogen excess in contrasting agricultural environments.

Denitrification is a key microbial-mediated reaction buffering the impact of agriculturally-derived nitrate loads. Groundwater denitrification capacity is often assessed by measuring the magnitude and patterns of dinitrogen excess, although this method can be biased by dissolved gasses exsolution and ebullition. To address this issue, shallow groundwater was sampled in two field sites via nested mini-wells on a monthly basis over an entire hydrological year and analysed for dissolved gasses, nitrate and physical parameters. Both sites are located in lowland areas of the Po River basin (Italy) and are characterized by intensive agriculture. The GUA site, a freshwater paleo-river environment, with a low content of organic matter (SOM) and oxic sub-oxic groundwater. The BAN site, a reclaimed brackish swamp environment, with abundant SOM and sulphidic-methanogenic groundwater. Groundwater samples evidenced a general deficit of dinitrogen and Argon concentrations, because of ebullition induced by a total dissolved gasses pressure exceeding the hydrostatic pressure. Ebullition was recorded only during winter at the reclaimed brackish soil and was triggered by methane exsolution. While in summer both sites were affected by ebullition because of the water table drawdown. Denitrification evaluated using dinitrogen excess via dinitrogen-Argon ratio technique, was not only affected by gas exsolution, but also by groundwater temperature fluctuations. In fact, the latter induced large biases in the calculated N2 excess even in the freshwater paleo-river environment. For these reasons, dinitrogen excess estimate with standard methods resulted to be unreliable in both lowland environments and a modified method is here presented to overcome this issue.

Intense rainfalls trigger nitrite leaching in agricultural soils depleted in organic matter.

Nitrate and ammonium are common inorganic contaminants of anthropogenic origin in many shallow aquifers around the world, while nitrite is less common, but it is most harmful than nitrate and ammonium due to its high reactivity. This paper presents evidence of nitrite accumulation after intense rainfalls in soil samples collected in an agricultural field characterized by organic matter chronic depletion. Moreover, an intact core from the same site was also collected to perform an unsaturated column experiment (60 cm long and 20 cm outer diameter) mimicking heavy rainfalls (230 mm in 2 days). Results from the field site showed nitrite accumulation (up to 0.45 mmol/kg) at 50-70 cm depth, just below the plough layer. The column experiment showed very high initial concentrations of nitrate and nitrite in the leachate and a progressive decrease of nitrate due to denitrification. The numerical flow model was calibrated versus the observed volumetric water contents and leachate flow rates. The numerical reactive transport model was calibrated versus the leachate concentrations of six dissolved species (ammonium, nitrate, nitrite, dissolved organic carbon, chloride and bromide). The optimized model resulted to be robustly calibrated providing insights on the kinetic rates driving the production, accumulation and leakage of nitrite, showing that incomplete denitrification is the source of nitrite. As far as the authors are aware, this is the first study reporting a clear link between high nitrite leaching rates and extreme rainfall events in lowland agricultural soils depleted in organic matter. The proposed methodology could be applied to quantify nitrite cycling processes in many other agricultural areas of the world affected by extreme rainfall events.

GALDIT-SUSI a modified method to account for surface water bodies in the assessment of aquifer vulnerability to seawater intrusion.

The salinization of coastal aquifers is one of the major environmental issue worldwide. Overexploitation is the most common reason of salinization, since it generates a piezometric inversion, which in turn leads to groundwater flow from the coast towards inland. This also occurs in water bodies connected to the sea like lagoons, rivers, torrents and wetlands. In this study, a modification of the GALDIT method including "SUperficial Seawater Intrusion (SUSI)" is proposed. Six new parameters were added to the classical ones. The analytical hierarchy process and the sensitivity analysis were performed for weights definition and validation of the proposed GALDIT-SUSI method. Two study areas, with different characteristics were chosen for the application of both methods: the coastal area of Epanomi (Greece) and the Po River lowland (Italy). The application of the standard GALDIT in both sites showed a poor discrimination of the vulnerability to seawater intrusion, confining it only in proximity to the coastline. Conversely, GALDIT-SUSI divided the two sites in five classes of vulnerability ranging from very low to very high, stressing the higher vulnerability of lagoons and wetland for Epanomi and lagoons and rivers for the Po River lowland. GALDIT-SUSI is easy to apply and versatile, since it can be adapted to the specific hydrogeological setting of the area of interest. Moreover, GALDIT-SUSI can be further improved to deal with other salinization mechanisms.

Direct measurement of dissolved dinitrogen to refine reactive modelling of denitrification in agricultural soils.

Nitrogen fertilizers used in agriculture often cause nitrate leaching towards shallow groundwater, especially in lowland areas where soil permeability, ploughing, clay content, and the flat topography minimizes surface runoff. The introduction of good agricultural practices to reduce the nitrate amount entering the groundwater system is crucial to ameliorate the kinetic control on nitrate denitrification capacity. With this aim, a series of anaerobic mesocosms, consisting of loamy and clay soils and nitrate rich water, were modelled using acetate and natural organic matter as electron donors. Acetate was chosen because it is the main intermediate in many biodegradation pathways of organic compounds, and hence it is a suitable carbon source for denitrification. To account for the spatial variability of soil parameters, the experiments were performed in triplicates. The geochemical code PHREEQC(3) was used to simulate kinetic denitrification, and equilibrium reactions of gas and mineral phases. The reactive modelling results highlighted a rapid acetate and nitrate degradation rate, a rapid production of dissolved inorganic carbon and dinitrogen, and a steady concentration of dissolved iron and sulphate, suggesting that the main pathway of nitrate attenuation is through denitrification; concomitantly excluding the occurrence of other processes leading to nitrate consumption. In the absence of acetate, the loamy soil, poor of natural organic matter, did not allow to complete the denitrification process. This modelling study investigates in detail the relationship between the denitrification process in natural soils, with excess and in limitation of organic substrates, and the occurrence and fate of dissolved dinitrogen analysed with a high precision membrane inlet mass spectrometer. Results demonstrate that modelling nitrate degradation processes as a whole, using geochemical datasets and codes, will improve the estimates of agricultural landscapes denitrification and support better nitrogen management, especially in lowland environments.

Multivariate statistical analysis to characterize/discriminate between anthropogenic and geogenic trace elements occurrence in the Campania Plain, Southern Italy.

Shallow aquifers are the most accessible reservoirs of potable groundwater; nevertheless, they are also prone to various sources of pollution and it is usually difficult to distinguish between human and natural sources at the watershed scale. The area chosen for this study (the Campania Plain) is characterized by high spatial heterogeneities both in geochemical features and in hydraulic properties. Groundwater mineralization is driven by many processes such as, geothermal activity, weathering of volcanic products and intense human activities. In such a landscape, multivariate statistical analysis has been used to differentiate among the main hydrochemical processes occurring in the area, using three different approaches of factor analysis: (i) major elements, (ii) trace elements, (iii) both major and trace elements. The elaboration of the factor analysis approaches has revealed seven distinct hydrogeochemical processes: i) Salinization (Cl-, Na+); ii) Carbonate rocks dissolution; iii) Anthropogenic inputs (NO3-, SO42-, U, V); iv) Reducing conditions (Fe2+, Mn2+); v) Heavy metals contamination (Cr and Ni); vi) Geothermal fluids influence (Li+); and vii) Volcanic products contribution (As, Rb). Results from this study highlight the need to separately apply factor analysis when a large data set of trace elements is available. In fact, the impact of geothermal fluids in the shallow aquifer was identified from the application of the factor analysis using only trace elements. This study also reveals that the factor analysis of major and trace elements can differentiate between anthropogenic and geogenic sources of pollution in intensively exploited aquifers.