Hydrogeochemical and isotopic characterization of the Gioia Tauro coastal Plain (Calabria - southern Italy): A multidisciplinary approach for a focused management of vulnerable strategic systems.

This work pursues the hydro-geochemical and isotopic characterization of the complex groundwater system of the Gioia Tauro Plain, one of the most important industrialized and agricultural coastal areas of southern Italy. The anthropic pressure exposes the water resources at risk of depletion and quality degradation making the plain groundwater a system of high scientific and social interest. The plain is characterized by a shallow aquifer, mostly recharged by local rains and a deep aquifer apparently less influenced by local precipitation. Both aquifers are mainly Ca-HCO3 waters except for localized sectors where Na-HCO3, Na-Cl and Ca-SO4 waters are present. In deep aquifer, both prolonged interaction with sedimentary rocks, mainly deriving from the erosion of crystalline rocks, and direct cation exchange represent the primary factors controlling the formation of Na-HCO3 waters. Mixing processes between these waters and either connate brine and/or deep thermal waters contribute to the formation of isolated high salinity Na-Cl-rich waters. In shallow aquifer, inputs of N-rich sewage and agriculture-related contaminants, and SOx emissions in proximity of the harbor are responsible of the increasing nitrate and sulphate concentrations, respectively. The Cl/Br and NO3/Cl ratios highlight contamination mainly linked to agricultural activities and contribution of wastewater. Along the northern boundary, the warmest groundwater (Na-Cl[SO4]) were found close to a bend of the main strike-slip fault system, locally favouring the rising of B- and Li-rich deep waters, testifying the influence of geological-structural features on deep water circulation. Despite the high-water demand, a direct marine intrusion is localized in a very restricted area, where we observed an incipient groundwater-seawater mixing (seawater contribution ≤7 %). The qualitative and quantitative conditions of the shallow aquifer still have acceptable levels because of the relatively high recharge inflow. A reliable hydrogeochemical conceptual model, able to explain the compositional variability of the studied waters, is proposed.

Use of reaction path modelling to investigate the evolution of water chemistry in shallow to deep crystalline aquifers with a special focus on fluoride.

Crystalline aquifers are layered systems in which the hydrogeological path of waters extends from highly weathered, shallow and porous rocks to poorly weathered, deep and fissured rocks. This varying hydrogeological setting influences the water chemistry in different ways. The paper aims to reconstruct the water-rock interaction process in these various environments starting from a solid reactant represented by an average granite rock and several waters from the shallow aquifer. Afterwards, the water-rock interaction processes occurring in the deep environment are reconstructed, varying the geochemical conditions (primary reactants, secondary mineral phases allowed to precipitate, fO2 and fCO2), with a special focus on fluoride (F-). The evolution from the F-poor, Ca-HCO3 facies to the F-rich, Na-HCO3 water type of high pH was simulated using reaction path modelling. The obtained results show that the theoretical evolution trends well reproduce both shallow and deep water samples providing detailed information on the behavior of fluoride and other relevant constituents (i.e., Na, K, Ca, Mg, SiO2). The performed model represents a flexible and powerful tool for environmental research, applicable in other areas hosting F-rich groundwater.

Arsenic polluted waters: Application of geochemical modelling as a tool to understand the release and fate of the pollutant in crystalline aquifers.

Arsenic (As) is one of the most investigated elements worldwide due to its negative impact on the natural system. Its geochemical behavior depends on several geogenic processes, which can cause hazardous enrichment into natural waters, even in remote areas, far from anthropogenic sources. In this work the arsenic pollution issue has been addressed by studying water-rock interaction processes and applying reaction path modelling as a tool to understand the rock-to-water release of As and the fate of this natural pollutant in crystalline aquifers. In-depth geochemical characterization of several water samples discharging from crystalline aquifers was performed. The obtained data were used to fix the boundary conditions and validate the modelling outcomes. The performed modelling allowed to reconstruct the water-rock interaction processes which occur (i) in shallow and relatively shallow crystalline aquifers in which no As anomalies were observed and (ii) in As-rich areas, coupling reaction path modelling of granite dissolution with adsorption of dissolved As onto precipitating crystalline and amorphous Fe(III)-oxyhydroxides given the widespread presence of these phases in the studied environment. The results of the geochemical modelling are in agreement with the analytical data and reproduce them satisfactorily. The performed geochemical modelling is of high environmental significance because it is a flexible and powerful tool that correctly defines the water-rock interaction processes occurring in crystalline aquifers, providing valuable data to improve the knowledge on As behavior, not only in the study area, but also in similar geological settings worldwide. Therefore, the present research has broad future perspectives in the environmental field.

A multivariate non-parametric approach for estimating probability of exceeding the local natural background level of arsenic in the aquifers of Calabria region (Southern Italy).

The concept of natural background level (NBL) aims at distinguishing the natural and anthropogenic contributions to concentrations of specific contaminants, as groundwater management and protection tools. This is usually defined as a unique value at a regional scale, even when the hydrogeological and geochemical features of a certain territory are far from homogeneous. The concentration of target contaminants is affected by multiple hydrogeochemical processes. This is the case of arsenic in the Calabria region, where concentrations are definitely variable in groundwater. To overcome the limitation of a traditional approach and to include the intrinsic hydrogeological and geochemical heterogeneity into the definition of the natural contribution to As content in groundwater, an integrated probabilistic approach to the NBL assessment combining aquifer-based preselection criteria and multivariate non-parametric geostatistics was proposed. In detail, different NBL values were selected, based on the aquifer type and/or hydrogeochemical features. Then, these aquifer-based NBL values of arsenic were used in the Probability Kriging method to map the probability of exceedance and to provide contamination risk management tools. This multivariate geostatistical approach that takes advantage of the physico-chemical variables used in the aquifer-based NBL values definition allowed mapping the probability of exceedance of As in a physically-based way. The hydrogeochemical diversity of the study area and all the processes affecting As concentrations in the aquifers have been considered too. As a result, the obtained map was characterized by a short-range and long-range variability due to local hydrogeochemical anomalies and water-rock interaction and/or atmospheric precipitation. By this approach, the NBL exceedance probability maps proved to be less "noisy", because the local hydrogeochemical conditions were filtered, and more capable of pointing out anthropogenic inputs or very anomalous natural contributions, which need to be investigated more in detail and properly managed.

Geochemical modeling of chromium release in natural waters and treatment by RO/NF membrane processes.

In this work, a geochemical approach was used as strong-scientific tool for pre-selection of suitable remediation systems to treat Cr-contaminated groundwaters. The geochemical characterization allowed to select Nanofiltration (NF) and Reverse Osmosis (RO) as suitable remediation processes, whereas through a new geochemical modeling, the evolution of water chemistry during the water-rock interaction was also studied. The new reaction path modelling was performed re-evaluating the role of Fe as main oxidant in the system and the analytic concentrations of relevant solutes, including Cr(VI), were reproduced. The spring with the highest Cr(VI) content was treated to lower its concentration below the threshold values. A laboratory-scale set-up was used to carry out both NF and RO experiments. The experiments were conducted on different commercial membranes varying the operating pressures. The results showed high Cr(VI) rejections (around 95%) for all tested membranes, leading to Cr(VI) concentrations below the threshold limits. The high flux, obtained already at lower operating pressures, combined with high selectivity towards Cr(VI) makes NF a favorable remediation option.