Water-Rock Interaction Processes: A Local Scale Study on Arsenic Sources and Release Mechanisms from a Volcanic Rock Matrix.

Arsenic is a potentially toxic element (PTE) that is widely present in groundwater, with concentrations often exceeding the WHO drinking water guideline value (10.0 µg/L), entailing a prominent risk to human health due to long-term exposure. We investigated its origin in groundwater in a study area located north of Rome (Italy) in a volcanic-sedimentary aquifer. Some possible mineralogical sources and main mechanisms governing As mobilization from a representative volcanic tuff have been investigated via laboratory experiments, such as selective sequential extraction and dissolution tests mimicking different release conditions. Arsenic in groundwater ranges from 0.2 to 50.6 µg/L. It does not exhibit a defined spatial distribution, and it shows positive correlations with other PTEs typical of a volcanic environment, such as F, U, and V. Various potential As-bearing phases, such as zeolites, iron oxyhydroxides, calcite, and pyrite are present in the tuff samples. Arsenic in the rocks shows concentrations in the range of 17-41 mg/kg and is mostly associated with a minor fraction of the rock constituted by FeOOH, in particular, low crystalline, containing up to 70% of total As. Secondary fractions include specifically adsorbed As, As-coprecipitated or bound to calcite and linked to sulfides. Results show that As in groundwater mainly originates from water-rock interaction processes. The release of As into groundwater most likely occurs through desorption phenomena in the presence of specific exchangers and, although locally, via the reductive dissolution of Fe oxy-hydroxides.

Groundwater quality trend and trend reversal assessment in the European Water Framework Directive context: an example with nitrates in Italy.

Groundwater resources are of utmost importance in sustaining water related ecosystems, including humans. The long-lasting impacts from anthropogenic activities require early actions, owing to the natural time lag in groundwater formation and renewal. The European Union (EU) policy, within the implementation of the Water Framework Directive (WFD), requires Member States to identify and reverse any significant and sustained upward trend in the concentration of pollutants, defining specific protection measures to be included in the River Basin Management Plans (RBMP). In Italy, official guidelines for trend and trend reversal assessment have been published recently. Statistical methods, such as the Mann-Kendall test for trend analysis and the Sen's method for estimating concentration scenarios, should be applied at the fixed terms stated by the WFD implementation cycles to identify upward trends, while the Pettitt test is proposed for the identification of trend reversal. In this paper, we present an application of a slightly modified version of the Italian Guidelines to a groundwater body in Northern Italy featuring nitrate pollution and discuss its advantages and limitations. In addition to Pettitt test, for the trend reversal analysis, we apply the Mann-Kendall test in two sections and compare the results. We conclude that this method seems more reliable than Pettitt test to identify a reversal point in quality time series. The overall procedure can be easily applied to any groundwater body defined at risk across Europe, for the assessment of the upward trends of pollutants and their reversal, even with little chemical monitoring data. Although focused on the EU legislative framework, this procedure may be relevant for a wider context, allowing to individuate upward trend as early warning for contamination processes in an integrated water resources management context.

A multi-method approach for the assessment of natural background levels in groundwater.

The assessment of geochemical Natural Background Levels (NBLs) in groundwater, aims at distinguishing the naturally high levels of geogenic compounds from anthropogenic pollution. This is a fundamental issue in groundwater management, in particular when the concentration of inorganic compounds exceeds the threshold values set for the evaluation of the groundwater chemical status, as requested by environmental regulations. In this paper, we describe a new procedure that integrates the pre-selection method and statistical techniques, using the example of two case studies. The pre-selection aims to identify suitable groundwater samples for the NBLs assessment. The nitrate concentration threshold, for the removal of the groundwater samples affected by human activities, is established locally through different graphical and statistical approaches. Then, the statistical distribution of each compound is analyzed and the outliers are identified. Normality tests on the datasets allow one to select the most appropriate value, e.g. one percentile, to be adopted as NBL within the data distribution. In the selected case studies, we have defined the NBLs for As, F, Mn, Fe and SO4. The two sites are part of a volcanic-sedimentary aquifer in central Italy, where the geochemical background is frequently well above the standards for human consumption. The results of the simple and easily reproducible pre-selection method are strengthened by integration with statistical techniques, notably in selecting the appropriate percentile. New criteria are suggested for the choice of the nitrate threshold to be used for the pre-selection of uncontaminated samples.

Disentangling natural and anthropogenic impacts on groundwater by hydrogeochemical, isotopic and microbiological data: Hints from a municipal solid waste landfill.

Within human-impacted areas, high levels of inorganic compounds in groundwater are broadly and preventively attributed to local anthropogenic pollution, thoroughly disregarding geogenic natural background levels. Particularly in landfills, a proper evaluation of the significant adverse environmental effects should be completed through a detailed groundwater characterization, and appropriate reference values established prior to landfill onset. However, the monitoring network may lack a full hydrogeological representativeness of the site and of the background conditions of groundwater. This study aimed at disentangling natural and anthropogenic impacts through a synoptic analysis of hydrogeochemical, isotopic and microbiological characteristics of groundwaters from a municipal solid waste landfill area in Central Italy. Samples were collected during four seasonal monitoring surveys from the mostly anoxic aquifer underlying the target area. Field parameters, inorganic and organic compounds, environmental isotopes, faecal contamination, and microbial community characteristics were determined, along with a detailed hydrogeological conceptual model. Key inorganic contaminants (As, Fe and Mn) exceeded the local threshold values in most of the sampling points, while organic contamination was generally very low. Stable isotopes suggested that groundwater originated mainly from local rainfall, except at one monitoring points where tritium levels might indicate moderate impact. Microbiological data and the microbial community characterization, assessed by flow cytometry and BIOLOG assays, provided further supportive information, also highlighting fundamental effects of groundwater quality alterations. Overall, an integrated multi-parametric approach proved suitable to distinguish geogenic and anthropogenic impacts, thus improving strategies and schemes for protection and management of groundwaters in landfills and waste related industrial areas.