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.

Deriving environmental quality standards for perfluorooctanoic acid (PFOA) and related short chain perfluorinated alkyl acids.

The evidence that in Northern Italy significant sources of perfluoroalkylacids (PFAA) are present induced the Italian government to establish a Working Group on Environmental Quality Standard (EQS) for PFAA in order to include some of them in the list of national specific pollutants for surface water monitoring according to the Water Framework Directive (2000/60/EC). The list of substances included perfluorooctanoate (PFOA) and related short chain PFAA such as perfluorobutanoate (PFBA), perfluoropentanoate (PFPeA), perfluorohexanoate (PFHxA) and perfluorobutanesulfonate (PFBS), which is a substitute of perfluorooctanesulfonate. For each of them a dossier collects available data on regulation, physico-chemical properties, emission and sources, occurrence, acute and chronic toxicity on aquatic species and mammals, including humans. Quality standards (QS) were derived for the different protection objectives (pelagic and benthic communities, predators by secondary poisoning, human health via consumption of fishery products and water) according to the European guideline. The lowest QS is finally chosen as the relevant EQS. For PFOA a QS for biota was derived for protection from secondary poisoning and the corresponding QS for water was back-calculated, obtaining a freshwater EQS of 0.1µgL-1. For PFBA, PFPeA, PFHxA and PFBS threshold limits proposed for drinking waters were adopted as EQS.

Combining natural background levels (NBLs) assessment with indicator kriging analysis to improve groundwater quality data interpretation and management.

The natural background level (NBL) concept is revisited and combined with indicator kriging method to analyze the spatial distribution of groundwater quality within a groundwater body (GWB). The aim is to provide a methodology to easily identify areas with the same probability of exceeding a given threshold (which may be a groundwater quality criteria, standards, or recommended limits for selected properties and constituents). Three case studies with different hydrogeological settings and located in two countries (Portugal and Italy) are used to derive NBL using the preselection method and validate the proposed methodology illustrating its main advantages over conventional statistical water quality analysis. Indicator kriging analysis was used to create probability maps of the three potential groundwater contaminants. The results clearly indicate the areas within a groundwater body that are potentially contaminated because the concentrations exceed the drinking water standards or even the local NBL, and cannot be justified by geogenic origin. The combined methodology developed facilitates the management of groundwater quality because it allows for the spatial interpretation of NBL values.

The sustainable pumping rate concept: lessons from a case study in central Italy.

The term sustainable pumping rate (SPR) is defined as the maximum pumping rate that can be maintained indefinitely without mining an aquifer, and is different from the concept of safe yield (SY), which takes into account also aspects related to the much wider concept of sustainability. The assessment of the SPR for the case study of Petrignano d'Assisi, an alluvial aquifer located in Central Italy, shows the need for a reliable estimate of the global water budget of the aquifer, particularly of the recharge under undisturbed conditions; however, the latter is not sufficient, because the SPR is affected also by the geometry of the aquifer, the hydraulic conductivity pattern, the variation of recharge/discharge ratio induced by the abstractions, and so on. All these aspects are analyzed by means of a numerical flow model calibrated both under undisturbed conditions (1974) and under exploitation conditions (1998 to 2004). The steady-state modeling results show that the relation between recharge and abstractions both at local and global scale is a key point in order to estimate a long-term SPR. Moreover, as it could be necessary to overexploit the aquifer for short periods, e.g., during drought episodes, the estimate of SPR must be performed also in transient conditions, in order to take into account the characteristic time of depletion and the successive recovery.