Proposal for an integrated method of natural background levels assessment in groundwater

Natural Background Level (NBL), geochemical approach, statistical methods

Arsenic-fluoride co-contamination in groundwater: Background and anomalies in a volcanic-sedimentary aquifer in central Italy

Abstract In a volcanic-sedimentary aquifer in central Italy, we investigate the co-existence of arsenic and fluoride in groundwater, aiming at identifying the most probable processes deductible at regional/groundwater body scale leading to the observed co-contamination in groundwater. Further, the areas at risk for human health where high concentrations can produce a significant risk to human health have been investigated. The study area is located in Latium (Central Italy) where silica-undersaturated alkali-potassic formations of Plio-Pleistocene age largely outcrop above marine and continental sand and clay deposits (Neogene) and continental alluvial deposits (Lower Pleistocene–Middle Pleistocene). Geochemical data from groundwater at 322 wells and 76 springs have been analyzed through statistical methods including clustering/PCA and geostatistical analysis. The results show exceedances of the drinking water standards for F (1.5 mg/L) and As (10.0 μg/L) in 29% and 55% of the sampled groundwater, respectively. Multivariate statistics suggest a widespread process of water-rock interaction with the K-alkaline volcanic formations releasing As, F, K, Si, V, Rb and PO4 to the groundwater. As and F show a good correlation (Pearson's r = 0.61, Spearman's rs = 0.59) and define a separate PCA component, confirming that their background in groundwater might be governed by a common process. Kriging interpolations have been used to study the spatial distribution of the two parameters, identifying areas with the highest concentrations and highest probability of exceeding the standards for human consumption. Moreover, by resampling the As-F data with the jackknife technique it was possible to identify the variations of their correlation index in the study area, due to specific As or F anomalies. While in the peripheral areas of the volcanic districts, dominated by sedimentary deposits, the As-F correlation index does not present important fluctuations, Indicator Kriging shows specific As or F correlation anomalies within the volcanic groundwater bodies and along the Tyrrhenian coastline. These anomalies seem to correspond to the zones with the highest thermal flux and/or are located near important structural lineaments. Fluoride correlation anomalies close to mining sites (fluorite) have also been observed. We hypothesize that, unlike the regional co-contamination, these local anomalies are related to the upwelling of geothermal fluids along fracture/fault systems that mix with cold groundwater, or to the interaction with mineral deposits particularly enriched of these elements

A proposal for groundwater sampling guidelines: application to a case study in Southern Latium

Groundwater monitoring , body status,  best sampling techniques,  quaternary alluvial,  pyroclastic deposit

Physiological Profiling and Functional Diversity of Groundwater Microbial Communities in a Municipal Solid Waste Landfill Area

The disposal of municipal solid wastes in landfills represents a major threat for aquifer environments at the global scale. The aim of this study was to explore how groundwater geochemical characteristics can influence the microbial community functioning and the potential degradation patterns of selected organic substrates in response to different levels of landfill-induced alterations. Groundwaters collected from a landfill area were monitored by assessing major physical-chemical parameters and the microbiological contamination levels (total coliforms and fecal indicators—Colilert-18). The aquatic microbial community was further characterized by flow cytometry and Biolog EcoPlatesTM assay. Three groundwater conditions (i.e., pristine, mixed, and altered) were identified according to their distinct geochemical profiles. The altered groundwaters showed relatively higher values of organic matter concentration and total cell counts, along with the presence of fecal indicator bacteria, in comparison to samples from pristine and mixed conditions. The kinetic profiles of the Biolog substrate degradation showed that the microbial community thriving in altered conditions was relatively more efficient in metabolizing a larger number of organic substrates, including those with complex molecular structures. We concluded that the assessment of physiological profiling and functional diversity at the microbial community level could represent a supportive tool to understand the potential consequences of the organic contamination of impacted aquifers, thus complementing the current strategies for groundwater management

Assessing Natural Background Levels in the Groundwater Bodies of the Apulia Region (Southern Italy)

Defining natural background levels (NBL) of geochemical parameters in groundwater is a key element for establishing threshold values and assessing the environmental state of groundwater bodies (GWBs). In the Apulia region (Italy), carbonate sequences and clastic sediments host the 29 regional GWBs. In this study, we applied the Italian guidelines for the assessment of the NBLs, implementing the EU Water Framework Directive, in a south-European region characterized by the typical Mediterranean climatic and hydrologic features. Inorganic compounds were analyzed at GWB scale using groundwater quality data measured half-yearly from 1995 to 2018 in the regional groundwater monitoring network (341 wells and 20 springs). Nitrates, chloride, sulfate, boron, iron, manganese and sporadically fluorides, boron, selenium, arsenic, exceed the national standards, likely due to salt contamination along the coast, agricultural practices or natural reasons. Monitoring sites impacted by evident anthropic activities were excluded from the dataset prior to NBL calculation using a web-based software tool implemented to automate the procedure. The NBLs resulted larger than the law limits for iron, manganese, chlorides, and sulfates. This methodology is suitable to be applied in Mediterranean coastal areas with high anthropic impact and overexploitation of groundwater for agricultural needs. The NBL definition can be considered one of the pillars for sustainable and long-term groundwater management by tracing a clear boundary between natural and anthropic impacts

eNaBLe, an On-Line Tool to Evaluate Natural Background Levels in Groundwater Bodies

Inorganic compounds in groundwater may derive from both natural processes and anthropogenic activities. The assessment of natural background levels (NBLs) is often useful to distinguish these sources. The approaches for the NBLs assessment can be classified as geochemical (e.g., the well-known pre-selection method) or statistical, the latter involving the application of statistical procedures to separate natural and anthropogenic populations. National Guidelines for the NBLs assessment in groundwater have been published in Italy (ISPRA 155/2017), based mainly on the pre-selection method. The Guidelines propose different assessment paths according to the sample size in spatial/temporal dimension and the type of the distribution of the pre-selected dataset, taking also into account the redox conditions of the groundwater body. The obtained NBLs are labelled with a different confidence level in function of number of total observations/monitoring sites, extension of groundwater body and aquifer type (confined or unconfined). To support the implementation of the Guidelines, the on-line tool evaluation of natural background levels (eNaBLe), written in PHP and using MySQL as DBMS (DataBase Management System), has been developed. The main goal of this paper is to describe the functioning of eNaBLe and test the tool on a case study in central Italy. We calculated the NBLs of As, F, Fe and Mn in the southern portion of the Mounts Vulsini groundwater body, within the volcanic province of Latium (Central Italy), also separating the reducing and oxidizing facies. Specific results aside, this study allowed to verify the functioning and possible improvements of the online tool and to identify some criticalities in the procedure NBLs assessment at the groundwater body scal

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

Lycopene in atherosclerosis prevention: an integrated scheme of the potential mechanisms of action from cell culture studies.

Increasing evidence suggests that lycopene may protect against atherosclerosis, although, the exact mechanism(s) is still unknown. Because lycopene is an efficient antioxidant, it has been proposed for a long time that this property may be responsible for its beneficial effects. Consistent with this, the carotenoid has been demonstrated to inhibit ROS production in vitro and to protect LDL from oxidation. However, recently, other mechanisms have been evoked and include: prevention of endothelial injury; modulation of lipid metabolism through a control of cholesterol synthesis and oxysterol toxic activities; reduction of inflammatory response through changes in cytokine production; inhibition of smooth muscle cell proliferation through regulation of molecular pathways involved in cell proliferation and apoptosis. Focusing on cell culture studies, this review summarizes the experimental evidence for a role of lycopene in the different phases of atherosclerotic process