Geochemistry, stable isotopes and statistic tools to estimate threshold and source of nitrate in groundwater (Sardinia, Italy).

In the European Union, nitrate vulnerable zone (NVZ) should be designed for the mitigation of nitrate (NO3-) contamination caused by agricultural practices. Before establishing new NVZ, the sources of NO3- must be recognized. A geochemical and multiple stable isotopes approach (hydrogen, oxygen, nitrogen, sulfur and boron) and statistical tools were applied to define the geochemical characteristics of groundwater (60 samples), calculate the local NO3- threshold and assess potential sources of NO3- contamination in two study areas (hereafter Northern and Southern), located in a Mediterranean environment (Sardinia, Italy). Results of the integrated approach applied to two case study, permits to highlight the strengths of integrating geochemical and statistical methods to provide nitrate source identification as a reference by decision makers to remediate and mitigate nitrate contamination in groundwater. Hydrogeochemical features in the two study areas were similar: near neutral to slightly alkaline pH, electrical conductivity in the range of 0.3 to 3.9 mS/cm, and chemical composition ranging from Ca-HCO3- at low salinity to Na-Cl- at high salinity. Concentrations of NO3- in groundwater were in the range of 1 to 165 mg/L, whereas the nitrogen reduced species were negligible, except few samples having NH4+ up to 2 mg/L. Threshold values in the studied groundwater samples were between 4.3 and 6.6 mg/L NO3-, which was in agreement with previous estimates in Sardinian groundwater. Values of δ34S and δ18OSO4 of SO42- in groundwater samples indicated different sources of SO42-. Sulfur isotopic features attributed to marine SO42- were consistent with groundwater circulation in marine-derived sediments. Other source of SO42- were recognize due to the oxidation of sulfide minerals, to fertilizers, manure, sewage fields, and SO42- derived from a mix of different sources. Values of δ15N and δ18ONO3 of NO3- in groundwater samples indicated different biogeochemical processes and NO3- sources. Nitrification and volatilization processes might have occurred at very few sites, and denitrification was likely to occur at specific sites. Mixing among various NO3- sources in different proportions might account for the observed NO3- concentrations and the nitrogen isotopic compositions. The SIAR modeling results showed a prevalent NO3- source from sewage/manure. The δ11B signatures in groundwater indicated the manure to be the predominant NO3- source, whereas NO3- from sewage was recognized at few sites. Geographic areas showing either a predominant process or a defined NO3- source where not recognize in the studied groundwater. Results indicate widespread contamination of NO3- in the cultivated plain of both areas. Point sources of contamination, due to agricultural practices and/or inadequate management of livestock and urban wastes, were likely to occur at specific sites.

Detailed Geogenic Radon Potential Mapping Using Geospatial Analysis of Multiple Geo-Variables-A Case Study from a High-Risk Area in SE Ireland.

A detailed investigation of geogenic radon potential (GRP) was carried out near Graiguenamanagh town (County Kilkenny, Ireland) by performing a spatial regression analysis on radon-related variables to evaluate the exposure of people to natural radiation (i.e., radon, thoron and gamma radiation). The study area includes an offshoot of the Caledonian Leinster Granite, which is locally intruded into Ordovician metasediments. To model radon release potential at different points, an ordinary least squared (OLS) regression model was developed in which soil gas radon (SGR) concentrations were considered as the response value. Proxy variables such as radionuclide concentrations obtained from airborne radiometric surveys, soil gas permeability, distance from major faults and a digital terrain model were used as the input predictors. ArcGIS and QGIS software together with XLSTAT statistical software were used to visualise, analyse and validate the data and models. The proposed GRP models were validated through diagnostic tests. Empirical Bayesian kriging (EBK) was used to produce the map of the spatial distribution of predicted GRP values and to estimate the prediction uncertainty. The methodology described here can be extended for larger areas and the models could be utilised to estimate the GRPs of other areas where radon-related proxy values are available.

A Study of Natural Radioactivity Levels and Radon/Thoron Release Potential of Bedrock and Soil in Southeastern Ireland.

Radon (222Rn) and thoron (220Rn) account for almost two-thirds of the annual average radiation dose received by the Irish population. A detailed study of natural radioactivity levels and radon and thoron exhalation rates was carried out in a legislatively designated "high radon" area, as based on existing indoor radon measurements. Indoor radon concentrations, airborne radiometric data and stream sediment geochemistry were collated, and a set of soil samples were taken from the study area. The exhalation rates of radon (E222Rn) and thoron (E220Rn) for collected samples were determined in the laboratory. The resultant data were classified based on geological and soil type parameters. Geological boundaries were found to be robust classifiers for radon exhalation rates and radon-related variables, whilst soil type classification better differentiates thoron exhalation rates and correlated variables. Linear models were developed to predict the radon and thoron exhalation rates of the study area. Distribution maps of radon and thoron exhalation rates (range: E222Rn [0.15-1.84] and E220Rn [475-3029] Bq m-2 h-1) and annual effective dose (with a mean value of 0.84 mSv y-1) are presented. For some parts of the study area, the calculated annual effective dose exceeds the recommended level of 1 mSv y-1, illustrating a significant radiation risk. Airborne radiometric data were found to be a powerful and fast tool for the prediction of geogenic radon and thoron risk. This robust method can be used for other areas where airborne radiometric data are available.

Stream water chemistry in the arsenic-contaminated Baccu Locci mine watershed (Sardinia, Italy) after remediation.

The abandoned Pb-As Baccu Locci mine represents the first and only case of mine site remediation in Sardinia, Italy. Arsenic is the most relevant environmental concern in the Baccu Locci stream watershed, with concentrations in surface waters up to and sometimes over 1 mg/L. The main remediation action consisted in creation of a "storage site", for the collection of contaminated materials from different waste-rock dumps and most of tailings piles occurring along the Baccu Locci stream. This paper reports preliminary results on the level of contamination in the Baccu Locci stream after the completion of remediation measures. Post-remediation stream water chemistry has not substantially changed compared to the pre-remediation situation. In particular, dissolved As maintains an increasing trend along the Baccu Locci stream, with a concentration of about 400 µg/L measured at a distance of 7 km from the storage site. Future monitoring will provide fundamental information on the effectiveness of remediation actions conducted and their applicability to other mine sites in Sardinia. At the stage of mine site characterisation of future remediation plans, it is recommended to pay more attention to the understanding of mineralogical and geochemical processes responsible for pollution. Moreover, mixing of materials with different composition and reactivity in a storage site should require careful consideration and long-term leaching tests.

Benthic foraminifera as bio-indicators of trace element pollution in the heavily contaminated Santa Gilla lagoon (Cagliari, Italy).

In order to assess the response of benthic foraminifera to trace element pollution, a study of benthic foraminiferal assemblages was carried out into sediment samples collected from the Santa Gilla lagoon (Sardinia, Italy). The lagoon has been contaminated by industrial waste, mainly trace elements, as well as by agricultural and domestic effluent. The analysis of surficial sediment shows enrichment in trace elements, including Cr, Cu, Hg, Ni, Pb and Zn. Biotic and abiotic data, analyzed with multivariate techniques of statistical analysis, reveal a distinct separation of both the highly polluted and less polluted sampling sites. The innermost part of the lagoon, comprising the industrial complex at Macchiareddu, is exposed to a high load of trace elements which are probably enhanced by their accumulation in the finer sediment fraction. This area reveals lower diversity and higher percentages of abnormalities when compared to the outermost part of the lagoon.

The chemical state of arsenic in minerals of environmental interest--an XPS and an XAES study.

A systematic analytical study using X-ray photoelectron spectroscopy (XPS) and X-ray induced Auger electron spectroscopy (XAES) has been carried out to characterize the chemical state of arsenic in complex environmental samples. The conventional approach, which relies on the chemical shift of the core levels As3d, provides ambiguous results in determining the chemical environment of arsenic. A more accurate approach, based on the Auger parameter and on the Wagner (Chemical State) plot, which combines AsLMM kinetic energy and As3d binding energy, was adopted. This novel method for determining the chemical state of arsenic was employed to completely characterize arsenic in complex environmental samples.