Spatial distribution, geochemical processes of high-content fluoride and nitrate groundwater, and an associated probabilistic human health risk appraisal in the Republic of Djibouti.

In the northern East African Rift System, the Republic of Djibouti relies exclusively on groundwater, with levels of fluoride (up to 14 mg/L) and nitrate (up to 256 mg/L) posing potential health risks. To address this, 362 samples were considered, including 133 shallow groundwater samples, along with new and previously published data dating back to 2012 on deep (88) and thermal (141) groundwater samples. To understand the enrichment mechanisms, dissolved anion and cation constituents, geochemical and thermodynamic tools, and stable isotope ratios, such as δ2H(H2O), δ18O(H2O), δ15N(NO3-), and δ18O(NO3-), were used. In particular, two activity diagrams (Mg2+ vs. Ca2+ and Na+ vs. Ca2+), focused on aqueous and solid fluoride species in an updated thermodynamic dataset of 15 fluoride-bearing minerals, are shown for the first time. The dataset offers new and valuable insights into fluoride geochemistry (classic thermodynamic datasets combined with geochemical codes rely solely on fluorapatite and fluorite F-bearing minerals). Activity diagrams and geochemical modeling indicate that mineral dissolution primarily drives groundwater fluoride enrichment in all water types, whereas the elevated nitrate levels may stem from organic fertilizers like animal manure, as indicated by nitrate isotopes and NO3-/Cl- vs Cl- diagrams. Despite the arid climate and 2H18O enrichment in shallow waters, evaporation seems to play a minor role. Monte Carlo simulations and sensitivity analysis were used to assess the health risks associated with elevated F- and NO3- concentrations. Mapping-related spatial distribution analysis identified regional contamination hotspots using a global Moran's I and GIS tools. One fluoride and three nitrate contamination hotspots were identified at a p-value of 0.05. Groundwater chemistry revealed that 88 % of groundwater being consumed exceeded the permissible levels for fluoride and nitrate, posing potential health risks, particularly for teenagers and children. This study pinpoints specific areas with excessive nitrate and fluoride contamination, highlighting a high non-carcinogenic risk.

Climate change and its effect on groundwater quality.

Knowing water quality at larger scales and related ground and surface water interactions impacted by land use and climate is essential to our future protection and restoration investments. Population growth has driven humankind into the Anthropocene where continuous water quality degradation is a global phenomenon as shown by extensive recalcitrant chemical contamination, increased eutrophication, hazardous algal blooms, and faecal contamination connected with microbial hazards antibiotic resistance. In this framework, climate change and related extreme events indeed exacerbate the negative trend in water quality. Notwithstanding the increasing concern in climate change and water security, research linking climate change and groundwater quality remain early. Additional research is required to improve our knowledge of climate and groundwater interactions and integrated groundwater management. Long-term monitoring of groundwater, surface water, vegetation, and land-use patterns must be supported and fortified to quantify baseline properties. Concerning the ways climate change affects water quality, limited literature data are available. This study investigates the link between climate change and groundwater quality aquifers by examining case studies of regional carbonate aquifers located in Central Italy. This study also highlights the need for strategic groundwater management policy and planning to decrease groundwater quality due to aquifer resource shortages and climate change factors. In this scenario, the role of the Society of Environmental Geochemistry is to work together within and across geochemical environments linked with the health of plants, animals, and humans to respond to multiple challenges and opportunities made by global warming.

Origin of nitrate and sulfate sources in volcano-sedimentary aquifers of the East Africa Rift System: An example of the Ali-Sabieh groundwater (Republic of Djibouti).

Within the East African Rift System (EARS), the complex Ali-Sabieh aquifers system, located in the south of the Republic of Djibouti, was overexploited and subjected to anthropogenic and/or geogenic pollution with high concentrations of dissolved nitrate (up to 181 mg/l) and sulfates (up to 1540 mg/l). This study is the first undertaken on the hydrochemistry of this aquifer system, combining geochemical tools and multi-isotope - δ2H(H2O), δ18O(H2O), δ18O(SO4), δ34S(SO4), δ15N(NO3), δ18O(NO3), δ13C(DIC), and 14C- was used to decipher the origin and fate of different nitrate and sulfate sources to groundwater. The groundwater samples of the region show a chemical evolution from fresh Ca(Na)-bicarbonate to brackish Na-Cl , mainly due to water-rock interaction. The combined chloride and water isotope data show that evaporation and transpiration are present, with the latter occurring primarily in the shallow alluvial aquifer waters. Inspection of δ15N(NO3) vs. δ18O(NO3) and NO3/Cl vs. Cl diagrams show that dissolved nitrates are primarily of anthropogenic origin. In particular, higher nitrate concentrations may be related to animal manure used as organic fertilizers during agricultural activities. Sulfates are from a natural origin related to the interaction of water with gypsum of hydrothermal or sedimentary origin. SO4/Cl ratio and isotopic composition show that dissolved sulfates in saline and ancient groundwater of the Cretaceous sandstone aquifer (between 7.4 ± 2.2 and 5.8 ± 1.4 k-years before the present) are generated by interaction with gypsum from oxidation of pre-existing (Jurassic?) sulfides. This work highlight that isotopic ratios of the two molecules -δ18O(SO4), δ34S(SO4), δ15N(NO3), δ18O(NO3)- are not sufficient for tracing the origin of nitrate and sulfates in groundwater, but that a complete hydrogeochemical study is needed. In the absence of this, the relatively high concentration of chloride and sulfates could be wrongly linked to the anthropogenic source of nitrate (manure or sewage).

Changes in groundwater trace element concentrations before seismic and volcanic activities in Iceland during 2010-2018.

We analysed temporal variations of trace element concentrations in groundwater from a 101 m-deep borehole (HA01) in northern Iceland during 2010-2018 and compared them with seismic and volcanic events that occurred in the same period to identify potential hydrogeochemical precursors. An increase of B, Al, V, Li and Mo concentrations started from eight months to one month before the 2014 Bárðarbunga eruption (~115 km from HA01), a major rifting event in central Iceland, while Ga and V concentrations began to increase one day and one month after the onset of the event, respectively. We also found that concentrations of some trace elements (Li, B, Ga, Mo, Sr, Rb and Fe) significantly increased before an Mw 5.0 earthquake that occurred ~80 km from the borehole in 2018. However, other notable hydrogeochemical changes were detected during the monitoring period without apparent correlation with the seismic and volcanic events in the region. This study shows that the systematic long-term hydrogeochemical monitoring in seismic and volcanic areas is critical to advance the science of seismic and eruptive precursors. Furthermore, the use of statistical tools, such as Principal Component Analysis (PCA) and Change Point (CP) detection can help identify the most useful chemical elements and validate the trend variability of those elements in the time series, reducing arbitrary choices of pre-seismic and pre-volcanic hydrogeochemical anomalies as potential precursors.

Climatic factors influencing the isotope composition of Italian olive oils and geographic characterisation.

The purpose of this study was to investigate the possibility of identifying oil source areas by means of simple measurements on the natural samples avoiding time-consuming sample treatments. The oxygen and carbon isotopic values of 150 samples of extra-virgin olive oil from eight different Italian regions and from three different years of production were measured according to well-established techniques. Statistical treatments of the results obtained show a very good correlation of the delta(18)O of oil with latitude, mean annual temperature, and mean relative humidity at the collection site. No correlation is found with elevation and mean annual precipitation. The shift of the oil delta(18)O per degree centigrade of the mean annual temperature is quantitatively close to that calculated for atmospheric precipitation in continental areas. Accordingly, in our measurements, the year of oil production can be identified on the basis of the delta(18)O value (mean 2004 temperatures were higher than 2005 temperatures). On the contrary, the oil delta(13)C values show no correlation with the above variables but only with latitude and, consequently, are less suitable for discriminating the geographic origin of oil. However, the delta(13)C values are suitable to indicate biological differentiation while the delta(18)O values are not.

Continuous-flow delta18O measurements: new approach to standardization, high-temperature thermodynamic and sulfate analysis.

The continuous-flow method for the determination of the O-isotope composition of solid samples has significant advantages over off-line extraction methods, but the problem has arisen of the standardization of results that has only partially been resolved by the use of water standards. We propose a new approach to standardization that uses carbothermic reduction of calcium carbonate standards catalyzed by high-purity AgCl. Analytical accuracy, precision, variance homogeneity and long-term stability are proven. Preliminary data on the barium sulfate delta18O analyses are reported, with a closer look at the different results obtained by off-line and on-line methods on intercomparison standards NBS-127 and MSS3.