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

Abstract

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.

Keywords: Djibouti; Fluoride mineral thermodynamics; Health risk assessment; High F(−) and high NO(3)(−) groundwater; Hydrogeochemical processes; Monte Carlo simulation.