Rapid economic expansion poses serious problems for groundwater resources in arid areas, which typically have high rates of groundwater depletion. In this study, integration of hydrochemical investigations involving chemical and statistical analyses are conducted to assess the factors controlling hydrochemistry and potential pollution in an arid region. Fifty-four groundwater samples were collected from the Dhurma aquifer in Saudi Arabia, and twenty-one physicochemical variables were examined for each sample. Spatial patterns of salinity and nitrate were mapped using fitted variograms. The nitrate spatial distribution shows that nitrate pollution is a persistent problem affecting a wide area of the aquifer. The hydrochemical investigations and cluster analysis reveal four significant clusters of groundwater zones. Five main factors were extracted, which explain >77% of the total data variance. These factors indicated that the chemical characteristics of the groundwater were influenced by rock–water interactions and anthropogenic factors. The identified clusters and factors were validated with hydrochemical investigations. The geogenic factors include the dissolution of various minerals (calcite, aragonite, gypsum, anhydrite, halite and fluorite) and ion exchange processes. The anthropogenic factors include the impact of irrigation return flows and the application of potassium, nitrate, and phosphate fertilizers. Over time, these anthropogenic factors will most likely contribute to further declines in groundwater quality.

Salinization and nitrate pollution are generally ascertained as the main issues affecting coastal aquifers worldwide. In arid zones, where agricultural activities also result in soil salinization, both phenomena tend to co-exist and synergically contribute to alter groundwater quality, with severe negative impacts on human populations and natural ecosystems’ wellbeing. It becomes therefore necessary to understand if and to what extent integrated hydrogeochemical tools can help in distinguishing among possible different salinization and nitrate contamination origins, in order to provide adequate science-based support to local development and environmental protection. The alluvial plain of Bou-Areg (North Morocco) extends over about 190 km² and is separated from the Mediterranean Sea by the coastal Lagoon of Nador. Its surface is covered for more than 60% by agricultural activities, although the region has been recently concerned by urban population increase and tourism expansion. All these activities mainly rely on groundwater exploitation and at the same time are the main causes of both aquifer and lagoon water quality degradation. For this reason, it was chosen as a case study representative of the typical situation of coastal aquifers in arid zones worldwide, where a clear identification of salinization and pollution sources is fundamental for the implementation of locally oriented remedies and long-term management strategies. Results of a hydrogeochemical investigation performed between 2009 and 2011 show that the Bou-Areg aquifer presents high salinity (often exceeding 100 mg/L in TDS) due to both natural and anthropogenic processes. The area is also impacted by nitrate contamination, with concentrations generally exceeding the WHO statutory limits for drinking water (50 mg/L) and reaching up to about 300 mg/L, in both the rural and urban/peri-urban areas. The isotopic composition of dissolved nitrates (δ¹⁵NNO₃ and δ¹⁸ONO) was used to constrain pollution drivers. The results indicate two main origins for human-induced pollution: (i) manure and septic effluents, especially in urban areas, and (ii) synthetic fertilizers in agricultural areas. In the latter, δ¹⁵N-enriched values highlight a mixture of those sources, possibly related to unbalanced fertilization and agricultural return flow. Boron isotopes (δ¹¹B) were hence studied to further distinguish the nitrate origin in the presence of multiple sources and mixing processes. The results indicate that in the study area, the high geochemical background for B and Cl, associated to the complex water-rock interaction processes, limit the application of the coupled δ¹¹B and δ¹⁵N isotopic systematics to the detection of sources of groundwater pollution. In fact, despite the exceedingly high nitrate contents, the depleted δ¹¹B values that characterize synthetic fertilizers and sewage leakages could not be detected. Therefore, even if in saline groundwater the anthropogenic contribution has a negligible effect in terms of salinity input, with both sewage and irrigation water not very charged, the associated nitrate content fuels up water-rock interaction processes, eventually leading to a mineralization increase.