Nitrate isotopic values are often used as a tool to understand sources of contamination in order to effectively manage groundwater quality. However, recent literature describes that biogeochemical reactions may modify these values. Therefore, data interpretation is difficult and often vague. We provide a discussion on this topic and complement the study using halides as comparative tracers assessing an aquifer underneath a sub-humid to humid region in NE Mexico. Hydrogeological information and stable water isotopes indicate that active groundwater recharge occurs in the 8000km(2) study area under present-day climatic and hydrologic conditions. Nitrate isotopes and halide ratios indicate a diverse mix of nitrate sources and transformations. Nitrate sources include organic waste and wastewater, synthetic fertilizers and soil processes. Animal manure and sewage from septic tanks were the causes of groundwater nitrate pollution within orchards and vegetable agriculture. Dairy activities within a radius of 1,000 m from a sampling point significantly contributed to nitrate pollution. Leachates from septic tanks caused nitrate pollution in residential areas. Soil nitrogen and animal waste were the sources of nitrate in groundwater under shrubland and grassland. Partial denitrification processes helped to attenuate nitrate concentration underneath agricultural lands and grassland, especially during summer months.

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The La Paz aquifer system (Baja California Sur, Mexico) is under severe anthropogenic pressure because of high groundwater abstraction for urban supply (city of La Paz, around 222,000 inhabitants) and irrigated agriculture (1900ha). In consequence, seawater has infiltrated the aquifer, forcing the abandonment of wells with increased salinity. The objective of this study was to assess seawater intrusion, understand the hydrogeochemical processes involved and estimate the contribution of seawater in the wells tested. The aquifer comprises mainly the alluvial filling and marine sediments of a tectonic graben oriented north-south, in contact with the Gulf of California. Groundwater samples were collected in 47 locations and analyzed for major constituents. A subset of 23 samples was analyzed for strontium and boron concentrations and isotopic signatures (Sr/Sr and δB). Results were interpreted using standard hydrochemical plots along with ad hoc plots including isotopic data. Seawater intrusion was confirmed by several hydrogeochemical indicators, such as the high salinity in areas of intense pumping or the Na-Ca exchange occurring in sediments that were previously in chemical equilibrium with fresh water. However, seawater contribution was not sufficient to explain the observed concentrations and isotopic signatures of Sr and B. According to the isotopic data, desorption processes triggered by a modification in chemical equilibrium and an increase in ionic strength by seawater intrusion significantly increased Sr and probably B concentrations in groundwater. From a calculation of seawater contribution to the wells, it was estimated that one-third of the sampled abstraction wells were significantly affected by seawater intrusion, reaching concentrations that would limit their use for human supply or even irrigated agriculture. In addition, significant agricultural pollution (nitrates) was detected. Planned management of the aquifer and corrective measures are needed in order to invert the salinization process before it severely affects water resources in the long term.

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The quality of the groundwater supplying drinking water to the Guadalajara metropolitan area has deteriorated due to both endogenic and exogenic processes. Previous studies of this complex neotectonic volcanic environment suggest that the sources of contamination here are underground fluids derived from an active volcanic center and surface wastewater derived from regional land-use intensification. This study uses isotopic, gaseous, and chemical signatures to more comprehensively characterize this groundwater flow and its contamination paths. Groundwater is mainly recharged at the La Primavera Caldera to the west and is discharged into the Santiago River to the east. The exception to this trend is the Toluquilla area, where groundwater most likely represents rainfall originating from outside the basin limits. Evaporation affects groundwater in these areas, especially waters that have been affected by recycling below urban areas in the Atejamac area and by intensive agricultural activity in the Toluquilla area. Additionally, we present evidence that groundwater flow through alluvial sediments and tuffs in deeper wells mixes with a lower aquifer unit in basaltic-andesitic rocks, which are in contact with hydrothermal fluids. Groundwater ages range from postbomb in the western and northwestern regions of the study area (i.e., the Atemajac aquifer unit) to Late Pleistocene in the southern and southeastern regions (i.e., the Toluquilla aquifer unit). Recently recharged water records little mixing and is located mostly in or near the La Primavera volcanic system. As groundwater undergoes gravitational flow towards discharge areas, it mixes with older water components. Chloride and sodium concentrations above natural background levels are primarily related to volcanic activity, nitrate is associated with human activities, and sulfate originates from both anthropogenic sources and water-rock interactions. Nitrate originating from land-use activities (such as sewers, septic tanks, landfills, and agricultural fields) that is introduced into the deeper part of the groundwater system is expected to travel with the groundwater to the discharge areas because oxidizing conditions will prevent microbial reduction. See Supplementary Information.This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.