Groundwater from the La Paz arid coastal aquifer in Baja California, Mexico, is essentially the only source of drinking water for the local population and tourists, as well as irrigation water for agricultural needs. The intensive exploitation of the aquifer and water cycling has resulted in groundwater abatement (up to 10 m) and high salinity (up to *5800 mg l -1 ). A study using hydrochemistry, isotopic (deuterium, oxygen-18 and carbon-14) and gaseous tracers (chlorofluorocarbons CFC-11, CFC-12, CFC-113), as well as multivariate statistics, was developed to elucidate groundwater composition, flow and occurrence. Groundwater is of meteoric origin, and a large proportion is subject to evaporation. The primary natural recharge is generated in the El Novillo and Las Cruces ranges, and groundwater subsequently flows in a SE-NW direction toward the coast. The initial water type is the result of discordant dissolution of silicate minerals and ion exchange on soils. In the lower plain portion, the aquifer system is recharged from irrigation return flow and seawater intrusion, which significantly affects groundwater chemistry. Nitrate and chloride concentrations indicate that groundwater is highly affected by an overuse of fertilizers in agricultural activities, but there is little effect from urban activities. Seawater intrusion has progressed rapidly during the past decade, and the impact currently extends 13 km inland. Radiocarbon residence time calculations suggest that groundwater is modern, with the exception of Chametla and El Centerario sites in the central and western lowlands with ages of up to *5000 years. These waters indicate an additional recharge source for the upconing of fossil groundwater or regional flow.

Abstract. Groundwater chemistry and isotopic data from 40 production wells in the Atemajac and Toluquilla valleys, located in and around the Guadalajara metropolitan area, were determined to develop a conceptual model of groundwater flow processes and mixing. Stable water isotopes (δ 2 H, δ 18 O) were used to trace hydrological processes and tritium ( 3 H) to evaluate the relative contribution of modern water in samples. Multivariate analysis including cluster analysis and principal component analysis were used to elucidate distribution patterns of constituents and factors controlling groundwater chemistry. Based on this analysis, groundwater was classified into four groups: cold groundwater, hydrothermal groundwater, polluted groundwater and mixed groundwater. Cold groundwater is characterized by low temperature, salinity, and Cl and Na concentrations and is predominantly of Na-HCO 3 -type. It originates as recharge at "La Primavera" caldera and is found predominantly in wells in the upper Atemajac Valley. Hydrothermal groundwater is characterized by high salinity, temperature, Cl, Na and HCO 3 , and the presence of minor elements such as Li, Mn and F. It is a mixed-HCO 3 type found in wells from Toluquilla Valley and represents regional flow circulation through basaltic and andesitic rocks. Polluted groundwater is characterized by elevated nitrate and sulfate concentrations and is usually derived from urban water cycling and subordinately from agricultural return flow. Mixed groundwaters between cold and hydrothermal components are predominantly found in the lower Atemajac Valley. Twenty-seven groundwater samples contain at least a small fraction of modern water. The application of a multivariate mixing model allowed the mixing proportions of hydrothermal fluids, polluted waters and cold groundwater in sampled water to be evaluated. This study will help local water authorities to identify and dimension groundwater contamination, and act accordingly. It may be broadly applicable to other active volcanic systems on Earth.

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.

Groundwater chemistry and isotopic data from 40 production wells in the Atemajac and Toluquilla valleys, located in and around the Guadalajara metropolitan area, were determined to develop a conceptual model of groundwater flow processes and mixing. Stable water isotopes (δ 2 H, δ 18 O) were used to trace hydrological processes and tritium ( 3 H) to evaluate the relative contribution of modern water in samples. Multivariate analysis including cluster analysis and principal component analysis were used to elucidate distribution patterns of constituents and factors controlling groundwater chemistry. Based on this analysis, groundwater was classified into four groups: cold groundwater, hydrothermal groundwater, polluted groundwater and mixed groundwater. Cold groundwater is characterized by low temperature, salinity, and Cl and Na concentrations and is predominantly of Na-HCO 3 -type. It originates as recharge at "La Primavera" caldera and is found predominantly in wells in the upper Atemajac Valley. Hydrothermal groundwater is characterized by high salinity, temperature, Cl, Na and HCO 3 , and the presence of minor elements such as Li, Mn and F. It is a mixed-HCO 3 type found in wells from Toluquilla Valley and represents regional flow circulation through basaltic and andesitic rocks. Polluted groundwater is characterized by elevated nitrate and sulfate concentrations and is usually derived from urban water cycling and subordinately from agricultural return flow. Mixed groundwaters between cold and hydrothermal components are predominantly found in the lower Atemajac Valley. Twenty-seven groundwater samples contain at least a small fraction of modern water. The application of a multivariate mixing model allowed the mixing proportions of hydrothermal fluids, polluted waters and cold groundwater in sampled water to be evaluated. This study will help local water authorities to identify and dimension groundwater contamination, and act accordingly. It may be broadly applicable to other active volcanic systems on Earth.