Chemical and isotopic tracers combined with mixing models for tracking nitrate contamination in the Pampa de Pocho aquifer, Argentina.

In recent years, it has become evident that human activities have significantly disrupted the nitrogen cycle surpassing acceptable environmental thresholds. In this study, chemical and isotopic tracers were combined with a mathematical mass balance model (EMMA), PHREEQC inverse mixing model, and statistical analyses to evaluate groundwater quality, across an area experiencing substantial human activities, with a specific focus on tracing the origin of nitrate (NO3-) with potential water mixing processes. This multi-technique approach was applied to an unconfined aquifer underlying an agricultural area setting in an inter-mountain depression (i.e., the "Pampa de Pocho Plain" in Argentina). Here, the primary identified geochemical processes occurring in the investigated groundwater system include the dissolution of carbonate salts, cation exchange, and hydrolysis of alumino-silicates along with incorporating ions from precipitation. It was observed that the chemistry of groundwater, predominantly of sodium bicarbonate with sulfate water types, is controlled by the area's geology, recharge from precipitation, and stream water infiltration originating from the surrounding hills. Chemical results reveal that 60% of groundwater samples have NO3- concentrations exceeding the regional natural background level, confirming the impact of human activities on groundwater quality. The dual plot of δ15NNO3 versus δ18ONO3 values indicates that groundwater is affected by NO3- sources overlapping manure/sewage with organic-rich soil. The mathematical EMMA model and PHREEQC inverse modeling, suggest organic-rich soil as an important source of nitrogen in the aquifer. Here, 64 % of samples exhibit a main mixture of organic-rich soil with manure, whereas 36 % of samples are affected mainly by a mixture of manure and fertilizer. This study demonstrates the utility of combining isotope tracers with mathematical modeling and statistical analyses for a better understanding of groundwater quality deterioration in situations where isotopic signatures of contamination sources overlap.

Nitrate sources and transformation processes in groundwater of a coastal area experiencing various environmental stressors.

In coastal salinized groundwater systems, contamination from various nitrate (NO3) inputs combined with complex hydrogeochemical processes make it difficult to distinguish NO3 sources and identify potential NO3 transformtation processes. Effective field-based NO3 studies in coastal areas are needed to improve the understanding of NO3 contamination dynamics in groundwater of such complex coastal systems. This study focuses on a typical Mediterranean coastal agricultural area, located in Tunisia, experiencing substantial NO3 contamination from multiple anthropogenic sources. Here, multiple isotopic tracers (δ18OH2O, δ2HH2O, δ15NNO3, δ18ONO3, and δ11B) combined with a Bayesian isotope MixSIAR model are used (i) to identify the major NO3 sources and their contributions, and (ii) to describe the potential NO3 transformation processes. The measured NO3 concentrations in groundwater are above the natural baseline threshold, suggesting anthropogenic influence. The measured isotopic composition of NO3 indicates that manure, soil organic matter, and sewage are the potential sources of NO3, while δ11B values constrain the NO3 contamination to manure; a finding that is supported by the results of MixSIAR model revealing that manure-derived NO3 dominates over other likely sources. Nitrate derived from manure in the study area is attributed to organic fertilizers used to promote crop growth, and livestock that deposit manure directly on the ground surface. Evidence for ongoing denitrification in groundwaters of the study area is supported by an enrichment in both 15N and 18O in the remaining NO3, although isotopic mass balances between the measured and the theoretical δ18ONO3 values also suggest the occurrence of nitrification. The simultaneous occurrence of these biogeochemical processes with heterogeneous distribution across the study area reflect the complexity of interactions within the investigated coastal aquifer. The multiple isotopic tracer approach used here can identify the effect of multiple NO3 anthropogenic activities in coastal environments, which is fundamental for sustainable groundwater resources management.

Multi-tracer approach to understand nitrate contamination and groundwater-surface water interactions in the Mediterranean coastal area of Guerbes-Senhadja, Algeria.

Implementing sustainable groundwater resources management in coastal areas is challenging due to the negative impacts of anthropogenic stressors and various interactions between groundwater and surface water. This study focuses on nitrate contamination and transport via groundwater-surface water exchange in a Mediterranean coastal area (Guerbes-Senhadja region, Algeria) that is heavily affected by anthropogenic activities. A multi-tracer approach, integrating hydrogeochemical and isotopic tracers (δ2HH2O, δ18OH2O, 3H, δ15NNO3 and δ18ONO3), is combined with a Bayesian isotope mixing model (MixSIAR) to (i) elucidate the nitrate sources and their apportionments in water systems, and (ii) describe potential interactions between groundwater and surface water. Results from nitrate isotopic composition and the MixSIAR model show that nitrate concentrations mainly originate from sewage and manure sources. Nitrate derived from the sewage is attributed to urban and rural wastewater discharge, whereas nitrate derived from the manure is related to animal manure used to fertilise agricultural areas. High apportionments of nitrate-based atmospheric precipitation are identified in groundwater and surface water; a finding that is specific to this study. The multi-origin stresses combined with evidence of interactions between surface water and groundwater contribute to negatively impacting large parts of the study coastal area. The outcomes of this study are expected to contribute to sustainable management of coastal ecosystems by drawing more attention towards groundwater use and protection. Furthermore, this study may improve scientists' ability to predict the behavior of anthropogenically impacted coastal ecosystems and help decision-makers elsewhere to prepare suitable environmental strategies for other coastal ecosystems currently undergoing an early stage of groundwater resources deterioration.

Combined effects of seawater intrusion and nitrate contamination on groundwater in coastal agricultural areas: A case from the Plain of the El-Nil River (North-Eastern Algeria).

This study focuses on coastal aquifers subject to uncontrolled land use development by investigating the combined effects of seawater intrusion and nitrate contamination. The research is undertaken in a Mediterranean coastal agricultural area (Plain of the El-Nil River, Algeria), where water resources are heavily impacted by anthropogenic activities. A multi-tracer approach, integrating hydrogeochemical and isotopic tracers (δ2HH2O, δ18OH2O, δ15NNO3 and δ18ONO3), is combined with a hydrochemical facies evolution diagram, and a Bayesian isotope mixing model (MixSIAR) to assess seawater contamination with its inland intrusion, and distinguish the nitrate sources and their apportionment. Results show that seawater intrusion is circumscribed to the sector neighboring the Mediterranean Sea, with two influencing functions including classic inland intrusion through the aquifer, and upstream seawater impact through the river mouth connected to the Mediterranean Sea. Groundwater and surface water samples reveal nitrate concentrations above the natural baseline threshold, suggesting anthropogenic influence. Results from nitrate isotopic composition, NO3 and Cl concentrations, and the MixSIAR model show that nitrate concentrations chiefly originate from sewage and manure sources. Nitrate derived from the sewage is related to wastewater discharge, whereas nitrate derived from the manure is attributed to an excessive use of animal manure to fertilise agricultural areas. The dual negative impact of seawater intrusion and nitrate contamination degrades water quality over a large proportion of the study area. The outcomes of this study are expected to contribute to effective and sustainable water resources management in the Mediterranean coastal area. Furthermore, this study may improve scientists' ability to predict the combined effect of various anthropogenic stressors on coastal environments and help decision-makers elsewhere to prepare suitable environmental strategies for other regions currently undergoing an early stage of water resources deterioration.

Chloride-salinity as indicator of the chemical composition of groundwater: empirical predictive model based on aquifers in Southern Quebec, Canada.

The present study first describes the variations in concentrations of 12 chemical elements in groundwater relative to salinity levels in Southern Quebec (Canada) groundwater systems, and then uses this data to develop an empirical predictive model for evaluating groundwater chemical composition relative to salinity levels. Data is drawn from a large groundwater chemistry database containing 2608 samples. Eight salinity classes were established from lowest to highest chloride (Cl) concentrations. Graphical analyses were applied to describe variations in major, minor, and trace element concentrations relative to salinity levels. Results show that the major elements were found to be dominant in the lower salinity classes, whereas Cl becomes dominant at the highest salinity classes. For each of the major elements, a transitional state was identified between domination of the major elements and domination of Cl. This transition occurred at a different level of salinity for each of the major elements. Except for Si, the minor elements Ba, B, and Sr generally increase relative to the increase of Cl. The highest Mn concentrations were found to be associated with only the highest levels of Cl, whereas F was observed to be more abundant than Mn. Based on this analysis of the data, a correlation table was established between salinity level and concentrations of the chemical constituents. We thus propose a predictive empirical model, identifying a profile of the chemical composition of groundwater relative to salinity levels, to help homeowners and groundwater managers evaluate groundwater quality before resorting to laborious and costly laboratory analyses.

Constraining a Flow Model with Field Measurements to Assess Water Transit Time Through a Vadose Zone.

The modeling of thick vadose zones is particularly challenging because of difficulties in collecting a variety of measured sediment properties, which are required for parameterizing the model. Some models rely on synthetic data, whereas others are simplified by running as homogeneous sediment domains and relying on a single set of sediment properties. Few studies have simulated flow processes through a thick vadose zone using real and comprehensive data sets comprising multiple measurements. Here, we develop a flow model for a 7-m-thick vadose zone. This model, combining the numerical codes CTRAN/W with SEEP/W, includes the measured sediment hydraulic properties of the investigated vadose zone and incorporates the actual climate and subsurface conditions of the study site (precipitations, water-table elevations, and stable isotope data). The model is calibrated by fitting the simulated and measured vertical profiles of water content. Our flow model calculates a transit time of 1 year for the travel of water through the 7-m vadose zone; this estimate matches stable isotope-based results obtained previously for this site. A homogeneous sediment domain flow model, which considers only a single set of sediment properties, produces a transit time that is approximately half the duration of that of the heterogeneous flow model. This difference highlights the importance of assuming heterogeneous material within models of thick vadose zones and testifies to the advantage gained when using real sediment hydraulic properties to parametrize a flow model.

Identifying groundwater degradation sources in a Mediterranean coastal area experiencing significant multi-origin stresses.

This study investigates the multiple contamination sources of a coastal Mediterranean aquifer in northeastern Algeria that is bordered by two rivers and neighboring densely populated areas. Hydrogeochemical and isotopic groundwater characterization is carried out, including the analyses of major elements, water stable isotopes δ2H-H2O and δ18O-H2O, and stable isotopes of nitrate δ15N-NO3 and δ18O-NO3, and then integrated into the history of land use over the study area. Groundwater nitrate concentrations ranging from 1.6 to 235 mg/L with a median value of 69 mg/L are evidence of the degradation of groundwater quality induced by anthropogenic sources. The combined of δ15N-NO3 and δ18O-NO3 ratios showed that nitrate in groundwater is attributable to (i) the uncontrolled development of inadequate private sanitation systems over the study area, and (ii) the unsafe application of animal manure to fertilize crops. Very active saltwater intrusion is confirmed by several hydrogeochemical indicators. Interestingly, the intrusion mechanism appears to be more complex than a direct intrusion from the Mediterranean Sea. During the high-water period, saltwater intrusion may also originate from the two rivers bordering the aquifer, via upstream migration of seawater through the river mouths. The heavier ratios in δ2H-H2O and δ18O-H2O of surface water collected from the rivers suggest that water from the Mediterranean Sea is mixing with water in the rivers. Multi-source contamination not only contributes to complex chemical reactions within the aquifer, but also contributes, via the cumulative effect of the various sources, to affecting large parts of the study area. The present study may serve as a warning to the effect that historical land-use practices may exert seriously deleterious impacts on groundwater quality and greatly limit conditions for the sustainable management of Mediterranean coastal areas.