Risk of groundwater contamination widely underestimated because of fast flow into aquifers.

Groundwater pollution threatens human and ecosystem health in many regions around the globe. Fast flow to the groundwater through focused recharge is known to transmit short-lived pollutants into carbonate aquifers, endangering the quality of groundwaters where one quarter of the world's population lives. However, the large-scale impact of such focused recharge on groundwater quality remains poorly understood. Here, we apply a continental-scale model to quantify the risk of groundwater contamination by degradable pollutants through focused recharge in the carbonate rock regions of Europe, North Africa, and the Middle East. We show that focused recharge is the primary reason for widespread rapid transport of contaminants to the groundwater. Where it occurs, the concentration of pollutants in groundwater recharge that have not yet degraded increases from <1% to around 20 to 50% of their concentrations during infiltration. Assuming realistic application rates, our simulations show that degradable pollutants like glyphosate can exceed their permissible concentrations by 3 to 19 times when reaching the groundwater. Our results are supported by independent estimates of young water fractions at 78 carbonate rock springs over Europe and a dataset of observed glyphosate concentrations in the groundwater. They imply that in times of continuing and increasing industrial and agricultural productivity, focused recharge may result in an underestimated and widespread risk to usable groundwater volumes.

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.

Correcting Laser-Based Water Stable Isotope Readings Biased by Carrier Gas Changes.

Recently, laser-based water stable isotope spectrometers have become popular as they enable previously impossible approaches of environmental observations. Consequently, they have been subjected to increasingly heterogeneous atmospheric conditions. However, there is still a severe lack of data on the impact of nonstandardized gas matrices on analyzer performances. Against this background, we investigated the influence of changing proportions of N2, O2, and CO2 in the carrier gas on the isotope measurements of a typical laser-based water stable isotope analyzer (Picarro L2120-i). We combined environmentally relevant mixtures of N2, O2, and CO2 with referenced, flash-evaporated water and found that isotope readings of the same water were altered by up to +14.57‰ for δ(18)O and -35.9‰ for δ(2)H. All tested relationships between carrier gas changes and respective isotope readings were strongly linearly correlated (R(2) > 0.99). Furthermore, an analyzer-measured variable allowed for reliable postcorrection of the biased isotope readings, which we additionally tested on field data. Our findings are of importance for environmental data obtained by analyzers based on the same technology. They are relevant for assays where inconsistent gas matrices or a mismatch in this regard between unknown and reference analyses cannot be excluded, which is in particular common when investigating the soil-vegetation-atmosphere continuum.

Compound-Specific Stable Isotope Fractionation of Pesticides and Pharmaceuticals in a Mesoscale Aquifer Model.

Compound-specific isotope analysis (CSIA) receives increasing interest for its ability to detect natural degradation of pesticides and pharmaceuticals. Despite recent laboratory studies, CSIA investigations of such micropollutants in the environment are still rare. To explore the certainty of information obtainable by CSIA in a near-environmental setting, a pulse of the pesticide bentazone, the pesticide metabolite 2,6-dichlorobenzamide (BAM), and the pharmaceuticals diclofenac and ibuprofen was released into a mesoscale aquifer with quasi-two-dimensional flow. Concentration breakthrough curves (BTC) of BAM and ibuprofen demonstrated neither degradation nor sorption. Bentazone was transformed but did not sorb significantly, whereas diclofenac showed both degradation and sorption. Carbon and nitrogen CSIA could be accomplished in similar concentrations as for "traditional" priority pollutants (low µg/L range), however, at the cost of uncertainties (0.4-0.5‰ (carbon), 1‰ (nitrogen)). Nonetheless, invariant carbon and nitrogen isotope values confirmed that BAM was neither degraded nor sorbed, while significant enrichment of (13)C and in particular (15)N corroborated transformation of diclofenac and bentazone. Retardation of diclofenac was reflected in additional (15)N sorption isotope effects, whereas isotope fractionation of transverse dispersion could not be identified. These results provide a benchmark on the performance of CSIA to monitor the reactivity of micropollutants in aquifers and may guide future efforts to accomplish CSIA at even lower concentrations (ng/L range).

Biodegradation: Updating the concepts of control for microbial cleanup in contaminated aquifers.

Biodegradation is one of the most favored and sustainable means of removing organic pollutants from contaminated aquifers but the major steering factors are still surprisingly poorly understood. Growing evidence questions some of the established concepts for control of biodegradation. Here, we critically discuss classical concepts such as the thermodynamic redox zonation, or the use of steady state transport scenarios for assessing biodegradation rates. Furthermore, we discuss if the absence of specific degrader populations can explain poor biodegradation. We propose updated perspectives on the controls of biodegradation in contaminant plumes. These include the plume fringe concept, transport limitations, and transient conditions as currently underestimated processes affecting biodegradation.

Effect of particle density on microplastics transport in artificial and natural porous media.

The occurrence and persistence of microplastics (MPs) in natural environments are of increasing concern. Along with this, the transport of MPs in sediments has been investigated mainly focusing on the effect of plastic size and shape, media size effect, and solution chemistry. Yet, the influence of particle density is only partially understood. Therefore, column experiments on the transport of variably buoyant MPs in saturated natural sediments and glass beads were conducted, and transport parameters were quantified using a two-site kinetic transport model with a depth-dependent blocking function (the amount of retained MPs does not decrease at a constant rate with increasing depth, the majority of MPs were retained near the column inlet). Neutral, sinking, and buoyant MPs within the same size range were selected, with stable water isotope applied as conservative tracer to explore water and MP movement in the tested sediments. The results showed that 95.5 ± 1.4% of sinking MPs remained in columns packed with gravel, followed by buoyant and neutral MPs, thus indicating that particle density does affect MP mobility. Similar recovered amounts of MPs were found in columns packed with glass beads, indicating that tested sediment types do not affect the deposition behavior of MPs. The breakthrough curves of MPs were accurately described by the selected model. However, the simulated retention profiles overestimated the observed MP amount in layers closest to the column inlet. The coupled experimental and modeled results suggest an enhanced retention of sinking MPs, while neutrally and buoyant MPs exhibit a higher mobility in comparison. Thus, neutral or buoyant MPs can potentially pose a higher contamination risk to subsurface porous media environments compared to sinking MPs. Discrepancies between observed and simulated retention profiles indicate that future model development is needed for advancing the MP deposition as affected by particle density.

Experimental and simulated microplastics transport in saturated natural sediments: Impact of grain size and particle size.

Microplastics (MPs) present in terrestrial environments show potential leaching risk to deeper soil layers and aquifer systems, which threaten soil health and drinking water supply. However, little is known about the environmental fate of MPs in natural sediments. To examine the MPs transport mechanisms in natural sediments, column experiments were conducted using different natural sediments and MPs (10-150 µm) with conservative tracer. Particle breakthrough curves (BTCs) and retention profiles (RPs) were numerically interpreted in HYDRUS-1D using three different models to identify the most plausible deposition mechanism of MPs. Results show that the retention efficiency for a given particle size increased with decreasing grain size, and RPs exacerbated their hyper-exponential shape in finer sediments. Furthermore, the amounts of MPs present in the effluent increased to over 85 % as MPs size decreased to 10-20 µm in both gravel and coarse sand columns, while all larger MPs (125-150 µm) were retained in the coarse sand column. The modeling results suggested that the blocking mechanism becomes more important with increasing particle sizes. In particular, the attachment-detachment without blocking was the most suited parameterization to interpret the movement of small MPs, while a depth-dependent blocking approach was necessary to adequately describe the fate of larger particles.

Hydrogeological assessment of a major spring discharging from a calcarenitic aquifer with implications on resilience to climate change.

Groundwater is a vital source of freshwater, serving ecological, environmental, and societal needs. In regions with springs as a predominant source, such as the Northern Apennines (Italy), resilience of these springs to climate-induced recharge changes is crucial for water supply and ecosystem preservation. In this study, Nadìa Spring in the Northern Apennines is examined through an unprecedented array of multidisciplinary analyses to understand its resilience and unique characteristics. The Nadìa Spring's exceptional response, characterized by a sustained base flow even in the face of drought, is attributed to a combination of factors including a substantial groundwater reservoir, a complex network of faults/fractures, slope instabilities, and karst dissolution. The investigation reveals a dual porosity system in the aquifer, consisting of fast-flow conduits and a diffuse fracture network. While fast-flow conduits contribute to rapid responses during high-flow conditions, the diffuse system becomes predominant during low-flow periods. This dual porosity structure helps the spring maintain a consistent base flow in the face of climate-induced recharge fluctuations. The study shows that Nadìa Spring exhibits remarkable resilience to year-to-year variations in recharge, as evidenced by stable minimum discharge values. While the spring has undergone a decline in discharge over the past century due to long-term climate change, it is becoming more resilient over interdecadal timescales due to transition to a diffuse drainage system that mitigates the impact of reduced recharge. The availability of a century-long spring discharge monitoring was a crucial piece of information for understanding the spring's discharge response and drawing conclusions about its long-term resilience to recharge fluctuations. Continuing long-term monitoring and research in the future will be essential to validate and expand upon these findings in the context of changing climatic conditions. This research serves as a model for assessing strategic groundwater discharge points in geological settings similar to the Northern Apennines.

Hydrochemical and isotopic studies providing a new functional model for the coastal aquifers in Douala Coastal Sedimentary Basin (DCSB)/Cameroon.

A new conceptual model of the hydrogeological systems in Cameroon's Douala Coastal Sedimentary Basin (DCSB) was constructed. The model is based upon the basin's known geology, plus data from recent field campaigns that allowed the collection of rainwater and groundwater samples for analyses of stable isotopes (δ2H, δ18O, δ13C), radiogenic isotopes (3H, 14C), and water chemistry. Aquifer characteristics that were thereby deciphered include recharge, isotopic distributions, residence times, and mixing processes. Rainfall samples (mean δ18O = -2.0 ‰; mean δ2H = -6.80 ‰; weighted mean = -2.4 ‰ δ18O, -9.85 ‰ δ2H) scatter along two distinct lines, thus indicating that local rainfall events undergo processes during convective events, variability in humidity, amount effects, and seasonal variations. Stable isotope values of river water samples are close to the weighted mean of local precipitation, with some downstream enrichment. The Quaternary/Mio-Pliocene superficial aquifer system (depth < 70 m) and the intermediate Oligocene/Upper Eocene aquifer system (depth: 70 to 200 m) exhibit evidence of similar fractionation processes through an enrichment gradient of δ-values. The enrichment is more pronounced at the top of the superficial aquifer, which is very exposed to direct rainfall water infiltration, evaporation, and amount effects. The depth profiles of δ-values coupled to water chemistry and tritium contents, evidence leakage between (i) the superficial system's Quaternary alluvium sands and Mio-Pliocene sands; and (ii) the superficial and intermediate systems. Thus, the aquifers that contain modern, post nuclear groundwater are characterized by flow exchanges and direct recharge from rainfall events. In contrast, the Upper Eocene system has depleted δ-values and lower bicarbonate contents, suggesting not only that this system was recharged by rapid infiltration (with limited effect of evaporation), but that this recharge occurred during a cooler time in the past. The residence times (computed from 14C dates) indicate uncorrected ages ranging from hundreds to thousands of years.

Carbon isotope effects in the sorption of chlorinated ethenes on biochar and activated carbon.

As an alternative to activated carbon, biochar is a promising, environmentally friendly sorbent that can be used to remove organic groundwater pollutants, such as chlorinated ethenes (CEs). Stable isotope fractionation in biofilters is used to quantify pollutant degradation and to distinguish degradation from pollutant sorption on e.g. biochar. However, the sorption of CEs on biochar, and the potential abiotic fractionation processes remain to be tested. The sorption process of CEs and ethene on activated carbon and biochar was investigated with regard to the isotope effects for the differentiation from microbial degradation processes. Results from physical and chemical characterization of biochar indicated that biochar feedstock and pyrolysis conditions determined sorption performance depending on the surface chemistry and the pore size distribution of the coarse sorbent particles. The sorption capacity of the activated carbon was significantly higher with highly chlorinated ethenes, but similar to the biochars with low chlorination. Apparent carbon isotope fractionation factors (ε) of +0.1 to -4.4 ‰ were found above measurement uncertainties of GC/IRMS. The extent of isotope enrichment of the 13C bearing isotopologues in the residual aqueous phase (ε < 0) was characteristic for individual pairs of pollutant and sorbent material and could be related to pore-filling processes limited by the micropore size distribution of sorbent materials and the chemical properties of sorbed pollutants. Especially the large isotope fractionation during the sorption of ethene led to the assumption that diffusion processes within the pore matrix of the sorbent particles contributed to the observed isotope effects, but should still be considered a property of sorption. Concluding on the results indicated that sorption processes can have a significant contribution to carbon isotope fractionation in CEs and ethene. These should not be neglected in the evaluation of biofilters for groundwater purification, in which CEs are simultaneously degraded by microbes.

Global and local meteoric water lines for δ17O/δ18O and the spatiotemporal distribution of Δ'17O in Earth's precipitation.

Recently, δ17O and its excess (Δ'17O) have become increasingly significant "triple-oxygen-isotope" indicators of distinctive hydrological processes in hydrology and climatology. This situation mirrors the research regarding δ18O and δ2H in the 1960s towards a solid theoretical base and a surge in application examples and field studies worldwide. Currently, systematic global measurements for δ17O in precipitation are still lacking. As a result, attempts have been made to define a Global δ17O/δ18O Meteoric Water Line (GMWL), often by using regional or local datasets of varying systematicity. Different definitions of the global reference slope (λref) for determining Δ'17O values have been proposed, by ongoing debate around a proposed consensus value of 0.528. This study used worldwide samples archived in the IAEA Global Network of Isotopes in Precipitation (GNIP) to (a) derive a δ17O/δ18O GMWL based on four-year monthly records from 66 GNIP stations, (b) formulate local δ17O/δ18O meteoric water lines (LMWL) for these stations' areas, and (c) evaluate regional and seasonal variations of Δ'17O in precipitation. The GMWL for δ17O/δ18O was determined to be δ'17O = 0.5280 ± 0.0002 δ'18O + 0.0153 ± 0.0013, in keeping with the consensus value. Furthermore, our results suggested that using a line-conditioned 17O-excess is a viable alternative over the global λref in the context of regional hydrology and paleoclimatology interpretations; however, without challenging the global λref as such.

Balancing precision and throughput of δ 17O and Δ'17O analysis of natural waters by Cavity Ringdown Spectroscopy.

δ 17O and Δ'17O are emerging tracers increasingly used in isotope hydrology, climatology, and biochemistry. Differentiating small relative abundance changes in the rare 17O isotope from the strong covariance with 18O imposes ultra-high precision requirements for this isotope analysis. Measurements of δ 17O by Cavity Ringdown Spectroscopy (CRDS) are attractive due to the ease of sample preparation, automated throughput, and avoidance of chemical conversions needed for isotope-ratio mass spectrometry. However, the CRDS approach requires trade-offs in measurement precision and uncertainty. In this protocol document, we present the following:•New analytical procedures and a software tool for conducting δ 17O and Δ'17O measurements by CRDS.•Outline a robust uncertainty framework for Δ'17O determinations.•Description of a CRDS performance framework for optimizing throughput, instrumental stability, and Δ'17O measurement precision and accuracy.

From the Mountain to the Valley: Drivers of Groundwater Prokaryotic Communities along an Alpine River Corridor.

Rivers are the "tip of the iceberg", with the underlying groundwater being the unseen freshwater majority. Microbial community composition and the dynamics of shallow groundwater ecosystems are thus crucial, due to their potential impact on ecosystem processes and functioning. In early summer and late autumn, samples of river water from 14 stations and groundwater from 45 wells were analyzed along a 300 km transect of the Mur River valley, from the Austrian alps to the flats at the Slovenian border. The active and total prokaryotic communities were characterized using high-throughput gene amplicon sequencing. Key physico-chemical parameters and stress indicators were recorded. The dataset was used to challenge ecological concepts and assembly processes in shallow aquifers. The groundwater microbiome is analyzed regarding its composition, change with land use, and difference to the river. Community composition and species turnover differed significantly. At high altitudes, dispersal limitation was the main driver of groundwater community assembly, whereas in the lowland, homogeneous selection explained the larger share. Land use was a key determinant of the groundwater microbiome composition. The alpine region was more diverse and richer in prokaryotic taxa, with some early diverging archaeal lineages being highly abundant. This dataset shows a longitudinal change in prokaryotic communities that is dependent on regional differences affected by geomorphology and land use.

Sources of major elements and nutrients in the water cycle of an undisturbed river basin - Samothraki Island, Greece.

We studied the origin of elements of an undisturbed stream basin during the dry season as derived by atmospheric inputs and lithological processes. Α mass balance model was applied taking into account atmospheric (rain and vapor) inputs and their origin from marine aerosol and dust, as well as the contribution of rock mineral weathering and dissolution of soluble salts. The model results were enhanced using element enrichment factors, element ratios and water stable isotopes. Weathering and dissolution of bedrock and soil minerals contributed the main element portions, besides sodium and sulfate that chiefly derived from wet deposition. Vapor was shown to contribute water to inland waters of the basin. However, rain was the main source of elements compared to vapor, with marine aerosol being the only atmospheric chloride source, contributing also over 60 % of atmospheric sodium and magnesium. Silicate derived from mineral weathering (mainly plagioclase and amorphous silica), while soluble salt dissolution contributed the main portions of the rest of major elements. In headwater springs and streams, element concentrations were more affected by atmospheric inputs and silicate mineral weathering was more intense, contrary to lowland waters that were more affected by soluble salt dissolution. Effective self-purification processes were mirrored in low nutrient levels, despite the significant inputs from wet deposition, with rain being more important contributor than vapor for the majority of nutrient species. Relatively high nitrate concentrations in headwaters were attributed to increased mineralization and nitrification, while the downstream nitrate diminishing was due to prevailing denitrification processes. The ultimate goal of this study is to contribute in establishing stream elements' reference conditions using mass balance modeling approaches.

Stable isotope patterns of German rivers with aspects on scales, continuity and network status.

In Germany, river monitoring for tritium started in the early 1970s. Today this monitoring network consists of 50 stations and includes stable isotopes. The stable isotope time series to the end of 2021 are at least four years and for some stations up to 30 years long. Daily river water samples were collected during an extraordinary dry season from October 2018 until end of January 2019 from six selected stations of the Rhine and five stations of the Elbe basin. The most dominating stable isotope effects in river water are the seasonal and altitude effects, but also a continental effect is visible. The isotopes indicate snow and ice melt contributions in the Rhine and Danube during the summer months and a consecutive dilution of these signals by mixing with tributary rivers. Close to the coasts in northern Germany, stable isotope patterns reflect influence of seawater and tides. Daily patterns during the dry season 2018/2019 surprisingly do not exhibit extreme changes but rather trends of enhanced groundwater contribution. Long-term continual data across scales are important for comparing and identifying hydrological processes in German river basins of different size and mean catchment altitudes, and highlight the benefits of a co-organized national network.

Heavy rainfall following a summer drought stimulates soil redox dynamics and facilitates rapid and deep translocation of glyphosate in floodplain soils.

We present field data on the effects of heavy rainfall after drought on the mobility of glyphosate and redox conditions in a clayey floodplain soil. By applying glyphosate together with deuterated water as conservative tracer in combination with time resolved in situ redox potential measurements, the spatial and temporal patterns of water infiltration and pesticide transport as well as the concomitant changes of the redox conditions were revealed. Our findings demonstrate that shrinkage cracks in dry soils can serve as effective transport paths for atmospheric oxygen, water and glyphosate. The rain intensity of a typical summer storm event (approx. 25 mm within one hour) was sufficient to translocate deuterated water and glyphosate to the subsoil (50 cm) within 2 hours. Soil wetting induced partial closure of the shrinkage cracks and stimulated microbial activity resulting in pronounced dynamics of in situ soil redox conditions. Redox potentials in 40 to 50 cm depth dropped permanently to strongly reducing conditions within hours to days but fluctuated between reducing and oxidizing conditions in 10 to 30 cm depth. Our findings highlight the close link between the presence of macropores (shrinkage cracks), heavy rainfall after drought, redox dynamics and pesticide translocation to the subsoil and thus call for further studies addressing the effects of dynamic redox conditions as a limiting factor for glyphosate degradation.

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.

Transport and bacterial interactions of three bacterial strains in saturated column experiments.

The impact of bacteria-solid and bacteria-bacteria interactions on the transport of Klebsiella oxytoca, Burkholderia cepacia G4PR1, and Pseudomonas sp. #5 was investigated in saturated sand column experiments (L = 114 mm; ø = 33 mm) under constant water velocities (∼ 5 cm · h(-1)). Bacterial strains were injected into the columns as pulses either individually, simultaneously, or successively. A one-dimensional mathematical model for advective-dispersive transport and for irreversible and reversible bacterial kinetic sorption was used to analyze the bacterial breakthrough curves. Different sorption parameters were obtained for each strain in each of the three experimental setups. In the presence of other bacteria, sorption parameters for B. cepacia G4PR1 remained similar to results from individual experiments, indicating the presence of other bacteria generally had a lesser influence on its migration than for the other bacteria. K. oxytoca is more competitive for the sorption sites when simultaneously injected with the other bacteria. Ps. sp. #5 generally yielded the greatest detachment rates and the least affinity to attach to the sand, indicative of its mobility in groundwater systems. The results of this study clearly indicate both bacteria-solid and bacteria-bacteria interactions influence the migration of bacteria. A more complete understanding of such interactions is necessary to determine potential migration in groundwater systems.

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.