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.

Biomass and nutrient dynamics of major green tides in Ireland: Implications for biomonitoring.

The control of macroalgal bloom development is central for protecting estuarine ecosystems. The identification of the nutrients limiting the development of macroalgal blooms, and their most likely sources is crucial for management strategies. Three Irish estuaries (Argideen, Clonakilty and Tolka) affected by green tides were monitored from June 2016 to August 2017. During each sampling occasion, biomass abundances, tissue N and P contents, and δ15N were determined for tubular and laminar morphologies of Ulva. All estuaries showed maximum biomass during summer and minimum during winter. Tissue nutrient contents revealed P rather than N limitation. The δ15N during the peak bloom indicated agriculture as the most likely source of nitrogen in the Argideen and Clonakilty, and urban wastewaters in the Tolka. No differences in the δ15N, and the tissue nutrients content were observed between morphologies. The period between May and July is most suitable for bioassessment of green tides.

New Ag3 PO4 comparison material for stable oxygen isotope analysis.

RATIONALE: A silver phosphate reference material (Ag3 PO4 ) for the measurement of stable oxygen isotope compositions is much needed; however, it is not available from the authorities distributing reference materials. This study aims to fill this gap by calibrating a new Ag3 PO4 stable isotope comparison material produced by the University of Natural Resources and Life Sciences (BOKU). METHODS: Aliquots of Ag3 PO4 were distributed to four laboratories who frequently measure the δ18 O value in Ag3 PO4 ; the University of Natural Resources and Life Sciences (BOKU), the University of Western Australia (UWA), the University of Helsinki (UH), and the Helmholtz Centre for Environmental Research (UFZ). The instruments used to perform the measurements were high-temperature conversion elemental analysers coupled with continuous flow isotope ratio mass spectrometers. The working gas δ18 O value was set to 0‰ and the normalization was done by a three-point linear regression using the reference materials IAEA-601, IAEA-602, and NBS127. RESULTS: The mean δ18 O value of the new BOKU Ag3 PO4 comparison material on the VSMOW-SLAP scale is 13.71‰ and the combined uncertainty is estimated as ±0.34‰. This estimated uncertainty is within the range typical for comparison materials of phosphates and sulphates. Consistent results from the different laboratories probably derived from similar instrumentation, and use of the same reference materials and normalization procedure. The matrix effect of the different reference materials used in this study was deemed negligible. CONCLUSIONS: The BOKU Ag3 PO4 can be used as an alternative comparison material for stable oxygen isotope analysis and is available for stable isotope research laboratories to facilitate calibration.

Disentangling multiple chemical and non-chemical stressors in a lotic ecosystem using a longitudinal approach.

Meeting ecological and water quality standards in lotic ecosystems is often failed due to multiple stressors. However, disentangling stressor effects and identifying relevant stressor-effect-relationships in complex environmental settings remain major challenges. By combining state-of-the-art methods from ecotoxicology and aquatic ecosystem analysis, we aimed here to disentangle the effects of multiple chemical and non-chemical stressors along a longitudinal land use gradient in a third-order river in Germany. We distinguished and evaluated four dominant stressor categories along this gradient: (1) Hydromorphological alterations: Flow diversity and substrate diversity correlated with the EU-Water Framework Directive based indicators for the quality element macroinvertebrates, which deteriorated at the transition from near-natural reference sites to urban sites. (2) Elevated nutrient levels and eutrophication: Low to moderate nutrient concentrations together with complete canopy cover at the reference sites correlated with low densities of benthic algae (biofilms). We found no more systematic relation of algal density with nutrient concentrations at the downstream sites, suggesting that limiting concentrations are exceeded already at moderate nutrient concentrations and reduced shading by riparian vegetation. (3) Elevated organic matter levels: Wastewater treatment plants (WWTP) and stormwater drainage systems were the primary sources of bioavailable dissolved organic carbon. Consequently, planktonic bacterial production and especially extracellular enzyme activity increased downstream of those effluents showing local peaks. (4) Micropollutants and toxicity-related stress: WWTPs were the predominant source of toxic stress, resulting in a rapid increase of the toxicity for invertebrates and algae with only one order of magnitude below the acute toxic levels. This toxicity correlates negatively with the contribution of invertebrate species being sensitive towards pesticides (SPEARpesticides index), probably contributing to the loss of biodiversity recorded in response to WWTP effluents. Our longitudinal approach highlights the potential of coordinated community efforts in supplementing established monitoring methods to tackle the complex phenomenon of multiple stress.

Benzene degradation in contaminated aquifers: Enhancing natural attenuation by injecting nitrate.

Natural attenuation processes depend on the availability of suitable electron acceptors. At the megasite Zeitz, concentrations of the main contaminant benzene were observed to increase constantly in the lower aquifer to levels of more than 2.5 mM. This was accompanied by decreasing concentrations of sulphate (SO42-), which has been previously shown to be the main electron acceptor for benzene oxidation at this site, resulting in an electron acceptor-limited, sulphidic benzene plume. Therefore, a field experiment was conducted to stimulate benzene biodegradation by injecting nitrate (NO3-) into the sulphidic benzene plume aiming (i) to recycle sulphate by nitrate-dependent sulphide oxidation, and (ii) to serve as direct electron acceptor for benzene oxidation. Within 60 days, 6.74 tons sodium nitrate (NaNO3) were injected into the lower aquifer, and the resulting biogeochemical effects within the benzene plume were monitored for more than one year by chemical and microbiological analyses of groundwater samples taken from various depths of ten monitoring wells located in three observation lines downstream of nitrate injection. Nitrate was microbiologically consumed, as shown by changes in δ15N-NO3- and δ18O-NO3- values, partial nitrite accumulation, and changing ratios of Na+/NO3-. Main electron donors for nitrate reduction were reduced sulphur compounds, verified by changing δ34S-SO42- and δ18O-SO42- values, partially increasing sulphate concentrations, and strongly increasing abundances of typical sulphur-oxidizing, nitrate-reducing bacterial taxa within the nitrate plume. The general absent hydrogen isotope fractionation of benzene, also in the sulphidic, nitrate-free part of the plume, indicates that benzene was not biodegraded by sulphate-reducing consortia. However, detected small carbon isotope fractionation of benzene points to in situ benzene biodegradation processes in the plume, probably supported by nitrate. In conclusion, nitrate injection resulted in changing redox conditions and recycling of sulphate in the sulphidic, sulphate-depleted benzene plume due to microbial oxidation of reduced sulphur species, leading to presumably favored conditions for in situ benzene biodegradation.

The arrival of a red invasive seaweed to a nutrient over-enriched estuary increases the spatial extent of macroalgal blooms.

The red seaweed Agarophyton vermiculophyllum is an invasive species native to the north-west Pacific, which has proliferated in temperate estuaries of Europe, North America and Africa. Combining molecular identification tools, historical satellite imagery and one-year seasonal monitoring of biomass and environmental conditions, the presence of A. vermiculophyllum was confirmed, and the invasion was assessed and reconstructed. The analysis of satellite imagery identified the first bloom in 2014 and revealed that A. vermiculophyllum is capable of thriving in areas, where native bloom-forming species cannot, increasing the size of blooms (ca. 10%). The high biomass found during the peak bloom (>2 kg m-2) and the observation of anoxic events indicated deleterious effects. The monitoring of environmental conditions and biomass variability suggests an essential role of light, temperature and phosphorous in bloom development. The introduction of this species could be considered a threat for local biodiversity and ecosystem functioning in a global change context.

Anoxic nitrogen cycling in a hydrocarbon and ammonium contaminated aquifer.

Nitrogen fate and transport through contaminated groundwater systems, where N is both ubiquitous and commonly limits pollutant attenuation, must be re-evaluated given evidence for new potential microbial N pathways. We addressed this by measuring the isotopic composition of dissolved inorganic N (DIN = NH4+, NO2-, and NO3-) and N functional gene abundances (amoA, nirK, nirS, hszA) from 20 to 38 wells across an NH4+, hydrocarbon, and SO42- contaminated aquifer. In-situ N attenuation was confirmed on three sampling dates (0, +6, +12 months) by the decreased [DIN] (4300 - 40 µM) and increased δ15N-DIN (5‰-33‰) over the flow path. However, the assumption of negligible N attenuation within the plume was complicated by the presence of alternative electron acceptors (SO42-, Fe3+), both oxidizing and reducing functional genes, and N oxides within this anoxic zone. Active plume N cycling was corroborated using an NO2- dual isotope based model, which found the fastest (∼10 day) NO2- turnover within the N and electron donor rich central plume. Findings suggest that N cycling is not always O2 limited within chemically complex contaminated aquifers, though this cycling may recycle the N species rather than attenuate N.

Occurrence of greenhouse gases in the aquifers of the Walloon Region (Belgium).

This work aims to (1) identify the most conductive conditions for the generation of greenhouses gases (GHGs) in groundwater (e.g., hydrogeological contexts and geochemical processes) and (2) evaluate the indirect emissions of GHGs from groundwater at a regional scale in Wallonia (Belgium). To this end, nitrous oxide (N2O), methane (CH4) and carbon dioxide (CO2) concentrations and the stable isotopes of nitrate (NO3-) and sulphate were monitored in 12 aquifers of the Walloon Region (Belgium). The concentrations of GHGs range from 0.05µg/L to 1631.2µg/L for N2O, 0µg/L to 17.1µg/L for CH4, and 1769 to 100,514ppm for the partial pressure of CO2 (pCO2). The highest average concentrations of N2O and pCO2 are found in a chalky aquifer. The coupled use of statistical techniques and stable isotopes is a useful approach to identify the geochemical conditions that control the occurrence of GHGs in the aquifers of the Walloon Region. The accumulation of N2O is most likely due to nitrification (high concentrations of dissolved oxygen and NO3- and null concentrations of ammonium) and, to a lesser extent, initial denitrification in a few sampling locations (medium concentrations of dissolved oxygen and NO3-). The oxic character found in groundwater is not prone to the accumulation of CH4 in Walloon aquifers. Nevertheless, groundwater is oversaturated with GHGs with respect to atmospheric equilibrium (especially for N2O and pCO2); the fluxes of N2O (0.32kgN2O-NHa-1y-1) and CO2 (27kgCO2Ha-1y-1) from groundwater are much lower than the direct emissions of N2O from agricultural soils and fossil-fuel-related CO2 emissions. Thus, indirect GHG emissions from the aquifers of the Walloon Region are likely to be a minor contributor to atmospheric GHG emissions, but their quantification would help to better constrain the nitrogen and carbon budgets.

River water infiltration enhances denitrification efficiency in riparian groundwater.

Nitrate contamination in ground- and surface water is a persistent problem in countries with intense agriculture. The transition zone between rivers and their riparian aquifers, where river water and groundwater interact, may play an important role in mediating nitrate exports, as it can facilitate intensive denitrification, which permanently removes nitrate from the aquatic system. However, the in-situ factors controlling riparian denitrification are not fully understood, as they are often strongly linked and their effects superimpose each other. In this study, we present the evaluation of hydrochemical and isotopic data from a 2-year sampling period of river water and groundwater in the riparian zone along a 3rd order river in Central Germany. Based on bi- and multivariate statistics (Spearman's rank correlation and partial least squares regression) we can show, that highest rates for oxygen consumption and denitrification in the riparian aquifer occur where the fraction of infiltrated river water and at the same time groundwater temperature, are high. River discharge and depth to groundwater are additional explanatory variables for those reaction rates, but of minor importance. Our data and analyses suggest that at locations in the riparian aquifer, which show significant river water infiltration, heterotrophic microbial reactions in the riparian zone may be fueled by bioavailable organic carbon derived from the river water. We conclude that interactions between rivers and riparian groundwater are likely to be a key control of nitrate removal and should be considered as a measure to mitigate high nitrate exports from agricultural catchments.

Tomography of anthropogenic nitrate contribution along a mesoscale river.

Elevated nitrate concentrations are a thread for water supply and ecological integrity in surface water. Nitrate fluxes obtained by standard monitoring protocols at the catchment outlet strongly integrate spatially and temporally variable processes such as mobilization and turnover. Consequently, inference of dominant nitrate sources is often problematic and challenging in terms of effective river management and prioritization of measures. Here, we combine a spatially highly resolved assessment of nitrate concentration and fluxes along a mesoscale catchment with four years of monitoring data at two representative sites. The catchment is characterized by a strong land use gradient from pristine headwaters to lowland sub-catchments with intense agricultural land use and wastewater sources. We use nitrate concentrations in combination with hydrograph separation and isotopic fingerprinting methods to characterize and quantify nitrate source contribution. The hydrological analysis revealed a clear dominance of base flow during both campaigns. However, the absolute amounts of discharge differed considerably from one another (outlet: 1.42m3s-1 in 2014, 0.43m3s-1 in 2015). Nitrate concentrations are generally low in the pristine headwaters (<3mgL-1) and increase downstream (15 to 16mgL-1) due to the contribution of agricultural and wastewater sources. While the agricultural contribution did not vary in terms of nitrate concentration and isotopic signature between the years, the wastewater contribution strongly increased with decreasing discharge. Wastewater-borne nitrate load in the entire catchment ranged between 19% (2014) and 39% (2015). Long-term monitoring of nitrate concentration and isotopic composition in two sub-catchment exhibits a good agreement with findings from spatially monitoring. In both datasets, isotopic composition indicates that denitrification plays only a minor role. The spatially highly resolved monitoring approach helped to pinpoint hot spots of nitrate inputs into the stream while the long-term information allowed to place results into the context of intra-annual variability.

Discharge Driven Nitrogen Dynamics in a Mesoscale River Basin As Constrained by Stable Isotope Patterns.

Nitrate loads and corresponding dual-isotope signatures were used to evaluate large scale N dynamics and trends in a river catchment with a strong anthropogenic gradient (forest conservation areas in mountain regions, and intensive agriculturally used lowlands). The Bode River catchment with an area of 3200 km(2) in the Harz Mountains and central German lowlands was investigated by a two years monitoring program including 133 water sampling points each representing a subcatchment. Based on discharge data either observed or simulated by the mesoscale hydrological model (mHM) a load based interpretation of hydrochemical and isotope data was conducted. Nitrate isotopic signatures in the entire catchment are influenced by (I) the contribution of different nitrogen sources, (II) by variable environmental conditions during the formation of nitrate, and (III) by a minor impact of denitrification. For major tributaries, a relationship between discharge and nitrate isotopic signatures is observed. This may in part be due to the fact, that during periods of higher hydrologic activity a higher wash out of isotopically lighter nitrate formed by bacterial nitrification processes of reduced or organic soil nitrogen occurs. Beyond that, in-stream denitrification seems to be more intense during periods of low flow.

Multi-species measurements of nitrogen isotopic composition reveal the spatial constraints and biological drivers of ammonium attenuation across a highly contaminated groundwater system.

Groundwater under industrial sites is characterised by heterogeneous chemical mixtures, making it difficult to assess the fate and transport of individual contaminants. Quantifying the in-situ biological removal (attenuation) of nitrogen (N) is particularly difficult due to its reactivity and ubiquity. Here a multi-isotope approach is developed to distinguish N sources and sinks within groundwater affected by complex industrial pollution. Samples were collected from 70 wells across the two aquifers underlying a historic industrial area in Belgium. Below the industrial site the groundwater contained up to 1000 mg N l(-1) ammonium (NH4(+)) and 300 mg N l(-1) nitrate (NO3(-)), while downgradient concentrations decreased to ∼1 mg l(-1) DIN ([DIN] = [NH4(+)N] + [NO3(-)N] + [NO2(-)N]). Mean δ(15)N-DIN increased from ∼2‰ to +20‰ over this flow path, broadly confirming that biological N attenuation drove the measured concentration decrease. Multi-variate analysis of water chemistry identified two distinct NH4(+) sources (δ(15)NNH4(+) from -14‰ and +5‰) within the contaminated zone of both aquifers. Nitrate dual isotopes co-varied (δ(15)N: -3‰ - +60‰; δ(18)O: 0‰ - +50‰) within the range expected for coupled nitrification and denitrification of the identified sources. The fact that δ(15)NNO2(-) values were 50‰-20‰ less than δ(15)NNH4(+) values in the majority of wells confirmed that nitrification controlled N turnover across the site. However, the fact that δ(15)NNO2(-) was greater than δ(15)NNH4(+) in wells with the highest [NH4(+)] shows that an autotrophic NO2(-) reduction pathway (anaerobic NH4(+) oxidation or nitrifier-denitrification) drove N attenuation closest to the contaminant plume. This direct empirical evidence that both autotrophic and heterotrophic biogeochemical processes drive N attenuation in contaminated aquifers demonstrates the power of multiple N isotopes to untangle N cycling in highly complex systems.

Regional nitrogen dynamics in the TERENO Bode River catchment, Germany, as constrained by stable isotope patterns.

Interactions between hydrological characteristics and microbial activities affect the isotopic composition of dissolved nitrate in surface water. Nitrogen and oxygen isotopic signatures of riverine nitrate in 133 sampling locations distributed over the Bode River catchment in the Harz Mountains, Germany, were used to identify nitrate sources and transformation processes. An annual monitoring programme consisting of seasonal sampling campaigns in spring, summer and autumn was conducted. δ(15)N and δ(18)O of nitrate and corresponding concentrations were measured as well as δ(2)H and δ(18)O of water to determine the deuterium excess. In addition, precipitation on 25 sampling stations was sampled and considered as a potential input factor. The Bode River catchment is strongly influenced by agricultural land use which is about 70 % of the overall size of the catchment. Different nitrogen sources such as ammonia (NH4) fertilizer, soil nitrogen, organic fertilizer or nitrate in precipitation show partly clear nitrate isotopic differences. Processes such as microbial denitrification result in fractionation and lead to an increase in δ(15)N of nitrate. We observed an evident regional and partly temporal variation of nitrate isotope signatures which are clearly different between main landscape types. Spring water sections within the high mountains contain nitrate in low concentrations with low δ(15)NNO3 values of -3 ‰ and high δ(18)ONO3 values up to 13 ‰. High mountain stream water sub-catchments dominated by nearly undisturbed forest and grassland contribute nitrate with δ(15)NNO3 and δ(18)ONO3 values of -1 and -3.5 ‰, respectively. In the further flow path, which is affected by an increasing agricultural land use and urban sewage, we recognized an increase in δ(15)NNO3 and δ(18)ONO3 up to 22 and 18 ‰, respectively, with high variations during the year. A correlation seems to exist between the percentage of agricultural land use area and the corresponding δ(15)NNO3 values for sub-catchments. A shift towards heavier isotope values in stream water samples taken in July 2012 is significant (p-value = 6 · 10(-6)) compared to samples from March and October 2012. We also see a season-depending impact of microbial denitrification. Denitrification, especially evident in the lowlands, predominantly takes place in the riverbeds. In addition, mixing processes of different nitrate sources and temperature-depending biological processes such as nitrification have to be taken into consideration. Constant-tempered groundwater does not play a noticeable role in the processes of the stream water system. As constrained from oxygen isotope signatures, precipitation associated with low nitrate concentrations does not have an obvious impact on stream water nitrate in the high mountain region.

Stable H and O isotope variations reveal sources of recharge in Dhofar, Sultanate of Oman.

Due to the ability of stable water isotopes to characterize the origin of water and connected processes of groundwater recharge, we used the isotope variations of hydrogen and oxygen in different water sources for assessing the recharge process in the Dhofar region. δ(18)O and δ(2)H of precipitation, spring water, and groundwater cover a range from -10 to +2 and from -70 to +7 ‰ (vs Vienna Standard Mean Ocean Water), respectively, and correlate in a linear relationship close to the Global Meteoric Water Line. No obvious evaporation processes are detected. A clear signal of the recent precipitation is given by the annual monsoon. The monsoon signal is confirmed by several springs existing in the south at the foot of the Dhofar mountains and sources at Gogub above 450 m and Tawi Atir at 650 m above sea level. They occur here first in the form of water intercepted by trees as stemflow and throughflow. The isotope signature of groundwater in the Dhofar mountains reflects the climatic conditions at the time of recharge and the lithological features of the limestone matrix. To the north, the isotope patterns of the groundwater are continuously depleted from the monsoon signal along the outcropping aquifer D (Lower Umm Er Radhuma). Here, a more negative signature towards the wells in the Najd desert region was observed. Cyclone water that flooded wadis in the Dhofar region occasionally, as observed in November 2011, falls isotopically into the same range as we observed in the fossil groundwater. Taking into account the different sources of precipitation and groundwater and thus a clear distinction of the isotopic composition of the water sources, we conclude a recharge process divided into a southward and a northward component in the Dhofar region.

Stable sulfur and oxygen isotope fractionation of anoxic sulfide oxidation by two different enzymatic pathways.

The microbial oxidation of sulfide is a key reaction of the microbial sulfur cycle, recycling sulfur in its most reduced valence state back to more oxidized forms usable as electron acceptors. Under anoxic conditions, nitrate is a preferential electron acceptor for this process. Two enzymatic pathways have been proposed for sulfide oxidation under nitrate reducing conditions, the sulfide:quinone oxidoreductase (SQR) pathway and the Sox (sulfur oxidation) system. In experiments with the model strains Thiobacillus denitrificans and Sulfurimonas denitrificans, both pathways resulted in a similar small sulfur and oxygen isotope fractionation of -2.4 to -3.6‰ for (34)S and -2.4 to -3.4‰ for (18)O. A similar pattern was detected during the oxidation of sulfide in a column percolated with sulfidic, nitrate amended groundwater. In experiments with (18)O-labeled water, a strong oxygen isotope fractionation was observed for T. denitrificans and S. denitrificans, indicating a preferential incorporation of (18)O-depleted oxygen released as water by nitrate reduction to nitrogen. The study indicates that nitrate-dependent sulfide oxidation might be monitored in the environment by analysis of (18)O-depleted sulfate.

No nitrification in lakes below pH 3.

Lakes affected by acid mine drainage (AMD) or acid rain often contain elevated concentrations of ammonium, which threatens water quality. It is commonly assumed that this is due to the inhibition of microbial nitrification in acidic water, but nitrification was never directly measured in mine pit lakes. For the first time, we measured nitrification by (15)NH4Cl isotope tracer addition in acidic as well as neutral mine pit lakes in Spain and Germany. Nitrification activity was only detected in neutral lakes. In acidic lakes no conversion of (15)NH4(+) to (15)NO3(-) was observed. This was true both for the water column as well as for biofilms on the surface of macrophytes or dead wood and the oxic surface layer of the sediment. Stable isotope analysis of nitrate showed (18)O values typical for nitrification only in neutral lakes. In a comparison of NH4(+) concentrations in 297 surface waters with different pH, ammonium concentrations higher 10 mg NH4-N L(-1) were only observed in lakes below pH 3. On the basis of the results from stable isotope investigations and the examination of a metadata set we conclude that the lower limit for nitrification in lakes is around pH 3.

Characterization of the relationship between microbial degradation processes at a hydrocarbon contaminated site using isotopic methods.

Decisions to employ monitored natural attenuation (MNA) as a remediation strategy at contaminated field sites require a comprehensive characterization of the site-specific biodegradation processes. In the present study, compound-specific carbon and hydrogen isotope analysis (CSIA) was used to investigate intrinsic biodegradation of benzene and ethylbenzene in an aquifer with high levels of aromatic and aliphatic hydrocarbon contamination. Hydrochemical data and isotope fractionation analysis of sulfate and methane was used complementarily to elucidate microbial degradation processes over the course of a three year period, consisting of six sampling campaigns, in the industrial area of Weißandt-Gölzau (Saxony-Anhalt, Germany). Enrichment of (13)C and (2)H isotopes in the residual benzene and ethylbenzene pool downgradient from the pollution sources provided evidence of biodegradation of BTEX compounds at this site, targeting both compounds as the key contaminants of concern. The enrichment of heavy sulfur isotopes accompanied by decreasing sulfate concentrations and the accumulation of isotopically light methane suggested that sulfate-reducing and methanogenic processes are the major contributors to overall biodegradation in this aquifer. Along the contaminant plume, the oxidation of methane with δ(13)C(CH4) values of up to +17.5‰ was detected. This demonstrates that methane formed in the contaminant source can be transported along groundwater flow paths and be oxidized in areas with higher redox potentials, thereby competing directly with the pollutants for electron acceptors. Hydrochemical and isotope data was summarized in a conceptual model to assess whether MNA can be used as viable remediation strategy in Weißandt-Gölzau. The presented results demonstrate the benefits of combining different isotopic methods and hydrochemical approaches to evaluate the fate of organic pollutants in contaminated aquifers.

Stable isotope fractionation related to technically enhanced bacterial sulphate degradation in lignite mining sediments.

A mine dump aquifer in the Lusatian lignite mining district, Germany, is contaminated with acid mine drainage (AMD). The only natural process that can counteract the effects of the contamination is bacterial sulphate reduction. The technical measures chosen to handle the contamination include the injection of glycerol into the aquifer to supply electron donors and to accelerate the growth and activity of sulphate-reducing bacteria. An initial assessment of the hydrochemical conditions in the aquifer showed that sulphate concentrations are subject to alteration due to flow-related processes. Consequently, the decision whether sulphate reduction is occurring in the investigated aquifer section was based on the stable isotopic composition of dissolved sulphate and sulphide, which were used in combination with sulphate concentrations. The significant enrichment of both heavy sulphur and heavy oxygen in the remaining sulphate pool and a characteristic isotope fractionation pattern are a clear evidence for the activity of sulphate-reducing bacteria utilising the injected glycerol as an electron donor. This activity seemed to intensify over the observation period. The spatial distribution of sulphate reduction activity, however, appeared to be highly inhomogeneous. Rather than occurring ubiquitously, sulphate reduction activity seemed to concentrate in a defined reaction zone. Regardless of the inhomogeneous distribution, the overall turnover of sulphate during the period of investigation proves the applicability of this enhanced natural attenuation method to handle the restoration of aquifers contaminated with AMD.