Tracking sources of unsaturated zone and groundwater nitrate contamination using nitrogen and oxygen stable isotopes at the Hanford site, Washington

The nitrogen and oxygen isotopic compositions of nitrate in pore water extracts from unsaturated zone (UZ) core samples and groundwater samples indicate at least four potential sources of nitrate in groundwaters at the U.S. DOE Hanford Site in south-central Washington. Natural sources of nitrate identified include microbially produced nitrate from the soil column (delta15N of 4 - 8 per thousand, delta18O of -9 to 2 per thousand) and nitrate in buried caliche layers (delta15N of 0-8 per thousand, delta 18O of -6to 42 per thousand). Isotopically distinctindustrial sources of nitrate include nitric acid in low-level disposal waters (delta15N approximately per thousand, delta 18O approximately 23%o) per thousandnd co-contaminant nitrate in high-level radioactive waste from plutonium processing (6'5delta1of 8-33 % o, per thousand18delta oO -9 to 7%0). per thousandThe isotopic compositions of nitrate from 97 groundwater wells with concentrations up to 1290 mg/L NO3- have been analyzed. Stable isotope analyses from this study site, which has natural and industrial nitrate sources, provide a tool to distinguish nitrate sources in an unconfined aquiferwhere concentrations alone do not. These data indicate that the most common sources of high nitrate concentrations in groundwater at Hanford are nitric acid and natural nitrate flushed out of the UZ during disposal of low-level wastewater. Nitrate associated with high-level radioactive UZ contamination does not appear to be a major source of groundwater nitrate at this time.     

Sources and processes affecting sulfate in a karstic groundwater system of the Franconian Alb, southern Germany

Chemical and isotope analyses on groundwater sulfate and 3H measurements on groundwaterwere used to determine the sulfate sources and sulfur transformation processes in a heterogeneous karst aquifer of the Franconian Alb, southern Germany. Sulfate was found to be derived from atmospheric deposition. Young groundwater was characterized by high sulfate concentrations and delta34S values similar to those of recent atmospheric sulfate deposition. However, the delta18O values of groundwater SO4(2-) were depleted by several per mil with respect to those of atmospheric deposition. This isotopic shift is indicative of mineralization of carbon-bonded S in the vadose zone of the karst system. In groundwater with mean residence times of more than 60 years, a trend of increasing delta34S values and delta18O values with decreasing sulfate concentrations was observed. This trend could not be solely explained by preindustrial atmospheric sulfate deposition with higher delta34S values, and hence, we conclude that bacterial (dissimilatory) sulfate reduction in the porous matrix of the karst aquifer must have occurred. This process has the potential to contribute to long-term biodegradation of contaminants in the porous rock matrix representing the dominantwater reservoir of the fissured porous karst aquifer.     

Identifying sources of nitrogen to Hanalei Bay, Kauai, utilizing the nitrogen isotope signature of macroalgae

Sewage effluent, storm runoff, discharge from polluted rivers, and inputs of groundwater have all been suggested as potential sources of land derived nutrients into Hanalei Bay, Kauai. We determined the nitrogen isotopic signatures (delta(15)N) of different nitrate sources to Hanalei Bay along with the isotopic signature recorded by 11 species of macroalgal collected in the Bay. The macroalgae integrate the isotopic signatures of the nitrate sources over time, thus these data along with the nitrate to dissolved inorganic phosphate molar ratios (N:P) of the macroalgae were used to determine the major nitrate source to the bay ecosystem and which of the macro-nutrients is limiting algae growth, respectively. Relatively low delta(15)N values (average -0.5% per hundred) were observed in all algae collected throughout the Bay; implicating fertilizer, rather than domestic sewage, as an important external source of nitrogen to the coastal water around Hanalei. The N:P ratio in the algae compared to the ratio in the Bay waters imply that the Hanalei Bay coastal ecosystem is nitrogen limited and thus, increased nitrogen input may potentially impact this coastal ecosystem and specifically the coral reefs in the Bay. Identifying the major source of nutrient loading to the Bay is important for risk assessment and potential remediation plans.     

Effect of storage on the isotopic composition of nitrate in bulk precipitation

Stable isotopic analysis of atmospheric nitrate is increasingly employed to study nitrate sources and transformations in forested catchments. Large volumes have typically been required for delta18O and delta15N analysis of nitrate in precipitation due to relatively low nitrate concentrations. Having bulk collectors accumulate precipitation over an extended time period allows for collection of the required volume as well as reducing the total number of analyses needed to determine the isotopic composition of mean annual nitrate deposition. However, unfiltered precipitation left in collectors might be subject to microbial reactions that can alter the isotopic signature of nitrate in the sample. Precipitation obtained from the Turkey Lakes Watershed was incubated under conditions designed to mimic unfiltered storage in bulk precipitation collectors and monitored for changes in nitrate concentration, delta15N, and delta18O. Results of this experiment indicated that no detectable nitrate production or assimilation occurred in the samples during a two-week incubation period and that atmospheric nitrate isotopic ratios were preserved. The ability to collect unfiltered precipitation samples for an extended duration without alteration of nitrate isotope ratios is particularly useful at remote study sites where daily retrieval of samples may not be feasible.     

Decadal geochemical and isotopic trends for nitrate in a transboundary aquifer and implications for agricultural beneficial management practices

Nitrate contamination of aquifers is a global agricultural problem. Agricultural beneficial management practices (BMPs) are often promoted as a means to reduce nitrate contamination in aquifers through producer optimized management of inorganic fertilizer and animal manure inputs. In this study, decadal trends (1991-2004) in nitrate concentrations in conjunction with 3H/3He groundwater ages and nitrate stable isotopes (delta15N, delta18O) were examined to determine whether BMPs aimed at reducing aquifer-scale nitrate contamination in the transboundary Abbotsford-Sumas aquifer were effective. A general trend of increasing nitrate concentrations in young groundwater (< approximately 5 yr) suggested that voluntary BMPs were not having a positive impact in achieving groundwater quality targets. While the stable isotope data showed that animal manure was and still is the prevalent source of nitrate in the aquifer, a recent decrease in delta15N in nitrate suggests a BMP driven shift away from animal wastes toward inorganic fertilizers. The coupling of long-term monitoring of nitrate concentrations, nitrate isotopes, and 3H/3He age dating proved to be invaluable, and they should be considered in future assessments of the impact of BMPs on nutrients in groundwaters. The findings reveal that BMPs should be better linked to groundwater nutrient monitoring programs in order to more quickly identify BMP deficiencies, and to dynamically adjust nutrient loadings to help achieve water quality objectives.     

Tracing atmospheric nitrate deposition in a complex semiarid ecosystem using delta17O

The isotopic composition of nitrate collected from aerosols, fog, and precipitation was measured and found to have a large 17O anomaly with delta17O values ranging from 20 percent per thousand to 30% percent per thousand (delta17O = delta17O - 0.52(delta18O)). This 17O anomaly was used to trace atmospheric deposition of nitrate to a semiarid ecosystem in southern California. We demonstrate that the delta17O signal is a conserved tracer of atmospheric nitrate deposition and is a more robust indicator of N deposition relative to standard delta18O techniques. The data indicate that a substantial portion of nitrate found in the local soil, stream, and groundwater is of atmospheric origin and does not undergo biologic processing before being exported from the system.     

Saturated zone denitrification: potential for natural attenuation of nitrate contamination in shallow groundwater under dairy operations

We present results from field studies at two central California dairies that demonstrate the prevalence of saturated-zone denitrification in shallow groundwater with 3H/ 3He apparent ages of < 35 years. Concentrated animal feeding operations are suspected to be major contributors of nitrate to groundwater, but saturated zone denitrification could mitigate their impact to groundwater quality. Denitrification is identified and quantified using N and O stable isotope compositions of nitrate coupled with measurements of excess N2 and residual NO3(-) concentrations. Nitrate in dairy groundwater from this study has delta15N values (4.3-61 per thousand), and delta18O values (-4.5-24.5 per thousand) that plot with delta18O/delta15N slopes of 0.47-0.66, consistent with denitrification. Noble gas mass spectrometry is used to quantify recharge temperature and excess air content. Dissolved N2 is found at concentrations well above those expected for equilibrium with air or incorporation of excess air, consistent with reduction of nitrate to N2. Fractionation factors for nitrogen and oxygen isotopes in nitrate appear to be highly variable at a dairy site where denitrification is found in a laterally extensive anoxic zone 5 m below the water table, and at a second dairy site where denitrification occurs near the water table and is strongly influenced by localized lagoon seepage.     

Indirect emissions of nitrous oxide from regional aquifers in the United Kingdom

Diffuse pollution of groundwater by agriculture has caused elevated concentrations of nitrate (NO3-) and nitrous oxide (N2O) in regional aquifers. N2O is an important "greenhouse" gas, yet there are few estimates of indirect emissions of N2O from regional aquifers. In this study, high concentrations of N2O (mean 602 nM) were measured in the unconfined Chalk aquifer of eastern England, in an area of intensive agriculture. In contrast, pristine groundwaters from upland regions of England and Scotland, with predominantly natural vegetation cover, were found to have much lower concentrations of N2O (mean 27 nM). A positive relationship between N2O and NO3- concentrations and delta18O-NO3 values of between 3.36 and 16.00/1000 suggest that nitrification is the principal source of N2O. A calculated emission factor (EF5-g) of 0.0019 for indirect losses of N2O from Chalk groundwater is an order of magnitude lower than the value of 0.015 currently used in the Intergovernmental Panel on Climate Change (IPCC) methodology for assessing agricultural emissions. A flux of N2O from the major UK aquifers of 0.04 kg N2O-N ha(-1) a(-1) has been calculated using two approaches and suggests that indirect losses of N2O from regional aquifers are much less significant (<1%) than direct emissions from agricultural soils.     

Carbon and nitrogen isotope variations in tree-rings as records of perturbations in regional carbon and nitrogen cycles

Increasing anthropogenic pollution from urban centers and fossil fuel combustion can impact the carbon and nitrogen cycles in forests. To assess the impact of twentieth century anthropogenic pollution on forested system carbon and nitrogen cycles, variations in the carbon and nitrogen isotopic compositions of tree-rings were measured. Individual annual growth rings in trees from six sites across Ontario and one in New Brunswick, Canada were used to develop site chronologies of tree-ring delta 15N and delta 13C values. Tree-ring 615N values were approximately 0.5% per hundred higher and correlated with contemporaneous foliar samples from the same tree, but not with delta 15N values of soil samples. Temporal trends in carbon and nitrogen isotopic compositions of these tree-rings are consistent with increasing anthropogenic influence on both the carbon and nitrogen cycles since 1945. Tree-ring delta 13C values and delta 15N values are correlated at both remote and urban-proximal sites, with delta 15N values decreasing since 1945 and converging on 1% per hundred at urban-proximal sites and decreasing but not converging on a single delta 15N value in remote sites. These results indicate that temporal trends in tree-ring nitrogen and carbon isotopic compositions record the regional extent of pollution.     

Anaerobic methane oxidation in a landfill-leachate plume

The alluvial aquifer adjacent to Norman Landfill, OK, provides an excellent natural laboratory for the study of anaerobic processes impacting landfill-leachate contaminated aquifers. We collected groundwaters from a transect of seven multilevel wells ranging in depth from 1.3 to 11 m that were oriented parallel to the flow path. The center of the leachate plume was characterized by (1) high alkalinity and elevated concentrations of total dissolved organic carbon, reduced iron, and methane, and (2) negligible oxygen, nitrate, and sulfate concentrations. Methane concentrations and stable carbon isotope (delta13C) values suggest anaerobic methane oxidation was occurring within the plume and at its margins. Methane delta13C values increased from about -54 per thousand near the source to > -10 per thousand downgradient and at the plume margins. The isotopic fractionation associated with this methane oxidation was -13.6+/-1.0 per thousand. Methane 13C enrichment indicated that 80-90% of the original landfill methane was oxidized over the 210-m transect. First-order rate constants ranged from 0.06 to 0.23 per year, and oxidation rates ranged from 18 to 230 microM/y. Overall, hydrochemical data suggest that a sulfate reducer-methanogen consortium may mediate this methane oxidation. These results demonstrate that natural attenuation through anaerobic methane oxidation can be an important sink for landfill methane in aquifer systems.     

Ecohydrological factors affecting nitrate concentrations in a phreatic desert aquifer in northwestern China

Aerobic conditions in desert aquifers commonly allow high nitrate (NO3-) concentrations in recharge to persist for long periods of time, an important consideration for N-cycling and water quality. In this study, stable isotopes of NO3- (delta15N(NO3) and delta18O(NO3)) were used to trace NO3- cycling processes which affect concentrations in groundwater and unsaturated zone moisture in the arid Badain Jaran Desert in northwestern China. Most groundwater NO3- appears to be depleted relative to Cl- in rainfall concentrated by evapotranspiration, indicating net N losses. Unsaturated zone NO3- is generally higher than groundwater NO3- in terms of both concentration (up to 15 476 microM, corresponding to 3.6 mg NO3(-)-N per kg sediment) and ratios with Cl-. Isotopic data indicate that the NO3- derives primarily from nitrification, with a minor direct contribution of atmospheric NO3- inferred for some samples, particularly in the unsaturated zone. Localized denitrification in the saturated zone is suggested by isotopic and geochemical indicators in some areas. Anthropogenic inputs appear to be minimal, and variability is attributed to environmental factors. In comparison to other arid regions, the sparseness of vegetation in the study area appears to play an important role in moderating unsaturated zone NO3- accumulation by allowing solute flushing and deterring extensive N2 fixation.     

Using delta15N- and delta18O-values to identify nitrate sources in karst ground water, Guiyang, southwest China

Nitrate pollution of the karstic groundwater is an increasingly serious problem with the development of Guiyang, the capital city of Guizhou Province, southwest China. The higher content of NO3- in groundwater compared to surface water during both summer and winter seasons indicates that the karstic groundwater system cannot easily recover once contaminated with nitrate. In order to assess the sources and conversion of nitrate in the groundwater of Guiyang, we analyzed the major ions, delta(15)N-NH4+, delta(15)N-NO3-, and delta(18)O-NO3- in surface and groundwater samples collected during both summer and winter seasons. The results show that nitrate is the major dominant species of nitrogen in most water samples and there is a big variation of nitrate sources in groundwater between winter and summer season, due to fast response of groundwater to rain or surface water in the karst area. Combined with information on NO3- /Cl-, the variations of the isotope values of nitrate in the groundwater show a mixing process of multiple sources of nitrate, especially in the summer season. Chemical fertilizer and nitrification of nitrogen-containing organic materials contribute nitrate to suburban groundwater, while the sewage effluents and denitrification mainly control the nitrate distribution in urban groundwater.     

Stable isotope analysis reveals lower-order river dissolved inorganic carbon pools are highly dynamic

River systems draining peaty catchments are considered a source of atmospheric CO2,thus understanding the behavior of the dissolved inorganic carbon pool (DIC) is valuable. The carbon isotopic composition, delta13C(DIC), and concentration, [DIC], of fluvial samples collected diurnally, over 14 months, reveal the DIC pools to be dynamic in range (-22 to -4.9% per hundred, 0.012 to 0.468 mmol L(-1) C), responding predictably to environmental influences such as changing hydrologic conditions or increased levels of primary production. delta(18)O of dissolved oxygen (DO) corroborates the delta(13)C(DIC) interpretation. A nested catchment sampling matrix reveals that similar processes affect the DIC pool and thus delta(13)C(DIC) across catchment sizes. Not so with [DIC]: at high flow, the DIC export converges across catchment size, but at low flow catchments diverge in their DIC load. Contextualizing delta(13)C with discharge reveals that organic soil-waters and groundwaters comprise end-member sources, which in varying proportions constitute the fluvial DIC pool. Discharge and pH describe well [DIC] and delta(13)C(DIC), allowing carbon to be apportioned to each end-member from continuous profiles, demonstrated here for the hydrological year 2003-2004. This approach is powerful for assessing whether the dynamic response exhibited here is ubiquitous in other fluvial systems at the terrestrial-aquatic interface or in larger catchments.     

Nitrate contamination in groundwater on an urbanized dairy farm

Urbanization of rural farmland is a pervasive trend around the globe, and maintaining and protecting adequate water supplies in suburban areas is a growing problem. Identification of the sources of groundwater contamination in urbanized areas is problematic, but will become important in areas of rapid population growth and development. The isotopic composition of NO3 (delta15N(NO3) and delta18O NO3), NH4 (delta15N(NH4)), groundwater (delta2H(wt) and delta18O(wt)) and chloride/bromide ratios were used to determine the source of nitrate contamination in drinking water wells in a housing development that was built on the site of a dairy farm in the North Carolina Piedmont, U.S. The delta15N(NO3) and delta18O NO3 compositions imply that elevated nitrate levels at this site in drinking well water are the result of waste contamination, and that denitrification has not significantly attenuated the groundwater nitrate concentrations. delta15N(NO3) and delta18O(NO3) compositions in groundwater could not differentiate between septic effluent and animal waste contamination. Chloride/ bromide ratios in the most contaminated drinking water wells were similar to ratios found in animal waste application fields, and were higher than Cl/Br ratios observed in septic drain fields in the area. delta18O(wt) was depleted near the site of a buried waste lagoon without an accompanying shift in delta2H(wt) suggesting water oxygen exchange with CO2. This water-CO2 exchange resulted from the reduction of buried lagoon organic matter, and oxidation of the released gases in aerobic soils. delta18O(wt) is not depleted in the contaminated drinking water wells, indicating that the buried dairy lagoon is not a source of waste contamination. The isotope and Cl/Br ratios indicate that nitrate contamination in these drinking wells are not from septic systems, but are the result of animal waste leached from pastures into groundwater during 35 years of dairy operations which did not violate any existing regulations. Statutes need to be enacted to protect the health of the homeowners that require well water to be tested prior to the sale of homes built on urbanized farmland.     

Using ¹⁷O to investigate nitrate sources and sinks in a semi-arid groundwater system

We apply a triple isotope approach for nitrate that utilizes Δ(17)O as a conservative tracer, in combination with δ(18)O and δ(15)N, to assess source/sink dynamics of groundwater nitrate beneath alluvial washes in a semiarid urban setting. Other studies have used δ(18)O and δ(15)N to determine nitrate sources and cycling, but the atmospheric δ(18)O signature can be overprinted by biogeochemical processes. In this study, δ(18)O and δ(15)N values of nitrate were coupled with δ(17)O values of nitrate to quantify atmospheric nitrate inputs and denitrification amounts. Results show generally low groundwater nitrate concentrations (<0.2 mmol/L) throughout the basin; high nitrate concentrations (up to 1 mmol/L) with evidence for some denitrification were detected in areas where effluent was the predominant source of recharge to groundwater. Furthermore, the denitrification was inferred from elevated δ(18)O and δ(15)N values which were reinforced by increases in observed δ(17)O values. Finally, relatively low, but significant atmospheric nitrate concentrations were measured in groundwater (up to 6% of total nitrate). This study concludes that the triple isotope approach improves determination of the proportion of atmospheric nitrate and the significance of denitrification in natural waters, allowing us to develop a conceptual model of the biogeochemical processes controlling nitrogen in an urban setting.     

Catchment-scale quantification of hyporheic denitrification using an isotopic and solute flux approach

A dual-isotope and solute flux mass-balance was used to elucidate the processes that lead to attenuation of nitrogen contamination in an agriculturally impacted river. The River Wensum drains a lowland catchment with an area of 570 km2 in East Anglia, eastern England. Analysis of nitrate concentration, δ1?N(NO?) and δ1?O(NO?) of samples from the River Wensum collected from upstream locations to the catchment outlet through all seasons and flow conditions showed a consistent pattern of increasing isotope values with decreasing nitrate concentrations downstream. δ1?N(NO?) and δ1?O(NO?) of catchment surface water and groundwater samples revealed a dominant influence from microbially cycled and nitrified source-nitrogen, which results in high nitrate concentrations in Chalk groundwater and upstream in the River Wensum. Denitrification of Chalk groundwater-baseflow in the hyporheic zone results in the downstream trend observed in the river. Hyporheic denitrification is estimated to remove 931 kg/day of nitrate-nitrogen by the catchment outlet, representing 31% of the potential riverine nitrate load. The use of dual-isotope and solute flux modeling at the catchment scale is a novel application to quantify denitrification within the river valley, demonstrating the importance of hyporheic zone processes in attenuating the impacts of anthropogenic contamination of hydrologic systems.     

Do ponds cause arsenic-pollution of groundwater in the Bengal basin? An answer from West Bengal

We report time-series data collected over two years for delta18O, delta2H, and Ca, Mg, K, and Cl, concentrations for 10 ponds in, and upflow of, an As-polluted region of southern West Bengal. We compare the compositions of As-polluted groundwaters from wells with the compositions of waters in ponds upflow, and within the range of influence, of the wells. Conservative tracers (delta18O, delta2H, K), and other tracers (Ca, Mg) that are likely conservative in the waters, showthat pondwater and groundwater are distinct and do not overlap in composition. These data show that water from ponds cannot be identified in As-polluted groundwater, so putative DOC in pondwater cannot be mixing into the As-polluted groundwater we have sampled. Separate estimates of the degree of recharge from ponds to groundwater, using calculations based on temporal variations in salt content and isotopic composition in ponds, and salt-balance, show that insignificant amounts of As-polluted groundwater are derived via pond recharge. It follows that pondwater in the study area does not contribute significant mass to arsenic-polluted groundwater and so does not provide organic matterto aquifers in amounts sufficientto drive reduction of iron oxyhydroxides and hence arsenic pollution.     

Response of the nitrogen isotopic composition of tree-rings following tree-clearing and land-use change

Clear-cutting of forests affects the nitrogen cycle and the nitrogen isotopic composition of bioavailable ammonium and nitrate in the soil. Here, we have used nitrogen isotopic variations of tree-rings in red oak (Quercus rubra) and white oak (Quercus alba) as indicators of changes in the nitrogen cycle on a local scale. The delta15N values of late-wood from trees at two remnant forest stands in Ontario, Canada, that underwent large-scale tree-clearing and permanent land-use change at different times were measured. Trees from the perimeter of each stand record a marked 1.5-2.5 per thousand increase in the delta15N values of their tree-rings relative to the values in trees from the center of the stand, with the shift synchronous with the tree-clearing and land-use change. This shift was most likely due to increased rates of nitrification and nitrate leaching in the soil as a result of tree-clearing combined with permanent changes in hydrology and probable fertilizer use accompanying the change in land-use. Nitrogen concentration in tree-rings was not affected bytree-clearing and the associated change in land-use. These results indicate that changes in nitrogen cycling in forest ecosystems, whether due to climate change, land-use change, or other environmental changes (increased O3, other atmospheric pollutants, insects, etc.), can be faithfully monitored with nitrogen isotopic compositions of tree-rings and that dendrogeochemical analysis can be incorporated into studies of the effects of long-term anthropogenic effects on forest ecosystems.     

Assessment of groundwater pollution in Tokyo using PPCPs as sewage markers

While the occurrence of pharmaceuticals and personal care products (PPCPs) in groundwater has typically been reported in bank filtration sites, irrigated fields, septic tanks, and sewage disposal practices, fewer studies have been conducted in highly urbanized areas, where infiltration of treated or untreated sewage is not supposed to be a source of groundwater recharge. Furthermore, little is known about the occurrence of various kinds of PPCPs in relation to microbial indicators in groundwater from different types of aquifers. Thus, we examined the city-wide occurrence of selected PPCPs (diethyltoluamide, crotamiton, ethenzamide, propyphenazone, carbamazepine, and caffeine) and E. coli in 50 groundwaters from unconfined aquifers (<30 m in depth) and confined aquifers (up to 500 m in depth) in Tokyo, where unintended groundwater contamination could take place due to decrepit sewer networks. PPCPs were detected in unconfined aquifers and springs (23/34 samples, 68%), and in confined aquifers (7/16 samples, 44%). Compared with published results for sewage influents, concentrations of PPCPs, excluding caffeine, were generally 1-2 orders of magnitude lower, while in some samples concentrations were quite comparable. The high occurrence rate of PPCPs, even in confined aquifers, indicated that such aquifers are not always protected from pollution by sewage near the land surface. Among the PPCPs analyzed, carbamazepine and crotamiton were most frequently detected, which would appear to be owing to their high persistence, combined with the high concentration of crotamiton in sewage. Crotamiton was detected in all four E. coli-positive groundwaters, and thus may potentially serve as a precautionary indicator of E. coli contamination. Using carbamazepine as a sewage marker, we estimated that 0.8%-1.7% of the dry-weather flow of sewage was leaking out into the unconfined aquifers.     

Evidence for incorporation of H2S in groundwater fulvic acids from stable isotope ratios and sulfur K-edge X-ray absorption near edge structure spectroscopy

Groundwater samples collected in a shallow oxic and reduced deep groundwater system revealed the influence of dissolved sulfide on the chemical and isotopic composition of fulvic acid associated sulfur. Stable isotope compositions of groundwater sulfate and fulvic acid sulfur and sulfur K-edge X-ray absorption near edge structure (XANES) spectroscopy data were used to determine the sources and processes affecting fulvic acid sulfur in the aquifer. A delta34S value of 2.2 per thousand for the shallow groundwater sulfate and a delta34S value of fulvic acids of 4.9 per thousand accompanied by a contribution of up to 49% of the most oxidized sulfur species (S+6) documented that fulvic acid sulfur is mainly derived from soil S compounds such as ester sulfates, with delta34S values similar to those of atmospheric sulfate deposition. In contrast, in the deep groundwater system with elevated delta34S values in groundwater sulfate of up to 20per thousand due to bacterial sulfate reduction, delta34S values in fulvic acid sulfur were negative and were up to 22per thousand lower compared to those of groundwater sulfate. Furthermore, reduced sulfur compounds constituted a significantly higher proportion of total fulvic acid sulfur in the deep groundwater compared to fulvic acids in shallow groundwater, supporting the hypothesis that fulvic acids act as a sink for dissolved hydrogen sulfide in the deep aquifer. Our results suggest that the combination of sulfur K edge XANES spectroscopy and stable isotope analysis on fulvic acids represents a powerful tool to elucidate the role of fulvic acids in the sulfur cycle in groundwater.