Perchlorate in pleistocene and holocene groundwater in north-central New Mexico

Groundwater from remote parts of the Middle Rio Grande Basin in north-central New Mexico has perchlorate (ClO4-) concentrations of 0.12-1.8 micro/L. Because the water samples are mostly preanthropogenic in age (0-28000 years) and there are no industrial sources in the study area, a natural source of the ClO4- is likely. Most of the samples have Br-, Cl-, and SO4(2-) concentrations that are similar to those of modern bulk atmospheric deposition with evapotranspiration (ET) factors of about 7-40. Most of the ET values for Pleistocene recharge were nearly twice that for Holocene recharge. The N03-/Cl- and CIO-/Cl-ratios are more variable than those of Br-/Cl- or S04(2-)/Cl-. Samples thought to have recharged under the most arid conditions in the Holocene have relatively high N03-/Cl- ratios and low delta 15N values (+1 per mil (% per thousand)) similar to those of modern bulk atmospheric N deposition. The delta 18O values of the N03- (-4 to 0% per thousand) indicate that atmospheric N03- was not transmitted directly to the groundwater but may have been cycled in the soils before infiltrating. Samples with nearly atmospheric N03-/CI- ratios have relatively high Cl04- concentrations (1.0-1.8 ug/L) with a nearly constant Cl04-/CI- mole ratio of (1.4 +/- 0.1) x 10(-4), which would be consistent with an average Cl04-concentration of 0.093 0.005 ,ug/L in bulk atmospheric deposition during the late Holocene in north-central NM. Samples thought to have recharged under wetter conditions have higher delta 15N values (+3 to +8 % per thousando), lower NO3-/Cl- ratios, and lower ClO4-/Cl- ratios than the ones most likely to preserve an atmospheric signal. Processes in the soils that may have depleted atmospherically derived NO3-also may have depleted ClO4- to varying degrees prior to recharge. If these interpretations are correct, then ClO4- concentrations of atmospheric origin as high as 4 microg/L are possible in preanthropogenic groundwater in parts of the Southwest where ET approaches a factor of 40. Higher Cl04- concentrations in uncontaminated groundwater could occur in recharge beneath arid areas where ET is greater than 40, where long-term accumulations of atmospheric salts are leached suddenly from dry soils, or where other (nonatmospheric) natural sources of ClO4- exist.     

Regional patterns in the isotopic composition of natural and anthropogenic nitrate in groundwater, High Plains, U.S.A

Mobilization of natural nitrate (NO3-) deposits in the subsoil by irrigation water in arid and semiarid regions has the potential to produce large groundwater NO3-concentrations. The use of isotopes to distinguish between natural and anthropogenic NO3- sources in these settings could be complicated by the wide range in delta15N values of natural NO3-. An approximately 10 000 year record of paleorecharge from the regionally extensive High Plains aquifer indicates that delta15N values for NO3- derived from natural sources ranged from 1.3 to 12.3 per thousand and increased systematically from the northern to the southern High Plains. This collective range in delta15N values spans the range that might be interpreted as evidence for fertilizer and animal-waste sources of NO3-; however, the delta15N values for NO3- in modern recharge (< 50 years) under irrigated fields were, for the most part, distinctly different from those of paleorecharge when viewed in the overall regional context. An inverse relation was observed between the delta15N[NO3-] values and the NO3-/Cl- ratios in paleorecharge that is qualitatively consistent with fractionating losses of N increasing from north to south in the High Plains. N and O isotope data for NO3- are consistent with both NH3 volatilization and denitrification, having contributed to fractionating losses of N prior to recharge. The relative importance of different isotope fractionating processes may be influenced by regional climate patterns as well as by local variation in soils, vegetation, topography, and moisture conditions.     

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.     

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.     

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 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.     

Tracking the sources of nitrate in groundwater using coupled nitrogen and boron isotopes: a synthesis

Nitrate (NO3) is one of the world's major pollutants of drinking water resources. Although recent European Directives have reduced input from intensive agriculture, NO3 levels in groundwater are approaching the drinking water limit of 50 mg L(-1) almost everywhere. Determining the sources of groundwater contamination is an important first step toward improving its quality by emission control. It is with this aim that we review here the benefit of using a coupled isotopic approach (delta15N and delta11B), in addition to conventional hydrogeological analyses, to trace the origin of NO3 in water. The studied watersheds include both fractured bedrock and alluvial (subsurface and deep) hydrogeological contexts. The joint use of nitrogen and boron isotope systematics in each context deciphers the origin of NO3 in the groundwater and allows a semi-quantification of the contributions of the respective pollution sources (mineral fertilizers, wastewater, and animal manure).     

Widespread presence of naturally occurring perchlorate in high plains of Texas and New Mexico

Perchlorate (CLO4-) occurrence in groundwater has previously been linked to industrial releases and the historic use of Chilean nitrate fertilizers. However, recently a number of occurrences have been identified for which there is no obvious anthropogenic source. Groundwater from an area of 155,000 km2 in 56 counties in northwest Texas and eastern New Mexico is impacted bythe presence of ClO4-. Concentrations were generally low (<4 ppb), although some areas are impacted by concentrations up to 200 ppb. ClO4- distribution is not related to well type (public water system, domestic, agricultural, or water-table monitoring) or aquifer (Ogallala, Edward Trinity High Plains, Edwards Trinity Plateau, Seymour, or Cenozoic). Results from vertically nested wells strongly indicate a surface source. The source of ClO4- appears to most likely be atmospheric deposition. Evidence supporting this hypothesis primarily relates to the presence of ClO4- in tritium-free older water, the lack of relation between land use and concentration distribution, the inability of potential anthropogenic sources to account for the estimated mass of ClO4-, and the positive relationship between conserved anions (e.g., IO3-, Cl-, SO4(-2)) and ClO4-. The ClO4- distribution appears to be mainly related to evaporative concentration and unsaturated transport. This process has led to higher ClO4- and other ion concentrations in groundwater where the water table is relatively shallow, and in areas with lower saturated thickness. Irrigation may have accelerated this process in some areas by increasing the transport of accumulated salts and by increasing the number of evaporative cycles. Results from this study highlight the potential for ClO4- to impact groundwater in arid and semi-arid areas through long-term atmospheric deposition.     

Impacts of land use change on nitrogen cycling archived in semiarid unsaturated zone nitrate profiles, southern High Plains, Texas

Nitrate (NO3) profiles in semiarid unsaturated zones archive land use change (LUC) impacts on nitrogen (N) cycling with implications for agricultural N management and groundwater quality. This study quantified LUC impacts on NO3 inventories and fluxes by measuring NO3 profiles beneath natural and rainfed (nonirrigated) agricultural ecosystems in the southern High Plains (SHP). Inventories of NO3-N under natural ecosystems in the SHP normalized by profile depth are extremely low (2-10 kg NO3-N/ha/m), in contrast to those in many semiarid regions in the southwestern U.S. Many profiles beneath cropland (9 of 19 profiles) have inventories at depth that range from 28-580 kg NO3--N/ha/m (median 135 kg/ha/m) that correspond to initial cultivation, dated using soil water Cl. These inventories represent 74% (median) of the total inventories in these profiles. This NO3 most likely originated from cultivation causing mineralization and nitrification of soil organic nitrogen (SON) in old soil water (precultivation) and is attributed to enhanced microbial activity caused by increased soil wetness beneath cropland (median matric potential -42 m) relative to that beneath natural ecosystems (median -211 m). The SON source is supported by isotopes of NO3 (delta15N: +5.3 to +11.6; delta18O: +3.6 to +12.1). Limited data in South Australia suggest similar processes beneath cropland. Mobilization of the total inventories in these profiles caused by increased drainage/ recharge related to cultivation in the SHP could increase current NO3-N levels in the underlying Ogallala aquifer by an additional 2-26 mg/L (median 17 mg/L).     

Evaluating regional patterns in nitrate sources to watersheds in National Parks of the Rocky Mountains using nitrate isotopes

In the Rocky Mountains, there is uncertainty about the source areas and emission types that contribute to nitrate (NO3) deposition, which can adversely affect sensitive aquatic habitats of high-elevation watersheds. Regional patterns in NO3 deposition sources were evaluated using NO3 isotopes in five National Parks, including 37 lakes and 7 precipitation sites. Results indicate that lake NO3 ranged from detection limit to 38 microeq/L, delta18O (NO3) ranged from -5.7 to +21.3% per thousand, and delta15N (NO3) ranged from -6.6 to +4.6 per thousand. delta18O (NO3) in precipitation ranged from +71 to +78% per thousand. delta15N (NO3) in precipitation and lakes overlap; however, delta15N (NO3) in precipitation is more depleted than delta15N (NO3) in lakes, ranging from -5.5 to -2.0 per thousand. delta15N (NO3) values are significantly related (p < 0.05) to wet deposition of inorganic N, sulfate, and acidity, suggesting that spatial variability of delta15N (NO3) over the Rocky Mountains may be related to source areas of these solutes. Regional patterns show that NO3 and delta15N (NO3) are more enriched in lakes and precipitation from the southern Rockies and at higher elevations compared to the northern Rockies. The correspondence of high NO3 and enriched delta15N (NO3) in precipitation with high NO3 and enriched delta15N (NO3) in lakes, suggests that deposition of inorganic N in wetfall may affect the amount of NO3 in lakes through a combination of direct and indirect processes such as enhanced nitrification.     

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.     

Identification of anthropogenic and natural inputs of sulfate and chloride into the karstic ground water of Guiyang, SW China: combined delta37Cl and delta34S approach

Because of active exchange between surface and groundwater of a karstic hydrological system, the groundwater of Guiyang, the capital city of Guizhou Province, southwest China, has been seriously polluted by anthropogenic inputs of NO3-, SO4(2-), Cl-, and Na+. In this work, delta37Cl of chloride and delta34S variations of sulfate in the karstic surface/groundwater system were studied, with a main focus to identify contaminant sources, including their origins. The surface, ground, rain, and sewage water studied showed variable delta37Cl and delta34S values, in the range of -4.1 to +2.0 per thousand, and -20.4 to +20.9 per thousand for delta37Cl and delta34S (SO4(2-)), respectively. The rainwater samples yielded the lowest delta37Cl values among those observed to date for aerosols and rainwater. Chloride in the Guiyang area rain waters emanated from anthropogenic sources rather than being of marine origin, probably derived from HCl (g) emitted by coal combustion. By plotting 1/SO4(2-) vs delta34S and 1/Cl- vs delta37Cl, respectively, we were able to identify some clusters of data, which were assigned as atmospheric deposition (acid rain component), discharge from municipal sewage, paleo-brine components in clastic sedimentary rocks, dissolution of gypsum mainly in dolomite, oxidation of sulfide minerals in coal-containing clastic rocks, and possibly degradation of chlorine-containing organic matter. We conclude that human activities give a significant input of sulfate and chloride ions, as well as other contaminants, into the studied groundwater system through enhanced atmospheric deposition and municipal sewage, and that multiple isotopic tracers constitute a powerful tool to ascertain geochemical characteristics and origin of complex contaminants in groundwater.     

Widespread natural perchlorate in unsaturated zones of the southwest United States

A substantial reservoir (up to 1 kg ha(-1)) of natural perchlorate is present in diverse unsaturated zones of the arid and semi-arid southwestern United States. The perchlorate co-occurs with meteoric chloride that has accumulated in these soils throughout the Holocene [0 to 10-15 ka (thousand years ago)] and possibly longer periods. Previously, natural perchlorate widely believed to be limited to the Atacama Desert, now appears widespread in steppe-to-desert ecoregions. The perchlorate reservoir becomes sufficiently large to affect groundwater when recharge from irrigation or climate change flushes accumulated salts from the unsaturated zone. This new source may help explain increasing reports of perchlorate in dry region agricultural products and should be considered when evaluating overall source contributions.     

Nitrogen isotopes as indicators of NO(x) source contributions to atmospheric nitrate deposition across the midwestern and northeastern United States

Global inputs of NO(x) are dominated by fossil fuel combustion from both stationary and vehicular sources and far exceed natural NO(x) sources. However, elucidating NO(x) sources to any given location remains a difficult challenge, despite the need for this information to develop sound regulatory and mitigation strategies. We present results from a regional-scale study of nitrogen isotopes (delta15N) in wet nitrate deposition across 33 sites in the midwestern and northeastern U.S. We demonstrate that spatial variations in delta15N are strongly correlated with NO(x) emissions from surrounding stationary sources and additionally that delta15N is more strongly correlated with surrounding stationary source NO(x) emissions than pH, SO4(2-), or NO3- concentrations. Although emission inventories indicate that vehicle emissions are the dominant NO(x) source in the eastern U.S., our results suggest that wet NO3- deposition at sites in this study is strongly associated with NO(x) emissions from stationary sources. This suggests that large areas of the landscape potentially receive atmospheric NO(y) deposition inputs in excess of what one would infer from existing monitoring data alone. Moreover, we determined that spatial patterns in delta15N values are a robust indicator of stationary NO(x) contributions to wet NO3- deposition and hence a valuable complement to existing tools for assessing relationships between NO3- deposition, regional emission inventories, and for evaluating progress toward NO(x) reduction goals.     

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.     

Effects of natural water ions and humic acid on catalytic nitrate reduction kinetics using an alumina supported Pd-Cu catalyst

Catalytic nitrate reduction was evaluated for the purpose of drinking water treatment. Common anions present in natural waters and humic acid were evaluated for their effects on NO3(-) hydrogenation over a bimetallic supported catalyst (Pd-Cu/gamma-Al2O3). Groundwater samples, with and without powder activated carbon (PAC) pretreatment, were also evaluated. In the absence of inhibitors the NO3- reduction rate was 2.4 x 10(-01) L/min g cat. However, the addition of constituents (SO4(2-), SO3(2-), HS-, CI-, HCO3-, OH-, and humic acid) on the order of representative concentrations for drinking water decreased the NO3- reduction rate. Sulfite, sulfide, and elevated chloride decreased the NO3- reduction rate by over 2 orders of magnitude. Preferential adsorption of Cl- inhibited NO3- reduction to a greater extent than NO2- reduction. Partial regeneration of catalysts exposed to SO3(2-) was achieved by using a dilute hypochlorite solution, however Cu dissolution occurred. Dissolved constituents in the groundwater sample decreased the NO3- reduction rate to 3.7 x 10(-03) L/min g cat and increased ammonia production. Removal of dissolved organic matter from the groundwater using PAC increased the NO3- reduction rate to 5.06 x 10(-02) L/min g cat and decreased ammonia production. Elemental analyses of catalysts exposed to the natural groundwater suggest that mineral precipitation may also contribute to catalyst fouling.     

Hydrodynamic and microbial processes controlling nitrate in a fissured-porous karst aquifer of the Franconian Alb, southern Germany

Concentrations and stable isotope compositions of nitrate from 11 karst springs in the Franconian Alb (southern Germany) were determined during low flow and high flow conditions to assess sources and processes affecting groundwater nitrate. During low flow, nitrate concentrations in groundwater were around 0.10 mM in springs draining forested catchments, whereas in agricultural areas nitrate concentrations were typically higher reaching up to 0.93 mM. The isotopic composition of groundwater nitrate during low flow (delta15N values of -3.1 to 6.7% per hundred, delta180 values of +2.1 to 4.0% per hundred) in concert with concentration data suggests that nitrate is formed by nitrification in forest and agricultural soils. In addition, synthetic fertilizer N that has undergone immobilization and subsequent remineralization likely constitutes an additional nitrate source in agriculturally used catchments. During recharge conditions, concentrations and delta15N values of groundwater nitrate changed little, but delta18O values were significantly elevated (up to 24.5%o per hundred suggesting that around 25% of the nitrate was directly derived from atmospheric deposition. Groundwater dating revealed that low nitrate concentrations in groundwater (_> or =0 years) are consistent with a mixture of old low nitrate-containing and young water, the latter being affected by anthropogenic N inputs predominantly in the agriculturally used catchment areas during the last few decades. Thermodynamic and hydrogeological evidence also suggests that denitrification may have occurred in the porous rock matrix of the karst aquifer. This study demonstrates that a combination of hydrodynamic, chemical, and isotopic approaches provides unique insights into the sources and the biogeochemical history of nitrate in karst aquifers, and therefore constitutes a valuable tool for assessing the vulnerability of karst aquifers to nitrate pollution in dependence on land use and assessing their self-purification capacity.     

Monitoring oxidation of chlorinated ethenes by permanganate in groundwater using stable isotopes: laboratory and field studies

Permanganate injection is increasingly applied for in situ destruction of chlorinated ethenes in groundwater. This laboratory and field study demonstrates the roles that carbon isotope analysis can play in the assessment of oxidation of trichloroethene (TCE) by permanganate. In laboratory experiments a strong carbon isotope fractionation was observed during oxidation of TCE with similar isotopic enrichment factors (-25.1 to -26.8 per thousand) for initial KMnO4 concentrations between 67 and 1,250 mg/L. At the field site, a single permanganate injection episode was conducted in a sandy aquifer contaminated with TCE as dense nonaqueous liquid (DNAPL). After injection, enriched delta13C values of up to +204% and elevated Cl- concentrations were observed at distances of up to 4 m from the injection point. Farther away, the Cl- increased without any change in delta13C of TCE suggesting that Cl- was not produced locally but migrated to the sampling point Except for the closest sampling location to the injection point, the delta13C rebounded to the initial 613C again, likely due to dissolution of DNAPL Isotope mass balance calculations made it possible to identify zones where TCE oxidation continued to occur during the rebound phase. The study indicates that delta13C values can be used to assess the dynamics between TCE oxidation and dissolution and to locate zones of oxidation of chlorinated ethenes that cannot be identified from the Cl- distribution alone.     

Limitations of using delta 18O for the source identification of nitrate in agricultural soils

The stable isotopic composition (delta 15N and delta 18O) of nitrate was analyzed in two lysimeter field experiments in order to identify the conditions under which the dual isotope approach can be applied to identify the main source of nitrate in agricultural soils. The first field experiment involved six lysimeters beneath fields that had been fertilized for 10 yr with the same type of fertilizer (NH4NO3; delta 15N = +1.2@1000, delta 18O = +18.6@1000). The isotope ratios of NO3- in the leachate (delta 15N approximately 0@1000; delta 18O approximately +2@1000) could not be interpreted in a conventional way with either fertilizer or soil organic nitrogen as main sources. These results provided clear evidence for the microbial immobilization and subsequent mineralization and nitrification to NO3- (mineralization-immobilization turnover concept). This process masked the original oxygen isotope ratio of the fertilizer source during the summer when microbial activity was high. A second experiment involving the application of Ca(NO3)2 to three lysimeters during the winter confirmed that the dual isotope approach remains valid for the source identification of nitrate under conditions of low microbial activity. The study reveals the limitation of the dual isotope approach to characterize nitrate sources under biologically active conditions and the ability to quantify microbial processes when the main sources can be controlled.     

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.