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Long-term phosphorus (P) fertilization results in P accumulation in agricultural soil and increases the risk of P leaching into water bodies. However, evaluating P leaching into groundwater is challenging, especially in clay soil with a high P sorption capacity. This study examined whether the combination of PO 4 oxygen isotope (δ 18 O PO4 ) analysis and the P saturation ratio (PSR) was useful to identify P enrichment mechanisms in groundwater. We investigated the groundwater and possible P sources in Kubi, western Japan, with intensive citrus cultivation. Shallow groundwater had oxic conditions with high PO 4 concentrations, and orchard soil P accumulation was high compared with forest soil. Although the soil had a high P sorption capacity, the PSR was above the threshold, indicating a high risk of P leaching from the surface orchard soil. The shallow groundwater δ 18 O PO4 values were higher than the expected isotopic equilibrium with pyrophosphatase. The high PSR and δ 18 O PO4 orchard soil values indicated that P leaching from orchard soil was the major P enrichment mechanism. The Bayesian mixing model estimated that 76.6% of the P supplied from the orchard soil was recycled by microorganisms. This demonstrates the utility of δ 18 O PO4 and the PSR to evaluate the P source and biological recycling in groundwater.

Identifying phosphorus (P) sources is critical for solving eutrophication and controlling P in aquatic environments. Phosphate oxygen isotopes (δ 18 O p ) have been used to trace P sources. However, the application of this method has been greatly restricted due to δ 18 O P values from the potential source having wide and overlapping ranges. In this research, P sources were traced by combining δ 18 O p with multiple stable isotopes of nitrogen (δ 15 N), hydrogen (δD), and dissolved inorganic carbon (δ 13 C). Then, a Bayesian-based Stable Isotope Analysis in R (SIAR) model and IsoSource model were used to estimate the proportional contributions of the potential sources in the Tuojiang River. δ 18 O p was not in equilibrium with ambient water, and statistically significant differences in the δ 18 O p values were found between the potential sources, indicating that δ 18 O p can be used to trace the P sources. δ 15 N, δD, and δ 13 C could assist δ 18 O p in identifying the main sources of P. The SIAR and IsoSource models suggested that industrial and domestic sewage was the largest contributor, followed by phosphate rock and phosphogypsum and agricultural sewage. The uncertainty of the calculation results of the SIAR model was lower than that of the IsoSource model. These findings provide new insights into tracing P sources using multiple stable isotopes in watersheds.

Until now, there has been a lack of knowledge regarding the vertical profiles of nitrate formation in the urban boundary layer (BL) based on triple oxygen isotopes. Here, we conducted vertical measurements of the oxygen anomaly of nitrate (Δ 17 O-NO 3 - ) on a 325 m meteorological tower in urban Beijing during the winter and summer. The simultaneous vertical measurements suggested different formation mechanisms of nitrate aerosols at ground level and 120 and 260 m in the winter due to the less efficient vertical mixing under stable atmospheric conditions. Particularly, different chemical processes of nitrate aerosols at the three heights were found between clean days and polluted days in the winter. On clean days, nocturnal chemistry (NO 3 + HC and N 2 O 5 uptake) contributed to nitrate production equally with OH/H 2 O + NO 2 at ground level, while it dominated aloft (contributing 80% of nitrate production at 260 m), due to the higher aerosol liquid water content and O 3 concentration there. On polluted days, nocturnal reactions dominated the formation of nitrate at the three heights. Particularly, the contribution of the OH/H 2 O + NO 2 pathway to nitrate production increased from the ground level to 120 m might be attributed to the hydrolysis of NO 2 to HONO and then further photolysis to OH radicals in the day. In contrast, the proportion of N 2 O 5 + H 2 O decreased at 260 m, likely due to the low relative humidity aloft that inhibited the N 2 O 5 hydrolysis reactions in the residual layer. Our results highlighted that the differences between meteorology and gaseous precursors could largely affect particulate nitrate formation at different heights within the polluted urban BL.

Formation pathways and sources of atmosphere nitrate (NO 3 - ) have attracted much attention as NO 3 - had detrimental effects on Earth's ecosystem and climate change. Here, we measured nitrogen (δ 15 N-NO 3 - ) and oxygen (δ 18 O-NO 3 - and Δ 17 O-NO 3 - ) isotope compositions in nitrate aerosols at the Qomolangma station (QOMS) over the Himalayan-Tibetan Plateau (HTP) to quantify the formation mechanisms and emission sources of nitrate at the background site. At QOMS, the enhanced NO 3 - concentrations were observed in the springtime. The average δ 15 N-NO 3 - , δ 18 O-NO 3 - , and Δ 17 O-NO 3 - values were 0.4 ± 4.9, 64.7 ± 11.5 and 27.6 ± 6.9‰, respectively. Seasonal variations of isotope ratios at QOMS can be explained by the different emissions and formation pathways to nitrate. The average fractions of NO 2 + OH and N 2 O 5 + H 2 O to nitrate production were estimated to be 43 and 52%, respectively, when the NO 3 + hydrocarbon (HC)/dimethyl sulfide (DMS) (NO 3 + HC/DMS) pathway was assumed to be 5%. Using stable isotope analysis in the R (SIAR) model, the relative contributions of biomass burning (BB), biogenic soil emission, traffic, and coal combustion to nitrate were estimated to be 28, 25, 24, and 23%, respectively, on yearly basis. By FLEXible PARTicle (FLEXPART) dispersion model, we highlighted that NO x from BB emission over South Asia that had undergone N 2 O 5 + H 2 O processes enhanced the nitrate concentrations in the springtime over the HTP region.

Nitrogen (N) sources are widely distributed in the complex urban environment. High-resolution data elucidating N sources in the residential catchments are not available. We used stable isotopes of N and oxygen (O) of nitrate (δ(18)O-NO3(-) and δ(15)N-NO3(-)) along with δ(18)O and hydrogen (δD) of water (H2O) to understand the sources and transformations of N in residential stormwater runoff. Stormwater runoff samples were collected over 25 stormwater events at 5 min intervals using an autosampler installed at the residential catchment outlet pipe that drained 31 low-density homes with a total drainage area of 0.11 km(2). Bayesian mixing model results indicated that atmospheric deposition (range 43-71%) and chemical N fertilizers (range <1-49%) were the dominant NO3-N sources in the stormwater runoff and that there was a continuum of source changes during the stormwater events. Further, the NO3-N transport in the stormwater runoff from the residential catchment was driven by mixing of multiple sources and biotic (i.e., nitrification) processes. This work suggests that a better understanding of N transport and sources is needed to reduce N export and improve water quality in urban water systems.

Atmospheric dust deposition can be a significant source of phosphorus (P) in some tropical forests, so information on the origins and solubility of atmospheric P is needed to understand and predict patterns of forest productivity under future climate scenarios. We characterized atmospheric dust P across a seasonal cycle in a tropical lowland rain forest on Barro Colorado Nature Monument (BCNM), Republic of Panama. We traced P sources by combining remote sensing imagery with the first measurements of stable oxygen isotopes in soluble inorganic phosphate (δ(18)OP) in dust. In addition, we measured soluble inorganic and organic P concentrations in fine (<1 μm) and coarse (>1 μm) aerosol fractions and used this data to estimate the contribution of P inputs from dust deposition to the forest P budget. Aerosol dry mass was greater in the dry season (December to April, 5.6-15.7 μg m(-3)) than the wet season (May to November, 3.1-7.1 μg m(-3)). In contrast, soluble P concentrations in the aerosols were lower in the dry season (980-1880 μg P g(-1)) than the wet season (1170-3380 μg P g(-1)). The δ(18)OP of dry-season aerosols resembled that of nearby forest soils (∼19.5‰), suggesting a local origin. In the wet season, when the Trans-Atlantic Saharan dust belt moves north close to Panama, the δ(18)OP of aerosols was considerably lower (∼15.5‰), suggesting a significant contribution of long-distance dust P transport. Using satellite retrieved aerosol optical depth (AOD) and the P concentrations in aerosols we sampled in periods when Saharan dust was evident we estimate that the monthly P input from long distance dust transport during the period with highest Saharan dust deposition is 88 ± 31 g P ha(-1) month(-1), equivalent to between 10 and 29% of the P in monthly litter fall in nearby forests. These findings have important implications for our understanding of modern nutrient budgets and the productivity of tropical forests in the region under future climate scenarios.

Explosives used in construction have been implicated as sources of NO3(-) contamination in groundwater, but direct forensic evidence is limited. Identification of blasting-related NO3(-) can be complicated by other NO3(-) sources, including agriculture and wastewater disposal, and by hydrogeologic factors affecting NO3(-) transport and stability. Here we describe a study that used hydrogeology, chemistry, stable isotopes, and mass balance calculations to evaluate groundwater NO3(-) sources and transport in areas surrounding a highway construction site with documented blasting in New Hampshire. Results indicate various groundwater responses to contamination: (1) rapid breakthrough and flushing of synthetic NO3(-) (low δ(15)N, high δ(18)O) from dissolution of unexploded NH4NO3 blasting agents in oxic groundwater; (2) delayed and reduced breakthrough of synthetic NO3(-) subjected to partial denitrification (high δ(15)N, high δ(18)O); (3) relatively persistent concentrations of blasting-related biogenic NO3(-) derived from nitrification of NH4(+) (low δ(15)N, low δ(18)O); and (4) stable but spatially variable biogenic NO3(-) concentrations, consistent with recharge from septic systems (high δ(15)N, low δ(18)O), variably affected by denitrification. Source characteristics of denitrified samples were reconstructed from dissolved-gas data (Ar, N2) and isotopic fractionation trends associated with denitrification (Δδ(15)N/Δδ(18)O ≈ 1.31). Methods and data from this study are expected to be applicable in studies of other aquifers affected by explosives used in construction.

The measurement of δ(2)H and δ(18)O in water samples by laser absorption spectroscopy (LAS) are adopted increasingly in hydrologic and environmental studies. Although LAS instrumentation is easy to use, its incorporation into laboratory operations is not as easy, owing to extensive offline data manipulation required for outlier detection, derivation and application of algorithms to correct for between-sample memory, correcting for linear and nonlinear instrumental drift, VSMOW-SLAP scale normalization, and in maintaining long-term QA/QC audits. Here we propose a series of standardized water-isotope LAS performance tests and routine sample analysis templates, recommended procedural guidelines, and new data processing software (LIMS for Lasers) that altogether enables new and current LAS users to achieve and sustain long-term δ(2)H and δ(18)O accuracy and precision for these important isotopic assays.

The analysis of the stable hydrogen and oxygen isotope composition of water using cavity ring-down spectroscopy (CRDS) instruments utilizing infrared absorption spectroscopy have been comprehensively tested. However, potential limitations of infrared spectroscopy for the analysis of highly saline water have not yet been evaluated. In this study, we assessed uncertainty arising from elevated salt concentrations in water analyzed on a CRDS instrument and the necessity of a correction procedure. We prepared various solutions of mixed salts and separate solutions with individual salts (NaCl, KCl, MgCl2, and CaCl2) using deionized water with a known stable isotope composition. Most of the individual salt and salt mixture solutions (some up to 340 g L(-1)) had δ-values within the range usual for CRDS analytical uncertainty (0.1‰ for δ (18)O and 1.0‰ for δ (2)H). Results were not compromised even when the total load of salt in the vaporizer reached ∼38.5 mg (equivalent to build up after running ∼100 ocean water samples). Therefore, highly saline mixtures can be successfully analyzed using CRDS, except highly concentrated MgCl2 solutions, without the need for an additional correction if the vaporizer is frequently cleaned and MgCl2 concentration in water is relatively low.

Selenate (SeO(4)(2-)) reduction to elemental selenium is an important Se immobilization process in subsurface environments that could be mediated by Fe(II)-rich minerals or selenate-respiring microorganisms. We report the kinetic isotope effects for (18)O within selenate during abiotic reactions with iron-bearing hydroxides within laboratory experiments. Selenate was reduced to Se(0) by a green rust (chloride interlayer type) and ferrous hydroxide, the two known environmentally relevant mineral reductants for selenate. Reaction kinetics are described by a rapid, low-fractionating uptake step caused by diffusive exchange between selenate and chloride followed by a slower, high-fractionating reduction step caused by electron transfer from structural Fe(II). The dual-phase kinetics cannot be described with the traditional Rayleigh fractionation model; however, well after the initial uptake step, the extent of selenate reaction is well correlated with δ(18)O values in accordance with the Rayleigh model. Selenate-(18)O enrichment (εO) was nearly identical for reaction with chloride green rust (22.7 ± 2.2‰) and ferrous hydroxide (22.1 ± 1.1‰) which suggests a common reduction mechanism by structural Fe(II). The minor enrichment due to anion exchange alone (1.4 ± 0.2‰) was confirmed using iowaite, a nonredox active Mg(II)-Fe(III) layered double hydroxide. Our εO results may contribute to Se isotope forensics to identify selenate reduction within field sites and to possibly distinguish between abiotic and biotic reduction processes.

The input of phosphorus (P) through atmospheric deposition can be a major source of P to fresh water bodies and may strongly affect their biogeochemistry. In Lake Kinneret (LK), northern Israel, dust deposition provides a significant fraction of the bioavailable P input. Here, we demonstrate that the oxygen isotopic composition of resin-extractable inorganic phosphate (δ(18)OP) in dust particles can be used to identify the phosphate source. Samples of soils with both natural vegetation and agricultural cover were collected upwind of LK and found to have distinct δ(18)OP value ranges (17.4-18.2‰ and 19.3-22.1‰, respectively). The δ(18)OP values for dust, collected continuously over LK during June 2011 to March 2012, were in the same range as agricultural soils. The dust concentration in the air decreased from the dry to the wet season and was correlated with a decrease in P concentration in air, yet no correlation was found between these parameters and dust δ(18)OP. Dust deposited during short-term desert dust events was characterized by a combination of high δ(18)OP values ranging from 22.2‰ to 22.7‰ and high concentrations of dust in the air. The data we present demonstrates a new application of δ(18)OP measurements for direct estimation of dust-P sources to lakes, as well as the potential for tracing dust-P on larger scales.

Many previous studies have used δ(15)N and δ(18)O of nitrate (δ(15)NNO3 and δ(18)ONO3) to determine the nitrate sources in rivers but were subject to substantial uncertainties and limitations, especially associated with evaluating the atmospheric contribution. The Δ(17)O of nitrate (Δ(17)ONO3) has been suggested as an unambiguous tracer of atmospheric NO3(-) and may serve as an additional nitrate source constraint. In the present study, triple nitrate isotopes (δ(15)NNO3, Δ(17)ONO3, and δ(18)ONO3) were used for the first time to assess the sources and sinks of nitrate in the Yellow River (YR) basin, which is the second longest river in China. Results showed that the Δ(17)ONO3 of the water from the YR ranged from 0‰ to 1.6‰ during two normal-water seasons. This suggested that unprocessed atmospheric nitrate accounted for 0-7% of the total nitrate in the YR. The corrected δ(15)NNO3 and δ(18)ONO3 values with atmospheric imprints being removed indicated that the main terrestrial sources of nitrate were sewage/manure effluents in the upstream of the YR and manure/sewage effluents and ammonium/urea-containing fertilizer in the middle and lower reaches which made comparable contributions to the nitrate. In addition, there was a significant positive relationship between δ(15)NNO3 and δ(18)ONO3 values of river water (p < 0.01) which may signal the presence of denitrification. This study indicates that the triple nitrate isotope method is useful for assessing the nitrate sources in rivers, especially for the measurements of atmospheric nitrate contribution.

The aim of this study was to assess how the excavation of the Äspö Hard Rock Laboratory tunnel has impacted on sources and mixing of groundwater in fractured crystalline (granitoidic) bedrock. The tunnel is 3600 m long and extends to a depth of 460 m at a coastal site in Boreal Europe. The study builds on a unique data set consisting of 1117 observations on chloride and δ(18)O of groundwater collected from a total of 356 packed-off fractures between 1987 and 2011. On the basis of the values of these two variables in selected source waters, a classification system was developed to relate the groundwater observations to source and postinfiltration mixing phenomena. The results show that the groundwater has multiple sources and a complex history of transport and mixing, and is composed of at least glacial water, marine water, recent meteoric water, and an old saline water. The tunnel excavation has had a large impact on flow, sources, and mixing of the groundwater. Important phenomena include upflow of deep-lying saline water, extensive intrusion of current Baltic Sea water, and substantial temporal variability of chloride and δ(18)O in many fractures.

Analyses of δ(18)O of nitrate (NO(3)(-)) have been widely used in partitioning NO(3)(-) sources. However the δ(18)O value of NO(3)(-) produced from nitrification (microbial NO(3)(-)) is commonly estimated using the δ(18)O of environmental water and molecular oxygen in a 2:1 ratio. Here our laboratory incubation of nine temperate forest soils across a 1500 m elevation gradient demonstrates that microbial NO(3)(-) has lower δ(18)O values than the predicted using the 2:1 ratio (by 5.2-9.5‰ at low elevation sites), in contrast to previous reports showing higher δ(18)O values (up to +15‰) than their predicted values. Elevated δ(18)O values of microbial NO(3)(-) were observed at high elevation sites where soil was more acidic, perhaps due to accelerated O-exchange between nitrite, an intermediate product of nitrification, and water. Lower δ(18)O of microbial NO(3)(-) than the predicted and from previous observations suggests that the contribution of anthropogenic N inputs, such as fertilizer and atmospheric deposition, to a given ecosystem and the progress of denitrification in nitrogen removal are greater than we know. More than half of the δ(18)O of stream NO(3)(-) lower than the predicted value along the elevation gradient also indicate the impropriety using the 2:1 ratio for differentiating NO(3)(-) sources.

In batch experiments, we studied the isotope fractionation in N and O of dissolved nitrate during dentrification. Denitrifying strains Thauera aromatica and "Aromatoleum aromaticum strain EbN1" were grown under strictly anaerobic conditions with acetate, benzoate, and toluene as carbon sources. (18)O-labeled water and (18)O-labeled nitrite were added to the microcosm experiments to study the effect of putative backward reactions of nitrite to nitrate on the stable isotope fractionation. We found no evidence for a reverse reaction. Significant variations of the stable isotope enrichment factor ε were observed depending on the type of carbon source used. For toluene (ε(15)N, -18.1 ± 0.6‰ to -7.3 ± 1.4‰; ε(18)O, -16.5 ± 0.6‰ to -16.1 ± 1.5‰) and benzoate (ε(15)N, -18.9 ± 1.3‰; ε(18)O, -15.9 ± 1.1‰) less negative isotope enrichment factors were calculated compared to those derived from acetate (ε(15)N, -23.5 ± 1.9‰ to -22.1 ± 0.8‰; ε(18)O, -23.7 ± 1.8‰ to -19.9 ± 0.8‰). The observed isotope effects did not depend on the growth kinetics which were similar for the three types of electron donors. We suggest that different carbon sources change the observed isotope enrichment factors by changing the relative kinetics of nitrate transport across the cell wall compared to the kinetics of the intracellular nitrate reduction step of microbial denitrification., (© 2012 American Chemical Society)

The stable oxygen isotope compositions of soil phosphate (δ(18)O(p)) were suggested recently to be a tracer of phosphorus cycling in soils and plants. Here we present a survey of bioavailable (resin-extractable or resin-P) inorganic phosphate δ(18)O(p) across natural and experimental rainfall gradients, and across soil formed on sedimentary and igneous bedrock. In addition, we analyzed the soil HCl-extractable inorganic δ(18)O(p), which mainly represents calcium-bound inorganic phosphate. The resin-P values were in the range 14.5-21.2‰. A similar range, 15.6-21.3‰, was found for the HCl-extractable inorganic δ(18)O(p), with the exception of samples from a soil of igneous origin that show lower values, 8.2-10.9‰, which indicate that a large fraction of the inorganic phosphate in this soil is still in the form of a primary mineral. The available-P δ(18)O(p) values are considerably higher than the values we calculated for extracellular hydrolysis of organic phosphate, based on the known fractionation from lab experiments. However, these values are close to the values expected for enzymatic-mediated phosphate equilibration with soil-water. The possible processes that can explain this observation are (1) extracellular equilibration of the inorganic phosphate in the soil; (2) fractionations in the soil are different than the ones measured at the lab; (3) effect of fractionation during uptake; and (4) a flux of intercellular-equilibrated inorganic phosphate from the soil microbiota, which is considerably larger than the flux of hydrolyzed organic-P.

Some uranium mill tailings disposal cells were constructed on dark-gray shale of the Upper Cretaceous Mancos Shale. Shale of this formation contains contaminants similar to those in mill tailings. To establish the contributions derived from the Mancos, we sampled 51 locations in Colorado, New Mexico, and Utah. Many of the groundwater samples were saline with nitrate, selenium, and uranium concentrations commonly exceeding 250, 000, 1000, and 200 μg/L, respectively. Higher concentrations were limited to groundwater associated with shale beds, but were not correlated with geographic area, stratigraphic position, or source of water. The elevated concentrations suggest that naturally occurring contamination should be considered when evaluating groundwater cleanup levels. At several locations, seep water was yellow or red, caused in part by dissolved organic carbon concentrations up to 280 mg/L. Most seeps had (234)U to (238)U activity ratios greater than 2, indicating preferential leaching of (234)U. Seeps were slightly enriched in (18)O relative to the meteoric water line, indicating limited evaporation. Conceptually, major ion chemical reactions are dominated by calcite dissolution following proton release from pyrite oxidation and subsequent exchange by calcium for sodium residing on clay mineral exchange sites. Contaminants are likely released from organic matter and mineral surfaces during weathering.

The mineral waste from some mines has the capacity to trap and store CO(2) within secondary carbonate minerals via the process of silicate weathering. Nesquehonite [MgCO(3)·3H(2)O] forms by weathering of Mg-silicate minerals in kimberlitic mine tailings at the Diavik Diamond Mine, Northwest Territories, Canada. Less abundant Na- and Ca-carbonate minerals precipitate from sewage treatment effluent deposited in the tailings storage facility. Radiocarbon and stable carbon and oxygen isotopes are used to assess the ability of mine tailings to trap and store modern CO(2) within these minerals in the arid, subarctic climate at Diavik. Stable isotopic data cannot always uniquely identify the source of carbon stored within minerals in this setting; however, radiocarbon isotopic data provide a reliable quantitative estimate for sequestration of modern carbon. At least 89% of the carbon trapped within secondary carbonate minerals at Diavik is derived from a modern source, either by direct uptake of atmospheric CO(2) or indirect uptake though the biosphere. Silicate weathering at Diavik is trapping 102-114 g C/m(2)/y within nesquehonite, which corresponds to a 2 orders of magnitude increase over the background rate of CO(2) uptake predicted from arctic and subarctic river catchment data.

Global models have indicated agriculturally impacted rivers and streams may be important sources of the greenhouse gas nitrous oxide (N(2)O). However, there is significant uncertainty in N(2)O budgets. Isotopic characterization can be used to help constrain N(2)O budgets. We present the first published measurements of the isotopic character of N(2)O emitted from low (2-4) order streams. Isotopic character of N(2)O varied seasonally, among streams, and over diel periods. On an annual basis, δ(18)O of emitted N(2)O (+47.4 to +51.4‰; relative to VSMOW) was higher than previously reported for larger rivers, but δ(15)N of emitted N(2)O (-16.2 to +2.4‰ among streams; relative to atmospheric N(2)) was similar to that of past studies. On an annual basis, all streams emitted N(2)O with lower δ(15)N than tropospheric N(2)O. Given these streams have elevated nitrate concentrations which are associated with enhanced N(2)O fluxes, this supports the hypothesis that streams are contributing to the accumulation of (15)N-depleted N(2)O in the troposphere.

The Changjiang River is the largest freshwater river in China. Here, the sources and variability in nitrate of the Changjiang River are assessed for the first time using dual isotopic approach. Water samples were collected once in August 2006 from the main channel of the Changjiang and its major tributaries. The concentrations and isotopic composition of nitrate were then analyzed for the waters in the Changjiang River. The delta(15)N and delta(18)O of NO(3)(-) ranges from 7.3 per thousand to 12.9 per thousand and 2.4 per thousand to 11.2 per thousand in the Changjiang River waters, respectively. The ranges of isotopic compositions of nitrate suggested that nitrification (including "modified fertilizer") and urban sewage effluent are the major sources of nitrate in the Changjiang River. The high delta(18)O-NO(3)(-) values were observed in the water of the upper reaches, indicated that the current drought might be one important reason for shifting of isotopes in the special sampling period. In addition, there was a strong positive relationship between delta(15)N-NO(3)(-) and delta(18)O-NO(3)(-), which indicated that denitrification added to the enrichment of heavy isotopes of nitrate.

Perchlorate (ClO4-) is a common groundwater constituent with both synthetic and natural sources. A potentially important source of ClO4- is past agricultural application of ClO4(-)-bearing natural NO3- fertilizer imported from the Atacama Desert, Chile, but evidence for this has been largely circumstantial. Here we report ClO4- stable isotope data (delta37Cl, delta18O, and delta17O), along with other supporting chemical and isotopic environmental tracer data, to document groundwater ClO4 contamination sources and history in parts of Long Island, New York. Sampled groundwaters were oxic and ClO4- apparently was not affected by biodegradation within the aquifers. Synthetic ClO4- was indicated by the isotopic method in groundwater near a fireworks disposal site at a former missile base. Atacama ClO4- was indicated in agricultural and urbanizing areas in groundwaters with apparent ages > 20 years. In an agricultural area, ClO4- concentrations and ClO4-/NO3- ratios increased with groundwater age, possibly because of decreasing application rates of Atacama NO3- fertilizers and/or decreasing ClO4- concentrations in Atacama NO3- fertilizers in recent years. Because ClO4-/NO3- ratios of Atacama NO3- fertilizers imported in the past (approximately 2 x 10(-3) mol mol(-1)) were much higher than the CO4-/NO3- ratio of recommended drinking-water limits (7 x 10(-5) mol mol(-1) in New York), ClO4- could exceed drinking-water limits even where NO3- does not, and where Atacama NO3- was only a minor source of N. Groundwater ClO4- with distinctive isotopic composition was a sensitive indicator of past Atacama NO3- fertilizer use on Long Island and may be common in other areas that received NO3- fertilizers from the late 19th century through the 20th century.

The oxygen isotopic composition of dissolved inorganic phosphate (delta18Op) in many aquatic ecosystems is not in isotopic equilibrium with ambient water and, therefore, may reflect the source delta18Op. Identification of phosphate sources to water bodies is critical for designing best management practices for phosphate load reduction to control eutrophication. In order for delta18Op to be a useful tool for source tracking, the delta18Op of phosphate sources must be distinguishable from one another; however, the delta18Op of potential sources has not been well characterized. We measured the delta18Op of a variety of known phosphate sources, including fertilizers, semiprocessed phosphorite ore, particulate aerosols, detergents, leachates of vegetation, soil, animal feces, and wastewater treatment plant effluent. We found a considerable range of delta18Op, values (from +8.4 to +24.9 per thousand) for the various sources, and statistically significant differences were found between several of the source types. delta18Op measured in three different fresh water systems was generally not in equilibrium with ambient water. Although there is overlap in delta18Op values among the groups of samples, our results indicate that some sources are isotopically distinct and delta18Op can be used for identifying phosphate sources to aquatic systems.

The Tibetan Plateau (including the Himalayas) is one of the most remote and cold regions in the world. It has very limited to nonexistent industry but is adjacent to the two most populous and rapidly industrializing countries (China and India) and thus provides a unique location for studying the atmospheric transport of mercury. Here we report the first study on the atmospheric transport of mercury to the Tibetan Plateau. The total mercury profiles in four snowpits from glaciers above 5700 m asl along a southwest-northeast transect across the central Tibetan Plateau were obtained in 2005-2006. In general, the total mercury concentrations in the snow samples ranged from < 1 to 9 ng L(-1), increasing northeastward from the southernmost site at Mount Everest. Higher total mercury concentrations were found in the snow deposited in the nonmonsoon season, as indicated by seasonal variation of delta18O values and major ions in the snowpack. The annual atmospheric depositional flux of total Hg was estimated to range from 0.74 to 2.97 microg m(-2) yr(-1) in the region, the majority of which occurred via particulate matter deposition.

The stable isotope composition of waters (delta2H, delta18O) can be used as a natural tracer of hydrologic processes in systems affected by acid mine drainage. We investigated the delta2H and delta18O values of pore waters from four oxidizing sulfidic mine tailings impoundments in different climatic regions of Chile (Piuquenes at La Andina with Alpine climate, Cauquenes and Carén at El Teniente with Mediterranean climate, and Talabre at the Chuquicamata deposit with hyperarid climate). No clear relationship was found between altitude and isotopic composition. The observed displacement of the tailings pore waters from the local meteoric water line toward higher delta18O values (by approximately +2 per thousand delta18O relative to delta2H) is partly due to water-rock interaction processes, including hydration and O-isotope exchange with sulfates and Fe(III) oxyhydroxides produced by pyrite oxidation. In most tailings, from the saturated zone toward the surface, isotopically different zones can be distinguished. Zone I is characterized by an upward depletion of 2H and 18O in the pore waters from the saturated zone and the lowermost vadose zone, due to ascending diffused isotopically light water triggered by the constant loss of water vapor by evaporation at the surface. In zone II, the capillary flow of a mix of vapor and liquid water causes an evaporative isotopic enrichment in 2H and 18O. At the top of the tailings in dry climate a zone III between the capillary zone and the surface contains isotopically light diffused and atmospheric water vapor. In temperate climates, the upper part of the profile is affected by recent rainfall and zone III may not differ isotopically from zone II.

Sulfate aerosols are harmful as respirable particles. They also play a role as cloud condensation nuclei and have radiative effects on global climate. A combination of delta18O-SO4 data with catchment sulfur mass balances was used to constrain processes affecting S cycling in the atmosphere and spruce forests of the Czech Republic. Extremely high S fluxes via spruce throughfall and runoff were measured at Jezeri (49 and 80 kg S ha(-1) yr(-1), respectively). The second catchment, Na Lizu, was 10 times less polluted. In both catchments, delta18O-SO4 decreased in the following order: open-area precipitation > throughfall > runoff. The delta18O-SO4 values of throughfall exhibited a seasonal pattern at both sites, with maxima in summer and minima in winter. This seasonal pattern paralleled delta18O-H2O values, which were offset by -18 per thousand. Sulfate in throughfall was predominantly formed by heterogeneous (aqueous) oxidation of SO2. Wet-deposited sulfate in an open area did not show systematic delta18O-SO4 trends, suggesting formation by homogeneous (gaseous) oxidation and/or transport from large distances. The percentage of incoming S that is organically cycled in soil was similar under the high and the low pollution. High-temperature 18O-rich sulfate was not detected, which contrasts with North American industrial sites.

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 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.

We examined the oxygen and sulfur isotope fractionation of sulfate during anaerobic degradation of toluene by sulfate-reducing bacteria in culture experiments with Desulfobacula toluolica as a type strain and with an enrichment culture Zz5-7 obtained from a benzene, toluene, ethylbenzene, and xylene (BTEX)-contaminated aquifer. Sulfur isotope fractionation can show considerable variation upon sulfate reduction and may react extremely sensitively to changes in environmental conditions. In contrast, oxygen isotope fractionation seems to be less sensitive to environmental changes. Our results clearly indicate that oxygen isotope fractionation is dominated by isotope exchange with ambient water. To verify our experimental results and to test the applicability of oxygen and sulfur isotope investigations under realistic field conditions, we evaluated isotope data from two BTEX-contaminated aquifers presented in the recent literature. On a field scale, bacterial sulfate reduction may be superimposed by processes such as dispersion, adsorption, reoxidation, or mixing. The dual isotope approach enables the identification of such sulfur transformation processes. This identification is vital for a general qualitative evaluation of the natural attenuation potential of the contaminated aquifer.

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.

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.

FeS2 (pyrite) is known to react with water and dissolved molecular oxygen to form sulfate and iron oxyhydroxides. This process plays a large role in the environmentally damaging phenomenon known as acid mine drainage. An outstanding scientific issue has been whether the oxygen in the sulfate and oxyhydroxide product was derived from water and/or dissolved oxygen. By monitoring the reaction in situ with horizontal attenuated total reflectance infrared spectroscopy, it was found that when using 18O isotopically substituted water, the majority of the infrared absorbance due to sulfate product red-shifted approximately 70 cm(-1) relative to the absorbance of sulfate using H(2)16O as a reactant. Bands corresponding to the iron oxyhydroxide product did not shift. These results indicate water as the primary source of oxygen in the sulfate product, while the oxygen atoms in the iron oxyhydroxide product are obtained from dissolved molecular oxygen.

Perchlorate is known to be a minor component of the hyperarid Atacama Desert salts, and its origin has long been a subject of speculation. Here we report the first measurement of the triple-oxygen isotope ratios (18O/16O and 17O/16O) for both man-made perchlorate from commercial sources and natural perchlorate extracted from Atacama soils. We found that the delta 18O values (i.e., normalized 18O/ 16O ratios) of man-made perchlorate were at -18.4+/-1.2%, whereas natural perchlorate has a variable delta 18O value, ranging from -4.5% to -24.8%. The delta 18O and delta 17O values followed the bulk Earth's oxygen isotope fractionation line for man-made perchlorate, but all Atacama perchlorates deviated from this line, with a distinctly large and positive 170 anomaly ranging from +4.2% to +9.6%. These findings provide a tool for the identification and forensics of perchlorate contamination in the environment. Additionally, they confirm an early speculation that the oxidation of volatile chlorine by 03 and the formation of HClO4 can be a sink (albeit a minor one) for atmospheric chlorine.

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.

Stable sulfur isotope measurements (delta34S) made on samples collected from a 2 m snowpit on the Inilchek Glacier, Tien Shan Mountains (42.16 degrees N, 80.25 degrees E, 5100 m) are used to estimate sources of sulfate (SO4(2-)) in high-elevation Central Asian precipitation. Comparison of snowpit oxygen isotope (delta18O) data with previous work constrains the age of the snowpit samples to the summer season during which they were retrieved (1999). Delta34S measurements were made at 10 cm resolution (20 samples total), with delta34S values ranging from 0.4/1000 during background ([SO4(2-)] < 1 microequiv L(-1)) periods to 19.4/1000 during a single high [SO4(2-)] event. On the basis of the significant correlation (r = 0.87) between [SO4(2-)] and delta34S values, coupled with major ion concentration time series and concentration ratios, we suggest a two-component mixing system consisting of evaporite dust and anthropogenic SO4(2-) to explain the observed delta34S values. Using a regression model, we estimate that during the 1999 summer season 60% of the deposited SO4(2-) was from an evaporite dust source, while 40% of the SO4(2-) was from anthropogenic sources. Due to the potentially large and unconstrained range of delta34S values for both evaporite and anthropogenic SO4(2-) sources in Asia, the error in our estimates is difficult to assess. However, the delta34S data from the 1999 Tien Shan snowpit provide the first unambiguous identification of evaporite and anthropogenic SO4(2-) in high-elevation Asian precipitation, and future ice core studies using improved analysis techniques and source delta34S values can provide detailed information on sulfur biogeochemistry and anthropogenic impacts in Asian alpine regions.

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.