Evaluating groundwater nitrate and other physicochemical parameters of the arid and semi-arid district of DI Khan by multivariate statistical analysis.

Nitrate as an important water pollutant, causing eutrophication was analyzed in Pakistan at different water sources (hand pump (HP), bore hole (BH) and tube well (TW)) to assess the contamination level caused by NO3-. NO3- concentrations in the HP water samples were 31 mg L-1 to 59 mg L-1, in BH 20 mg L-1 to 79 mg L-1 while in TW water samples it was between 29 to 55 mg L-1. The association of NO3- with other selected parameter in groundwater can be determined by using statistical approaches. Different physicochemical parameters (pH, electrical conductivity (EC), temperature and dissolved oxygen (DO)) were studied in groundwater samples of the research district. The Pearson correlation coefficient (r) for groundwater characteristics were calculated. Hierarchical Cluster Analysis (HCA) was used to categorize samples based on their groundwater quality similarities and to find links between groundwater quality factors. The key relationship of the groundwater for HP samples on EC and TDS (r = 1) had a great correlation, while all other parameters correlations were lower (r = 0.40), BH's parameters on WT and WSD (r = 0.57), WT and pH (r = 0.57), EC and DO (r = 0.50), DO and TDS (0.50), EC and TDS (r = 1) had a quite high correlation, while all other parameters correlations were less than (r = 0.40), on the other hand, tube well parameters on TDS and EC (r = 1) had a perfect correlation, DO and pH (r = 0.75) parameters correlations were less than (r = 0.40).

Significant contributions of combustion-related sources to ammonia emissions.

Atmospheric ammonia (NH3) and ammonium (NH4+) can substantially influence air quality, ecosystems, and climate. NH3 volatilization from fertilizers and wastes (v-NH3) has long been assumed to be the primary NH3 source, but the contribution of combustion-related NH3 (c-NH3, mainly fossil fuels and biomass burning) remains unconstrained. Here, we collated nitrogen isotopes of atmospheric NH3 and NH4+ and established a robust method to differentiate v-NH3 and c-NH3. We found that the relative contribution of the c-NH3 in the total NH3 emissions reached up to 40 ± 21% (6.6 ± 3.4 Tg N yr-1), 49 ± 16% (2.8 ± 0.9 Tg N yr-1), and 44 ± 19% (2.8 ± 1.3 Tg N yr-1) in East Asia, North America, and Europe, respectively, though its fractions and amounts in these regions generally decreased over the past decades. Given its importance, c-NH3 emission should be considered in making emission inventories, dispersion modeling, mitigation strategies, budgeting deposition fluxes, and evaluating the ecological effects of atmospheric NH3 loading.

Formation Mechanisms and Source Apportionments of Airborne Nitrate Aerosols at a Himalayan-Tibetan Plateau Site: Insights from Nitrogen and Oxygen Isotopic Compositions.

Formation pathways and sources of atmosphere nitrate (NO3-) have attracted much attention as NO3- had detrimental effects on Earth's ecosystem and climate change. Here, we measured nitrogen (δ15N-NO3-) and oxygen (δ18O-NO3- and Δ17O-NO3-) 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 NO3- concentrations were observed in the springtime. The average δ15N-NO3-, δ18O-NO3-, and Δ17O-NO3- 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 NO2 + OH and N2O5 + H2O to nitrate production were estimated to be 43 and 52%, respectively, when the NO3 + hydrocarbon (HC)/dimethyl sulfide (DMS) (NO3 + 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 NOx from BB emission over South Asia that had undergone N2O5 + H2O processes enhanced the nitrate concentrations in the springtime over the HTP region.

Important contributions of non-fossil fuel nitrogen oxides emissions.

Since the industrial revolution, it has been assumed that fossil-fuel combustions dominate increasing nitrogen oxide (NOx) emissions. However, it remains uncertain to the actual contribution of the non-fossil fuel NOx to total NOx emissions. Natural N isotopes of NO3- in precipitation (δ15Nw-NO3-) have been widely employed for tracing atmospheric NOx sources. Here, we compiled global δ15Nw-NO3- observations to evaluate the relative importance of fossil and non-fossil fuel NOx emissions. We found that regional differences in human activities directly influenced spatial-temporal patterns of δ15Nw-NO3- variations. Further, isotope mass-balance and bottom-up calculations suggest that the non-fossil fuel NOx accounts for 55 ± 7% of total NOx emissions, reaching up to 21.6 ± 16.6Mt yr-1 in East Asia, 7.4 ± 5.5Mt yr-1 in Europe, and 21.8 ± 18.5Mt yr-1 in North America, respectively. These results reveal the importance of non-fossil fuel NOx emissions and provide direct evidence for making strategies on mitigating atmospheric NOx pollution.

Multiyear Measurements on Δ17O of Stream Nitrate Indicate High Nitrate Production in a Temperate Forest.

Nitrification is a crucial step in ecosystem nitrogen (N) cycling, but scaling up from plot-based measurements of gross nitrification to catchments is difficult. Here, we employed a newly developed method in which the oxygen isotope anomaly (Δ17O) of nitrate (NO3-) is used as a natural tracer to quantify in situ catchment-scale gross nitrification rate (GNR) for a temperate forest from 2014 to 2017 in northeastern China. The annual GNR ranged from 71 to 120 kg N ha-1 yr-1 (average 94 ± 10 kg N ha-1 yr-1) over the 4 years in this forest. This result and high stream NO3- loss (4.2-8.9 kg N ha-1 yr-1) suggest that the forested catchment may have been N-saturated. At the catchment scale, the total N output of 10.7 kg N ha-1 yr-1, via leaching and gaseous losses, accounts for 56% of the N input from bulk precipitation (19.2 kg N ha-1 yr-1). This result indicates that the forested catchment is still retaining a large fraction of N from atmospheric deposition. Our study suggests that estimating in situ catchment-scale GNR over several years when combined with other conventional flux estimates can facilitate the understanding of N biogeochemical cycling and changes in the ecosystem N status.

Stable Sulfur Isotopes Revealed a Major Role of Transition-Metal Ion-Catalyzed SO2 Oxidation in Haze Episodes.

Secondary sulfate aerosols played an important role in aerosol formation and aging processes, especially during haze episodes in China. Secondary sulfate was formed via atmospheric oxidation of SO2 by OH, O3, H2O2, and transition-metal-catalyzed (TMI) O2. However, the relative importance of these oxidants in haze episodes was strongly debated. Here, we use stable sulfur isotopes (δ34S) of sulfate aerosols and a Rayleigh distillation model to quantify the contributions of each oxidant during a haze episode in Nanjing, a megacity in China. The observed δ34S values of sulfate aerosols showed a negative correlation with sulfur oxidation ratios, which was attributed to the sulfur isotopic fractionations during the sulfate formation processes. Using the average fractionation factor calculated from our observations and zero-dimensional (0-D) atmospheric chemistry modeling estimations, we suggest that OH oxidation was trivial during the haze episode, while the TMI pathway contributed 49 ± 10% of the total sulfate production and O3/H2O2 oxidations accounted for the rest. Our results displayed good agreement with several atmospheric chemistry models that carry aqueous and heterogeneous TMI oxidation pathways, suggesting the role of the TMI pathway was significant during haze episodes.

Triple oxygen isotopic evidence for atmospheric nitrate and its application in source identification for river systems in the Qinghai-Tibetan Plateau.

Nitrate source identification in river systems is important for water quality management. Recently, the oxygen isotopic anomaly of nitrate in atmospheric deposition (Δ17Oatm) is used to identify unprocessed atmospheric nitrate in river systems to reduce the uncertainty caused by the wide range of δ18O. In high-elevation regions, such as the Qinghai-Tibetan Plateau (QTP) featured with lower temperature and pressure as well as strong radiation, the Δ17Oatm might be different from that in low-elevation regions, but no relevant studies have been reported. In this work, Δ17Oatm in the QTP was studied, and the fingerprints of nitrate isotopes in synthetic fertilizer, livestock manure, domestic sewage, and soil organic nitrogen (SON) were identified and used to quantify various source contributions to riverine nitrate in the Yellow River and Changjiang River source regions located in the QTP during 2016-2017. The results showed that the average of Δ17Oatm in the QTP was 16.4‰, lower than the range (19-30‰) reported for the low-elevation regions. The possible mechanism is decreased O3 as well as increased hydroxyl and peroxy radical levels in the troposphere caused by the climate condition and ozone valley in the QTP will affect the production pathways of atmospheric nitrate. By combining the sewage discharge data with the output results of the SIAR (stable isotope analysis in R) model based on the stable isotope data, manure was determined to be one of the major sources to riverine nitrate for both rivers. The contributions of various sources to riverine nitrate were 47 ±â€¯10% for manure, 30 ±â€¯5% for SON, 10 ±â€¯4% for atmospheric precipitation, 9 ±â€¯2% for synthetic fertilizer, and 4 ±â€¯0% for sewage in the Yellow River source region. This study indicates that the unique atmospheric conditions in the QTP have led to a lower Δ17Oatm value, and atmospheric source makes a considerable contribution to riverine nitrate in the QTP.

Isotopic evidence for enhanced fossil fuel sources of aerosol ammonium in the urban atmosphere.

The sources of aerosol ammonium (NH4+) are of interest because of the potential of NH4+ to impact the Earth's radiative balance, as well as human health and biological diversity. Isotopic source apportionment of aerosol NH4+ is challenging in the urban atmosphere, which has excess ammonia (NH3) and where nitrogen isotopic fractionation commonly occurs. Based on year-round isotopic measurements in urban Beijing, we show the source dependence of the isotopic abundance of aerosol NH4+, with isotopically light (-33.8‰) and heavy (0 to +12.0‰) NH4+ associated with strong northerly winds and sustained southerly winds, respectively. On an annual basis, 37-52% of the initial NH3 concentrations in urban Beijing arises from fossil fuel emissions, which are episodically enhanced by air mass stagnation preceding the passage of cold fronts. These results provide strong evidence for the contribution of non-agricultural sources to NH3 in urban regions and suggest that priority should be given to controlling these emissions for haze regulation. This study presents a carefully executed application of existing stable nitrogen isotope measurement and mass-balance techniques to a very important problem: understanding source contributions to atmospheric NH3 in Beijing. This question is crucial to informing environmental policy on reducing particulate matter concentrations, which are some of the highest in the world. However, the isotopic source attribution results presented here still involve a number of uncertain assumptions and they are limited by the incomplete set of chemical and isotopic measurements of gas NH3 and aerosol NH4+. Further field work and lab experiments are required to adequately characterize endmember isotopic signatures and the subsequent isotopic fractionation process under different air pollution and meteorological conditions.

Enhanced nitrogen loss from rivers through coupled nitrification-denitrification caused by suspended sediment.

Present-day estimations of global nitrogen loss (N-loss) are underestimated. Commonly, N-loss from rivers is thought to be caused by denitrification only in bed-sediments. However, coupled nitrification-denitrification occurring in overlying water with suspended sediments (SPS) where oxic and anoxic/low oxygen zones may coexist is ignored for N-loss in rivers. Here the Yellow and Yangtze Rivers were taken as examples to investigate the effect of SPS, which exists in many rivers of the world, on N loss through coupled nitrification-denitrification with nitrogen stable (15N) isotopic tracer simulation experiments and in-situ investigation. The results showed even when SPS was surrounded by oxic waters, there were redox conditions that transitioned from an oxic surface layer to anoxic layer near the particle center, enabling coupled nitrification-denitrification to occur around SPS. The production rate of 15N2 from 15NH4+-N (R15N2-production) increased with increasing SPS concentration ([SPS]) as a power function (R15N2-production=a·[SPS]b) for both the SPS-water and bed sediment-SPS-water systems. The power-functional increase of nitrifying and denitrifying bacteria population with [SPS] accounted for the enhanced coupled nitrification-denitrification rate in overlying water. SPS also accelerated denitrification in bed-sediment due to increased NO3- concentration caused by SPS-mediated nitrification. For these two rivers, 1gL-1 SPS will lead to N-loss enhancement by approximately 25-120%, and the enhancement increased with organic carbon content of SPS. Thus, we conclude that SPS in overlying water is a hot spot for nitrogen loss in river systems and current estimates of in-stream N-loss are underestimated without consideration of SPS; this may partially compensate for the current imbalance of global nitrogen inputs and sinks.

Ab initio study of nitrogen and position-specific oxygen kinetic isotope effects in the NO + O3 reaction.

Ab initio calculations have been carried out to investigate nitrogen (k15/k14) and position-specific oxygen (k17/k16O & k18/k16) kinetic isotope effects (KIEs) for the reaction between NO and O3 using CCSD(T)/6-31G(d) and CCSD(T)/6-311G(d) derived frequencies in the complete Bigeleisen equations. Isotopic enrichment factors are calculated to be -6.7‰, -1.3‰, -44.7‰, -14.1‰, and -0.3‰ at 298 K for the reactions involving the 15N16O, 14N18O, 18O16O16O, 16O18O16O, and 16O16O18O isotopologues relative to the 14N16O and 16O3 isotopologues, respectively (CCSD(T)/6-311G(d)). Using our oxygen position-specific KIEs, a kinetic model was constructed using Kintecus, which estimates the overall isotopic enrichment factors associated with unreacted O3 and the oxygen transferred to NO2 to be -19.6‰ and -22.8‰, respectively, (CCSD(T)/6-311G(d)) which tends to be in agreement with previously reported experimental data. While this result may be fortuitous, this agreement suggests that our model is capturing the most important features of the underlying physics of the KIE associated with this reaction (i.e., shifts in zero-point energies). The calculated KIEs will useful in future NOx isotopic modeling studies aimed at understanding the processes responsible for the observed tropospheric isotopic variations of NOx as well as for tropospheric nitrate.

Fossil Fuel Combustion-Related Emissions Dominate Atmospheric Ammonia Sources during Severe Haze Episodes: Evidence from (15)N-Stable Isotope in Size-Resolved Aerosol Ammonium.

The reduction of ammonia (NH3) emissions is urgently needed due to its role in aerosol nucleation and growth causing haze formation during its conversion into ammonium (NH4(+)). However, the relative contributions of individual NH3 sources are unclear, and debate remains over whether agricultural emissions dominate atmospheric NH3 in urban areas. Based on the chemical and isotopic measurements of size-resolved aerosols in urban Beijing, China, we find that the natural abundance of (15)N (expressed using δ(15)N values) of NH4(+) in fine particles varies with the development of haze episodes, ranging from -37.1‰ to -21.7‰ during clean/dusty days (relative humidity: ∼ 40%), to -13.1‰ to +5.8‰ during hazy days (relative humidity: 70-90%). After accounting for the isotope exchange between NH3 gas and aerosol NH4(+), the δ(15)N value of the initial NH3 during hazy days is found to be -14.5‰ to -1.6‰, which indicates fossil fuel-based emissions. These emissions contribute 90% of the total NH3 during hazy days in urban Beijing. This work demonstrates the analysis of δ(15)N values of aerosol NH4(+) to be a promising new tool for partitioning atmospheric NH3 sources, providing policy makers with insights into NH3 emissions and secondary aerosols for regulation in urban environments.

Nitrogen Isotope Composition of Thermally Produced NOx from Various Fossil-Fuel Combustion Sources.

The nitrogen stable isotope composition of NOx (δ(15)N-NOx) may be a useful indicator for NOx source partitioning, which would help constrain NOx source contributions in nitrogen deposition studies. However, there is large uncertainty in the δ(15)N-NOx values for anthropogenic sources other than on-road vehicles and coal-fired energy generating units. To this end, this study presents a broad analysis of δ(15)N-NOx from several fossil-fuel combustion sources that includes: airplanes, gasoline-powered vehicles not equipped with a three-way catalytic converter, lawn equipment, utility vehicles, urban buses, semitrucks, residential gas furnaces, and natural-gas-fired power plants. A relatively large range of δ(15)N-NOx values was measured from -28.1‰ to 8.5‰ for individual exhaust/flue samples that generally tended to be negative due to the kinetic isotope effect associated with thermal NOx production. A negative correlation between NOx concentrations and δ(15)N-NOx for fossil-fuel combustion sources equipped with selective catalytic reducers was observed, suggesting that the catalytic reduction of NOx increases δ(15)N-NOx values relative to the NOx produced through fossil-fuel combustion processes. Combining the δ(15)N-NOx measured in this study with previous published values, a δ(15)N-NOx regional and seasonal isoscape was constructed for the contiguous U.S., which demonstrates seasonal and regional importance of various NOx sources.

Isotopic evidence for the occurrence of biological nitrification and nitrogen deposition processing in forest canopies.

This study examines the role of tree canopies in processing atmospheric nitrogen (Ndep ) for four forests in the United Kingdom subjected to different Ndep : Scots pine and beech stands under high Ndep (HN, 13-19 kg N ha(-1)  yr(-1) ), compared to Scots pine and beech stands under low Ndep (LN, 9 kg N ha(-1)  yr(-1) ). Changes of NO3 -N and NH4 -N concentrations in rainfall (RF) and throughfall (TF) together with a quadruple isotope approach, which combines δ(18) O, Δ(17) O and δ(15) N in NO3 (-) and δ(15) N in NH4 (+) , were used to assess N transformations by the canopies. Generally, HN sites showed higher NH4 -N and NO3 -N concentrations in RF compared to the LN sites. Similar values of δ(15) N-NO3 (-) and δ(18) O in RF suggested similar source of atmospheric NO3 (-) (i.e. local traffic), while more positive values for δ(15) N-NH4 (+) at HN compared to LN likely reflected the contribution of dry NHx deposition from intensive local farming. The isotopic signatures of the N-forms changed after interacting with tree canopies. Indeed, (15) N-enriched NH4 (+) in TF compared to RF at all sites suggested that canopies played an important role in buffering dry Ndep also at the low Ndep site. Using two independent methods, based on δ(18) O and Δ(17) O, we quantified for the first time the proportion of NO3 (-) in TF, which derived from nitrification occurring in tree canopies at the HN site. Specifically, for Scots pine, all the considered isotope approaches detected biological nitrification. By contrast for the beech, only using the mixing model with Δ(17) O, we were able to depict the occurrence of nitrification within canopies. Our study suggests that tree canopies play an active role in the N cycling within forest ecosystems. Processing of Ndep within canopies should not be neglected and needs further exploration, with the combination of multiple isotope tracers, with particular reference to Δ(17) O.

Oxygen and nitrogen isotopic composition of nitrate in commercial fertilizers, nitric acid, and reagent salts.

Nitrate is a key component of synthetic fertilizers that can be beneficial to crop production in agro-ecosystems, but can also cause damage to natural ecosystems if it is exported in large amounts. Stable isotopes, both oxygen and nitrogen, have been used to trace the sources and fate of nitrate in various ecosystems. However, the oxygen isotope composition of synthetic and organic nitrates is poorly constrained. Here, we present a study on the N and O isotope composition of nitrate-based fertilizers. The δ(15)N values of synthetic and natural nitrates were 0 ± 2 ‰ similar to the air N2 from which they are derived. The δ(18)O values of synthetic nitrates were 23 ± 3 ‰, similar to air O2, and natural nitrate fertilizer δ(18)O values (55 ± 5 ‰) were similar to those observed in atmospheric nitrate. The Δ(17)O values of synthetic fertilizer nitrate were approximately zero following a mass-dependent isotope relationship, while natural nitrate fertilizers had Δ(17)O values of 18 ± 2 ‰ similar to nitrate produced photochemically in the atmosphere. These narrow ranges of values can be used to assess the amount of nitrate arising from fertilizers in mixed systems where more than one nitrate source exists (soil, rivers, and lakes) using simple isotope mixing models.

Nitrogen stable isotope composition (δ15N) of vehicle-emitted NOx.

The nitrogen stable isotope ratio of NOx (δ(15)N-NOx) has been proposed as a regional indicator for NOx source partitioning; however, knowledge of δ(15)N values from various NOx emission sources is limited. This study presents a detailed analysis of δ(15)N-NOx emitted from vehicle exhaust, the largest source of anthropogenic NOx. To accomplish this, NOx was collected from 26 different vehicles, including gasoline and diesel-powered engines, using a modification of a NOx collection method used by the United States Environmental Protection Agency, and δ(15)N-NOx was analyzed. The vehicles sampled in this study emitted δ(15)N-NOx values ranging from -19.1 to 9.8‰ that negatively correlated with the emitted NOx concentrations (8.5 to 286 ppm) and vehicle run time because of kinetic isotope fractionation effects associated with the catalytic reduction of NOx. A model for determining the mass-weighted δ(15)N-NOx from vehicle exhaust was constructed on the basis of average commute times, and the model estimates an average value of -2.5 ± 1.5‰, with slight regional variations. As technology improvements in catalytic converters reduce cold-start emissions in the future, it is likely to increase current δ(15)N-NOx values emitted from vehicles.

Sources and transport of nitrogen in arid urban watersheds.

Urban watersheds are often sources of nitrogen (N) to downstream systems, contributing to poor water quality. However, it is unknown which components (e.g., land cover and stormwater infrastructure type) of urban watersheds contribute to N export and which may be sites of retention. In this study we investigated which watershed characteristics control N sourcing, biogeochemical processing of nitrate (NO3-) during storms, and the amount of rainfall N that is retained within urban watersheds. We used triple isotopes of NO3- (δ15N, δ18O, and Δ17O) to identify sources and transformations of NO3- during storms from 10 nested arid urban watersheds that varied in stormwater infrastructure type and drainage area. Stormwater infrastructure and land cover--retention basins, pipes, and grass cover--dictated the sourcing of NO3- in runoff. Urban watersheds were strong sinks or sources of N to stormwater depending on runoff, which in turn was inversely related to retention basin density and positively related to imperviousness and precipitation. Our results suggest that watershed characteristics control the sources and transport of inorganic N in urban stormwater but that retention of inorganic N at the time scale of individual runoff events is controlled by hydrologic, rather than biogeochemical, mechanisms.

Using 15N, 17O, and 18O to determine nitrate sources in the Yellow River, China.

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.

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.

Multiple isotope forensics of nitrate in a wild horse poisoning incident.

Multiple stable isotope analysis can be a powerful technique in forensic sciences. Oxygen and nitrogen isotopes were used to determine the source of nitrate that was responsible for the poisoning deaths of 71 wild horses in the Nevada desert. The nitrate was present in a water-filled hole known as 'the Main Lake depression.' Nitrate from the Main Lake depression had delta(18)O and delta(15)N values that were very positive (+32 per thousand, +37 per thousand), and Delta(17)O values of approximately +2 per thousand. The isotopic data suggested that the most probable source of the nitrate was nitrification of nitrogen from horse manure and urine that had leached into the pond. The delta(18)O signal suggested that extreme evaporative concentration had occurred, resulting in toxic levels of nitrate accumulating in the Main Lake depression. The study demonstrates the utility of the multiple stable isotope analysis approach for characterizing sources of nitrate.