Oxygen Isotope Composition Of Nitrate Research Articles

Influence of land use change on nitrate sources and pollutant enrichment in surface and groundwater of a growing urban area in Tanzania

In the present study, 3-year (1997, 2008 and 2017) satellite images as well as different hydro-chemical parameters, nitrogen and oxygen isotopic composition of nitrate were used to examine the impacts of land use and land cover change on surface and groundwater quality. Through isotopic composition, sources of surface and groundwater pollutants were also elucidated. The results showed significant land use transition whereby land use changed from forest and bare land to agricultural land and built-up areas. A slight reduction in the size of areas covered by water bodies was also observed. Results indicate differences in nitrate concentration that mirror land use changes. Samples with elevated levels of nitrate above 10 mg/L were located near agricultural fields and areas with intensive livestock keeping activities. In groundwater, ẟ15N-nitrate and ẟ18O-nitrate ranged from 3.2‰ to 20.1‰ with a mean value of 11.7 ± 1.8‰ and from 2.1‰ to 12.0‰ with mean value of 5.4 ± 1.8‰, respectively. In surface water, ẟ15N-nitrate and ẟ18O-nitrate ranged from 2.4‰ to 19.3‰ with mean value of 4.9 ± 1.4‰ and from 1.5‰ to 21.9‰ with a mean value of 13.5 ± 2.8‰, respectively. Isotopic composition data suggest sources of nitrate in both ground and surface water dominated by synthetic and organic fertilizer application and to a lesser extent a natural soil nitrate source.

How aerosol pH responds to nitrate to sulfate ratio of fine-mode particulate.

Aerosol acidity (pH), one of key properties of fine-mode particulate (PM2.5), depends largely on nitrate and sulfate in particle. The mass contribution of nitrate relative to sulfate in PM2.5 has tended to increase in many regions globally, but how this change affects aerosol pH remains in debate. In this way, we measured PM2.5 ionic species and oxygen isotopic composition of nitrate in the eastern China, and predicted aerosol pH using the ISORROPIA-II model. When nitrate to sulfate molar ratio increases and thus PM2.5 is gradually enriched in ammonium nitrate (NH4NO3), aerosol pH tends to increase. The oxidation of nitrogen dioxide (NO2) by hydroxyl radical is responsible for most of nitrate formation (generally above 60%). These indicate that nitrate formation through gas-to-particle conversion involving ammonia and nitric acid results in increasing aerosol pH with increasing molar ratio of nitrate to sulfate. Conversely, aerosol pH is expected to decrease with increasing relative abundance of nitrate as ammonia emissions are lowered. Our research concludes that it should be considered to reduce aerosol NH4NO3 by reducing the precursors of nitric oxide and ammonia emissions, to substantially improve the air quality (i.e., reduce PM2.5 levels and potential nitrate deposition) in China.

Global inorganic nitrate production mechanisms: comparison of a global model with nitrate isotope observations

Abstract. The formation of inorganic nitrate is the main sink for nitrogen oxides (NOx = NO + NO2). Due to the importance of NOx for the formation of tropospheric oxidants such as the hydroxyl radical (OH) and ozone, understanding the mechanisms and rates of nitrate formation is paramount for our ability to predict the atmospheric lifetimes of most reduced trace gases in the atmosphere. The oxygen isotopic composition of nitrate (Δ17O(nitrate)) is determined by the relative importance of NOx sinks and thus can provide an observational constraint for NOx chemistry. Until recently, the ability to utilize Δ17O(nitrate) observations for this purpose was hindered by our lack of knowledge about the oxygen isotopic composition of ozone (Δ17O(O3)). Recent and spatially widespread observations of Δ17O(O3) motivate an updated comparison of modeled and observed Δ17O(nitrate) and a reassessment of modeled nitrate formation pathways. Model updates based on recent laboratory studies of heterogeneous reactions render dinitrogen pentoxide (N2O5) hydrolysis as important as NO2 + OH (both 41 %) for global inorganic nitrate production near the surface (below 1 km altitude). All other nitrate production mechanisms individually represent less than 6 % of global nitrate production near the surface but can be dominant locally. Updated reaction rates for aerosol uptake of NO2 result in significant reduction of nitrate and nitrous acid (HONO) formed through this pathway in the model and render NO2 hydrolysis a negligible pathway for nitrate formation globally. Although photolysis of aerosol nitrate may have implications for NOx, HONO, and oxidant abundances, it does not significantly impact the relative importance of nitrate formation pathways. Modeled Δ17O(nitrate) (28.6±4.5 ‰) compares well with the average of a global compilation of observations (27.6±5.0 ‰) when assuming Δ17O(O3) = 26 ‰, giving confidence in the model's representation of the relative importance of ozone versus HOx (= OH + HO2 + RO2) in NOx cycling and nitrate formation on the global scale.

Nutrient distribution and nitrogen and oxygen isotopic composition of nitrate in water masses of the subtropical southern Indian Ocean

Abstract. The Indian Ocean subtropical gyre (IOSG) is one of five extensive subtropical gyres in the world's ocean. In contrast to those of the Atlantic and Pacific oceans, the IOSG has been sparsely studied. We investigate the water mass distributions based on temperature, salinity and oxygen data, and the concentrations of water column nutrients and the stable isotope composition of nitrate, using water samples collected between ∼30∘ S and the Equator during two expeditions: MSM 59/2 in 2016 and SO 259 in 2017. Our results are the first from this oceanic region and provide new information on nitrogen sources and transformation processes. We identify the thick layer of nutrient-depleted surface waters of the oligotrophic IOSG with nitrate (NO3-) and phosphate (PO43-) concentrations of < 3 and < 0.3 µmol kg−1, respectively (< 300 m; σ < 26.4 kg−1 m−3). Increased nutrient concentrations towards the Equator represent the northern limb of the gyre, which is characterized by typical strong horizontal gradients of the outcropping nutriclines. The influx of the Subantarctic Mode Water (SAMW) from the Southern Ocean injects oxygen-saturated waters with preformed nutrients, indicated by the increased N and O isotope composition of nitrate (δ15N > 7 ‰; δ18O > 4 ‰) at 400–500 m (26.6–26.7 kg−1 m−3), into the subtropical thermocline. These values reflect partial N assimilation in the Southern Ocean. Moreover, in the northern study area, a residue of nitrate affected by denitrification in the Arabian Sea is imported into intermediate and deep water masses (> 27.0 kg−1 m−3) of the gyre, indicated by an N deficit (N* ∼-1 to −4 µmol kg−1) and by elevated isotopic ratios of nitrate (δ15N > 7 ‰; δ18O > 3 ‰). Remineralization of partially assimilated organic matter, produced in the subantarctic, leads to a decoupling of N and O isotopes in nitrate and results in a relatively low Δ(15–18) value of < 3 ‰ within the SAMW. In contrast, remineralization of 15N-enriched organic matter from the Arabian Sea indicates higher Δ(15–18) values of > 4 ‰ within the Red Sea–Persian Gulf Intermediate Water (RSPGIW). Thus, the subtropical southern Indian Ocean is supplied by preformed nitrate from the lateral influx of water masses from regions exhibiting distinctly different N-cycle processes documented in the dual isotope composition of nitrate. Additionally, a significant contribution of N2 fixation between 20.36 and 23.91∘ S is inferred from reduced δ15N–NO3- values towards surface waters (upward decrease of δ15N ∼2.4 ‰), N* values of > 2 µmol kg−1 and a relatively low Δ(15–18) value of < 3 ‰. A mass and isotope budget implies that at least 32 %–34 % of the nitrate in the upper ocean between 20.36 and 23.91∘ S is provided from newly fixed nitrogen, whereas N2 fixation appears to be limited by iron or temperature south of 26∘ S.

Constraining the Oxygen Isotopic Composition of Nitrate Produced by Nitrification.

Measurements of the stable isotope ratios of nitrogen (15N/14N) and oxygen (18O/16O) in nitrate (NO3-) enable identification of sources, dispersal, and fate of natural and contaminant NO3- in aquatic environments. The 18O/16O of NO3- produced by nitrification is often assumed to reflect the proportional contribution of oxygen atom sources, water, and molecular oxygen, in a 2:1 ratio. Culture and seawater incubations, however, indicate oxygen isotopic equilibration between nitrite (NO2-) and water, and kinetic isotope effects for oxygen atom incorporation, which modulate the NO3- 18O/16O produced during nitrification. To investigate the influence of kinetic and equilibrium effects on the isotopic composition of NO3- produced from the nitrification of ammonia (NH3), we incubated streamwater supplemented with ammonium (NH4+) and increments of 18O-enriched water. Resulting NO3- 18O/16O ratios showed (1) a disproportionate sensitivity to the 18O/16O ratio of water, mediated by isotopic equilibration between water and NO2-, as well as (2) kinetic isotope discrimination during O atom incorporation from molecular oxygen and water. Empirically, the NO3- 18O/16O ratios thus produced fortuitously converge near the 18O/16O ratio of water. More elevated NO3- 18O/16O values commonly reported in soils and oxic groundwater may thus derive from processes additional to nitrification, including NO3- reduction.

Factors influencing the accuracy of the denitrifier method for determining the oxygen isotopic composition of nitrate.

The denitrifier method is widely used as a novel pretreatment method for the determination of nitrogen and oxygen isotope ratios as it can provide quantitative and high-sensitivity measurements. Nevertheless, the method is limited by relatively low measurement accuracy for δ18O. In this study, we analyzed the factors influencing the accuracy of δ18O determination, and then systematically investigated the effects of dissolved oxygen concentrations and nitrate sample sizes on estimates of the δ15N and δ18O of nitrate reference materials. The δ18O contraction ratio was used to represent the relationship between the measured difference and true difference between two reference materials. We obtained the following main results: (1) a gas-liquid ratio of 3:10 (v/v) in ordinary triangular flasks and a shaking speed of 120 r/min produced an optimal range (1.9 to 2.6 mg/L) in the concentration of dissolved oxygen for accurately determining δ18O, and (2) the δ18O contraction ratio decreased as nitrate sample size decreased within a certain range (1.0 to 0.1 μmol). Our results suggested that δ18O contraction is influenced mainly by dissolved oxygen concentrations in pure culture, and provided a model for improving the accuracy of oxygen isotope analysis.

Isotopic analysis of N and O in NO3- by selective bacterial reduction to N2O for groundwater pollution.

We describe a method to determine the nitrogen and oxygen isotopic composition of nitrate in groundwater samples ((15)N/(14)N and (18)O/(16)O, respectively), which is based on the analysis of nitrous oxide gas (N2O) that is produced quantitatively from nitrate by denitrifying bacteria. This method which is simple, inexpensive and effective in the removal of nitrite is greatly selective for NO2(-) and was used for mixed samples containing both NO2(-) and NO3(-) with little or no measurable cross-contamination. The precision of δ(15)N and δ(18)O are 0.3 and 0.17‰ respectively, compared to that of 0.1 and 0.5‰ abroad (Brand et al. in Org Geochem 21:585-594, 1994; Begley and Scrimgeour in Anal Chem 69(8): 1530-1535, 1997; Kornexl et al. in Rapid Commun Mass Spectrom 13(16):1685-1693, 1999; Böhlke et al. in Rapid Commun Mass Spectrom 17:1835-1846, 2003; Gehre and Strauch in Rapid Commun Mass Spectrom 17(13):1497-1503, 2003; Werner in Isot Environ Health Stud 39:85-104, 2003).

Investigating the preservation of nitrate isotopic composition in a tropical ice core from the Quelccaya Ice Cap, Peru

AbstractThe nitrogen and oxygen isotopic composition of nitrate in ice cores offers unique potential for examining reactive nitrogen oxide (NOx) budgets and oxidation chemistry of past atmospheres. A low‐latitude record is of particular interest given that the dominant natural sources of NOx and production of hydroxyl radical are most prevalent in the tropics. Any interpretation of nitrate in ice cores, however, must first consider that nitrate in snow is vulnerable to postdepositional loss and isotopic alteration. We report and assess the integrity of nitrate–δ15N, –δ18O, and –Δ17O in a 30 m ice core from a high‐elevation site in the central Andes. Clear seasonality in δ15N, δ18O, and nitrate concentration exists throughout most of the record and cannot be explained by photolysis or evaporation based on our current understanding of these processes. In contrast, nitrate in the upper ~12 m of the core and in a snowpit shows very different behavior. This may reflect alteration facilitated by recent melting at the surface. The relationships between δ15N, δ18O, Δ17O, and concentration in the unaltered sections can be interpreted in terms of mixing of nitrate from discrete sources. Transport effects and an englacial contribution from nitrification cannot be ruled out at this time, but the observed isotopic compositions are consistent with expected signatures of known NOx sources and atmospheric oxidation pathways. Specifically, nitrate deposited during the wet season reflects biogenic soil emissions and hydroxyl/peroxy radical chemistry in the Amazon, while dry season deposition reflects a lightning source and ozone chemistry at higher levels in the troposphere.

Oxygen isotopic composition of nitrate and nitrite produced by nitrifying cocultures and natural marine assemblages

The δ18O value of nitrate produced during nitrification (δ18ONO3,nit) was measured in experiments designed to mimic oceanic conditions, involving cocultures of ammonia‐oxidizing bacteria or ammonia‐oxidizing archaea and nitrite‐oxidizing bacteria, as well as natural marine assemblages. The estimates of ranged from −1.5‰ ± 0.1‰ to +1.3‰ ± 1.4‰ at δ18O values of water (H2O) and dissolved oxygen (O2) of 0‰ and 24.2‰ vs. Vienna Standard Mean Ocean Water, respectively. Additions of 18O‐enriched H2O allowed us to evaluate the effects of oxygen (O) isotope fractionation and exchange on . Kinetic isotope effects for the incorporation of O atoms were the most important factors for setting overall values relative to the substrates (O2 and H2O). These isotope effects ranged from +10‰ to +22‰ for ammonia oxidation (O2 plus H2O incorporation) and from +1‰ to +27‰ for incorporation of H2O during nitrite oxidation. values were also affected by the amount and duration of nitrite accumulation, which permitted abiotic O atom exchange between nitrite and H2O. Coculture incubations where ammonia oxidation and nitrite oxidation were tightly coupled showed low levels of nitrite accumulation and exchange (3% ± 4%). These experiments had values of −1.5‰ to +0.7‰. Field experiments had greater accumulation of nitrite and a higher amount of exchange (22% to 100%), yielding an average value of +1.9‰ ± 3.0‰. Low levels of biologically catalyzed exchange in coculture experiments may be representative of nitrification in much of the ocean where nitrite accumulation is low. Abiotic oxygen isotope exchange may be important where nitrite does accumulate, such as oceanic primary and secondary nitrite maxima.

Nitrogen and Oxygen Isotope Composition of Nitrate in Stream Water of Fuji River Basin

To identify the nitrate source and spatial distribution of nitrogen isotope values originated from forest and agricultural lands, fifty-seven stream water samples from Fuji River Basin were analyzed for nitrate concentration and nitrate-nitrogen (δ15N-NO3-) and oxygen (δ18O-NO3-) isotope values. The δ18O-NO3- showed that the nitrate originated through nitrification. These values were plotted against fraction of each land use category in the study catchments. The δ15N-NO3- was positively correlated with the fractions of agricultural and residential areas in the catchments. The increasing of δ15N-NO3- with fraction of agricultural area converged to 5.4‰ which was similar to a reported nitrate isotope value of groundwater at orchard area in Kofu-Basin. The increasing δ15N-NO3- with more than 1% residential area suggested that potential source of nitrate contamination was domestic aste water. An increase of δ15N-NO3- in the catchments with less than 98% forest area suggested the sources of nitrate contamination were thropogenic. The estimated value of δ15N-NO3- in forest catchment was 0.9±1.2‰.

Evaluating source, chemistry and climate change based upon the isotopic composition of nitrate in ice cores

A clear negative trend is found in the nitrogen isotopic ratios (15N/14N) of nitrate over the industrial period, based on a 100-meter ice core from Summit, Greenland. This record indicates that isotopic composition of ice core nitrate reflects changes in nitrogen oxide (NOx) source emissions and that post-industrial emissions of NOx have resulted in a 12‰ (vs. air N2) decline in δ15N of atmospheric nitrate over the last ~300 years. Interestingly, over the last glacial period (as recorded in the Greenland GISP2 ice core), the δ15N of nitrate changes by ~20‰ from a typical pre-industrial Holocene value of 10‰ to a mean glacial value of 28‰, despite the lack of a significant change in nitrate concentration. The more recent ice core record clearly indicates an influence of NOx emission sources, therefore suggesting that the glacial-interglacial change in δ15N may be a record of significant variations in the contribution of NOx sources, such as lightning, biomass burning, biogenic soil emissions and oxidation of nitrous oxide in the stratosphere. In contrast to the source changes recorded by the nitrogen isotopes, the oxygen isotopic record of atmospheric nitrate (18O/16O, 17O/16O) in ice cores has implications for reconstruction of past atmospheric oxidant levels. This is because the oxygen isotopic composition of nitrate reflects oxidation of NOx to nitrate in the atmosphere by oxidants such as ozone and hydroxy and peroxy radicals. Measurements of variations in the isotopic composition of atmospheric nitrate inferred from ice cores could be used to improve interpretation of other records of δ15N such as those from tree rings and/or sediments.

Oxygen isotopic fractionation in the photochemistry of nitrate in water and ice

We recently reported the first multiple oxygen isotope composition of nitrate (NO3−) in ice cores (Alexander et al., 2004). Postdepositional photolysis and volatilization may alter the isotopic signatures of snowpack nitrate. Therefore the precise assessment of the geochemical/atmospheric significance of O‐isotopic signatures requires information on the relative rates of photolysis (λ > 300 nm) of N16O3−, N16O217O−, and N16O218O− in ice. Here we report on 17O‐ and 18O‐fractionation in the 313‐nm photolysis of 10‐mM aqueous solutions of normal Fisher KNO3 (i.e., Δ17O = −0.2 ± 0.2‰) and 17O‐enriched USGS‐35 NaNO3 (Δ17O = 21.0 ± 0.4‰) between −30° and 25°C. We found that Fisher KNO3 undergoes mass‐dependent O‐fractionation, i.e., a process that preserves Δ17O = 0. In contrast, Δ17O in USGS‐35 NaNO3 decreased by 1.6 ± 0.4‰ and 2.0 ± 0.4‰ at 25°C, 1.2 ± 0.4‰ and 1.3 ± 0.4‰ at −5°C, and 0.2 ± 0.4‰ and 1.1 ± 0.4‰ at −30°C, after 12 and 24 hours, respectively. Since the small quantum yield (∼0.2%) of NO3− photodecomposition into (NO2 + OH) is due to extensive cage recombination of the primary photofragments rather than to intramolecular processes, the observed Δ17O decreases likely reflect competitive O‐isotope exchange of geminate OH‐radicals with H2O (Δ17O = 0) and escape from the solvent cage, in addition to residual O‐isotope mixing of the final photoproducts NO, NO2, NO2−, with H2O. At the prevailing low temperatures, photochemical processing will not impair the diagnostic value of O‐isotopic signatures in tracing the chemical ancestry of nitrate in polar ice.

Isotopic evidence for source changes of nitrate in rain at Bermuda

Rainwater collected on the island of Bermuda between January 2000 and January 2001 shows pronounced seasonal variation in the nitrogen and oxygen isotopic composition of nitrate. Higher 15N/14N and lower 18O/16O ratios are observed in the warm season (April–September) in comparison to the cool season (October–March): The mean δ15N of nitrate for the warm and cool seasons is −2.1‰ and −5.9‰ (versus air N2), respectively, while the mean δ18O is 68.6‰ and 76.9‰ (versus Vienna Standard Mean Ocean Water). The few cool season rain events that had high 15N/14N and low 18O/16O exhibited trajectory paths originating from the south, similar to those of warm season samples. Accordingly, the region from which air is transported to the island determines the 15N/14N and 18O/16O of the nitrate. The source region provides precursor nitrogen oxides (NOx), influencing the 15N/14N of nitrate, and contributes to the chemistry that produces nitrate from NOx, which determines the 18O/16O of nitrate. While the range in nitrate 15N/14N observed during the cool season is consistent with anthropogenic emissions from North America, the higher warm season 15N/14N suggests that lightning is a significant source of nitrate to Bermuda. The isotopic evidence for a significant southern source of nitrate to Bermuda helps to explain the previous observation of unexpectedly high nitrate concentrations in warm season rain. The 18O/16O of nitrate in rain at Bermuda is high throughout the year (δ18O = 60.3 to 86.5‰) as a result of interactions of precursor NOx with ozone, which has a high 18O/16O ratio. The lower nitrate 18O/16O in the warm season and in cool season air masses from the south is consistent with elevated concentrations of hydroxyl radical (OH), which dilutes the isotopic signal of ozone. Our limited data set suggests that the relative importance of the OH sink for NOx during the cool season varies spatially over as large a range as is observed between the warm and cool seasons.

Measurement of the oxygen isotopic composition of nitrate in seawater and freshwater using the denitrifier method.

We report a novel method for measurement of the oxygen isotopic composition (18O/16O) of nitrate (NO3-) from both seawater and freshwater. The denitrifier method, based on the isotope ratio analysis of nitrous oxide generated from sample nitrate by cultured denitrifying bacteria, has been described elsewhere for its use in nitrogen isotope ratio (15N/14N) analysis of nitrate. (1) Here, we address the additional issues associated with 18O/16O analysis of nitrate by this approach, which include (1) the oxygen isotopic difference between the nitrate sample and the N20 analyte due to isotopic fractionation associated with the loss of oxygen atoms from nitrate and (2) the exchange of oxygen atoms with water during the conversion of nitrate to N2O. Experiments with 18O-labeled water indicate that water exchange contributes less than 10%, and frequently less than 3%, of the oxygen atoms in the N20 product for Pseudomonas aureofaciens. In addition, both oxygen isotope fractionation and oxygen atom exchange are consistent within a given batch of analyses. The analysis of appropriate isotopic reference materials can thus be used to correct the measured 18O/16O ratios of samples for both effects. This is the first method tested for 18O/16O analysis of nitrate in seawater. Benefits of this method, relative to published freshwater methods, include higher sensitivity (tested down to 10 nmol and 1 microM NO3-), lack of interference by other solutes, and ease of sample preparation.

Determination of the total oxygen isotopic composition of nitrate and the calibration of a delta 17O nitrate reference material.

A thermal decomposition method was developed and tested for the simultaneous determination of delta 18O and delta 17O in nitrate. The thermal decomposition of AgNO3 allows for the rapid and accurate determination of 18O/ 16O and 17O/16O isotopic ratios with a precision of +/- 1.5 per thousand for delta 18O and +/- 0.11 per thousand for delta 17O (delta 17O = delta 17O - 0.52 x delta 18O). The international nitrate isotope reference material IAEA-NO3 yielded a delta 18O value of +23.6 per thousand and delta 17O of -0.2 per thousand, consistent with normal terrestrial mass-dependent isotopic ratios. In contrast, a large sample of NaNO3 from the Atacama Desert, Chile, was found to have delta 17O = 21.56 +/- 0.11 per thousand and delta 18O = 54.9 +/- 1.5 per thousand, demonstrating a substantial mass-independent isotopic composition consistent with the proposed atmospheric origin of the desert nitrate. It is suggested that this sample (designated USGS-35) can be used to generate other gases (CO2, CO, N2O, O2) with the same delta 17O to serve as measurement references for a variety of applications involving mass-independent isotopic compositions in environmental studies.

The oxygen isotope composition of nitrate generated by nitrification in acid forest floors

The oxygen isotope composition of nitrate is used increasingly for identifying the origin of nitrate in terrestrial and aquatic ecosystems. This novel isotope tracer technique is based on the fact that nitrate in atmospheric deposition, in fertilizers, and nitrate generated by nitrification in soils appear to have distinct oxygen isotope ratios. While the typical ranges of δ18O values of nitrate in atmospheric deposition and fertilizers are comparatively well known, few experimental data exist for the oxygen isotope composition of nitrate generated by nitrification in soils. The objective of this study was to determine δ18O values of nitrate formed by microbial nitrification in acid forest floors.Evidence from laboratory incubation experiments and field studies suggests that during microbial nitrification in acid forest floor horizons, up to two of the three oxygen atoms in newly formed nitrate are derived from water, particularly if ammonium is abundant and nitrification rates are high. It was, however, also observed that in ammonium-limited systems with low nitrification rates, significantly less than two thirds of the oxygen in newly formed nitrate can be derived from water oxygen, presumably as a result of heterotrophic nitrification. It can be concluded from the presented data that the δ18O values of nitrate formed by microbial nitrification in acid forest floors typically range between +2 and +14‰, assuming that soil water δ18O values vary between −15 and −5‰. Hence, oxygen isotope ratios of nitrate formed by nitrification in forest floors are usually distinct from those of other nitrate sources such as atmospheric deposition and synthetic fertilizers and, therefore, constitute a valuable qualitative tracer for distinguishing among these sources of nitrate. A quantitative source apportionment appears, however, difficult because of the wide range of δ18O values, particularly for atmospheric nitrate deposition and for nitrate from microbial nitrification.