Isotopic Composition Of Nitrate Research Articles

Radium and nitrogen isotopes tracing fluxes and sources of submarine groundwater discharge driven nitrate in an urbanized coastal area

The quantitative evaluations of nutrients delivered by submarine groundwater discharge (SGD) have been widely conducted worldwide, but sources of nutrients in the discharged submarine groundwater remain unclear. Identifying these sources of nutrients is essential to the protection and management of marine ecological environments. This study aims to evaluate the magnitudes of SGD and the associated nitrate in the Guangdong-Hongkong-Macao Greater Bay Area (GHM Greater Bay Area), China, and identify the sources of SGD-driven nitrate in this region using radioactive radium (Ra) isotopes (223Ra, 224Ra, and 228Ra) and stable nitrogen (N) and oxygen (O) isotope composition of nitrate (δ15N-NO3− and δ18O-NO3−). The results of the Ra mixing model show that the estimated SGD and the associated nitrate fluxes into the Greater Bay Area are (9.15 ± 1.26) × 108 m3/d and (3.77 ± 0.52) × 107 mol/d, respectively, both of which are comparable to the contributions from the Pearl River. Combing NO3− dual isotopic signatures of sampled coastal groundwater and five kinds of potential nitrate sources, we found that ammonium (NH4+) fertilizer and natural soil N are the two main sources of nitrate in discharged submarine groundwater and rivers. No anthropogenic inputs from manure or sewage waste were identified. This study provides significant insights into the establishment of effective management strategies for controlling SGD-nutrients into the bay and protecting the marine ecological environment.

Land use and episodic rainfall as drivers of nitrogen exports in subtropical rivers: Insights from δ15N-NO3−, δ18O-NO3− and 222Rn

Ongoing land-use intensification in subtropical catchments is expected to release more inorganic nitrogen to downstream coastal waters similar to historical changes in temperate ecosystems. Here, we examined spatial and temporal drivers of stream nitrogen loads across a subtropical land-use gradient using the isotopic compositions of nitrate (NO3−-N) and radon (222Rn), a natural groundwater tracer. We investigated eleven subtropical creeks/rivers over contrasting hydrological conditions in Australia. NOx-N (nitrite (NO2−-N) + nitrate (NO3−-N)) accounted for 13.1%, 34.0%, and 42.6% of total dissolved nitrogen (TDN-N) in forest, peri-urban and agricultural creeks, respectively. Following an 80 mm rain event, loads of dissolved inorganic nitrogen (DIN-N) from agriculture catchments reached 368 mg N m−2 catchment area day−1. Forest and peri-urban catchments had aquatic TDN-N loads 17.8% and 31.1% of loads from agricultural catchments. Radon observations suggest that nitrogen and phosphorus loads were driven primarily by surface runoff rather than groundwater discharge. The δ15N-NO3− and δ18O-NO3− values in the agriculture, forest and peri-urban catchments indicate fertilisers and soil nitrogen as the main sources of NO3−-N. However, one of the catchments (Double Crossing Creek) received a mixture of recirculated greywater and chemical nitrogen fertilisers. Isotopic signatures imply significant NO3−-N losses via denitrification during dry conditions. Groundwater discharge played a minor role because regional aquifers were not contaminated by nitrogen. Overall, intensive agricultural land use and episodic rainfall events were the major spatial and temporal drivers of nitrogen loads.

A Complete Isotope (δ15N, δ18O, Δ17O) Investigation of Atmospherically Deposited Nitrate in Glacial‐Hydrologic Systems Across the Third Pole Region

AbstractThe Himalayas and Tibetan Plateau, identified as the Third Pole (TP), is a unique region because of its insertion into global environmental and climatic changes. Deposition of atmospheric nitrate in this region is one of the most important sources of reactive nitrogen to glacial‐hydrologic system and ecosystems. The isotopic composition of atmospherically deposited nitrate preserved in ice bodies plays a central role in delineating environmental and climatic changes, present, and past. Here, we provide an overview of the complete isotopic compositions (δ15N, δ18O, and Δ17O) of nitrate in aerosol, snow, ice, and water samples (n = 46) collected across the Southern, Southeastern, Central, and Northern TP to constrain complex nitrogen cycles of the atmosphere, cryosphere, hydrosphere, and, potentially, the biosphere. A large variability of snow nitrate isotopic compositions is observed across the TP at different spatial scales (from a single glacier to the entire plateau), likely due to the complex landscape and relevant physical and chemical processes across the TP. Large nitrate Δ17O values are observed in water samples collected from the Mt. Everest region, highlighting the considerable fraction (up to 45%) of atmospheric nitrate to the nitrate load in this Himalayan hydrologic system. Our work reveals the complex chemical, depositional, and postdepositional processes over the TP that are greater than previously thought and identifies further comprehensive investigations, which entail using nitrate isotopic compositions as an identifier for nitrate source apportionment in various ecosystems and understanding past atmospheric and climatic conditions in this region.

Fresh biochar application provokes a reduction of nitrate which is unexplained by conventional mechanisms

Soil-applied biochar has been reported to possess the potential to mitigate nitrate leaching and thus, exert beneficial effects beyond carbon sequestration. The main objective of the present study is to confirm if a pine gasification biochar that has proven able to decrease soil-soluble nitrate in previous research can indeed exert such an effect and to determine by which mechanism. For this purpose, lysimeters containing soil-biochar mixtures at 0, 12 and 50 t biochar ha−1 were investigated in two different scenarios: a fresh biochar scenario consisting of fresh biochar and a fallow-managed soil, and an aged biochar scenario with a 6-yr naturally aged biochar in a crop-managed soil. Soil columns were assessed under a mimicked Mediterranean ambient within a greenhouse setting during an 8-mo period which included a barley crop cycle. A set of parameters related to nitrogen cycling, and particularly to mechanisms that could directly or indirectly explain nitrate content reduction (i.e., sorption, leaching, microbially-mediated processes, volatilisation, plant uptake, and ecotoxicological effects), were assessed. Specific measurements included soil solution and leachate ionic composition, microbial biomass and activity, greenhouse gas (GHG) emissions, N and O isotopic composition of nitrate, crop yield and quality, and ecotoxicological endpoints, among others. Nitrate content reduction in soil solution was verified for the fresh biochar scenario in both 12 and 50 t ha−1 treatments and was coupled to a significant reduction of chloride, sodium, calcium and magnesium. This effect was noticed only after eight months of biochar application thus suggesting a time-dependent process. All other mechanisms tested being discarded, the formation of an organo-mineral coating emerges as a plausible explanation for the ionic content decrease.

Stable nitrogen and oxygen isotope fractionation during precipitation of nitrate salt from saturated solutions.

Nitrate is an oxyanion similar to CO3 - and thus should undergo stable N and O isotope fractionation during dissolution or precipitation. This process should dominate abiotic soil nitrate processes in hyperarid regions of Earth and possibly Mars. The N and O isotope fractionations during the precipitation of nitrate salt from saturated solutions at ~20°C were determined by two methods: rapid precipitation by antisolvent crystallization and slow uninhibited precipitation in a desiccator. In the antisolvent crystallization procedure, increasing volumes of acetone were added to samples of saturated sodium and strontium nitrate solutions to instantaneously precipitate nitrate salt. In the slow procedure (requiring weeks), slow evaporative water loss drove the process. There was little difference between the two procedures. Using a Rayleigh model, the calculated N fractionation (15 εproduct-residual ) ranged from 1.69‰ to 2.77‰, whereas for O, the 18 εproduct-residual values were between 1.27‰ and 4.61‰. The N isotope fractionation between NO3 - and the metal solid is similar to that between C in dissolved CO3 -2 and carbonates. We found that O versus N isotope plots of soil nitrate in a cold/dry Antarctic chronosequence had slopes similar to those from the experiments, revealing abiotic transport. In the Atacama Desert, where the soil nitrates are a mix of biological and tropospheric nitrate, there is an inverse relationship between soil N and O isotopes. These two relationships were compared with the isotope composition of nitrate from Martian meteorite EETA79001. While the N and O isotope composition of the Martian nitrate is remarkably similar to that of the present Atacama Desert, the interpretation of the slope of the O versus N isotopes remains ambiguous due to the limited number of samples. Additional NO3 samples from Martian meteorites are needed to address the question of abiotic versus biotic alteration of NO3 - on Mars.

Quantitative identification of non-point sources of nitrate in urban channels based on dense in-situ samplings and nitrate isotope composition

Quantitative identification of non-point sources of nitrate in urban channels plays a critical role in effective nutrient management in urban regions. This is an emerging issue due to fast urbanization and the resultant complicated hydrological and hydraulic conditions in urban areas. In this study, we examine spatial-temporal characteristics of nitrogen concentration in urban channels based on dense in-situ samplings during a one-year period over a small urban catchment in China. We quantitatively identify nitrate sources into urban channels based on dual-isotope analyses and Bayesian isotope mixing model. Results show that nitrogen concentration peaks in winter as well as in urban channels and land surfaces in the urban core region. Sewage (47%) is the dominate contributor to NO3−-N in urban channels, followed by NH4+ in fertilizer (30%) as the second contributor. Sewage (NH4+ in fertilizer) contributes more NO3−-N to channels in winter (summer) with the proportion of 65% (44%), and more NO3−-N to urban core (suburban) channels with the proportion of 59% (42%). The rainfall and distribution of rainwater drains explain the monthly and spatial variations of contribution of NO3−-N sources well, respectively. In addition, less NO3−-N in the urban channels derives from nitrification, which is consistent with the results of high properties of NH4+-N/TN in this region. Our results highlight the key roles of land use types and rainfall in NO3−-N source apportionment, and provide support for the nitrogen management practices in urbanized regions.

Rainfall and conduit drainage combine to accelerate nitrate loss from a karst agroecosystem: Insights from stable isotope tracing and high-frequency nitrate sensing

Understanding where nitrate is mobilized from and under what conditions is required to reduce nitrate loss and protect water quality. Low frequency sampling may inadequately capture hydrological and biogeochemical processes that will influence nitrate behavior. We used high-frequency isotope sampling and in-situ nitrate sensing to explore nitrate export and transformation in a karst critical zone. Nitrate was mobilised during light rainfall, and transferred from soil layers to the karst matrix, where some nitrate was retained and denitrified. Nitrate isotopic composition changed rapidly during the rising limb of events and slowly during the falling limb. The main nitrate source was synthetic fertiliser (up to 80% during event flow), transported by conduit flow following high rainfall events, and this contribution increased significantly as discharge increased. Soil organic nitrogen contribution remained constant indicating at baseflow this is the primary source. Isotope source appointment of nitrate export revealed that synthetic fertilizer accounted for more than half of the total nitrate export, which is double that of the secondary source (soil organic nitrogen), providing valuable information to inform catchment management to reduce nitrate losses and fluvial loading. Careful land management and fertilizer use are necessary to avoid nitrate pollution in the karst agroecosystem, for example by timing fertilizer applications to allow for plant uptake of nitrate before rainfall can flush it from the soils into the karst and ultimately into catchment drainage.

Source Versus Recycling Influences on the Isotopic Composition of Nitrate and Nitrite in the East China Sea

AbstractNitrogen transfer processes and NO3− sources in the East China Sea (ECS) were analyzed using dual isotopes of NO3− and NO2−, the concentration and isotopes of dissolved O2 and N2 gases, nutrient concentrations, and the hydrological conditions. It was clear that the δ15N and δ18O values of NO3− in the Changjiang freshwater were 5.6–6.6‰ and 0.6–1.0‰, respectively, affected by human activities (fertilizer, sewage, and manure) and nitrification. Off the Changjiang Estuary to the ECS continental slope, the NO3− concentration was lower or exhausted in the upper water layers, where both available δ15N and δ18O values for NO3− were high related to phytoplankton assimilation. In the lower water layers, organic matter remineralization, nitrification, and coupled sedimentary nitrification and denitrification resulted in low NO3− isotope values. Moreover, in the upper water layers of the ECS continental slope, NO3− showed high δ15N and δ18O values and low Δ(15, 18) values affected by assimilation, nitrification, and N2 fixation. NO2− in the ECS was dominated by NH4+ oxidation, and NO2− oxidation plays an important role in depleting NO2− in δ15N values. An overall NO3− budget is built for the ECS shelf, indicating that open boundary exchanges of NO3− flux and isotopes through Kuroshio invasion and Taiwan Warm Current Water are comparable to outflow off the ECS shelf, and nitrogen transformation processes (such as NO3− assimilation and nitrification) play an important role in nitrogen cycle, and NO3− is modified on the ECS shelf.

Irrigation return flow causing a nitrate hotspot and denitrification imprints in groundwater at Tinwald, New Zealand

Abstract. Nitrate concentrations in groundwater have been historically high (N≥11.3 mg L−1) in an area surrounding Tinwald, Ashburton, since at least the mid-1980s. The local community is interested in methods to remediate the high nitrate in groundwater. To do this, they need to know where the nitrate is coming from. Tinwald groundwater exhibits two features stemming from irrigation with local groundwater (i.e. irrigation return flow). The first feature is increased concentrations of nitrate (and other chemicals and stable isotopes) in a “hotspot” around Tinwald. The chemical concentrations of the groundwater are increased by recirculation of water already relatively high in chemicals. The irrigation return flow coefficient C (irrigation return flow divided by irrigation flow) is found to be consistent with the chemical enrichments. The stable isotopes of the groundwater show a similar pattern of enrichment by irrigation return flow of up to 40 % and are also enriched by evaporation (causing a loss of about 5 % of the original water mass). Management implications are that irrigation return flow needs to be taken into account in modelling of nitrate transport through soil–groundwater systems and in avoiding overuse of nitrate fertiliser leading to greater leaching of nitrate to the groundwater and unnecessary economic cost. The second feature is the presence of “denitrification imprints” (shown by enrichment of the δ15N and δ18ONO3 values of nitrate) in even relatively oxic groundwaters. The denitrification imprints can be clearly seen because (apart from denitrification) the nitrate has a blended isotopic composition due to irrigation return flow and N being retained in the soil–plant system as organic N. The nitrate concentration and isotopic compositions of nitrate are found to be correlated with the dissolved oxygen (DO) concentration. This denitrification imprint is attributed to localised denitrification in fine pores or small-scale physical heterogeneity where conditions are reducing. The implication is that denitrification could be occurring where it is not expected because groundwater DO concentrations are not low.

Nitrate isotopic composition of sequential Hurricane Harvey wet deposition: Low latitude NOx sources and oxidation chemistry

Abstract Chemical characterization of hurricane wet deposition is integral to understanding how future extreme weather events will impact coastal biogeochemical cycles. Sequential Hurricane Harvey wet deposition samples (n = 7 over 20.5 h) were collected in southeastern Texas, U.S. and the isotopic composition of nitrate and water (δ15N–NO3-, δ18O–NO3- and δ18O–H2O, δ2H–H2O) and the concentrations of ammonium, anions, and dissolved organic carbon were measured. Areas of peak deposition (~1500 mm) received up to 75% of the region's typical average annual inorganic nitrogen wet deposition. After δ15N–NO3- values were corrected for potential fractionation effects, contributions of lightning, natural gas combustion, vehicle exhaust and biogenic sources to NO3− in wet deposition (43.7 ± 31.2%, 7.8 ± 6.1%, 42.6 ± 27.5% and 5.9 ± 5.3%, respectively) were determined using a Bayesian isotope mixing model. Results highlight the significance of natural-sourced nitrogen being deposited to terrestrial systems during hurricane events. The relatively low δ18O–NO3- (36.1 ± 3.0‰) emphasized the role played by hydroxyl and peroxy radicals in HNO3 formation during the tropical summer. An established global NOx oxidation model in combination with δ18O–NO3- approximates the significance of RO2 vs O3 oxidation of NO during the daytime (36.0% vs 64.0%, respectively) and results provide valuable insight to low-latitude atmospheric chemistry.

Differentiation Between Nitrate Aerosol Formation Pathways in a Southeast Chinese City by Dual Isotope and Modeling Studies

AbstractNitrate (NO3−), one of the most important inorganic aerosols in the atmosphere, is mainly formed by oxidation of NOx by the hydroxyl radical (OH) and ozone (O3) in urban atmospheres. However, the fractional contributions of its various oxidation pathways remain unclear. Here, we collected particulate matter with aerodynamic diameter less than 2.5 μm (PM2.5) samples in a second‐tier city in southeast China from 1 September to 31 December 2017 and measured the NO3− and nitrate isotopic compositions (δ15N and δ18O). The average concentration of NO3−, δ15N, and δ18O values were 14.7 ± 11.6 μg/m3, (+4.3 ± 4.3)‰, and (+71.8 ± 14.7)‰ with the ranges from 0.8 to 57.7 μg/m3, −10.5‰ to +12.5‰ and +34.5‰ to +91.9‰, respectively. All three species were significantly higher in winter than in summer. Based on a Bayesian mixing model with a dual isotope array for NO3−, contributions of (37.1 ± 33.4)%, (60.3 ± 32.2)%, and (2.6 ± 2.7)% to NO3− could be attributed to OH oxidation, N2O5 hydrolysis, and NO3 + hydrocarbon (HC) pathways, respectively. Higher OH radical concentrations with higher ratios of OH to O3 led to lower NO3− concentrations, while lower OH radical concentrations with higher ratios of O3 to OH led to higher contributions of N2O5 hydrolysis, forming higher NO3− concentrations in winter. Under low OH, an increased O3 to NOx ratio increased the contribution of the NO3 + HC pathway. The comprehensive analysis of the isotopic compositions of nitrate helped identify the importance of major oxidation pathways of NOx in this city.

A multi-approach assessment of land use effects on groundwater quality in a karstic aquifer

Groundwater represents almost half of the drinking water worldwide and more than one third of water used for irrigation. Agro-industrial activities affect water resources in several manners; one of the most important is leaching of agrochemical residues. This research identifies the major contributors of changes in groundwater quality comparing two contrasting land uses in a karstic area of the Yucatan peninsula as case study. Using a multiple approach, we assess the impact of land use with physicochemical data, multivariate analyses, hydrogeochemistry and nitrate isotopic composition. We confirmed that agricultural land use has a greater impact on groundwater quality, observed in higher concentration of nitrates, ammonium, potassium and electrical conductivity. Seasonality has an influence on phosphates and the chemical composition of the groundwater, increasing the concentration of dissolved substances in the rainy season. There was a clear effect of manure application in the agricultural zone and the nitrate isotopic composition of groundwater points toward recharge in certain areas. We consider that seasonality and land use effects are intertwined and sometimes difficult to separate, likely because of land use intensity and hydrogeochemical process at a local scale. Finally, we observed poor groundwater quality in the agricultural area during the wet season; thus, it is desirable to maintain non-agricultural areas that provide groundwater of appropriate quality.

In-situ nitrogen fate in the vadose zone of different soil types and its implications for groundwater quality in the Huaihe River Basin, China

This paper focused on nitrate fate in the vadose zone (VZ) and its implications for groundwater vulnerability under different soil types in the agricultural area of Huaihe River Basin, China. Isotopic compositions of nitrate (δ15N and δ18O) along with NO3− and Cl− concentrations were determined in the VZ-shallow groundwater continuum beneath silty-loam and silty-clay-loam, which are distinctive in texture and organic carbon (OC). In the soil zone ( 1 m in depth), however, the concurrent enrichment of δ15N–NO3− and δ18O–NO3− indicated the occurrence of denitrification, which showed a dependence on subsoil properties. Specifically, during wheat and maize land uses, denitrification removed as much as 76 %–88 % of the total nitrate where the subsoil was dominated by stratified OC-rich silty-clay-loam. In contrast, only 0 %–28 % of the nitrate was degraded via denitrification where the subsoil was composed of uniform, OC-depleted silty-loam. Furthermore, inactive denitrification and higher permeability in the silty-loam VZ implied higher groundwater vulnerability. This observation was consistent with the fact that groundwater NO3−–N concentration beneath silty-loam (11.24 mg L−1) was over two times higher than that of the silty-clay-loam (5.32 mg L−1), where stricter fertilization management and conservation strategies should be applied to protect groundwater quality.

Nitrate sources and the effect of land cover on the isotopic composition of nitrate in the catchment of the Rhône River

ABSTRACTThe Rhône River originates in the high Alps and drains an intensely cultivated and industrialised catchment before it discharges to the Gulf of Lion. We investigated the interaction of catchment geomorphology with nitrate sources (atmosphere, agriculture, and nitrification of soil organic matter) and removal processes in large and diverse watersheds on the basis of dual nitrate isotope signatures in river water.In March 2015, we took surface water samples along the Rhône River, including its main tributaries, and measured nutrient concentrations and the stable isotopic composition of nitrate (δ15N, δ18O and Δ17O), and water (δ18O-H2O).Results show that high altitude regions are dominated by nitrate from nitrification in pristine soils and atmospheric deposition, while nitrate in the downstream Rhône River originates mainly from nitrification of agricultural/urban sources. Parallel increases in δ15N and δ18O reflect the influence of primary production. Previous studies suggested robust correlations between land use and . Based on our observation that nitrate δ15N values at higher altitudes are lower than expected, we assume that lower nitrate δ15N values likely reflect limited nitrate consumption and lower soil nitrogen turnover rates. We propose that correlation between land use and nitrate δ15N is sensitive to slope and geomorphology.

Nitrate Isotopic Composition in Precipitation at a Chinese Megacity: Seasonal Variations, Atmospheric Processes, and Implications for Sources

AbstractNitrogen stable isotope composition (δ15N) of nitrate (NO3−) deposition can aid in source apportionment of its precursor emissions, nitrogen oxides (NOx), with implications in mitigation policy to address serious air pollution. However, potential δ15N fractionation during atmospheric NO3− formation may hinder accurate quantification of NOx contributions. Previously, NOx photochemical reactions have been suggested to be the dominant δ15N fractionation process in NO3− formation. Here, we have quantified the potential fractionation effects associated with NOx photochemical reactions based upon δ15N‐NO3− measured in 1 year of daily‐based bulk deposition samples in Shenyang, a megacity with distinct seasonal fossil fuel combustion in northeastern China. The mean δ15N was 0.9 ± 4.0‰ and ranged from −4.9 to 8.3‰, with the lowest and highest values observed during summer and winter, respectively. Calculated NOx photochemical equilibrium fractionation may account for up to 42% of the observed seasonal δ15N change in NO3− deposition. However, the relative NOx source contribution trends, estimated based upon a δ15N Bayesian mixing model, were insensitive to NOx photochemical fractionation considerations. Overall, NOx source partitioning based upon averaged year‐long δ15N of bulk NO3− deposition estimated the following relative trend in NOx emission sources: coal combustion > biomass burning = vehicle emissions ≫ soil emissions. Seasonally, the increase of coal combustion emissions from summer to winter drives the seasonality of δ15N in NO3− deposition, indicating a necessity to control NOx emissions from coal combustion to improve wintertime air quality.

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.

A Ti(III) reduction method for one-step conversion of seawater and freshwater nitrate into N2 O for stable isotopic analysis of 15 N/14 N, 18 O/16 O and 17 O/16 O.

The nitrogen and oxygen (δ15 N, δ18 O, and δ17 O values) isotopic compositions of nitrate (NO3 - ) are crucial tracers of nutrient nitrogen (N) sources and dynamics in aquatic systems. Current methods such as bacterial denitrification or Cd-azide reduction require laborious multi-step conversions or toxic chemicals to reduce NO3 - to N2 O for 15 N and 18 O isotopic analyses by isotope ratio mass spectrometry (IRMS). Furthermore, the 17 O composition of N2 O cannot be directly disentangled using IRMS because 17 O contributes to mass 45 (15 N). We describe a new one-step chemical conversion method that employs Ti(III) chloride to reduce nitrate to N2 O gas in septum sample vials. Sample preparation takes only a few minutes followed by a 24-h reaction producing N2 O gas (65-75% recovery) which partitions into the headspace. The N2 O headspace was measured for 15 N, 18 O and 17 O by IRMS or laser spectrometry. IRMS and laser spectrometric analyses gave accurate and reproducible N and O isotopic results down to 50 ppb (3.5 μM) NO3 -N, similar in precision to the denitrifier and Cd-azide methods. The uncertainties for dissolved nitrate reference materials (USGS32, USGS34, USGS35, IAEA-NO3 ) were ±0.2‰ for δ15 N values and ±0.3‰ for δ18 O values using IRMS. For laser-based N2 O isotope analyses the results were similar, with an δ17 O uncertainty of ±0.9‰ without any need for 15 N correction. Advantages of the Ti(III) reduction method are simplicity, low cost, and no requirement for toxic chemicals or anaerobic bacterial cultures. Minor corrections may be required to account for sample nitrate concentration variance and potential chemical interferences. The Ti(III) method is easily implemented into laboratories currently using N2 O headspace sampling apparatus. We expect that the Ti(III) method will promulgate the use of N and O isotopes of nitrate in important studies of nutrient dynamics and pollution in a wide range of aquatic ecosystems.

Global trends in marine nitrate N isotopes from observations and a neural network-based climatology

Abstract. Nitrate is a critical ingredient for life in the ocean because, as the most abundant form of fixed nitrogen in the ocean, it is an essential nutrient for primary production. The availability of marine nitrate is principally determined by biological processes, each having a distinct influence on the N isotopic composition of nitrate (nitrate δ15N) – a property that informs much of our understanding of the marine N cycle as well as marine ecology, fisheries, and past ocean conditions. However, the sparse spatial distribution of nitrate δ15N observations makes it difficult to apply this useful property in global studies or to facilitate robust model–data comparisons. Here, we use a compilation of published nitrate δ15N measurements (n=12 277) and climatological maps of physical and biogeochemical tracers to create a surface-to-seafloor, 1∘ resolution map of nitrate δ15N using an ensemble of artificial neural networks (EANN). The strong correlation (R2>0.87) and small mean difference (<0.05 ‰) between EANN-estimated and observed nitrate δ15N indicate that the EANN provides a good estimate of climatological nitrate δ15N without a significant bias. The magnitude of observation-model residuals is consistent with the magnitude of seasonal to interannual changes in observed nitrate δ15N that are not captured by our climatological model. The EANN provides a globally resolved map of mean nitrate δ15N for observational and modeling studies of marine biogeochemistry, paleoceanography, and marine ecology.

Isotopic evidence for seasonality of microbial internal nitrogen cycles in a temperate forested catchment with heavy snowfall

The Hokuriku district of central Japan receives high levels of precipitation during winter, largely in the form of snow. This study aimed to elucidate the internal nitrogen dynamics in this temperate forested region with heavy snowfall using the triple oxygen and nitrogen isotopic compositions of NO3−. The isotopic compositions of NO3− in atmospheric depositions (P and Tf), with terrestrial components of the soil layer (A0, S25, S55, and S90), ground water (G), and output (St) were measured from 2015 to 2016 in a forested catchment located in the southern area of the Ishikawa Prefecture, Japan. Seasonal distributions of Δ17O(NO3−) showed a decreasing trend from the inputs to outputs of the ecosystem. We found relatively constant Δ17O(NO3−) values in the output components (G and St), but found highly fluctuating Δ17O(NO3−) values resulting from the seasonal variations in the nitrification activity within soil waters. Specifically, we observed a lower nitrifying activity in the top soil layer throughout cold periods, presumably due to the input of cold melted snow water. The general trend of increasing δ15N(NO3−) value from the input to output components, with the changes in denitrification hotspots from shallow to deeper soil layer, can be observed between warm and cold periods. Thus, the seasonal changes of hotspots related to microbial nitrification and denitrification could be noted due to the seasonal changes in the isotopic compositions of nitrate. The estimated ecosystem-scale gross nitrification and denitrification rates are low; however, the output components are relatively stable with low concentrations of nitrate, indicating that the plant uptake of nitrogen most probably occurs at greater rates and scales in this forested ecosystem. Future nitrogen deposition and the vulnerable dynamics of snow melting are likely to have impactful consequences on such localities.

Nitrogen Cycle Dynamics Revealed Through δ18O-NO3− Analysis in California Groundwater

Nitrate is a significant water-quality issue in California, the United States as a whole, and the world. Critical to addressing nitrate contamination is understanding the presence and extent of denitrification, and further refining the techniques used to identify nitrate sources. The use and understanding of nitrate isotopic signatures to identify nitrate sources have advanced tremendously; however, knowledge gaps remain concerning specific fractionation pathways and the role of denitrification in altering source values. Using a large unique database of California groundwater nitrate isotopic compositions, we explored the utility of nitrate–oxygen isotope ratios in determining specific nitrate origins. Lawrence Livermore National Lab (LLNL) samples were supplemented by United States Geological Society (USGS) data to create a dataset of over 1200 dual-isotope results. Methods used at LLNL allowed for the determination of δ15N-NO3−, δ18O-NO3−, δ18O-H2O, δ2H-H2O, excess air, major dissolved gases, and excess N2. Results were examined for the degree to which δ18O-NO3− conforms to the model of nitrification in which two atoms of oxygen are sourced from ambient water and one from the atmosphere. Almost 80% of the results fall within one standard deviation of predicted values. However, 19% of samples had significantly higher values, suggesting the preservation of a synthetic nitrate source signature, mixing of sources, or widespread denitrification. Results were examined with respect to general land-use classifications and, while nitrate concentrations followed the expected pattern of being higher in agricultural settings, δ18O-NO3−patterns are complicated by application of N-fertilizer in various forms, and subsequent N cycling in the soil zone. We found that the current understanding of oxygen isotope-fractionation mechanisms cannot yet explain the prevalence of oxygen-isotope compositions with higher than predicted δ18O values, but when paired with related data such as land use and indicators of denitrification, oxygen-isotope compositions of nitrate can help to assess nitrogen cycle dynamics.