Values Of δ15N-NO3 Research Articles

Dual isotopic evidence of δ15N and δ18O for priority control of vehicle emissions in a megacity of East China: Insight from measurements in summer and winter

The source apportionment and main formation pathway of nitrate aerosols in China are not yet fully understood. In this study, PM2.5 samples were collected in Shanghai in the summer and winter of 2019. Water-soluble inorganic ions and isotopic signatures of stable nitrogen (δ15N-NO3−) and stable oxygen (δ18O-NO3−) in PM2.5 were determined. The results showed that NO3− was less important in summer (NO3−/SO42− = 0.4 ± 0.8), while it became the dominant species in winter (52.1 %). The average values of δ15N-NO3− and δ18O-NO3− in summer were + 2.0 ± 6.1 ‰ and 63.3 ± 9.4 ‰ respectively, which were significantly lower than those in winter (+7.2 ± 3.4 ‰ and 88.3 ± 12.1 ‰), indicating discrepancies between NOx sources and nitrate formation pathways. Both δ15N-NO3− and δ18O-NO3− were elevated at night, demonstrating that N2O5 hydrolysis contributed to the nocturnal nitrate increase even in summer. The contribution of the OH oxidation pathway to nitrate aerosols averaged at 70.5 ± 17.0 % in summer and N2O5 hydrolysis dominated the nitrate production in winter (approximately 80 %). On average, vehicle exhaust, coal combustion, natural gas burning, and soil emission contributed 50.7 %, 21.5 %, 15.9 %, and 11.9 %, respectively, to nitrate aerosols in summer, and contributed 56.8 %, 23.9 %, 13.6 %, and 5.7 %, respectively, to nitrate production in winter. Notably, natural gas burning is a non-negligible source of nitrate aerosols in Shanghai. In contrast to an inverse correlation between δ15N-NO3− and PM2.5, the value of δ18O-NO3− was positively correlated with nitrate concentration and aerosol liquid water content (ALWC) in winter, suggesting that explosive growth of nitrate was driven by continuous accumulation of N-depleted NOx and rapid N2O5 hydrolysis under calm and humid conditions. To continuously improve air quality, priority control should be given to vehicle emissions as the dominant source of NOx and volatile organic compounds (VOCs) in Shanghai.

The comprehensive evaluation of nitrate origin and transformation pathways in the oxic alluvial aquifer in Serbia.

Accurate pollution source identification is essential for establishing adequate water management strategies, particularly in groundwater with slow flow and prolonged recharge process allowing long-term pollution retention. An integrated study based on hydrogeochemical, dual isotopic (δ15NNO3 and δ18ONO3), and microbiological approaches (DN, IRB, and SRB BART tests) along with the statistical data processing was conducted to determine nitrate origin and fate in oxic alluvial groundwater source Ključ in Serbia. The findings from a comprehensive investigation, encompassing 20 groundwater sampling locations during the period 2010-2019, delineated three distinct zones - the hinterland (anthropogenic impact area-untreated sewage inflow), the middle zone (area of mixed influence from fertilizer application, accompanied by a mitigated anthropogenic impact), and the zone of riparian denitrification. Significant linear relationship between anthropogenic impact parameters (Na, Cl, B, NO3-, NH4+, and electrical conductivity) along with the isotopic signatures (δ15N-NO3- ranking from + 10.01 to + 11.18‰ and δ18O-NO3- ranking from + 1.15 to + 6.24‰) and grouped sampling objects by cluster analysis indicated that hinterland is burdened by the nitrates originating from anthropogenic impact. The cross-section of groundwater flow data, concurrent increase of NH4+, and pH levels, along with the highest values of δ15N-NO3- (+ 12.90‰) and δ18O-NO3- (+ 9.70‰), indicated area of fertilizers (urea) impact. BART test results, pH increase, and low oxygen concentration, along with the groundwater flow data in riparian zone, indicated the unfolding of denitrification process. Presented research emphasizes the importance, necessities, and advantages of simultaneous and complementary use of hydrogeochemical, microbiological, and isotopic data.

Mechanism of denitrification in subsurface-dammed Ryukyu limestone aquifer, southern Okinawa Island, Japan

Denitrification crucially regulates the attenuation of groundwater nitrate and is unlikely to occur in a fast-flowing aquifer such as the Ryukyu limestone aquifer in southern Okinawa Island, Japan. However, evidences of denitrification have been observed in several wells within this region. This study analyzed environmental isotopes (δ15NNO3 and ẟ18ONO3) to derive the rationale for denitrification at this site. Additionally, the presence of two subsurface dams in the study area may influence the processes involved in nitrate attenuation. Herein, we analyzed 150 groundwater samples collected spatially and seasonally to characterize the variations in the groundwater chemistry and stable isotopes during denitrification. The values of δ15NNO3 and δ18ONO3 displayed a progressive trend up to +59.7 ‰ and + 21 ‰, respectively, whereas the concentrations of NO3−–N decreased to 0.1 mg L−1. In several wells, the enrichment factors of δ15NNO3 ranged from −6.6 to −2.1, indicating rapid denitrification, and the δ15NNO3 to δ18ONO3 ratios varied from 1.3:1 to 2:1, confirming the occurrence of denitrification. Denitrification intensively proceeds under conditions of depleted dissolved oxygen concentrations (<2 mg L−1), sluggish groundwater flow with longer residence times, high concentrations of dissolved organic carbon (>1.2 mg L−1), and low groundwater levels during the dry season with precipitation rates of <100 mm per month (Jun–Sep). SF6 analysis indicated the exclusive occurrence of denitrification in specific wells with groundwater residence times exceeding 30 years. These wells are located in close proximity to the major NE–SW fault system in the Komesu area, where the hydraulic gradient was below 0.005. Detailed geological and lithological investigations based on borehole data revealed that subsurface dams did not cause denitrification while the major NE–SW fault system uplifted the impermeable basement rock of the Shimajiri Group, creating a lithological gap at an equivalent depth that ultimately formed a sluggish groundwater area, promoting denitrification.

Isotopic constraints on nitrate sources and cycling in Antarctic soils

While nitrate (NO3-) serves as a vital nutrient for soil organisms, the lack of knowledge on its sources and cycling in Antarctic soils does not allow to predict the possible effects of climate and environmental changes on the functioning of terrestrial ecosystems. Thus, the NO3- and its stable isotopes of Δ17ONO3, δ15NNO3, and δ18ONO3 were analyzed in Antarctic soils, collected in coastal ice-free areas of East Antarctica and the tip of the northern Antarctic Peninsula. The soil NO3- concentrations and isotopic values of Δ17ONO3, δ15NNO3, and δ18ONO3 were comparable across the latitudinal gradient except for soils collected beneath moss cushions in the Fildes Peninsula. The proportional calculation of Δ17ONO3 indicated that 93–97% of soil NO3- derived from nitrification process, whereas atmospheric deposition probably contributed to the NO3- budget for a fraction <10 %. The linear relationship between δ18ONO3 and δ15NNO3 suggested the occurrence in Antarctic soils of denitrification process and active cycling between NO3- and nitrite (NO2-). The NO3- assimilation in soil likely occurred, but at minimal rates. These findings provide new insights in the biogeochemical cycle of nitrogen (N) in Antarctic terrestrial ecosystems and seem to indicate that despite climatic and environmental changes along the wide latitudinal gradient, the sources and cycling of NO3- maintain a rather consistent pattern along coastal ice-free areas. The noteworthy increase of NO3- concentrations and δ15NNO3, δ18ONO3, and Δ17ONO3 values in soils collected under moss in the Fildes Peninsula could also suggest that the warming and the increased availability of liquid water will likely favor the developments of soil biotic communities and changes in the biogeochemical cycle of N in Antarctic terrestrial ecosystems.

Sources of nitrate in a heavily nitrogen pollution bay in Beibu Gulf, as identified using stable isotopes

Eutrophication, mainly caused by the oversupply of inorganic nitrogen and phosphate, has increased and become a serious environmental problem in the coastal bays of Beibu Gulf, a newly developing industry and port in South China. However, the sources of nitrate are poorly understood in the gulf. In this study, nitrate dual isotopes (δ15N-NO3- and δ18O-NO3-) and ammonium isotopes (δ15N-NH4+) were measured during the rainy season to identify the nitrate sources and elucidate their biogeochemical processes in Xi Bay, a semi-enclosed bay that is strongly affected by human activities in the Beibu Gulf. The results showed that a high dissolved inorganic nitrogen (DIN, 10.24-99.09 µmol L-1) was observed in Xi Bay, particularly in the bay mouth. The concentrations of DIN in the bay were 1.5 times higher than that in Qinzhou Bay and 1.7 times than that in Tieshangang Bay, which mainly influenced by the intensive human activities (i.e., industrial and port activities). In addition, lower values of δ15N-NO3- and δ18O-NO3- and higher values of δ15N-NH4+ were observed in the upper bay, suggesting that microbial nitrification occurs in the upper bay, which was the dominant nitrate source in the upper bay (39%). In addition to nitrification, external sources, including sewage and manure (33%), soil N (15%) and fertilizer (11%), contributed to the higher nutrients in the upper bay. In the lower bay, severe nitrogen pollution led to a weaker impact of biological processes on isotopic fractionation, although a high Chl a level (average of 7.47 µg L-1) was found in this region. The heavy nitrate pollution in the lower bay mainly originated from sewage and manure (54%), followed by soil N (26%) and fertilizer (17%). The contribution of the nitrate source from atmospheric deposition was relatively low in the bay (&amp;lt;3%). This study suggests that biogeochemical processes have little impact on nitrate dual isotopes under heavy nitrogen pollution, and isotopes are an ideal proxy for tracing nitrogen sources.

Reservoir NO3- pollution and chemical weathering: by dual isotopes of δ15N-NO3-, δ18O-NO3- and geochemical constraints.

Reservoir dams alter the nutrient composition and biogeochemical cycle. Thus, dual isotopes of δ18O-NO3- and δ15N-NO-3 and geochemical signatures were employed to study the NO3- pollution and chemical weathering in the Three Gorges Reservoir (TGR), China. This study found that the TGR dam alters the δ15N-NO3- composition and is enriched in the recharge period. Values of δ15N-NO3- varied from 4.5 to 12.9‰ with an average of 9.8‰ in the recharge period, while discharge period δ15N-NO3- ranged from 3.2 to 12.5‰, with an average of 9.3‰. δ18O-NO3- varies (1.2-11.3‰) with an average of 6.5‰ and (2.4-12.4‰) with an average of 7.5‰, in the recharge and discharge periods, respectively. Stable isotopic values sharply decreased fromupstream to downstream, indicating thedamming effects. δ18O-NO3- and δ15N NO3- confirm that sewage effluents, nitrification of soil organic material, and NH4+ fertilizers were the primary sources of NO3- in the reservoir. Carbonate weathering mainly provides ions to the reservoir. HCO3- + SO42- and Ca2+ + Mg2+ represent 90% of major ions in theTGR. Downstream sampling sites showed low solute concentration during the recharge period, indicating the dam effect on solute concentration. Ca-Mg-Cl-, Ca-HCO3- and Ca-Cl- were the main water types in theTGR. The average percentage of solutes contribution revealed the carbonate weathering, evaporites dissolution, silicate weathering, and atmospheric input were 51.9%, 41%, 7.8%, and 1.7% for the recharge period. In contrast, the discharge period contributed 66.4%, 29.2%, 10%, and 4.3%, respectively. TGR water is moderately suitable for irrigation, and hardness is high in drinking water. This study provides new insight into the dual isotopic approach and geochemical signatures to interpret the NO3- cycle and chemical weathering process under dam effects in the TGR. However, this isotopic application has some limitations in source identification, isotope fractionation, and transformation mechanisms of nitrate. Thus, further studies need to be done on these topicsfor a better undestanding.

Nitrate sources and nitrogen dynamics in a karst aquifer with mixed nitrogen inputs (Southwest China): Revealed by multiple stable isotopic and hydro-chemical proxies

The nitrate (NO3−) contamination of karst aquifers as an important drinking water reservoir is increasing globally. Understanding the behavior of nitrogen (N) in karst aquifers is imperative for effective groundwater quality management. This study combined multiple stable isotopes (δ2H-H2O, δ18O-H2O, δ13C-DIC, δ15N-NO3, and δ18O-NO3), including hydro-chemical data, with a tracer test and a Bayesian isotope mixing (SIAR) model to elucidate the NO3− sources and N cycling within the Babu karst aquifer in Guizhou Province, Southwest China. Nitrate isotopes and SIAR model revealed that manure and sewage, nitrogen fertilizer, and soil organic nitrogen were the three dominant NO3− sources in winter, contributing to 37%, 32%, and 31% to spring NO3−, and 38%, 31%, and 31% to surface water NO3−, respectively. The δ18O-NO3 values of sampled waters ranging from 0.3‰ to 13.7‰ (mean of 7.7 ± 3.0‰; N = 63) and the significant negative correlations between δ15N-NO3 and δ13C-DIC in the spring waters (P < 0.01) revealed that nitrification was the primary N transformation process in the Babu watershed. Whereas, denitrification might still occur locally, confirmed by the enriched values of δ15N-NO3 (14.3 ± 7.6‰; N = 6) and high denitrification extent (46.6 ± 22.2%; N = 6) in the springs from residential areas, and by elevated δ13C-DIC (−11.2 ± 0.6‰; N = 26) and δ15N-NO3 values (18.9 ± 5.2‰; N = 26) in the boreholes. During the base flow period, point-inputs of the AMD-impacted stream and sewage waters, and short transit time (<5 days) were conducive to nitrification processes in the karst conduit, resulting in elevated NO3− concentration and NO3−/Cl− ratio at the watershed outlet. Approximately 50% of NO3− flux at the outlet was derived from nitrification, indicating that a significant extent of nitrification occurred in the NH4+-contaminated karst conduit, which may be a new NO3− source to receiving rivers and lakes. This study provided an integrated method for exploring the N dynamics in contaminated karst aquifers. Moreover, the study highlighted that the point N sources control required particular attention for groundwater protection and restoration.

Using Dual Isotopes of Nitrate to Identify the Source of Nitrogen Pollution in the Songhua River Basin, Northeast China

Nitrogen pollution is a severe problem in the Songhua River Basin (SHR) in China. Samples were collected from 36 sections of the SHR during the high, low, and flat seasons of the river, and the main sources of nitrogen in the water were qualitatively analyzed with isotope data for nitrogen and oxygen of nitrate. The contribution rates of each major pollution source were quantitatively analyzed using the Iso Source mass balance model. The results from these experiments indicate that the values for δ15N-NO3 and δ18O-NO3 in the flat flow season range from 1.52‰ to 14.55‰ and −14.26‰ to 2.03‰, respectively. The values for δ15N-NO3 and δ18O-NO3 in the low flow season range from 6.66‰ to 15.46‰ and −5.82‰ to 65.70‰, respectively. In the low flow season, nitrogen comes from the input of domestic and manure sewage (53%) and soil organic N (45%). The values of δ15N-NO3 and δ18O-NO3 in the high flow season range from 2.07‰ to 14.24‰ and −3.99‰ to 8.03‰, respectively. In the high flow season, nitrogen comes from soil organic nitrogen (41%), domestic and manure sewage (32%), and nitrogen fertilizer (27%), which are the main sources of nitrogen pollution in the SHR. The conclusions from the qualitative and quantitative analysis of nitrogen sources in the SHR can provide a scientific basis for the source control and treatment of nitrogen pollution.

Sources of Nitrate in Ground Water Aquifers of the Semiarid Region of Tanzania

Nitrate isotopic values are often used as a tool to identify sources of nitrate in order to effectively manage ground water quality. In this study, the concentrations of NO3−, NO2−, and NH4+ from 50 boreholes and shallow wells in the Singida and Manyoni Districts were analyzed during the dry and wet seasons, followed by identification of nitrate sources using the hydrochemical method (NO3−/Cl−) and stable isotope (δ15N and δ18O) techniques. Results showed that NO2− and NH4+ concentrations were very low in both seasons due to the nitrification process. The concentrations of NO3− ranged from 2.4 ppm to 929.6 ppm with mean values of 118.5 ppm ± 118.5 ppm , during the dry season and from 2.4 ppm to 1620.0 ppm with mean values of 171.6 ppm ± 312.3 ppm , during the wet season. The higher NO3− contamination observed in the wet season could be due to rainfall which accelerated the surface runoff that collects different materials from various settings into the ground water sources. Nitrate source identification through hydrochemical technique revealed that most nitrates originated from sewage effluents and/or organic wastes such as manure. Likewise, the mean values of δ15N-NO3− ( + 20.90 ‰ ± 5.17 ‰ and + 18.30 ‰ ± 6.33 ‰ ) and the mean values of δ18O-NO3−( + 13.86 ‰ ± 3.18 ‰ and + 13.69 ‰ ± 3.97 ‰ ) suggest that 80% of boreholes and 52% of shallow wells were dominated with nitrate from sewage effluents and/or manure as most ground water sources were situated in densely populated areas with congested and poorly constructed onsite sanitation facilities such as pit latrines and manure. Therefore, to reduce nitrate pollution in the study area, a central sewer must be constructed to treat the discharged wastes. Also, groundwater harvesting should consider the proper principles for groundwater harvesting recommended by the respective authority to minimize chances of contamination and hence prevention of health risk.

Contemporary systematics of vadose zone nitrate capture by speleothem carbonate

The movement of nitrate through the vadose zone has major implications for environmental and human health. This issue is particularly prevalent in karst terrain where agricultural activity, thin soils and dual permeability compound the problem of high nitrate loading to the overlying ecosystem. However, a paucity of records which document vadose zone nitrate concentrations prior to the 21st century render legacy nitrate dynamics, source attribution and baseline conditions to be poorly parameterised. Speleothems growing within karst cave settings may provide an opportunity to obtain records of vadose zone nitrate contamination which extend throughout the anthropogenic era. Here, we use dual isotope analysis of δ15NNO3 and δ18ONO3 in a contemporary study at Cueva-cubío del Llanío, N. Spain, designed to examine the transformation of nitrate between surface to cave environment, taking account of biogeochemical transformation, karst hydrology and partitioning as controls on the delivery of nitrate to the speleothem record. Concentrations of nitrate within speleothem calcite are low (measured range of 0.05 mM to 0.37 mM) due to partitioning (DNO3) across the dripwater-calcite interface. Values of δ15NNO3 extracted from cave waters in Cueva-cubío del Llanío (range +2.0 to +7.0‰) are shown to be excellent indicators of nitrate source and demonstrate no fractionation during incorporation into speleothem carbonate (range of δ15NNO3 in speleothem carbonate +1.6‰ to +6.4‰). Values of δ18ONO3 contained within cave waters (range −2.5‰ to +6.0‰) and speleothem carbonate (range +12.3‰ to +32.3‰) reflect a mixed signal of source, biogeochemical processing and hydrological pathway, providing critical insight into the behaviour of the karst aquifer. Contemporary systematics at Cueva-cubío del Llanío therefore confirm speleothem carbonate contains an excellent record of vadose zone nitrate. Analysis of nitrate contained within speleothem carbonate from other regions confirms the ubiquitous nature of partitioning across the water‑carbonate interface and the use of speleothem nitrate isotopes for recording surface ecosystem processes and vadose zone behaviour. Application of these principles to dated speleothem records should provide critical timeseries of nitrate loading, enabling understanding and remediation against the presence of vadose zone legacy nitrate.

Identifying the sources of nitrate contamination using a combined dual isotope, chemical and Bayesian model approach in a tropical agricultural river: Case study in the Mun River, Thailand

Environmental issues triggered by increasing nitrate in agricultural river has become global concern. Identifying nitrate sources and transformation are crucial for water sources protection and eliminating nitrate contamination in an agricultural watershed. In this study, chemical and dual isotopic compositions of nitrate were employed to trace the nitrate sources and transformation processes, and proportional contribution of NO3− source were estimated by SIAR based on Bayesian model. NH4+ concentrations in middle Mun and lower Mun in wet season were significantly higher than NO3−, suggesting enhanced runoff processes by flood promote agricultural fertilized NH4+ leaching into the river. Higher Cl− concentration and NO3−/Cl− indicated that manure and sewage was the dominate nitrate source in the Lam Takhong River and the upper Mun. The overall values of δ15N-NO3− and δ18O-NO3− ranged from −3.9‰ to +16.6‰ and from −5.2‰ to +40.0‰, respectively. The results of nitrate isotopes indicated that NO3− mainly originated from soil N nitrogen, chemical fertilizer, and manure and sewage wastes. Spatially, soil N and chemical fertilizer contributed the most nitrate in the mainstream of lower Mun, middle Mun, and the Lam Takhong River; whereas over 60% of nitrate was derived from manure and sewage in the upper Mun. The spatial variation of water discharge and rainfall, together with the nitrate concentration and isotopes inferred that the nitrate sources and transformations in rain-fed river in tropical zone were distinguished from other rivers. High water discharge driven by rainfall events accelerated the nitrate export and the contribution of atmospheric deposition in wet season, and enlarged the contribution of manure and sewage in dry season. This study provided an example for further researches and approaches to assess the effects of tropical climate and agriculture on nitrate accumulation in watershed.

Quantification of Nitrate Sources to Groundwater in Karst Trough-valley Areas Based on Dual Stable Isotopes of δ15N-NO3- and δ18O-NO3- and the IsoSource Model

Due to the vulnerability of karst hydrological systems, nitrate pollution in karst groundwater has become a global common and serious environmental problem. In order to ensure drinking water safety, it is very important to accurately identify groundwater nitrate sources. The groundwater hydrochemistry and δ15N-NO3- and δ18O-NO3- isotopes were analyzed in samples taken from a suburb of Chongqing:the Longfeng karst trough-valley, which is mainly affected by agricultural activities, and the Longche karst trough-valley, which is primarily affected by urbanization. The IsoSource model was then used to quantify the groundwater nitrate sources. The results showed that:① The NO3- concentration in groundwater ranged from 19.31 mg·L-1 to 37.01 mg·L-1(mean of 28.21 mg·L-1) in the Longfeng karst trough-valley, and from 2.15 mg·L-1 to 27.69 mg·L-1(mean of 10.31 mg·L-1) in the Longche karst trough-valley. The groundwater NO3- concentration exhibited an obvious seasonal variation in both valleys. ② The δ15N-NO3- and δ18O-NO3- isotopes in groundwater in the Longfeng karst trough-valley ranged from 3.29‰ to 11.03‰ (mean of 6.74‰) and 0.88‰ to 7.51‰ (mean of 3.18‰), respectively. In contrast, groundwater in the Longche karst trough-valley presented higher δ15N-NO3- and δ18O-NO3- values that ranged from 5.25‰ to 11.40‰ (mean of 7.95‰) and 2.90‰ to 19.94‰ (mean of 11.18‰), respectively. The lower values of δ15N-NO3- and δ18O-NO3- in groundwater in the Longfeng karst trough-valley suggest that groundwater NO3- was mainly sourced from agricultural N fertilizer, while the higher values of δ15N-NO3- and δ18O-NO3- in groundwater in the Longche karst trough-valley indicate that groundwater NO3- was primarily sourced from domestic sewage. Moreover, such δ15N-NO3- and δ18O-NO3- values in groundwater indicate that nitrification was the primary process for nitrogen conversion in both valleys. Meanwhile, significant seasonal differences in groundwater δ15N-NO3- and δ18O-NO3- were observed in both valleys; the δ15N-NO3- and δ18O-NO3- values were higher during the dry season (means of 8.83‰ and 2.79‰, respectively) than during the rainy season (means of 4.64‰ and 3.58‰, respectively) in the Longfeng karst trough-valley, whereas the δ15N-NO3- and δ18O-NO3- values were lower during the dry season (means of 9.79‰ and 14.56‰, respectively) than during the rainy season (means of 5.12‰ and 7.8‰, respectively) in the Longche trough-valley. This suggests that there were differences in the seasonal NO3- sources to groundwater in both valleys. During the rainy season, the groundwater NO3- concentration in the Longfeng karst trough-valley was mainly due to the nitrification of NH4+ in precipitation and fertilizer as well as organic nitrogen in soil, whereas during the dry season, the groundwater NO3- concentration primarily originated from domestic sewage. In contrast, the groundwater NO3- concentration in the Longche karst trough-valley primarily originated from domestic sewage in both seasons. ③ The results of the IsoSource model indicated that the nitrification of NH4+ from fertilizer and rainwater was the primary NO3- source to groundwater (44.63% of the total) in the Longfeng trough valley, and was followed by domestic sewage (29.5%), soil organic nitrogen (22.38%), and NO3- from rainwater and fertilizer (<10%). During the rainy season, the groundwater NO3- concentration was mainly due to the nitrification of NH4+ from fertilizer and rainwater (52.25% of the total) in Longfeng trough-valley, while groundwater NO3- concentration primarily originated from domestic sewage during the dry season (41% of the total). In contrast, the groundwater NO3- concentration was mainly from domestic sewage (36.17%) in Longche karst trough-valley, and was followed by the nitrification of NH4+ from fertilizer and rainwater (23.5%), soil organic nitrogen (22.5%), and NO3- from rainwater and fertilizer (<10%). The groundwater NO3- concentration in the Longche karst trough-valley primarily originated from domestic sewage in both seasons, and accounted for 47% and 25% during the rainy season and dry season, respectively.

Stoichiometric flexibility and soil bacterial communities respond to nitrogen fertilization and neighbor competition at the early stage of primary succession

At the early stage of primary succession, there are deficient nutrient resources as well as competition stress among neighboring plants. Our aims were to elucidate the flexibility of tree seedlings’ stoichiometric relationships and their effects on soil microbial communities, and to determine the driving forces of species turnover during primary succession through the evaluation of carbon (C) : nitrogen (N) : phosphorus (P) stoichiometric relationships. We conducted an experiment testing N addition effect on two species from the early stage of primary succession, under intra- and interspecific competition conditions. Our results showed that higher values of δ15N-NO3− and δ13C were observed in Populus purdomii individuals than in Salix rehderiana after N application, which indicated a more efficient N uptake and water-use efficiency in P. purdomii plants. Furthermore, under N addition, the intraspecific competition of P. purdomii presented a higher urease activity, microbial biomass C (MBC), microbial N:P ratio (MBN:MBP), and phylogenetic diversity compared to the intraspecific competition of S. rehderiana. The results showed that P. purdomii seedlings influenced soil properties in a way that led to a positive feedback on their performance with an increasing N availability. In contrast, S. rehderiana seedlings influenced soil properties in a way that caused a negative feedback on their performance with increasing N. Such events can promote species turnover from Salix to Populus during succession. Additionally, DNA sequencing of soil bacterial communities showed differences in the composition of microbial communities in response to N fertilization and different competition patterns. Altogether, our results showed that plant, soil, and microbial community responses to N fertilization in a subalpine glacier forefield differed among tree species and competition patterns. This study brings new insight into mechanisms that drive species replacement and biogeochemical cycling during primary succession.

Assessment of the seasonal cycle of nitrate in PM2.5 using chemical compositions and stable nitrogen and oxygen isotopes at Nanchang, China

Nitrate (particulate NO3− and gas-phase HNO3) are the primary acidic ions in the atmosphere and play important roles in regional air pollution. However, quantification of the formation pathways of atmospheric nitrate are still poorly understood. Samples of PM2.5 were collected at Nanchang, China, from September 2017 to August 2018. The concentrations of water-soluble ions and the stable isotopic compositions of δ18O-NO3− and δ15N-NO3− were measured. Seasonal values of δ15N-NO3− (autumn:4.4 ± 2.8‰; winter: 6.6 ± 2.4‰; spring: 4.4 ± 2.0‰; summer: 3.1 ± 2.4‰) suggest that seasonal cycles of NO3− in PM2.5 are mainly affected by NOx sources. The highest concentrations of NO3−, aerosol liquid water content (ALWC), Cl−, NH4+, and the lowest concentration of OH were showed during winter. These parameters exhibited opposite trends during summer. δ18O-NO3− values in PM2.5 during autumn (79.2 ± 6.7‰) and spring (73 ± 6.3‰) were between those observed in winter (86.4 ± 5.9‰) and summer (60.7 ± 3.9‰). Values of δ18O-HNO3 endmembers produced via pathway of NO2 + OH (PNO2+OH), pathway of N2O5 + H2O (PN2O5+H2O) and pathways of NO3 + VOCs, N2O5 + Cl−, ClNO3 + H2O and 2NO2 + H2O (Pother) were evaluated during four seasons. The possible fractional contributions of different HNO3 formation pathways to PM2.5NO3− were assessed using the Bayesian isotope mixing model. The results show that the PNO2+OH contributes to 59 ± 5% and 12 ± 6% of HNO3 production during summer and winter, respectively. The possible fractional contributions of PN2O5+H2O in all seasons are comparable, but the contributions of Pother in winter are higher than those during summer. This study suggested that Pother may be important for wintertime NO3− formation and provides potential information for using chemical models to simulate atmospheric NO3− formation.

Tracing the Origin of Groundwater Nitrate in an Area Affected by Acid Rain Using Dual Isotopic Composition of Nitrate

Acid rain with a relatively high concentration of ammonium and nitrate can accelerate rock weathering. However, its impact on groundwater nitrate is uncertain. This study evaluated the dual isotopic composition of nitrate (δ15N-NO3- and δ18O-NO3-) from precipitation to groundwater in a rural mountainous area affected by acid rain. The average concentration for NH4+ is 1.25 mg/L and NO3- is 2.59 mg/L of acid rain. Groundwater NO3- concentrations ranged from &lt;0.05 to 11.8 mg/L (baseline), and NH4+ concentrations ranged from 0.06 to 0.28 mg/L. The results show that groundwater δ18O-NO3- values (-4.7‰ to +4.2‰) were lower than the values of rainfall δ18O-NO3- (+24.9‰ to +67.3‰), suggesting that rainfall NO3- contributes little to groundwater NO3-. Groundwater δ15N-NO3- values (+0.1‰ to +7.5‰) were higher than the values of δ15N-NO3- derived from the nitrification of rainfall NH4+ (less than -4.7‰ in the study area), suggesting that nitrification of rainfall NH4+ also contributes little to groundwater NO3-. This implies that rainfall NO3- and NH4+ have been utilized. The dual isotopic composition of nitrate shows that baseline groundwater NO3- is derived mainly from nitrification of soil nitrogen. The denitrification process is limited in the groundwater system. This study shows that the rainfall NO3- and NH4+ contribute little to groundwater NO3-, improving the understanding of the nitrogen cycle in areas with a high concentration of NH4+ and NO3- in rainfall.

Variations of Groundwater Quality in the Multi-Layered Aquifer System near the Luanhe River, China

Nitrate pollution is an environmental problem in the North China Plain. This paper investigates the variation of groundwater levels and nitrate concentrations in an alluvial fan of the Luanhe river, northeast of the North China Plain. Three transects perpendicular to the riverbank were selected to investigate the exchange between river water and groundwater, and nitrate concentration with its isotopic composition (δ15N-NO3 and δ18O-NO3). The results showed that the groundwater level decreased slightly during the dry season, and increased regularly during the period of river stage rise. The groundwater is recharged by the river over 10 months each year. The nitrate concentration in the groundwater and river water varied with seasons. The nitrate concentration of groundwater in wells near the river is affected by the river water, which varied in basically the same way as the river. The nitrate concentrations in the zone of groundwater level depression cone were lower than those in the wells near the river, due to the long-term pumping of groundwater. However, the nitrate concentrations of river water have little influence on those of groundwater in wells far from the river. The values of δ15N-NO3 and the relationship between the two isotopes (δ15N-NO3 and δ18O-NO3) suggested that NO3-N was mainly attributable to sewage, livestock manure and natural soil organic matter. Due to the existence of a groundwater depression cone near the river, nitrate contamination can be transported into the aquifer with the flow. The average time lag of nitrate migration from the river to the zone of groundwater level depression cone is different in different sections, which shows an increasing trend from the upstream to downstream along the river, with an average of two to six months. It is mainly related to the stratigraphic structure, the migration distance, the hydraulic conductivities of the aquifer and the riverbed sediment. Compared with the case of considering the silt layer, the time lag of nitrate migration is greater than that of the case of ignoring the silt layer. The results will provide useful information for detecting nitrate concentrations in the alluvial fan area of the Luanhe river, northeast of the NCP (North China Plain).

Tracing the sources of nitrate in the rivers and lakes of the southern areas of the Tibetan Plateau using dual nitrate isotopes

Based on a quantitative analysis of nitrate concentrations, the nitrate sources and temporal variability of the rivers, lakes, and wetlands of Tibet were assessed for the first time using dual isotope technology. Water samples were collected once in July 2017 for analysis of nitrate concentration and isotopic composition. The overall values of δ15N-NO3− and δ18O-NO3− ranged from +1.8‰ to +23.0‰, and from −6.3‰ to +22.2‰ respectively. Duel isotopic composition suggested that nitrification of soil organic nitrogen was the main source of nitrate in the Yalu Tsangpo River. Furthermore, anthropogenic nitrogen inputs become more important in downstream than upstream because of intensive agricultural activities and urban input. In the rivers of the Ngari District, nitrate is mainly derived from desert deposits, manure and sewage, and chemical fertilisers. Different rivers show different characteristics of nitrate sources depending on the location, topography, landform, and climate of the river basins. Animal manure, nitrification of soil organic matter, and desert deposits are mainly responsible for the shifting of nitrate isotopic signatures in lakes, which are minimally affected by human activities. In wetlands, biological nitrification and denitrification could be the main processes of nitrogen migration and transformation. These results provide useful information in revealing the fate of nitrate in different aquatic ecosystems and different areas of Tibet.

Origins of aerosol nitrate in Beijing during late winter through spring

Recent studies have identified aerosol nitrate (NO3−) as one of the most important inorganic ions; however, quantitative studies of aerosol NO3− sources are rarely undertaken. Total suspended particulate samples were collected in Beijing from 1 February to 31 May 2013, and water-soluble ions and δ15N-NO3− were analysed to examine the potential sources of aerosol NO3−. Using a Bayesian model, the fractional contributions of NOx from different sources to aerosol NO3− were quantified herein. The maximal concentrations of NO3−, Cl−, and K+, as well as values of δ15N-NO3− during the heating period (from 1 February to 15 March) implied that coal combustion was the dominant source of aerosol NO3−. Concentrations of NO3− and K+ in the transition period (from 16 March to 15 April, when heating is gradually reduced in northern China) were similar to those during the non-heating period (from 16 April to 31 May). However, δ15N-NO3− and Cl− were obviously higher in the transition period than those in the non-heating period, suggesting a shift in NO3− sources from the transition period to the non-heating period. The fractional contribution of NO3− from coal combustion was 70.6 ± 5.0% during the heating period, which confirms that coal combustion is the dominant source of NO3− in late winter to early spring 2013 in Beijing. The fractional contribution of biomass burning to aerosol NO3− obviously increased from the heating period to the non-heating period, indicating that biomass burning was an important source of NOx in late spring 2013 in Beijing. This study verified that reduced coal consumption and prohibition of biomass burning can lower aerosol NO3− concentrations in northern China.

Identification of sources and transformations of nitrate in the Xijiang River using nitrate isotopes and Bayesian model

Coupled nitrogen and oxygen isotopes of nitrate have proven useful in identifying nitrate sources and transformation in rivers. However, isotopic fractionation and low-resolution monitoring limit the accurate estimation of nitrate dynamics. In the present study, the spatio-temporal variations of nitrate isotopes (15N and 18O) and hydrochemical compositions (NO3− and Cl−) of river water were examined to understand nitrate sources in the Xijiang River, China. High-frequency sampling campaigns and isotopic analysis were performed at the mouth of the Xijiang River to capture temporal nitrate variabilities. The overall values of δ15N-NO3− and δ18O-NO3− ranged from +4.4‰ to +14.1‰ and from −0.3‰ to +6.8‰, respectively. The results of nitrate isotopes indicated that NO3− mainly originated from soil organic nitrogen (SON), chemical fertilizer (CF), and manure and sewage wastes (M&S). The negative correlation of nitrate isotopic values with NO3−/Cl− ratios suggested the importance of denitrification in NO3− loss. The results of Bayesian model with incorporation of isotopic fractionation during the denitrification showed that SON and CF contributed to the most (72–73%) nitrate in the wet season; whereas approximately 58% of nitrate was derived from anthropogenic inputs (M&S and CF) in the dry season. The nitrate flux was 2.08 × 105 tons N yr−1 during one hydrologic year between 2013 and 2014, with 86% occurring in the wet season. Long-term fluctuations in nitrate flux indicated that nitrate export increased significantly over the past 35 years, and was significantly correlated with nitrate concentrations. The seasonal pattern of nitrate dynamics indicated the mixing of nitrified NO3− and denitrified NO3− between surface flow and groundwater flow under different hydrological conditions. Overall, the present study quantitatively evaluates the spatio-temporal variations in nitrate sources in a subtropical watershed, and the high-frequency monitoring gives a better estimate of nitrate exports and proportional contributions of nitrate sources.

Tracking nitrate sources in the Chaohu Lake, China, using the nitrogen and oxygen isotopic approach.

The Chaohu Lake is highly polluted and suffers from severe eutrophication. Nitrate is a key form of nitrogen that can cause water quality degradation. In this study, hydrochemical and dual isotopic approaches were utilized to identify the seasonal variation of nitrate sources in the Chaohu Lake and its inflowing rivers. The average nitrate concentrations ([NO3-]) of the lake and its inflowing rivers were 89.9 and 140.8μmolL-1, respectively. The isotopic values of δ15N-NO3- and δ18O-NO3- in the lake ranged from - 1.01 to + 16.67‰ and from - 4.39 to + 22.20‰, respectively. The two major rivers had distinct isotopic compositions, with average δ15N-NO3- values of + 17.52 and + 3.51‰, and average δ18O-NO3- values of + 2.71 and + 7.47‰ for the Nanfei River and Hangbu River, respectively. The results show that soil organic ammonium and urban wastewater discharge were the main sources of nitrate in the Chaohu Lake, and nitrate assimilation was an important process affected [NO3-] and isotopic compositions, especially in the western Chaohu Lake. The elevated [NO3-] and δ15N-NO3- values in the western Chaohu Lake indicate the high influence of human activities. Urban wastewater discharge was the primary nitrate source in the Nanfei River and soil organic ammonium was the main source in the Hangbu River. Although nitrate from direct atmospheric deposition was low, its strong flushing effect can substantially improve riverine [NO3-] and nitrate loading from terrestrial ecosystem. The relatively high nitrate fluxes from the Hangbu River indicate that nitrogen loading from agricultural watershed is unneglectable in watershed nitrogen sources reduction strategies.