Seasonal nitrate variations, risks, and sources in groundwater under different land use types in a thousand-year-cultivated region, northwestern China.

The global public health concern of nitrate (NO3-) contamination in groundwater is particularly pronounced in irrigated agricultural regions. This paper aims to analyze the spatial distribution of groundwater NO3-, assess potential health risks for local residents, and quantitatively identify nitrate sources during different seasons and land use types in the Jinghuiqu Irrigation District, a region in northwestern China with a longstanding agricultural history. The investigation utilizes hydrochemical parameters, dual isotopic data, and the Bayesian stable isotope mixing model (MixSIAR). The findings underscore significant seasonal variations in the average concentrations of NO3-, with values of 87.72 mg/L and 101.87 mg/L during the wet and dry seasons, respectively. Furthermore, distinct fluctuations in nitrate concentration were observed across different land use types, whereby vegetable lands manifested the maximum concentration. Prolonged exposure to elevated nitrate concentrations may pose potential health risks to residents, especially in the dry season when the non-carcinogenic groundwater nitrate risk surges past its wet season counterpart. The MixSIAR analysis revealed that chemical fertilizers accounted for the majority of nitrate pollution in vegetable lands, both during the dry season (49.6%) and wet season (41.2%). In contrast, manure and sewage contributed significantly to NO3-concentrations in residential land during the wet (74.9%) and dry seasons (67.6%). For croplands, soil nitrogen emerged as a dominant source during the wet season (42.2%), while chemical fertilizers prevailed in the dry season (38.7%). In addition to source variations, the nitrate concentration of groundwater is further affected by hydrogeological conditions, with more permeable aquifers tending to display higher nitrate concentrations. Thus, targeted measures were proposed to modify or impede the nitrogen migration pathway, taking into consideration hydrogeological conditions and incorporating domestic sewage, organic fertilizer, and agricultural management practices.

Distribution, sources and main controlling factors of nitrate in a typical intensive agricultural region, northwestern China: Vertical profile perspectives.

Nitrate (NO3-) pollution of groundwater is a global concern in agricultural areas. To gain a comprehensive understanding of the sources and destiny of nitrate in soil and groundwater within intensive agricultural areas, this study employed a combination of chemical indicators, dual isotopes of nitrate (δ15N-NO3- and δ18O-NO3-), random forest model, and Bayesian stable isotope mixing model (MixSIAR). These approaches were utilized to examine the spatial distribution of NO3- in soil profiles and groundwater, identify key variables influencing groundwater nitrate concentration, and quantify the sources contribution at various depths of the vadose zone and groundwater with different nitrate concentrations. The results showed that the nitrate accumulation in the cropland and kiwifruit orchard at depths of 0-400 cm increased, leading to subsequent leaching of nitrate into deeper vadose zones and ultimately groundwater. The mean concentration of nitrate in groundwater was 91.89 mg/L, and 52.94% of the samples exceeded the recommended grade III value (88.57 mg/L) according to national standards. The results of the random forest model suggested that the main variables affecting the nitrate concentration in groundwater were well depth (16.6%), dissolved oxygen (11.6%), and soil nitrate (10.4%). The MixSIAR results revealed that nitrate sources vary at different soil depths, which was caused by the biogeochemical process of nitrate. In addition, the highest contribution of nitrate in groundwater, both with high and low concentrations, was found to be soil nitrogen (SN), accounting for 56.0% and 63.0%, respectively, followed by chemical fertilizer (CF) and manure and sewage (M&S). Through the identification of NO3- pollution sources, this study can take targeted measures to ensure the safety of groundwater in intensive agricultural areas.

Application of stable isotope of water and a Bayesian isotope mixing model (SIMMR) in groundwater studies: a case study of the Granvillebrook and Kingtom dumpsites.

The increase in groundwater salinity of the two major dumpsites in Sierra Leone has been a major concern for stakeholders. Therefore, this study employed geochemical and stable water isotope analyses to investigate the factors controlling groundwater salinity. The proportional sources of the groundwaters were also evaluated using the Bayesian isotope mixing model. The geochemical analysis showed that the groundwater chemistry in the Granvillebrook dumpsite is controlled by water-rock interaction and evaporation while that of the Kingtom is dominated by water-rock interaction and precipitation. The biplot of deuterium (δ2H) versus oxygen (δ18O) composition relative to the global meteoric water line confirms that the groundwaters of the study areas are of meteoric origin. The linear plot of electrical conductivity versus δ18O depicts that mineralization is the major factor impacting the groundwater salinity in the study areas. The stable isotope mixing model in R (SIMMR) suggests that 96.5% of the groundwaters in the study areas are recharged by precipitation while only 3.5% originated from surface water. The SIMMR model also depicts that groundwaters in the Granvillebrook dumpsite have been bridged by leachate (33.0%) and domestic wastewater (15.2%) while for the Kingtom dumpsite, 13% and 21.5% are contaminated by leachate and domestic wastewaters. Contrary to other previous studies, this research confirms the feasibility of using the Bayesian isotope mixing model to quantify the factors influencing groundwater salinity.

Drought reduces water uptake in beech from the drying topsoil, but no compensatory uptake occurs from deeper soil layers.

The intensity and frequency of droughts events are projected to increase in future with expected adverse effects for forests. Thus, information on the dynamics of tree water uptake from different soil layers during and after drought is crucial. We applied an in situ water isotopologue monitoring system to determine the oxygen isotope composition in soil and xylem water of European beech with a 2-h resolution together with measurements of soil water content, transpiration and tree water deficit. Using a Bayesian isotope mixing model, we inferred the relative and absolute contribution of water from four different soil layers to tree water use. Beech took up more than 50% of its water from the uppermost 5 cm soil layer at the beginning of the 2018 drought, but then reduced absolute water uptake from the drying topsoil by 84%. The trees were not able to quantitatively compensate for restricted topsoil water availability by additional uptake from deeper soil layers, which is related to the fine root depth distribution. Absolute water uptake from the topsoil was restored to pre-drought levels within 3 wk after rewetting. These uptake patterns help to explain both the drought sensitivity of beech and its high recovery potential after drought release.

APCS-MLR model: A convenient and fast method for quantitative identification of nitrate pollution sources in groundwater.

Nitrate (NO3-) contamination in groundwater has diverse sources and complicated transformation processes. To effectively control NO3- pollution in groundwater systems, quantitative and accurate identification of NO3- sources is critical. In this work, we applied hydrochemical characteristics and isotope analysis to determine NO3- source apportionment. For the first time, the NO3- source contributions were calculated using hydrochemical indicators combined with multivariate statistical model (PCA-APCS-MLR). The results interpret that chemical fertilizers (58.11%) and natural sources (22.69%) were the primary NO3- sources in the vegetable cultivation area (VCA) which were rather close to the estimation by Bayesian isotope mixing model (SIAR). In particular, the contributions of chemical fertilizers in the VCA differed by only 3.79% between the two methods. Compared with previous approaches e.g. SIAR, the key advantage of the proposed PCA-APCS-MLR model is that it only requires the hydrochemical indicators which can be easily measured. A series of complicated experiments including measurement of isotope data of NO3- in groundwater, monitoring of in-situ pollution source information and calculation of isotopic enrichment factor can be simply avoided. The PCA-APCS-MLR model offers a much more convenient and faster method to determine the contribution rates of NO3- pollution sources in groundwater.

Tracing biogeochemical subsidies from glacier runoff into Alaska's coastal marine food webs.

Nearly half of the freshwater discharge into the Gulf of Alaska originates from landscapes draining glacier runoff, but the influence of the influx of riverine organic matter on the trophodynamics of coastal marine food webs is not well understood. We quantified the ecological impact of riverine organic matter subsidies to glacier-marine habitats by developing a multi-trophic level Bayesian three-isotope mixing model. We utilized large gradients in stable (δ13 C, δ15 N, δ2 H) and radiogenic (Δ14 C) isotopes that trace riverine and marine organic matter sources as they are passed from lower to higher trophic levels in glacial-marine habitats. We also compared isotope ratios between glacial-marine and more oceanic habitats. Based on isotopic measurements of potential baseline sources, ambient water and tissues of marine consumers, estimates of the riverine organic matter source contribution to upper trophic-level species including fish and seabirds ranged from 12% to 44%. Variability in resource use among similar taxa corresponded to variation in species distribution and life histories. For example, riverine organic matter assimilation by the glacier-nesting seabirds Kittlitz's murrelet (Brachyramphus brevirostris) was greater than that of the forest-nesting marbled murrelet (B. marmoratus). The particulate and dissolved organic carbon in glacial runoff and near surface coastal waters was aged (12100-1500 years BP 14 C-age) but dissolved inorganic carbon and biota in coastal waters were young (530 years BP 14 C-age to modern). Thus terrestrial-derived subsidies in marine food webs were primarily composed of young organic matter sources released from glacier ecosystems and their surrounding watersheds. Stable isotope compositions also revealed a divergence in food web structure between glacial-marine and oceanic sites. This work demonstrates linkages between terrestrial and marine ecosystems, and facilitates a greater understanding of how climate-driven changes in freshwater runoff have the potential to alter food web dynamics within coastal marine ecosystems in Alaska.

Identifying sources and transformations of nitrate in different occurrence environments of carbonate rocks using a coupled isotopic approach (δ15N, δ18O, 87Sr/86Sr) in karst groundwater system, North China.

Karst water as the vital water supply source is an increasingly serious problem suffering from NO3- pollution. Identifying sources and transformations is the key to effectively controlling diffuse NO3- pollution. In this study, 25 karst groundwater samples were collected from the Xujiagou karst groundwater system in June 2023, and chemical variables and stable isotopes (δ15N, δ18O, 87Sr/86Sr) were determined in different occurrence environments of carbonate rocks (exposed, covered, and buried carbonate rock areas). The results showed that the karst groundwater is dominated by nitrification. Human activities have affected the water quality of karst groundwater. The nitrate concentration ranged from 5.69 to 124.22 mg/L, and 4 % exceeds the quality indexes of class III water in China's standard for groundwater quality (20 mg/L as NO3--N). NH4+ in fertilizer, manure and septic waste, and soil N were the main sources of nitrate pollution in the karst groundwater system. The distribution of NO3- sources is closely related to land-use types. Soil N (72.2 %) became the dominant nitrate source in the exposed area due to the small amount of urban land and the large distribution of forest and grassland. There were more cultivated land and large agricultural activities in the covered area, NH4+ in fertilizer (59.1 %) contributes the most to NO3- sources. The buried area dominated by urban land, the influence of human activities (densely population and agricultural production activities) caused the highest concentration and coefficient of variation of nitrate in this area, and manure and septic waste (64.2 %) were the most to NO3- sources. This study can provide an important scientific basis for the protection of karst groundwater, and provide theoretical support for the treatment of karst groundwater pollution sources in the "monoclinic paraclinal" strata in northern China.

Significant biomagnification of methylmercury in songbird nestlings through a rice-based food web: Insights from stable mercury isotopes.

To elucidate the sources and transfer of mercury (Hg) in terrestrial food chains, particularly in heavily Hg-contaminated rice paddy ecosystems, we collected rice leaves, invertebrates, and Russet Sparrow nestlings from a clear food chain and analyzed the dietary compositions and potential Hg sources using stable Hg isotopes coupled with a Bayesian isotope mixing model (BIMM). Our findings indicated that MeHg exposure is dominant through the dietary route, with caterpillars, grasshoppers, and katydids being the main prey items, while the less provisioned spiders, dragonflies, and mantises contributed the most of the Hg to nestlings. We found minimal MIF but certain MDF in this terrestrial food chain and identified two distinct MeHg sources of dietary exposure and maternal transfer. We firstly found that the dietary route contributed substantially (almost tenfold) more MeHg to the nestlings than maternal transfer. These findings offer new insights into the integration of Hg from the dietary route and maternal transfers, enhancing our understanding of fluctuating Hg exposure risk during the nestling stage. Our study suggested that Hg isotopes combined with BIMM is an effective approach for tracing Hg sources in birds and for gaining in-depth insight into the trophic transfers and biomagnification of MeHg in food chains.

Source and evolution of sulfate in the multi-layer groundwater system in an abandoned mine-Insight from stable isotopes and Bayesian isotope mixing model.

The source and evolution of sulfate (SO42-) in groundwater from abandoned mines are widely concerned environmental issues. Herein, major dissolved ions, multi-isotopes (δ34S, δ18Osulfate, δ2H and δ18Owater), machine learning (Self-organizing maps) and Bayesian isotope mixing model were used to identify the source and evolution of SO42- in an abandoned mine (Fengfeng mine, northern China) with a multi-layer groundwater system. Groundwater in the study area was mainly divided into three clusters (Cluster I, Cluster II and Cluster III), dominated by Na-SO4, Ca-SO4 and Ca-HCO3 types, respectively. According to δ2H and δ18Owater, groundwater in the study area mainly originated from atmospheric precipitation. δ34S, δ18Osulfate and SO42- suggested that bacterial sulfate reduction did not affect the SO42- isotopic composition. Dual SO42- isotopes, and MixSIAR model revealed that the main source of SO42- in the study area was pyrite oxidation/gypsum dissolution, accounting for an average of 57.4 % (gypsum), 71.24 % (pyrite oxidation) and 52.93 % (pyrite oxidation) of SO42- in the samples of Clusters I-III, respectively. Combined with the hydrochemical diagrams, the evolution of SO42- in different clusters of samples was derived. Cluster I was mainly gypsum dissolution; In contrast, Clusters II and III were mainly pyrite oxidation accompanied by carbonate dissolution, and Cluster II was also influenced by cation exchange. These findings will help in developing management strategies for protecting groundwater quality, which will provide a reference for the study of solute sources and S cycling in abandoned mines.

The mercury flow through a terrestrial songbird food chain in subtropical pine forest: Elucidated by Bayesian isotope mixing model and stable mercury isotopes.

In order to comprehend the transfer of inorganic mercury (IHg) and methylmercury (MeHg) within food chains in terrestrial pine forests, we collected samples of Great Tit nestlings, common invertebrates, plants, and soil in a subtropical pine forest and used Bayesian isotope mixing model analysis, Hg daily intake, and stable Hg isotopes to elucidate the flow of MeHg and IHg in these food chains. Results indicate that caterpillars and cockroaches are the predominant prey items for nestlings, accounting for a combined contribution of 81.5%. Furthermore, caterpillars, cockroaches, and spiders were found to contribute the most (∼80%) of both IHg and MeHg that dietary accumulated in nestlings. The provisoned invertebrates tend to supply more IHg and diluting the proportion of MeHg as total Hg (MeHg%). Notably, nestling feathers displayed the highest Δ199Hg values but a relatively lower MeHg%, suggesting an imbalanced incorporation of Hg from maternal transfer and dietary accumulation during the nestling stage. This study highlights the efficacy of nestlings as indicators for identifying Hg sources and transfers in avian species and food chains. However, caution must be exercised when using Hg isotope compositions in growing feathers, and the contribution of maternally transferred Hg should not be ignored.

Use of molecular composition and compound-specific isotope analysis for source appointment of PAHs in sediments of a highly industrialized area.

This study utilized both conventional molecular analysis and compound-specific isotopic techniques to identify the sources of polycyclic aromatic hydrocarbons (PAHs) in sediments of Ulsan Bay, South Korea. The concentrations of 15 traditional and 11 emerging PAHs were determined in sediments from 21 source sites and 26 bay sites. The concentrations and compositions of traditional and emerging PAHs varied significantly, even at sites close to the source areas. The results obtained from diagnostic ratios and the positive matrix factorization model for source identification were inconsistent in adjacent source areas. The δ13C profiles of PAHs, such as phenanthrene (Phe), fluoranthene (Fl), pyrene (Py), and benz[a]anthracene (BaA) in the sediments showed distinct features depending on the surrounding sources. In urban sediments, lighter δ13CPhe values were observed (mean: -25.1‰), whereas relatively heavier values of δ13CPy were found in petroleum industry areas (mean: -23.4‰). The Bayesian isotope mixing model indicates that the predominant source of PAHs in Ulsan Bay sediments was the petroleum industry (45%), followed by the non-ferrous metals industry (30%), automobile industry (18%), and urban areas (6.3%). These results demonstrated the utility of stable isotopes in assessing the sources and contributions of PAHs in small-scale regions. However, there are still limitations in compound-specific isotope analysis of PAHs, including insufficient end-members for each source, difficulty in analysis, and the influence of non-point sources; thus, further study is needed to expand its application.

Hydrochemical and isotopic fingerprints of groundwater origin and evolution in the Urangulan River basin, China's Loess Plateau.

The origin and evolution of groundwater in the Urangulan River basin area under growing concern as its situated in an economically and ecologically crucial area of China. In the present study, a combination of different methods (i.e. self-organizing maps (SOM), piper diagrams, ionic ratios, multiple isotopic analyses and Bayesian isotope mixing model) provided an efficient way for analysing groundwater origin and evolution. The hydrochemical type was found to be Ca-HCO3 in low TDS and Na + K-Cl or Na + K-SO4 in high TDS groundwater. According to the δ2H and δ18Owater values, groundwater in the study area mainly originated from atmospheric precipitation and was influenced by evaporation. In addition, the rock weathering in conjunction with the cation exchange completely dominated the geochemical evolution process. The dual SO42- isotope and Bayesian isotope mixing model showed that gypsum dissolution, fertilizer input and sewage input were the main sources of SO42- in the study area, accounting for an average of 30.2 %, 28.5 %, and 17.3 % of SO42- in the groundwater, respectively. Other than water-rock interactions, human activity (mining and irrigation) distributed throughout the study area in combination with the spatial characteristics was the dominant factor controlling the hydrochemical evolution. The results of this study provided a basis for understanding groundwater origin and evolution while facilitating the effective management and utilization of groundwater.

Combining metal and sulfate isotopes measurements to identify different anthropogenic impacts on dissolved heavy metals levels in river water.

Dissolved heavy metals (DHMs) contamination has raised global concern for ecological and human health development. Weathering of sulfide-bearing ore metals can produce acidic, sulfate-rich solutions in the presence of water and oxygen (O2), and DHMs are released to deprave the river water quality. Sulfur and oxygen isotope signatures (δ34SSO4 and δ18OSO4) could identify this pyrite-derived sulfate; however, it is yet not well known whether the δ34SSO4 and δ18OSO4 values could limit the DHMs sources and illustrate anthropogenic impacts on DHMs along the river corridor. We tried to solve this problem through field works in the Luohe River and Yihe River, two tributaries of the Yellow River, China, where metal sulfide mine activities mostly occurred upstream, but agricultural and domestic behaviors concentrated in the lower plain reaches. In the Luohe River upper areas, δ34SSO4 values had negative correlations with concentrations of cadmium (Cd) (p < 0.01), nickel (Ni) (p < 0.05), molybdenum (Mo) (p < 0.01), uranium (U) (p < 0.01), and SO42- (p < 0.01). However, as the δ34SSO4 values increased downstream in the Luohe River, concentrations of copper (Cu) (p < 0.05), mercury (Hg) (p < 0.05), Ni (p < 0.05), and SO42- (p < 0.01) simultaneously elevated. The Bayesian Isotope Mixing Model (BIMM) results via δ34SSO4 values demonstrated 64.3%-65.3% of SO42- from acid mine drainage (AMD) in the Luohe River's upper reaches and 63.5%-67.7% in the Yihe River's upper reaches, and about 33% from sewage and industrial effluents in the Luohe River's lower reaches and 27% in Yihe River's lower reaches. Our results confirmed the different anthropogenic impacts on the DHMs concentrations in Luohe River and Yihe River and provided a robust method for DHMs sources appointment and pollution management in river systems.

[Tracking Riverine Nitrate Sources and Transformations in the Yiluo River Basin by Nitrogen and Oxygen Isotopes].

The impacts of natural processes and anthropogenic input on riverine nitrate (NO-3) could be identified by NO-3 concentrations and nitrogen and oxygen isotope ratios (δ15N-NO-3 and δ18O-NO-3); however, the effects of variable land use on riverine NO-3 sources and transformations remain unclear. In particular, the human impacts on riverine NO-3 in mountain areas are still unknown. The Yihe River and Luohe River were used to elucidate this question due to their spatially heterogeneous land use. Hydrochemical compositions, water isotope ratios (δD-H2O and δ18O-H2O), and δ15N-NO-3 and δ18O-NO-3 values were utilized to constrain the NO-3 sources and transformations affected by different land use types. The results indicated that ① the mean nitrate concentrations in the Yihe River and Luohe River waters were 6.57 and 9.29 mg·L-1, the mean values of δ15N-NO-3 were 9.6‰ and 10.4‰, and the average δ18O-NO-3 values were -2.2‰ and -2.7‰, respectively. Based on the analysis of δ15N-NO-3 and δ18O-NO-3 values, the NO-3 in the Yihe and Luohe Rivers were derived from multiple sources, and nitrogen removal existed in the Luohe River, but the biological removal in the Yihe River was weak. ② The contributions of different nitrate sources were calculated using a Bayesian isotope mixing model (BIMM) based on δ15N-NO-3 and δ18O-NO-3 values of river water in the mainstream and tributaries with spatial locations. The results revealed that sewage and manure had major impacts on riverine nitrate in the upper reaches of both the Luohe River and Yihe River, where forest vegetation was widely distributed. However, the contributions from soil organic nitrogen and chemical fertilizer were higher in the upper reaches than in downstream ones. The contributions of sewage and manure still increased in the downstream reaches. Our results confirmed the primary impacts of point sources, e.g., sewage and manure, on riverine nitrate in the studied area, and the contributions of nonpoint sources, e.g., chemical fertilizer, had not increased as the agricultural activities elevated the downstream. Therefore, more attention should be paid to point source pollution treatment, and the high-quality development of ecological civilization in the Yellow River Basin should be maintained.

High atmospheric wet nitrogen deposition and major sources in two cities of Yangtze River Delta: Combustion-related NH3 and non-fossil fuel NOx.

High ammonia (NH3) and nitrogen oxide (NOx) emissions are related to serious air pollution in urban areas and the negative impacts of excessive reactive nitrogen (N) deposition on many ecosystems. However, whether there is a relationship between N deposition rates and their sources with urbanization or not remains unclear in many areas. Here, we investigated the deposition rates of ammonium (NH4+), nitrate (NO3-), dissolved organic N, and water-insoluble particular N from July 2017 to June 2018 at two urban and two suburban sites in the Yangtze River Delta (YRD). The δ15N values of precipitation NH4+ and NO3- were measured, and major sources were analyzed using a Bayesian isotope mixing model. Wet N deposition rates were higher in Yangzhou (developing city, 20.3-22.7 kg N ha-1 yr-1) than those in Nanjing (developed city, 19.4-20.5 kg N ha-1 yr-1), and were higher at urban sites (20.4-22.5 kg N ha-1 yr-1) than those at suburban sites (18.7-20.3 kg N ha-1 yr-1). δ15N values of precipitation NH4+ increased with an increase in precipitation pH because ambient acidity affects the equilibrium isotope fractionation between NH3 and NH4+ and wet scavenging coefficients of NH3 and particulate NH4+. For NH4+, combustion-related NH3 sources (62%-65% with 5.5-6.4 kg N ha-1 yr-1, including coal combustion, vehicle exhaust, and biomass burning) contributed more than volatilization NH3 sources (35%-38% with 2.9-3.9 kg N ha-1 yr-1, including fertilizer application and waste volatilization). For NO3-, non-fossil fuel NOx sources (50%-63% with 3.4-4.1 kg N ha-1 yr-1, including biomass burning and microbial N cycle) were comparable to fossil fuel NOx sources (37%-50% with 2.4-3.4 kg N ha-1 yr-1, including coal combustion and vehicle exhaust). This study evidenced high N deposition rates and the importance of combustion-related NH3 emissions and non-fossil fuel NOx emissions in city areas of the YRD.

Nitrate runoff loss and source apportionment in a typical subtropical agricultural watershed.

Nitrate (NO3-) loss and enrichment in water bodies caused by fertilization are a major environmental problem in agricultural areas. However, the quantitative contribution of different NO3- sources, especially chemical fertilizers (CF) and soil organic nitrogen (SON), to NO3- runoff loss remains unclear. In this study, a systematic investigation of NO3- runoff and its sources was conducted in a subtropical agricultural watershed located in Yujiang County, Jiangxi Province, China. A semi-monthly sampling was performed at the inlet and outlet from March 2018 to February 2019. Hydrochemical and dual NO3- isotope (15 N and 18O) approaches were combined to estimate the NO3- runoff loss and quantify the contribution of different sources with a Bayesian isotope mixing model. Source apportionment by Stable Isotope Analysis in R (SIAR) suggested that NO3- in runoff was mainly derived from nitrification of ammonium (NH4+) mineralized from SON (37-52%) and manure/sewage (M&S) (25-47%), while the contribution of CF was relatively small (14-25%). The contribution of various sources showed seasonal variations, with a greater contribution of CF in the wet growing season (March to August). Compared with the inlet which contributed 37-40% to runoff NO3-, SON contributed more at the outlet (49-52%). Denitrification in the runoff was small and appeared to be confined to the dry season (September to February), with an estimated NO3- loss of 2.73 kg N ha-1. The net NO3- runoff loss of the watershed was 34.5 kg N ha-1 yr-1, accounting for 15% of the annual fertilization rate (229 kg N ha-1 yr-1). Besides M&S (22%), fertilization and remineralization of SON (CF + SON) were the main sources for the NO3- runoff loss (78%), suggesting accelerated nitrification of NH4+ from CF (24%) and SON mineralization (54%). Our study indicates that NO3- runoff loss in subtropical agricultural watersheds is dominated by nonpoint source pollution from fertilization. SON played a more important role than CF. Besides, the contribution of sewage should not be neglected. Our data suggest that a combination of more rational fertilizer N application (CF), better management of SON, and better treatment of domestic sewage could alleviate NO3- pollution in subtropical China.

Isotope evidence for temporal and spatial variations of anthropogenic sulfate input in the Yihe River during the last decade.

Pyrite oxidation and sedimentary sulfate dissolution are the primary components of riverine sulfate (SO42-) and are predominant in global SO42- flux into the ocean. However, the proportions of anthropogenic SO42- inputs have been unclear, and their tempo-spatial variations due to human activities have been unknown. Thus, field work was conducted in a spatially heterogeneous human-affected area of the Yihe River Basin (YRB) during a wet year (2010) and drought years (2017/2018). Dual sulfate isotopes (δ34S-SO42- and δ18O-SO42-) and Bayesian isotope mixing models were used to calculate the variable anthropogenic SO42- inputs and elucidate their temporal impacts on riverine SO42- flux. The results of the mixing models indicated acid mine drainage (AMD) contributions increased from 56.1% to 83.1% of upstream sulfate and slightly decreased from 46.3% to 44.0% of midstream sulfate in 2010 and 2017/2018, respectively, in the Yihe River Basin. The higher upstream contribution was due to extensive metal-sulfide-bearing mine drainage. Sewage-derived SO42- and fertilizer-derived SO42- inputs in the lower reaches had dramatically altered SO42- concentrations and δ34S-SO42- and δ18O-SO42- values. Due to climate change, the water flow discharge decreased by about 70% between 2010 and 2017/2018, but the riverine sulfate flux was reduced by only about 58%. The non-proportional increases in anthropogenic sulfate inputs led to decreases in the flow-weighted average values of δ34S-SO42- and δ18O-SO42- from 10.3‰ to 9.9‰ and from 6.1‰ to 4.4‰, respectively. These outcomes confirm that anthropogenic SO42- inputs from acid mine drainage (AMD) have increased, but sewage effluents SO42- inputs have decreased.

Determining nitrate and sulfate pollution sources and transformations in a coastal aquifer impacted by seawater intrusion-A multi-isotopic approach combined with self-organizing maps and a Bayesian mixing model.

Over the past few decades, the La Paz aquifer system in Baja California Sur, Mexico, has been under severe pressure due to overexploitation for urban water supply and agriculture; this has caused seawater intrusion and deterioration in groundwater quality. Previous studies on the La Paz aquifer have focused mainly on seawater intrusion, resulting in limited information on nitrate and sulfate pollution. Therefore, pollution sources have not yet been identified sufficiently. In this study, an approach combining hydrochemical tools, multi-isotopes (δ2HH2O, δ18OH2O, δ15NNO3, δ18ONO3, δ34SSO4, δ18OSO4), and a Bayesian isotope mixing model was used to estimate the contribution of different nitrate and sulfate sources to groundwater. Results from the MixSIAR model revealed that seawater intrusion and soil-derived sulfates were the predominant sources of groundwater sulfate, with contributions of ~43.0% (UI90 = 0.29) and ~42.0% (UI90 = 0.38), respectively. Similarly, soil organic nitrogen (~81.5%, UI90 = 0.41) and urban sewage (~12.1%, UI90 = 0.25) were the primary contributors of nitrate pollution in groundwater. The dominant biogeochemical transformation for NO3- was nitrification. Denitrification and sulfate reduction were discarded due to the aerobic conditions in the study area. These results indicate that dual-isotope sulfate analysis combined with MixSIAR models is a powerful tool for estimating the contributions of sulfate sources (including seawater-derived sulfate) in the groundwater of coastal aquifer systems affected by seawater intrusion.

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.

Tracking nitrate and sulfate sources in groundwater of an urbanized valley using a multi-tracer approach combined with a Bayesian isotope mixing model.

Over the past decades, groundwater quality has deteriorated worldwide by nitrate pollution due to the intensive use of fertilizers in agriculture, release of untreated urban sewage and industrial wastewater, and atmospheric deposition. Likewise, groundwater is increasingly polluted by sulfate due to the release of domestic, municipal and industrial wastewaters, as well as through geothermal processes, seawater intrusion, atmospheric deposition, mineral dissolution, and acid rain. The urbanized and industrialized Monterrey valley has a long record of elevated nitrate and sulfate concentrations in groundwater with multiple potential pollution sources. This study aimed to track different sources and transformation processes of nitrate and sulfate pollution in Monterrey using a suite of chemical and isotopic tracers (δ2H-H2O, δ18O-H2O, δ15N-NO3, δ18O-NO3 δ34S-SO4, δ18O-SO4) combined with a probability isotope mixing model. Soil nitrogen and sewage were found to be the most important nitrate sources, while atmospheric deposition, marine evaporites and sewage were the most prominent sulfate sources. However, the concentrations of nitrate and sulfate were controlled by denitrification and sulfate reduction processes in the transition and discharge zones. The approach followed in this study is useful for establishing effective pollution management strategies in contaminated aquifers.