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基于氮、氧稳定同位素的流域硝酸盐溯源研究进展

Research advances in riverine nitrate source identification using stable isotopes of nitrogen and oxygen

  • 摘要: 硝酸盐作为水体主要污染物,其来源与贡献率可为制定流域水污染防治决策提供科学依据。不同氮源的氮、氧稳定同位素(δ15N和δ18O)具有相对稳定的特征差异,为水体硝酸盐来源识别提供了关键信息。近年来,随着氮、氧稳定同位素检测方法的创新和技术进步,水环境中硝酸盐源解析已从早期的单一同位素定性判别发展到双同位素定量解析,并与多同位素及贝叶斯混合模型(如SIAR、MixSIAR)结合,实现了复杂环境下多源氮素贡献率的定量区分。在总结水体硝酸盐氮、氧稳定同位素特征的基础上,基于文献统计分析,综述了氮、氧稳定同位素在河流系统中的研究热点,当前研究主要集中在溯源解析方面,分析了氮、氧稳定同位素测试方法的研究进展,重点论述了土地利用类型及降雨径流对硝酸盐氮、氧稳定同位素的影响,评述了氮、氧稳定同位素进行硝酸盐源解析技术从定性判别向定量解析的跨越发展历程,最后提出了未来的研究展望。现有的研究显示,化肥、土壤氮、生活污水、畜禽粪污、大气降水、工业废水等是河流主要的硝酸盐来源,其贡献率受土地利用格局、降雨过程及水文条件的显著调控。尽管氮、氧同位素技术在源解析与氮循环过程追踪方面展现出独特优势,但仍存在端元特征数据库不足以及动态过程研究中高频观测与时间序列分析相对薄弱等问题,未来研究应加强区域端元库建设,推动多同位素联用、微生物源示踪等多因子示踪体系与模型优化的融合,以提升源解析的精度与适用性。

     

    Abstract: Nitrate is a major water pollutant, and identifying its sources and quantifying their relative contributions provide an essential scientific basis for watershed water pollution control and management. Stable nitrogen and oxygen isotopes of nitrate, expressed as δ15N and δ18O, exhibit relatively consistent and distinguishable characteristics among different nitrogen sources, thereby providing critical information for source identification in aquatic environments. In recent years, with continuous innovations in nitrate isotope pretreatment methods and advances in analytical techniques, nitrate source apportionment in water environments has progressed from early qualitative discrimination based on a single isotope to quantitative analysis based on dual isotopes. This development has been further strengthened by the integration of multi-isotope approaches and Bayesian mixing models, such as SIAR and MixSIAR, which enable quantitative partitioning of multiple nitrogen sources under complex environmental conditions. Against this background, the present review synthesizes the characteristic ranges and interpretive significance of nitrate nitrogen and oxygen stable isotopes in aquatic systems, and, on the basis of bibliometric statistics, examines the major research hotspots concerning the application of these isotopes in riverine systems. Current studies are found to focus primarily on source identification and apportionment. Accordingly, this review summarizes the development of analytical methods for nitrate isotope measurement, discusses in detail the effects of land use and rainfall-runoff processes on nitrate δ15N and δ18O values, evaluates the methodological evolution of nitrate source analysis from qualitative identification to quantitative apportionment, and finally proposes priorities for future research. Existing studies indicate that the principal nitrate sources in rivers include chemical fertilizers, soil nitrogen, domestic sewage, livestock manure, atmospheric deposition, and industrial wastewater. The relative contributions of these sources are strongly regulated by land-use patterns, rainfall processes, and hydrological conditions. In agricultural areas, nitrate is commonly derived from fertilizer application, soil nitrification, and manure inputs, and its transport is closely associated with storm runoff, irrigation return flow, and leaching through the vadose zone. In forested catchments, nitrate is generally dominated by soil nitrogen transformation and atmospheric deposition, while strong vegetation uptake and soil retention often reduce overall nitrogen export. In wetlands, alternating aerobic and anaerobic conditions favor denitrification, which not only removes nitrate but also enriches the residual nitrate pool in δ15N and δ18O. In urban rivers, nitrate is frequently associated with domestic sewage, industrial discharges, and runoff from impervious surfaces, and its isotopic composition often reflects the combined effects of point-source inputs and in-stream biogeochemical processing. These findings demonstrate that nitrate isotopes can serve not only as tracers of pollution sources but also as indicators of nitrogen transformation processes such as nitrification and denitrification. Despite these distinct advantages, several limitations remain. End-member isotope databases are still inadequate, especially at regional scales where source signatures may vary substantially with local climate, geology, hydrology, and human activities. In addition, dynamic process studies remain relatively weak, particularly with respect to high-frequency observations and time-series analysis, which restricts the ability to capture rapid responses of nitrate sources and transformation pathways during storm events, seasonal transitions, and other hydrological disturbances. Uncertainty arising from source overlap, spatiotemporal variability in end-member compositions, and process-related isotope fractionation also continues to challenge robust source apportionment. Future studies should therefore prioritize the construction of regional end-member databases, strengthen high-frequency and process-oriented monitoring, and promote the integration of multi-isotope approaches with other tracers, including microbially derived indicators. Greater efforts should also be directed toward coupling multi-factor tracing systems with optimized quantitative models, so as to improve both the accuracy and the applicability of nitrate source apportionment. Such advances will enhance the capacity of stable isotope techniques to support precise diagnosis of nitrogen pollution and provide more reliable scientific support for watershed water quality protection and management.

     

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