中国北方典型岩溶河流硝酸盐来源解析及H2SO4和HNO3对流域岩石风化碳汇的影响
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国家自然科学基金面上项目(41877192);阜阳师范大学校级自然科学重点项目(2024FSKJ13ZD);安徽省高等学校科学研究项目(2023AH050397);阜阳师范大学校级自然科学一般项目(2022FSKJ03)


Identification of nitrate sources and effects of H2SO4 and HNO3 on carbonate weathering carbon sinks in typical karst rivers in northern China
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    摘要:

    定量评估中国北方岩溶河流碳酸盐岩风化和人为酸引起的碳源汇变化,对于我国实现"双碳"目标具有重要的现实意义。基于2019年旱季中国北方典型岩溶河流-玉符河地表水的野外监测数据,通过水文地球化学和多同位素指标(δ15NNO3、δ15NNH4、δ18ONO3和δ13CDIC)分析,结合贝叶斯同位素混合模型(Simmr)和水化学平衡法,对NO-3来源进行定量解析,并定量估算了碳酸(H2CO3)、硝酸(HNO3)和硫酸(H2SO4)对碳酸盐岩风化和CO2碳汇通量的影响。研究结果表明:① 水化学、δ15NNO3、δ15NNH4、δ18ONO3和Simmr模型揭示玉符河流域河水NO-3主要来源于土壤氮(34.6%-39.3%)和铵态氮肥(27.7%-39.9%),其次为硝态氮肥(9.5%-16.7%),污水粪肥和大气降水贡献比例较低,分别为7.1%-12%和4.4%-7.5%;② 离子比值和δ13CDIC揭示人为活动产生的HNO3和H2SO4显著地参与流域碳酸盐岩风化;③ 水化学平衡法估算H2CO3溶解碳酸盐所消耗的CO2量为锦阳川(JYC)>玉符河(YFR)>锦绣川(JXC)>二仙河(EXR),HNO3和H2SO4溶解碳酸盐岩所释放的CO2的量分别为EXR>JXC>JYC>YFR和EXR>JXC>YFR>JYC;④ 流域CO2净消耗量由高到低分别为JYC(+0.26 mmol/L)、YFR(+0.01 mmol/L)、JXC(-0.81 mmol/L)和EXR(-2.13 mmol/L);JYC和YFR表现为岩溶碳汇效应,而JXC和EXR则主要表现为碳源效应。故集约化农业施用还原性氮肥和硫肥形成的人为酸参与碳酸盐岩风化是导致中国北方岩溶区河流碳汇效应减弱的重要因素。本研究可为中国北方或温带岩溶区河流碳循环模型的构建和流域碳汇的精准评估提供重要的科学依据。

    Abstract:

    Accurately quantifying carbon source-sink changes resulting from carbonate weathering under the influence of anthropogenic acids (HNO3 and H2SO4) in karst rivers of northern China is of great practical significance for supporting China's "Carbon Peak and Carbon Neutrality" goals. This study focuses on the Yufu River (YFR), a typical karst river in northern China, based on a surface water survey conducted during the dry season of 2019. By integrating hydrogeochemical and isotopic tracer methods (δ15NNO3, δ15NNH4, δ18ONO3 and δ13CDIC) with the Bayesian isotope mixing model (Simmr) and hydrochemical mass balance (forward modeling), we quantitatively identified the sources of nitrate and evaluated the roles of H2CO3, HNO3, and H2SO4 in carbonate weathering and CO2 sequestration. The Simmr model constrained by hydrochemical parameters and dual nitrogen isotopic data revealed that the main sources of nitrate in the Yufu River catchment were soil nitrogen (34.6%-39.3%) and ammonium fertilizer (27.7%-39.9%), followed by nitrate fertilizer (9.5%-16.7%), with relatively lower contributions from sewage and manure (7.1%-12%) and atmospheric deposition (4.4%-7.5%). The ion ratios and δ13CDIC values indicated that in addition to natural carbonic acid, externally derived acids such as HNO3 and H2SO4 from anthropogenic activities significantly participated in carbonate weathering. Hydrochemical mass balance calculations showed that CO2consumption followed the order: Jinyangchuan (JYC)>YFR main stream>Jinxiuchuan (JXC)>Erxian River (EXR). The amounts of CO2 released by sulfuric acid and nitric acid-mediated carbonate weathering decreased in the sequences EXR>JXC>JYC>YFR and EXR>JXC>YFR>JYC, respectively, which may be related to variations in agricultural fertilizer intensity across sub-basins. Notably, the net CO2 consumption rates across four monitoring sites exhibited significant spatial differences: JYC (+0.26 mmol/L), YFR (+0.01 mmol/L), JXC (-0.81 mmol/L), and EXR (-2.13 mmol/L). Among these, the JYC demonstrated a clear karst carbon sink effect with net CO2 consumption, YFR was near carbon neutrality with approximately balanced CO2 flux, while JXC and EXR functioned as net carbon sources releasing CO2 into the atmosphere. These spatial variations reflect the complexity of hydrogeochemical processes and their influence on the carbon cycle across the watershed. The findings highlight that intensive application of reduced nitrogen and sulfur fertilizers in agriculture leads to significant anthropogenic acid involvement in carbonate weathering, which is a key factor weakening the riverine carbon sink effect in northern China's karst regions. This study provides an important scientific basis for constructing river carbon cycle models and accurately assessing watershed carbon sinks in northern China and other temperate karst areas.

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张结,袁周伟,张林,袁甲,邵明玉,石亮星,吕杰杰,靳孟贵.中国北方典型岩溶河流硝酸盐来源解析及H2SO4和HNO3对流域岩石风化碳汇的影响.生态学报,2026,46(6):3263~3278

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