Quantitative analysis of dissolved inorganic carbon sources in water bodies in the Lujiang river basin
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摘要: 溶解无机碳（DIC）是研究流域水体碳循环的重要指标之一。泸江流域内岩溶断陷盆地发育，水文地质条件独特，是研究流域水体碳迁移转化的良好选区。为了研究泸江流域河流水体水化学类型及DIC的来源问题，分析了该流域雨季14个地表水点、8个暗河点、10个泉点的水化学和碳同位素采样数据。结果表明：（1）流域内水化学类型主要是HCO3-Ca型，属于“碳酸盐岩风化型”；（2）通过分析离子关系图进一步确定了${\rm{SO}}_4^{2-}$与${\rm{NO}}_3^{-}$ 参与了流域岩石风化过程；（3）基于离子比值法计算得出，碳酸风化碳酸盐岩贡献比例平均为68.8%，硫酸/硝酸风化碳酸盐岩贡献比例平均为27.2%，硅酸盐岩风化对${\rm{HCO}}_3^{-}$贡献比例平均为3.9%，泸江流域水体岩石风化过程中，以碳酸风化碳酸盐岩为主；（4）根据碳同位素法验证，与实测值相比，暗河水和泉水理论平均值δ13CDIC_Th比较接近，而地表水则过于偏正，说明地表水中DIC来源不仅由岩石风化控制，还有河流水体内部的生物地球化学过程。相比较而言，地表河流处城镇化严重且存在明显农业活动，受人类活动影响显著。Abstract:
The watershed carbon cycle is an important part of the global carbon cycle, playing an important role in seeking global carbon sinks that have been missed. Dissolved inorganic carbon (DIC) is one of the important indicators for studying the carbon cycle of water bodies in the basin. As an important component of terrestrial ecosystems, karst water bodies containing high DIC concentrations play an important role in the global carbon cycle. The Lujiang river basin, a typical development area of karst graben basin, is an applicable place for us to study the carbon migration and transformation of water bodies. In order to study the hydrochemical types and sources of DIC in the rivers of the Lujiang river basin, sampling data of hydrochemistry and carbon isotope from 14 surface water points, 8 underground river points, and 10 spring points during the rainy season were analyzed. It is believed that exploring the proportional contribution of DIC sources in different water bodies may help to understand the sources and cycles of groundwater DIC under the influence of human activities, providing scientific references for water resource management. Firstly, this study determines the hydrochemical types of different water bodies through the Piper trilinear map and Schukalev classification. The results show that regardless of the type of water body in the study area, the hydrochemical type in the drainage basin is mainly HCO3-Ca, belonging to the "type of carbonate rock weathering". Due to the long interaction time between water and rock, the rock weathering in groundwater is more obvious than in surface water. Secondly, the analyses of ion sources in water bodies by Gibbs plot indicate the consistency in the hydrochemical composition, changes, and origin mechanisms between groundwater and surface water. The controlled mechanism belongs to the "leaching type of rock weathering". Thirdly, due to the widespread distribution of carbonate rocks in the study area, an analysis has been conducted on carbonate rock dissolution in order to distinguish the relative contribution of limestone and dolomite dissolution to the chemical ion compositions of water bodies in the watershed. It is found that there are additional sources of Mg2+ and Ca2+ in the surface water of the Lujiang river basin, while other acids participate in the chemical weathering reaction in the water bodies of the underground river points and spring points. Furthermore, it is determined that ${\rm{SO}}_4^{2-}$ and ${\rm{NO}}_3^{-}$ are involved in the rock weathering in the basin, which has caused a large disturbance to the hydrochemical characteristics of water bodies in the basin. The Lujiang river basin is mixed with carbonate and silicate rocks. Therefore, the main sources of ${\rm{HCO}}_3^{-}$ in water are classified into three types: carbonate rocks weathered and dissolved by carbonic acid, carbonate rocks weathered by sulfuric acid/nitric acid, and silicate rocks weathered by carbonic acid. Based on the quantitative analysis by ion ratio method, carbonate rocks weathered by carbonic acid contribute average 68.8% to HCO$_3^{−}$, carbonate rocks weathered by sulfuric acid/nitric acid 27.2%, and silicate rock weathered by carbonic acid 3.9%. During the weathering process of water bodies in the Lujiang river basin, carbonate rocks are mainly weathered by carbonic acid. Finally, the verification by carbon isotope method has been compared with the measured values to show that the theoretical average values of underground river water and spring water δ13CDIC_Th are relatively close, while the values of surface water are positive too, indicating that the source of DIC in surface water is not only controlled by rock weathering, but also by biogeochemical processes within river water bodies. In comparison, the areas of surface rivers are more significantly affected by human activities with severe urbanization and agricultural activities. -
图 1 泸江流域采样点位布设图（底图来自2011年开展的1∶25万水文地质调查图）
Figure 1. Layout map of sampling points in the Lujiang river basin (The base map is taken from the 1∶250,000 hydrogeology survey map in 2011.)
图 2 泸江流域夏季水化学Piper三线图
Figure 2. Piper three-line diagram of summer hydrochemistry in the Lujiang river basin
图 3 泸江流域溶解无机碳同位素的变化特征
(a.地表水拟合线y=0.02x−15.72，R2线性=0.119 b.暗河水拟合线y=−7.8e−3x−10.26，R2线性=0.035 c.泉水拟合线y=−0.02x−3.71，R2线性=0.547)
Figure 3. Changes of dissolved inorganic carbon isotopes in the Lujiang river basin
(a. the fitting line of surface water, y=0.02 x−15.72, R2 linearity=0.119; b. the fitting line of underground river water, y=−7.8e−3 x−10.26, R2 linearity=0.035; c. the fitting line of spring water, y=−0.02 x−3.71, R2 linearity=0.547)
图 5 Mg2+/Ca2+与${\rm{HCO}}_3^{-}$、${\rm{SO}}_4^{2-}$关系图
Figure 5. Relationship between Mg2+/Ca2+ and ${\rm{HCO}}_3^{-}$ and ${\rm{SO}}_4^{2-}$
图 7 基于离子比值法计算不同来源${\rm{HCO}}_3^{-}$贡献比例累积图
Figure 7. Cumulative ratios of ${\rm{HCO}}_3^{-}$ contribution from different sources calculated by the ion ratio method
图 8 不同水体类型的三个主要${\rm{HCO}}_3^{-}$来源的贡献比例分布图
Figure 8. Distribution of contribution ratios of three main ${\rm{HCO}}_3^{-}$ sources of different water body types
图 9 δ13CDIC实测值与根据端元模型估算出的δ13CDIC_Th
Figure 9. Measured values of δ13CDIC and estimated values based on the end element model δ13CDIC_Th
表 1 不同类型水体各指标
Table 1. Indicators of different types of water bodies
类型 参数 指标 K+ Na+ Ca2+ Mg2+ HCO$_3^{-} $ Cl− NO$_3^{-} $ SO$_4^{2-} $ SiO$_3^{2-} $ pH TDS EC 暗河水 最小值 0.4 0.3 57.3 11.7 248.0 0.8 6.6 3.1 8.1 7.5 231.0 407.5 最大值 2.9 10.6 98.7 25.3 374.0 9.3 21.2 70.7 70.6 8.0 720.0 651.0 均值 1.5 2.4 79.3 17.1 300.1 3.1 12.7 19.1 21.9 7.7 364.6 551.3 标准差 0.9 3.4 16.7 4.6 45.7 2.7 5.1 23.9 20.1 0.2 154.3 96.8 变异系数 0.6 1.4 0.2 0.3 0.2 0.9 0.4 1.3 0.9 0.0 0.4 0.2 地表水 最小值 0.8 1.2 2.2 1.1 21.0 0.8 0.3 5.4 7.1 1.8 58.7 88.7 最大值 17.4 17.9 71.5 30.4 275.0 34.6 20.5 114.0 47.1 8.2 513.0 564.0 均值 8.3 10.0 41.3 14.6 162.5 15.9 5.8 33.6 18.4 7.4 277.0 319.1 标准差 6.1 5.6 23.1 8.9 76.4 13.9 6.0 30.8 10.6 1.6 136.8 152.9 变异系数 0.7 0.6 0.6 0.6 0.5 0.9 1.1 0.9 0.6 0.2 0.5 0.5 泉水 最小值 0.3 0.5 71.4 7.0 323.0 0.4 0.7 3.7 9.5 7.1 213.0 366.9 最大值 2.1 11.4 136.0 42.7 485.0 18.0 28.7 51.7 18.3 7.8 709.0 787.0 均值 1.1 2.4 100.4 25.2 410.9 3.4 10.1 13.0 13.3 7.5 412.8 538.7 标准差 0.6 3.2 21.6 14.2 41.0 5.3 8.4 14.6 2.9 0.2 123.0 162.7 变异系数 0.6 1.4 0.2 0.6 0.1 1.6 0.8 1.1 0.2 0.0 0.3 0.3 注：pH为无量纲，电导率（EC）为μs·cm−1，其他指标为mg·L−1，变异系数为%。
Note: pH is dimensionless; electrical conductivity (EC) is μs·cm−1; other indexes are mg·L−1; variable coefficient is %.
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