地球科学进展

地球科学进展 ›› 2017, Vol. 32 ›› Issue (3): 307 -318. doi: 10.11867/j.issn.1001-8166.2017.03.0307

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非岩溶水和硫酸参与溶蚀对湘南地区地下河流域岩溶碳汇通量的影响
黄奇波 1, 2, 3( ), 覃小群 2, 3, *( ), 刘朋雨 2, 3, 张连凯 2, 3, 苏春田 1, 2, 3   
  1. 1.中国地质大学环境学院,湖北 武汉 430074
    2.中国地质科学院岩溶地质研究所, 广西 桂林 541004
    3.国土资源部广西岩溶动力学重点实验室,广西 桂林 541004
  • 收稿日期:2016-11-14 修回日期:2017-02-03 出版日期:2017-03-20
  • 通讯作者: 覃小群 E-mail:qbohuang@karst.ac.cn;qxq@karst.ac.cn
  • 基金资助:
    中国地质调查局地质调查项目“西江中下游岩溶峰林区1∶ 5万水文地质环境地质调查”(编号:121201107000150005);国家自然科学基金项目“半干旱岩溶区溶蚀作用季节分异与影响机制”(编号:41302211)资助

The Influence of Allogenic Water and Sulfuric Acid to Karst Carbon Sink in Karst Subterranean River in Southern Hu’nan

Qibo Huang 1, 2, 3( ), Xiaoqun Qin 2, 3( ), Pengyu Liu 2, 3, Liankai Zhang 2, 3, Chuntian Su 1, 2, 3   

  1. 1.Environmental School,China University of Geosciences, Wuhan 430074, China
    2.Institute of Karst Geology, Chinese Academy of Geological Sciences,Guilin 541004, China
    3.Karst Laboratory of Karst Dynamics, Ministry of Land and Resources & Guangxi Zhuang Autonomous Region, Guilin 541004, China
  • Received:2016-11-14 Revised:2017-02-03 Online:2017-03-20 Published:2017-03-20
  • About author:

    First author:Huang Qibo(1982-), male, Pingxiang City, Jiangxi Province, Associate Professor. Research areas include karst geo-hydrology and Karst environment with global chang.E-mail:qbohuang@karst.ac.cn

  • Supported by:
    Project supported by the China Geology Survey “Hydrogeological and environmental geological survey of 1∶ 50 000 in peak-forest karst area of the middle and lower reaches of the Xijiang River Basin” (No.121201107000150005);The National Natural Science Foundation of China “Seasonal different and influence mechanism of the dissolution in the semi-arid karst area”(No.41302211)
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研究非岩溶水和硫酸参与溶蚀对地下河流域岩溶碳汇通量的影响,有助于提高岩石风化碳汇通量估算精度,对于推进地质作用与全球气候变化研究意义重大。选取湘南北江上游武水河流域内4条典型地下河为对象,通过水化学对比分析,揭示硅酸盐岩风化对流域地下水化学的重要影响。运用Galy方法计算流域非岩溶地层中的硅酸盐岩风化消耗大气/土壤CO2对岩石风化碳汇的重要贡献,并评价了H2SO4参与下碳汇通量的扣除比例。结果显示:①流域内有非岩溶地层的L01,L02地下河, Na+,K+和SiO2浓度明显高于纯碳酸盐L03和L04地下河,非岩溶地层中的硅酸盐的风化对地下河水中K+,Na+,SiO2浓度有一定贡献;② 4条地下河的[Ca2++Mg2+]/[HCO3-]当量比值为1.05~1.15,[Ca2++Mg2+]/[HCO3-+SO42-]的当量比值为0.99~1.08,Ca2++Mg2+相对于HCO3-过量,过量的Ca2++Mg2+与SO42-相平衡,证实硫酸参与流域碳酸盐岩的溶蚀;③L01和L02地下河岩石风化消耗的CO2通量中非岩溶地层中的硅酸盐风化消耗所占比例分别为3.36%和2.22%,而L03和L04地下河中硅酸盐风化消耗比例小于0.50%,表明有非岩溶地层存在的地下河流域,其岩石风化消耗的CO2通量中硅酸盐风化消耗占有一定比例;④在考虑硫酸参与碳酸盐岩溶蚀时,4条地下河的碳汇通量分别扣除4.84%,4.52%,6.20%和9.36%。

关键词: 地下河, 碳酸盐岩风化, 硅酸盐岩风化, 碳汇通量, 硫酸

Evaluating the impact of allogenic water and sulfuric acid on karst carbon sink not only helps to improve the accurate calculation of soil CO2 uptake by rock weathering, but also obtains a complete understanding of the global carbon cycle. Groundwater samples were collected from four karst subterranean rivers watershed within different lithology strata in Wushui Basin, upstream of Beijiang Basin, Hunan Province, for revealing the important impact of silicate weathering on hydrochemistry of groundwater. To estimate the contribution of soil CO2 uptake by silicate weathering to CO2 uptake by rock weathering, the Galy model was employed in this article. The important impact of sulfuric acid on CO2 uptake by carbonate weathering resulting from the substitution of carbonic acid by protons from sulfuric acid was investigated. Our results showed that the concentration of Na+, K+ and SiO2 in L01,L02 subterranean river with silicate strata in watershed were higher than that in L03,L04 subterranean river without silicate strata in watershed, which implied that the contribution of silicate weathering to Na+,K+ and SiO2 was very important in watershed within silicate strata . The changeable equivalent ratio between (Ca2++Mg2+) and HCO3- was 1.05 to 1.15, and the value of [Ca2++Mg2+]/[HCO3-+SO42-] was 0.99 to 1.08. The concentrations of Ca2+ and Mg2+ exceeded the equivalent concentrations of HC3-, and the excess of Ca2+ and Mg2+cations were compensated by SO42-, which suggested that sulfuric acid has an important influence on carbonate dissolution. The contribution of soil CO2uptake by silicate weathering to CO2 consumption in L01 and L02 subterranean river were 3.36% and 2.22%, respectively, whereas the contribution in L03, L04 subterranean river were less than 0.50%, indicating that the contribution of soil CO2 uptake by silicate weathering was important in the subterranean river basin within silicate strata. Due to the contributions made by sulfuric acid, the CO2 consumption in four subterranean rivers decreased by 4.84%, 4.52%, 6.20%, 9.36%, respectively.

Key words: Karst subterranean rivers, Carbonate weathering, Silicate weathering, CO2 consumption flux, Sulfuric acid.

中图分类号: 

图1 研究区水地质图
Fig.1 Gological sketch map of study area
表1 4条地下河的流量和岩性特征
Table 1 The characteristic of lithology and discharge in four kart subterranean rivers
地下河名称 径流量/105m3 流域面积
/km2		 非岩溶地层
面积/km2		 非岩溶比例
/%
1~3月 4~6月 7~9月 10~12月 合计
L01(邓家地下河) 4.58 14.81 2.26 8.10 29.75 8.31 1.44 17.33
L02(百里地下河) 5.10 9.45 1.39 3.00 18.94 5.23 0.68 13.00
L03(大泉地下河) 7.83 8.63 5.31 8.09 29.86 5.04 0 0
L04(夏家地下河) 27.57 34.51 16.05 30.30 108.43 22.15 0 0
表2 4条地下河不同月主要离子组成
Table 2 Major ionic concentrations in different seasons from four karst subterranean rivers
名称 时间 T/
℃		 pH Ca2+ Mg2+ Na+ K+ HC O 3 - Cl- S O 4 2 - N O 3 - SiO2 TDS SIC pCO2/
Pa		 NICB
含量/%		 Ca2+
含量/%		 Mg2+
含量/%		 HC O 3 -
含量/%		 S O 4 2 -
含量/%
/(mmol/L) /(mg/L)
L01(邓家
地下河)		 3月 17.5 7.63 1.823 0.731 0.070 0.027 4.844 0.079 0.146 0.091 5.40 257.72 0.39 6 026 -0.96 68.8 27.6 93.9 2.8
6月 17.8 7.43 1.778 0.910 0.090 0.039 4.876 0.080 0.115 0.114 5.31 259.21 0.18 9 661 1.90 63.1 32.3 94.0 2.2
8月 18.0 7.15 1.718 0.864 0.085 0.052 4.530 0.104 0.132 0.130 5.64 247.99 -0.14 17 258 2.63 63.2 31.8 92.5 2.7
11月 17.6 7.21 1.566 0.876 0.062 0.027 4.386 0.054 0.095 0.092 5.74 230.97 -0.13 14 488 2.59 61.8 34.6 94.8 2.1
平均值 17.7 7.36 1.721 0.845 0.077 0.037 4.659 0.079 0.122 0.107 5.52 248.97 0.08 11 858 1.54 64.2 31.6 93.8 2.5
L02(百里
地下河)		 3月 17.2 7.65 1.783 0.485 0.074 0.012 4.290 0.050 0.118 0.055 5.21 229.14 0.35 5 105 -0.09 75.7 20.6 95.1 2.6
6月 17.5 7.24 1.768 0.534 0.037 0.022 4.342 0.041 0.073 0.057 6.16 226.11 0.05 6 486 0.84 74.9 22.6 96.2 1.6
8月 17.7 7.32 1.798 0.306 0.052 0.039 3.838 0.078 0.140 0.085 6.07 215.30 -0.05 13 428 0.22 81.9 13.9 92.7 3.4
11月 17.2 7.47 1.571 0.353 0.044 0.019 3.553 0.041 0.106 0.065 5.29 193.00 -0.01 9 931 0.51 79.1 17.8 94.4 2.8
平均值 17.4 7.42 1.730 0.420 0.052 0.023 4.006 0.052 0.109 0.065 5.68 215.89 0.09 8 738 0.37 77.9 18.7 94.6 2.6
L03(大泉
地下河)		 3月 18.0 7.73 2.049 0.177 0.023 0.010 4.114 0.056 0.133 0.099 4.74 227.39 0.49 4 111 -0.57 90.7 7.8 93.5 3.0
6月 18.1 7.57 2.033 0.167 0.025 0.019 3.975 0.046 0.128 0.104 5.23 221.74 0.31 5 768 0.73 90.6 7.4 93.5 3.0
8月 18.5 6.99 1.912 0.173 0.051 0.024 3.618 0.066 0.123 0.112 5.46 207.30 -0.32 20 277 2.44 88.5 8.0 92.3 3.1
11月 18.0 7.14 2.089 0.184 0.038 0.014 4.108 0.041 0.111 0.076 5.30 226.81 -0.09 16 106 1.66 89.8 7.9 94.7 2.6
平均值 18.2 7.36 2.021 0.175 0.034 0.017 3.954 0.052 0.124 0.098 5.18 220.81 0.10 11 566 1.07 89.9 7.8 93.5 2.9
L04(夏家
地下河)		 3月 17.7 7.87 1.702 0.399 0.023 0.011 3.648 0.052 0.208 0.111 4.12 211.68 0.49 2 630 0.12 79.7 18.7 90.8 5.2
6月 18.0 7.73 1.785 0.398 0.026 0.019 3.875 0.042 0.181 0.108 5.48 219.30 0.40 3 873 0.28 80.1 17.8 92.1 4.3
8月 18.1 7.65 1.867 0.446 0.038 0.019 4.090 0.073 0.201 0.132 5.08 233.60 0.36 4 920 -0.13 78.7 18.8 91.0 4.5
11月 17.8 7.60 1.806 0.409 0.036 0.013 3.942 0.037 0.148 0.087 5.14 219.06 0.28 5 321 1.34 79.8 18.1 93.6 3.5
平均值 17.9 7.71 1.790 0.413 0.031 0.016 3.888 0.051 0.184 0.109 4.96 220.91 0.38 4 186 0.40 79.6 18.4 91.9 4.4
图2 主要离子Piper图
Fig.2 Piper diagram of ionic concentration in the samplers
图3 地下河水饱和指数(SI C)与 pCO 2的关系
Fig.3 The correlation between SI C and pCO 2 in karst subterranean river
图4 4条地下河中Cl -与Na +的关系(a)和与K +的关系(b)
Fig.4 Variationsof Cl - vs. Na + (a)and vs. K + (b) in four karst subterranean river
图5 SiO 2含量与(Na ++K +)/(Na ++K ++Cl -)变化关系
Fig.5 Variations of SiO 2 vs. (Na ++K +)/(Na ++K ++Cl -) in karst subterranean river
图6 地下水SIc和 pCO 2季节动态
Fig.6 Temporal change of SIc and pCO 2 in karst subterranean river
图7 4条地下河中N O 3 - /Cl -与S O 4 2 - /Cl -的关系
Fig.7 Four variations of N O 3 - /Cl - vs. S O 4 2 - /Cl - in four karst subterranean river
图8 地下河Ca 2++Mg 2+与HC O 3 - + S O 4 2 - 关系
Fig.8 Ca 2++Mg 2+ vs.HC O 3 - + S O 4 2 - in karst subterranean river
图9 [Ca 2++Mg 2+]/[HC O 3 - ]与[S O 4 2 - ]/[HC O 3 - ]的当量比值关系
Fig.9 Equivalent ratios of [ Ca 2++ Mg 2+]/[ HC O 3 - ] vs.[ S O 4 2 - ] /[ HC O 3 - ] in karst subterranean rivers
表3 4条地下河岩石风化CO 2通量计算结果
Table 3 CO 2consumption flux by rock weathering in four karst subterranean rivers
名称 流量
/(105m3/a)		 流域面积
/km2		 碳酸风化硅
酸盐岩消耗
CO2		 碳酸风化碳
酸盐岩消耗
CO2		 碳酸和硫酸
风化碳酸盐
岩消耗CO2		 岩石的碳酸
风化消耗
CO2		 岩石的碳酸
和硫酸风化
消耗CO2		 硅酸盐岩
风化消耗比
/%		 碳汇通量
扣除比例
/%
/(103mol/(km2·a))
L01(邓家地下河) 29.75 8.31 27.39 829.78 788.32 857.17 815.72 3.36 4.84
L02(百里地下河) 18.94 5.23 16.13 746.14 711.65 762.26 727.78 2.22 4.52
L03(大泉地下河) 29.86 5.04 4.55 1 177.88 1 104.54 1 182.43 1 109.09 0.41 6.20
L04(夏家地下河) 108.43 22.15 2.81 945.17 856.46 947.98 859.27 0.33 9.36
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