外源酸作用下流域岩石风化与碳汇效应

李雪艳; 李灿锋; 杨克好; 陈瑞; 熊银洪; 王兴荣; 王传宇

doi:10.11932/karst20240402

外源酸作用下流域岩石风化与碳汇效应——以漾弓江为例

doi: 10.11932/karst20240402

中国地质调查局昆明自然资源综合调查中心/自然资源部自然生态系统碳汇工程技术创新中心, 云南昆明 650100

基金项目: 中国地质调查局地质调查项目（ZD20220135）

详细信息

作者简介:
李雪艳（1997－），女，助理工程师，硕士研究生，主要研究方向为岩溶碳循环。E-mail：lixueyan23@mail.cgs.gov.cn

通讯作者:
李灿锋（1989－），男，工程师，硕士研究生，主要研究方向为自然资源碳汇。E-mail：licanfeng@mail.cgs.gov.cn。

中图分类号: X141
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出版历程
- 收稿日期: 2023-11-27
- 录用日期: 2024-03-01
- 修回日期: 2024-03-01
- 刊出日期: 2024-08-25

Rock weathering and carbon sink effects under exogenous acid action: A case study of the Yanggong river

Kunming General Survey Center for Natural Resources, China Geological Survey/Technology Innovation Center for Natural Ecosystem Carbon Sink, Ministry of Natural Resources, Kunming, Yunnan 650100, China

摘要

摘要: 流域岩石风化是重要的碳源/汇过程，也是全球碳循环中的重要环节。外源酸参与流域岩石风化，影响碳元素的地球化学循环和流域碳源/汇效应。漾弓江属长江上游金沙江水系，流域岩石风化过程和碳汇效应尚不清楚。在2023年旱季和雨季分别采集了漾弓江的干流和主要支流的水样品（地表水点9个、地下水点6个），对主要离子浓度进行检测，并利用水化学平衡法和Galy估算模型分析该流域的岩风化类型，估算了碳酸与硫酸共同作用下的岩石风化CO₂消耗量。结果表明：（1）漾弓江流域水系离子成分主要源于硅酸盐岩和碳酸盐岩风化，水化学类型为HCO₃-Ca型或HCO₃-Ca·Mg型。（2）硫酸和碳酸共同参与了漾弓江流域的岩石风化过程。在不考虑硫酸作用时，漾弓江流域岩石风化的大气CO₂消耗量为38.35 t CO₂ ·km⁻²·a⁻¹，而当考虑了硫酸参与时，岩石风化碳汇量降至25.54 t CO₂ ·km⁻²·a⁻¹，扣除约33%，大大提高了计算精度。（3）漾弓江流域岩石风化的大气CO₂消耗量为4.27×10⁴ t CO₂·a⁻¹，是一个碳汇过程。硫酸参与流域岩石的风化改变了区域碳循环，这是全球碳循环模型不可忽略重要环节。
- 岩石风化 /
- 碳汇效应 /
- 硫酸 /
- 碳酸盐岩
Abstract: Rock weathering in the river basin is not only an essential carbon source and sink mechanism, but also an important link in the global carbon cycle. Rivers are indispensable components of water bodies, and the hydrochemistry of rivers is a representation of the degree to which weathering and denudation occur at the surface of the river basin. Therefore, it is possible for us to collect information on rock weathering in the river basin by conducting an analysis of the chemical compositions of rivers. In turn, the analytical results can be used for the estimation of weathering rates and the amount of carbon dioxide that is consumed by the Earth's atmosphere. The presence of exogenous acids in the process of rock weathering in the river basin has an impact on the geochemical cycling of carbon as well as the carbon source/sink effect. The chemical weathering rate of carbonatite is accelerated by sulfuric acid, but the weathering does not consume atmospheric carbon dioxide. As a result, the effect of sulfuric acid on carbonatite weathering should be taken into consideration when the amount of atmospheric carbon dioxide that is consumed by rock weathering in the basin is calculated.The Yanggong river is a part of the Jinsha river system located in the upper reaches of the Yangtze river. The process of rock weathering and the influence of carbon sinks in the Yanggong river basin are not yet fully understood. As a result of climate warming, the considerable increase in water output from the high-altitude area of this basin has accelerated the water cycle there. This will undoubtedly exert a strong influence on rock weathering rates and geochemical cycling processes that occur within the Yanggong river basin. In addition, a large number of coal layers are distributed in this basin, so the sulfuric acid produced by sulfide oxidation or the dissolution of carbonate rocks by sulfuric acid caused by human activities would also alter rock weathering rates in this basin. For this reason, it is necessary for us to do more research in order to quantify the effect of exogenous acids on rock weathering as well as on the carbon source and sink in the Yanggong river basin.In this study, water samples from main streams and major tributaries of the Yanggong river were collected during the dry and rainy seasons of 2023. The major concentrations of anion and cation, metasilicic acid, and total dissolved solids (TDS) in these water samples were examined. Additionally, different types of rock weathering in the Yanggong river basin were analyzed by the water chemical equilibrium method and the Galy estimation model. Finally, the amount of carbon dioxide that was consumed by rock weathering under the combined effect of carbonic acid and sulfuric acid was estimated. The findings indicated that the ionic compositions of the water system in the Yanggong river basin were mostly derived from the weathering of silicate and carbonate rocks, and the hydrochemical types were either the HCO₃-Ca type or the HCO₃-Ca·Mg type. Sulfuric acid and carbonic acid worked together to contribute to the process of rock weathering in this basin. The atmospheric CO₂ consumption of rock weathering in this basin was 38.35 t CO₂·km⁻²·a⁻¹ when sulfuric acid was not taken into consideration. However, when sulfuric acid participation was taken into consideration, the carbon sink of rock weathering was reduced to 25.54 t CO₂·km⁻²·a⁻¹, with a reduction of approximate 33%, which significantly improved the accuracy of the calculation. The atmospheric CO₂ flux consumed by carbonatite weathering contributed 95.5% of the total, which indicated dominance of the atmospheric CO₂ flux consumed by carbonatite weathering in the Yanggong river basin. The quantity of atmospheric CO₂ consumed by rock weathering in the Yanggong river basin is 4.27×10⁴ t CO₂·a⁻¹, suggesting a process of carbon sink. That sulfuric acid participated in the process of rock weathering in the river basin changed the regional carbon cycle is a significant link that cannot be overlooked in the model of the global carbon cycle. Meanwhile, in studies on the carbon source/sink effect of rock weathering in the river basin, it was essential for us to consider the regional geological background, particularly the types of minerals rich in sulfides.
- rock weathering /
- carbon sink effect /
- sulfuric acid /
- carbonic acid

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图 1 漾弓江流域及取样点图

Figure 1. Water system and sampling points in the Yanggong river basin

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图 2 漾弓江流域水体阴阳离子平衡图

Figure 2. Water anion and cation equilibrium in Yanggong river basin

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图 3 漾弓江流域水化学组成 Piper 三线图

Figure 3. Piper diagram of the hydrochemical compositions of the Yanggong river basin

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图 4 漾弓江采样点处河水Gibbs图 a：Cl⁻/（Cl⁻+${\rm{HCO}}_3^{-}$）与TDS的关系；b：Na⁺/（Na⁺+Ca²⁺）与TDS的关系

Figure 4. Gibbs plot of river water at the sampling points. a: the relationship between Cl⁻/(Cl⁻+${\rm{HCO}}_3^{-}$) and TDS. b: the relationship between Na⁺/(Na⁺+Ca²⁺) and TDS

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图 5 漾弓江水点中${\rm{HCO}}_3^{-}$/Na⁺与Ca²⁺/Na⁺的关系图

Figure 5. Relationship between [${\rm{HCO}}_3^{-}$/Na⁺] and [Ca²⁺/Na⁺] in the water points of Yanggong river

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图 6 硫酸参与漾弓江流域岩石风化的证据 a：(Ca²⁺+Mg²⁺)/${\rm{HCO}}_3^{-}$化学当量浓度的变化关系；b：(Ca²⁺+Mg²⁺)/(${\rm{HCO}}_3^{-}$+${\rm{SO}}_4^{2-}$)化学当量浓度的变化关系

Figure 6. Participation of sulfuric acid in the rock weathering. a: relationship between changes in chemical equivalent concentrations of [(Ca²⁺+Mg²⁺)/${\rm{HCO}}_3^{-}$]. b: relationship between changes in chemical equivalent concentrations of [(Ca²⁺+Mg²⁺)/(${\rm{HCO}}_3^{-}$+${\rm{SO}}_4^{2-}$)]

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图 7 水点[${\rm{SO}}_4^{2-}$/${\rm{HCO}}_3^{-}$]与[Ca²⁺+Mg²⁺]/[${\rm{HCO}}_3^{-}$]当量比关系图

Figure 7. Equivalence ratios between [${\rm{SO}}_4^{2-}$/${\rm{HCO}}_3^{-}$] and [[Ca²⁺+Mg²⁺]/[${\rm{HCO}}_3^{-}$]

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图 8 δ¹³C_DIC与${\rm{SO}}_4^{2-}$/${\rm{HCO}}_3^{-}$（摩尔比）关系

Figure 8. Relationship between δ¹³C_DIC and [${\rm{SO}}_4^{2-}$/${\rm{HCO}}_3^{-}$]

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表 1 漾弓江流域水体离子化学组成（雨季和旱季平均值）

Table 1. Ionic chemical compositions of water in the Yanggong river basin (averages of rainy and dry seasons)

名称	性质	pH	Ca²⁺	Mg²⁺	Na⁺	K⁺	${\rm{HCO}}_3^{-}$	${\rm{SO}}_4^{2-}$	Cl⁻	${\rm{NO}}_3^{-}$	TDS	H₂SiO₃	TZ⁺	TZ⁻
名称	性质	pH	mmol·L⁻¹								mg·L⁻¹
YGS1	支流	8.27	2.27	2.77	3.90	0.45	6.04	0.06	0.03	0.03	980.50	23.55	14.44	7.38
YGS2	支流	8.09	1.17	0.35	0.12	0.01	2.74	0.11	0.03	0.03	148.00	31.10	3.16	3.03
YGS3	干流	7.59	1.61	0.67	1.05	0.19	4.34	0.34	0.97	0.30	319.50	13.65	5.82	6.29
YGS4	支流	8.34	0.95	0.36	0.06	0.03	2.44	0.08	0.10	0.03	150.00	10.70	2.71	2.72
YGS5	支流	8.40	0.86	0.43	0.04	0.01	2.34	0.04	0.02	0.00	264.00	6.66	2.63	2.44
YGS6	泉水	8.81	0.69	0.46	0.05	0.01	2.05	0.04	0.03	0.01	129.00	5.20	2.35	2.18
YGS7	暗河出口	7.85	0.80	0.56	0.02	0.02	2.52	0.04	0.01	0.01	181.50	6.62	2.74	2.62
YGS8	泉水	8.28	0.97	0.58	0.19	0.04	3.18	0.17	0.02	0.01	185.00	3.84	3.34	3.55
YGS9	泉水	7.75	1.10	0.42	0.05	0.02	2.86	0.04	0.01	0.00	149.00	9.22	3.11	2.95
YGS10	干流	7.86	1.14	0.62	0.40	0.09	3.08	0.22	0.45	0.11	219.00	5.17	4.01	4.09
YGS11	总出口	8.47	1.37	0.79	0.39	0.09	3.60	0.33	0.42	0.11	336.00	9.32	4.79	4.79
YGS12	泉水	8.70	1.44	0.81	0.31	0.05	2.93	0.49	0.27	0.07	251.00	39.90	4.86	4.25
YGS13	支流	8.37	1.58	0.97	0.46	0.15	3.82	0.50	0.54	0.12	341.50	11.45	5.72	5.49
YGS14	泉水	8.85	0.42	0.50	0.02	0.01	1.47	0.05	0.03	0.00	160.00	1.65	1.86	1.59
YGS15	支流	8.22	1.17	0.46	0.09	0.03	2.34	0.55	0.03	0.02	207.00	12.55	3.38	3.49

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表 2 漾弓江流域碳汇通量估算

Table 2. Estimation of carbon flux in the Yanggong river basin

名称	流量	流域面积	${\rm{HCO}}_3^{-}$ 通量	硅酸盐岩风化		碳酸盐岩风化			岩石风化速率	碳通量合计
	流量	流域面积	${\rm{HCO}}_3^{-}$ 通量	溶蚀速率	碳酸溶蚀硅酸盐岩 CO₂消耗	溶蚀速率	碳酸溶蚀碳酸盐岩 CO₂消耗量	碳酸和硫酸溶蚀碳酸盐岩 CO₂消耗量	岩石风化速率	碳通量合计
	10⁸ m³·a⁻¹	km²	t CO₂·km⁻²·a⁻¹	mm·ka⁻¹	t CO₂ ·km⁻²·a⁻¹	mm·ka⁻¹	t CO₂·km⁻²·a⁻¹	t CO₂ ·km⁻²·a⁻¹	mm·ka⁻¹	t CO₂·km⁻²·a⁻¹	t CO₂ ·a⁻¹
木家桥	1.81	820	37.32	2.30	4.31	19.86	18.38	14.62	22.16	18.93	15 528.92
金河断面	7.60	1 670	59.49	4.41	1.15	24.40	33.94	24.39	39.26	25.54	42 667.04

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