碳酸盐岩水热协同混合溶蚀作用机理的数值试验研究

侯文隽; 龚星; 刘锋; 李红中

doi:10.11932/karst20230411

碳酸盐岩水热协同混合溶蚀作用机理的数值试验研究

doi: 10.11932/karst20230411

侯文隽^{1, 2,},
龚星^{1, 2, ,},
刘锋¹,
李红中³

1.
广东工业大学土木与交通工程学院, 广东广州 510006
2.
中国地质科学院岩溶地质研究/自然资源部、广西岩溶动力学重点实验室, 广西桂林 541004
3.
广东省交通规划设计研究院集团股份有限公司, 广东广州 510507

基金项目: 国家自然科学基金—青年科学基金项目（42002249）；自然资源部/广西岩溶动力学重点实验室开放课题基金项目（KDL201802）；国家重点研发项目（2017YFB0903703）；广东省重点领域研发计划项目（2019B110207001）

详细信息

作者简介:
侯文隽（1994－），男，博士研究生，主要从事环境岩土与水文地质。E-mail：111909003@mail2.gdut.edu.cn

通讯作者:
龚星（1987－），女，博士，讲师，主要从事水文环境地质环境研究。E-mail：xing_g@gdut.edu.cn

中图分类号: P641.3
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出版历程
- 收稿日期: 2021-08-12
- 修回日期: 2021-10-14
- 刊出日期: 2023-11-28

Numerical experiment on the mechanism of mixing corrosion of carbonate rocks by hydrothermal synergistic effect

HOU Wenjuan^{1, 2
,},
GONG Xing^{1, 2
, ,},
LIU Feng¹,
LI Hongzhong³

1.
School of Civil and Transportation Engineering, Guangdong University of Technology, Guangzhou, Guangdong 51006, China
2.
Institute of Karst Geology, CAGS/Key Laboratory of Karst Dynamic, MNR & GZAR, Guilin, Guangxi 541004, China
3.
Guangdong Communication Planning & Design Institute Group Co., Ltd, Guangzhou, Guangdong 510507, China

摘要

摘要: 在封闭岩溶水系统中，当水化学组分或温度不同的饱和地下水发生混合时，将增加地下水的碳酸盐矿物溶解度，产生新的溶蚀能力。为了揭示常见地下水混合情况下的饱和溶液混合溶蚀和温度混合溶蚀协同作用机理，文章采用水文地球化学软件PHREEQC模拟了土壤入渗水与浅层地下水、深循环热水与浅层地下水、深部流体与浅层地下水混合条件下的碳酸钙溶蚀反应，讨论了地下水温度、二氧化碳分压（$ {P}_{{\text{CO}}_{\text{2}}} $）以及端元溶液混合比例对水热协同混合溶蚀作用强度的影响。研究结果表明：天然地下水混合条件下的水热协同混合溶蚀作用能够增加已经饱和地下水的溶蚀能力，混合溶液补充溶蚀能力由强到弱依次为：深部流体与浅层地下水混合，深循环热水与浅层地下水混合，土壤入渗水与浅层地下水混合；在土壤入渗水与浅层地下水混合、深循环热水与浅层地下水混合情况下，水热协同混合溶蚀作用以饱和溶液混合溶蚀作用为主，温度混合溶蚀作用为辅，在深部流体与浅层地下水混合条件下，虽然温度变化会使得饱和溶液析出碳酸钙沉淀，但混合溶液整体上仍表现为较强的侵蚀性。岩溶水系统中的水热协同混合溶蚀作用强度受温度和$ {P}_{{\text{CO}}_{\text{2}}} $变化同步控制，端元溶液温度和$ {P}_{{\text{CO}}_{\text{2}}} $差异越大，其水热协同混合溶蚀能力越强，端元溶液混合比例接近时，最有利于碳酸钙溶解。研究成果揭示饱和溶液溶蚀和温度混合溶蚀的协同作用机理，能够为碳酸盐岩地区水、地热、油气资源储存空间勘探提供理论依据。
- 碳酸盐岩 /
- 地下水混合 /
- 温度 /
- 二氧化碳分压 /
- 混合比例
Abstract: Karst water systems can be divided into open systems and closed systems. In the open system, mixed groundwater dissolves carbonate minerals mainly by the unsaturated corrosion. However, in the closed system, groundwater has been saturated with carbonate minerals after long-term runoff flow. When saturated groundwater with different hydrochemical components or at different temperatures mixed, the solubility of carbonate minerals in groundwater increases, and new corrosion capacity of groundwater generates. The mixing corrosion of saturated solution and temperature mixing corrosion are important dynamics for the chemical dissolution of carbonate aquifer system. The existing research about the interaction mechanism of mixing corrosion of carbonate rocks mainly focuses on the mixing corrosion of single saturated solution or temperature mixing corrosion, and the mechanism of hydrothermal synergistic dissolution in different groundwater mixing situations needs to be further studied. In order to reveal the synergistic mechanism between mixing corrosion of saturated solution and temperature mixing corrosion, this study uses hydro-geochemistry software PHREEQC to simulate the dissolution of calcium carbonate under static mixing conditions of groundwater, including the mixing of infiltrated soil water and shallow groundwater, the mixing of deep-flowing geothermal groundwater and shallow groundwater, and the mixing of deep fluid and shallow groundwater. Moreover, the impact of temperatures, $ {P}_{{\text{CO}}_{\text{2}}} $ of different end-member groundwater and the mixing ratios of end-member water on the intensity of mixing corrosion by hydrothermal synergistic effect is discussed here. The results show, (1) The mixing corrosion by hydrothermal synergistic effect can enhance the supplementary corrosion capacity of saturated groundwater which descends in order as the mixing of deep fluid and shallow groundwater, the mixing of deep-flowing geothermal water and shallow groundwater, and the mixing of infiltrated soil water and shallow groundwater. (2) When the mixing of infiltrated soil water and shallow groundwater occurs, the mixing corrosion capacity by hydrothermal synergistic effect is lower than that of mixing corrosion of single saturated solution, but higher than that of single temperature mixing corrosion. The main reason is that the change of solution temperature weakens the complementary corrosion capacity of mixed solution. (3) Under the condition of mixing deep-flowing geothermal groundwater and shallow groundwater, the mixing corrosion of saturated solution in deep-flowing geothermal groundwater has more effects on the hydrothermal synergistic corrosion than the temperature mixing corrosion. (4) When the deep fluid mixes with the shallow groundwater, the corrosion capacity of mixed solution is weaker than that of the mixing corrosion of saturated solution at single low-temperature, but stronger than that of mixing corrosion at single high-temperature. Although the change of temperature in the mixture causes the calcium carbonate precipitation, the mixing corrosion by hydrothermal synergistic effect still dissolves calcium carbonate. (5) The intensity of mixing corrosion by hydrothermal synergistic effect in the karst water system is controlled synchronously by the change of temperature and $ {P}_{{\text{CO}}_{\text{2}}} $ of mixing solutions. The variation law of mixing corrosion capacity cannot be judged by the effect of mixing corrosion of single saturated solution or temperature mixing corrosion. (6) The greater differences in temperature and $ {P}_{{\text{CO}}_{\text{2}}} $ between two end-member solutions lead to higher dissolution capacity of mixing corrosion by hydrothermal synergistic effect. The dissolution of calcium carbonate is the largest when the mixing ratios of end-member solutions are similar, and the dissolution decreases with the increase of mixing ratio differences of end-member solutions, which shows that the full mixing of natural groundwater is conducive to the mixing corrosion by hydrothermal synergistic effect. The study results provide a theoretical basis for the mixing corrosion mechanism and regulation of carbonate rocks dissolution under groundwater seepage conditions, and further enrich the theoretical research on karst development mechanism.
- carbonate rock /
- groundwater mixing /
- temperature /
- partial pressure of carbon dioxide /
- mixing ratio

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图 1 常见地下水混合情况的地质模型示意图

Figure 1. Geological model of common conditions of groundwater mixing

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图 2 场景1模拟结果

Figure 2. Simulation results of situation 1

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图 3 场景2模拟结果

Figure 3. Simulation results of situation 2

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图 4 场景3模拟结果

Figure 4. Simulation results of situation 3

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图 5 常见地下水混合场景中模式I、I′、Ⅲ的碳酸钙补充溶蚀量计算结果示意图（a为场景1、b为场景2、c为场景3，空心圆和三角表示混合溶液Ca²⁺实际含量，实心圆和三角表示混合溶液Ca²⁺平衡含量）

Figure 5. Calculation results of supplemental dissolution of calcium carbonate in model I, I′ and Ⅲ in common situations of groundwater mixing (Fig. a for situation 1, Fig. b for situation 2 and Fig. c for situation 3). Hollow circles and triangles represent actual Ca²⁺ content in the mixed solution; solid circles and triangles represent the equilibrium Ca²⁺ content of the mixed solution.)

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表 1 碳酸钙混合溶蚀端元溶液热化学参数

Table 1. Thermochemical parameters of mixing corrosion of end-member solution of calcium carbonate

溶液编号	溶液类型	温度/(℃)		$ {P}_{{\text{CO}}_{\text{2}}} $/(×10⁴ Pa)		SI_c
溶液编号	溶液类型	文献取值	试验值	文献取值	试验值	文献取值	试验值
1	浅层地下水	多年平均气温^[26]	20	0.05~0.19^[27]	0.1	−0.19~0.15^[27]	0
2	土壤入渗水	略高于地下水^[28]	22	0.05~0.4^[29]	0.2	−1.96~1.21^[29]	0
3	深循环热水	32~136^{[19, 20]}	50	0.05~0.6^[19]	0.5	0.10~0.18^[19]	0
4	深部流体	42~185^[30]	90	2.6~7.2^[25]	5	−0.2~0.66^[25]	0
注：SI_c为溶液中CaCO₃饱和指数。 Note: SI_c is the saturation index of CaCO₃ in solution

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表 2 碳酸钙水热协同混合溶蚀作用数值试验方案

Table 2. Numerical test scheme of mixing corrosion of calcium carbonate by hydrothermal synergistic effect

模式		温度	$ {P}_{{\text{CO}}_{\text{2}}} $
饱和溶液混合溶蚀作用（T_A=T_B，P_A≠P_B）	Ⅰ	T_A=T_B=T₁	P_A=P₁ P_B=P₂、P₃、P₄
饱和溶液混合溶蚀作用（T_A=T_B，P_A≠P_B）	Ⅰ′	T_A=T_B=T₂、T₃、T₄	P_A=P₁ P_B=P₂、P₃、P₄
温度混合溶蚀作用（T_A≠T_B，P_A=P_B）	Ⅱ	T_A=T₁ T_B=T₂、T₃、T₄	P_A=P_B=P₁
温度混合溶蚀作用（T_A≠T_B，P_A=P_B）	Ⅱ′	T_A=T₁ T_B=T₂、T₃、T₄	P_A=P_B=P₂、P₃、P₄
饱和溶液混合溶蚀和温度混合溶蚀协同作用（T_A≠T_B，P_A≠P_B）	Ⅲ	T_A=T₁ T_B=T₂、T₃、T₄	P_A=P₁ P_B=P₂、P₃、P₄
注：T表示温度，P表示$ {P}_{{\text{CO}}_{\text{2}}} $，下标A、B表示混合条件下的两种端元溶液，下标1、2、3、4分别对应表1中对应编号的溶液。 Note: T represents temperature, P represents $ {P}_{{\text{CO}}_{\text{2}}} $. Subscripts of A and B stand for two end-member solutions in mixing situations. Subscripts of 1, 2, 3 and 4 correspond to the corresponding numbered solutions in Tab. 1.

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