方解石在不同水环境中的溶解与沉淀作用

马诚佑; 康志强; 张立浩; 玄惠灵; 农培杰; 潘树芬; 孔琪琪; 朱义年; 朱宗强

doi:10.11932/karst20230102

方解石在不同水环境中的溶解与沉淀作用

doi: 10.11932/karst20230102

1.
桂林理工大学地球科学学院, 广西桂林 541006
2.
桂林理工大学广西环境污染控制理论与技术重点实验室, 广西桂林 541006
3.
桂林理工大学环境科学与工程学院, 广西桂林 541006

基金项目: 国家自然科学基金项目（42063003；41763012）；广西自然科学基金项目（2018GXNSFAA050044）

详细信息

作者简介:
马诚佑（1994－），男，硕士研究生，研究方向为岩溶区环境地球化学。E-mail：machengyou2022@163.com

通讯作者:
朱宗强（1982－），男，博士，教授，研究方向为岩溶区重金属污染土壤修复。E-mail：zhuzongqiang@glut.edu.cn

中图分类号: P642.25
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出版历程
- 收稿日期: 2021-12-11
- 刊出日期: 2023-02-25

Dissolution and precipitation of calcite in different water environments

1.
College of Earth Sciences, Guilin University of Technology, Guilin, Guangxi 541006, China
2.
Guangxi Key Laboratory of Environmental Pollution Control Theory and Technology, Guilin University of Technology, Guilin, Guangxi 541006, China
3.
College of Environmental Science and Engineering, Guilin University of Technology, Guilin, Guangxi 541006, China

摘要

摘要: 方解石的溶解与沉淀是各种岩溶地质作用的基础，但对其在不同水环境条件下的溶解过程和溶解度有待深入研究。文章通过实验研究了天然方解石（CaCO₃）在不同水环境中的溶解作用。结果表明，方解石在纯净水、空气饱和水、CO₂饱和水、初始pH=3的溶液和初始pH=9的溶液中溶解时，Ca浓度随着溶解时间的增加呈现缓慢升高并趋于稳定，在溶解4 080 h后达到0.444 4~0.469 6 mmol·L⁻¹、0.402 0~0.415 4 mmol·L⁻¹、0.573 9~0.659 7 mmol·L⁻¹、1.098 1 mmol·L⁻¹和0.448 9 mmol·L⁻¹；方解石（CaCO₃）在纯净水中溶解时溶度积（K_sp）为10^{−8.48±0.08}~10^{−8.48±0.13}，吉布斯生成自由能ΔG_f˚[CaCO₃]为−1 129.82±0.51~−1 129.87±0.76 kJ·mol⁻¹。在天然水中溶解时，桂林漓江水中Ca和Mg的浓度在达到饱和状态后呈现下降趋势；广西北海海水相对于碳酸盐矿物处于饱和或过饱和状态；桂林雁山和丫吉地下水相对于方解石、文石和白云石处于饱和或过饱和状态。研究结果进一步证明了水环境对方解石溶解的显著影响，研究结果可为岩溶地质作用的地球化学模拟提供参考。
- 方解石 /
- 溶解作用 /
- 溶度积 /
- 吉布斯生成自由能
Abstract: Dissolution and precipitation of calcite are the basis of various karst geological processes, but the dissolution process and solubility of calcite under different water environmental conditions need to be further studied. In this paper, the dissolution of natural calcite (CaCO₃) was studied in different types of water at room temperature. The analysis of chemical composition and the characterization of X-Ray Diffraction (XRD) and Scanning Electron Microscope (SEM) showed that when calcite respectively dissolved in pure water, air-saturated water, CO₂-saturated water, the HCl solution of initial pH=3 and the NaOH solution of initial pH=9, both of its chemical composition and crystal structure did not change significantly; the aqueous Ca concentrations increased with time and attained an equilibrium or steady state, respectively reaching the values of 0.4444-0.4696 mmol·L⁻¹, 0.4020-0.4154 mmol·L⁻¹, 0.5739-0.6597 mmol·L⁻¹, 1.0981 mmol·L⁻¹ and 0.4489 mmol·L⁻¹, 4,080 hours after dissolution. For the dissolution of calcite in pure water, air-saturated water, CO₂-saturated water and the HCl solution of initial pH=3, the pH values increased with time and reached 8.06-8.40 at the end of test. For the dissolution in the NaOH solution of initial pH=9, the pH values increased rapidly to 9.71 with time, and then decreased slowly to an equilibrium or stable state around 8.31. The calculation results with the PHREEQC software indicated that after the dissolution in pure water, air-saturated water, CO₂-saturated water, the HCl solution of initial pH=3 and the NaOH solution of initial pH=9 for 2,640−4,080 hours, the aqueous solutions were undersaturated with all the possible minerals and did not precipitate to form aragonite (Saturation Index, SI=−0.09-−0.30), dolomite (SI=−2.03-−3.79), magnesite (SI=−3.00-−4.77) and other carbonate minerals. The solubility product (K_sp) and the Gibbs free energy of formation (ΔG_f˚) for calcite (CaCO₃) were estimated from the dissolution in pure water to be 10^{−8.48±0.08}−10^-8.48±0.13 and 1,129.82±0.51-−1,129.87±0.76 kJ·mol⁻¹, respectively. The solubility product (K_sp) of calcite (10^−8.48) is higher than that of rhodochrosite (10^−10.58), otavite (10⁻¹²), spherocobaltite (10^−9.98) and smithsonite (10⁻¹⁰), indicating that the carbonate precipitation method can be applied to fix heavy metals such as Mn, Cd, Co and Zn in soils and waters, which can effectively reduce their mobility and bioavailability in the environment. After dissolution in the seawater collected from Guangxi Beihai and the groundwater from Guilin Yanshan for 4,080 hours, the surface scanning analysis of Energy Dispersive Spectrometer (EDS) showed that calcite samples contained the components of (Ca_0.96Mg_0.06) CO₃ and (Ca_0.99Mg_0.01) CO₃, respectively. The slight increase in Mg content was related to the higher Mg concentration in the seawater (1,056 mg·L⁻¹) and the groundwater (6.70 mg·L⁻¹). In general, after 4,080 hours of dissolution, the pH variation in different types of natural water was listed in the order of river water (10.31) > seawater (8.80) > groundwater (8.03-8.28); the variation of Ca concentrations in different types of natural water was listed in the order of seawater > groundwater > river water; the variation of the total concentrations of HCO₃+CO₃ was in the order of groundwater > seawater > river water. For the dissolution in natural water, Ca and Mg concentrations in the river water collected from Guilin Lijiang River initially increased to a steady state and then decreased; the SI values of calcite, aragonite and dolomite increased slowly with time, and attained a saturated or oversaturated state after 1,680-hour, 1,920-hour and 2,160-hour, respectively. Thedecrease in Ca and Mg concentrations of the river water indicated that the precipitation of calcite, aragonite and dolomite might occur. For the dissolution in the seawater collected from Guangxi Beihai, the seawater was always saturated or oversaturated with calcite, aragonite, dolomite and magnesite, and the SI values decreased slowly at the beginning and then increased slowly after 720 hours, and finally repectively reached 0.84-1.06, 0.65-0.88, 2.40-2.95 and 0.60-0.76 after 2,640 hours. For the dissolution in the groundwater collected from Guilin Yanshan, the groundwater was always oversaturated or saturated with calcite and aragonite, while it was always saturated or undersaturated with dolomite and magnesite. The SI values decreased slowly at the beginning, then increased slowly after 720 hours, and finally reached 0.14-0.22, −0.06-0.02, −0.25-−0.03 and −1.36-−1.26, respectively after 2,640 hours. For the dissolution in the groundwater collected from Guilin Yaji, the groundwater was always oversaturated or saturated with calcite and aragonite, while it was always saturated or undersaturated with dolomite and magnesite. The SI values decreased slowly at the beginning and then increased slowly after 12 to 48 hours, but decreased slightly once again to a steady state after 480 hours and respectively reached 0.20-0.35, 0.02-0.15, −0.17-−0.04 and −1.50-−1.32 after 2,640 hours. The results further illustrate the significant influence of the water environment on calcite dissolution and can provide a reference for the geochemical simulation of karst geological processes.
- calcite /
- dissolution /
- solubility product /
- Gibbs free energy of formation

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图 1 方解石在不同水溶液中溶解前和溶解4080 h后的XRD图谱

Figure 1. XRD patterns of calcite before and after dissolution in different types of water for 4,080 h

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图 2 方解石在不同水溶液中溶解前和溶解4 080 h后的扫描电镜图

Figure 2. SEM images‎ of calcite before and after dissolution in different types of water for 4,080 h

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图 3 方解石在不同水溶液中溶解时液相的变化

Figure 3. Aqueous variation during the dissolution of calcite in different types of water

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图 4 方解石在天然水中溶解时Ca和Mg浓度与碳酸盐矿物饱和指数的关系

Figure 4. Relation between Ca and Mg concentrations and saturation indexes of carbonate minerals during the dissolution of calcite in types of natural water

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表 1 地表水和地下水的理化特性

Table 1. Physicochemical characteristics of surface water and groundwater

样品	pH	EC / μs·cm⁻¹	浓度 / mg·L⁻¹
样品	pH	EC / μs·cm⁻¹	Ca	Mg	Mn	Fe	Na	K	${\rm{HCO}}_3^{-}$+${\rm{CO}}_3^{2-}$	Cl⁻	${\rm{NO}}_3^{-}$	${\rm{SO}}_4^{2-}$
漓江水	7.49	134.9	20.37	1.52	−	0.05	2.60	1.29	57.81	3.92	4.76	10.29
北海海水	7.94	41 700	340.4	1 056	0.20	−	6 509	222	119.59	1478	−	2 114
雁山地下水	7.63	365	67.22	6.70	0.01	−	2.56	0.40	227.18	4.88	5.53	17.64
丫吉地下水	7.86	335	61.87	3.50	0.01	0.03	1.44	3.26	200.04	3.28	3.90	12.51

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表 2 方解石（CaCO₃）在不同水环境中的溶解（25 ℃）

Table 2. Dissolution of calcite (CaCO₃) in different types of water at 25 ℃

样品号	溶解时间 / h	pH	浓度 / mmol·L⁻¹		log_IAP (≈log_K_sp)	log_IAP平均值	ΔG_f° / kJ·mol⁻¹	ΔG_f°平均值 / kJ·mol⁻¹
样品号	溶解时间 / h	pH	Ca	HCO₃+CO₃	log_IAP (≈log_K_sp)	log_IAP平均值	ΔG_f° / kJ·mol⁻¹	ΔG_f°平均值 / kJ·mol⁻¹
纯净水1	2 640	8.64	0.452 1	0.640 0	−8.42	−8.48	−1 129.52	−1 129.82
	3 360	8.51	0.457 4	0.818 6	−8.44	±0.08	−1 129.60	±0.51
	4 080	8.30	0.469 6	0.851 0	−8.56		−1 130.33
纯净水2	2 640	8.68	0.425 9	0.736 7	−8.35	−8.48	−1 129.11	−1 129.87
	3 360	8.50	0.426 7	0.761 8	−8.50	±0.13	−1 129.96	±0.76
	4 080	8.31	0.444 4	0.798 6	−8.60		−1 130.53
空气饱和水1	2 640	8.38	0.380 5	0.712 7	−8.39	−8.47	−1 129.31	−1 129.78
	3 360	8.27	0.407 0	0.737 3	−8.48	±0.08	−1 129.86	±0.47
	4 080	8.17	0.415 4	0.734 6	−8.54		−1 130.18
空气饱和水2	2 640	8.23	0.352 8	0.681 5	−8.41	−8.46	−1 129.45	−1 129.74
	3 360	8.16	0.388 2	0.684 5	−8.46	±0.05	−1 129.73	±0.30
	4 080	8.08	0.402 0	0.714 2	−8.51		−1 130.04
CO₂饱和水1	2 640	8.68	0.568 1	1.037 3	−8.41	−8.50	−1 129.44	−1129.94
	3 360	8.56	0.583 4	1.020 8	−8.48	±0.10	−1 129.82	±0.61
	4 080	8.37	0.573 9	1.014 6	−8.60		−1 130.55
CO₂饱和水2	2 640	8.74	0.661 7	1.208 9	−8.40	−8.51	−1 129.40	−1 130.03
	3 360	8.55	0.681 4	1.217 1	−8.53	±0.11	−1 130.15	±0.63
	4 080	8.40	0.659 7	1.173 3	−8.60		−1 130.53
pH=3溶液	2 640	8.25	1.107 3	0.805 6	−8.37	−8.46	−1 129.23	−1 129.74
	3 360	8.11	1.103 3	0.796 9	−8.50	±0.09	−1 129.98	±0.51
	4 080	8.06	1.098 1	0.797 0	−8.51		−1 130.01
pH=9溶液	2 640	8.70	0.404 7	0.785 5	−8.33	−8.46	−1 128.99	−1 129.73
	3 360	8.51	0.438 9	0.797 3	−8.46	±0.13	−1 129.75	±0.74
	4 080	8.31	0.4489	0.830 5	−8.58		−1 130.43
桂林漓江水	2 640	8.73	0.459 1	0.783 8	−7.90	−7.81
	3 360	8.59	0.263 7	0.423 0	−7.95	±0.22
	4 080	8.80	0.236 0	0.427 9	−7.59
广西北海海水	2 640	9.12	8.759 2	1.7307	−7.45	−7.50
	3 360	9.62	8.6831	1.5843	−7.61	±0.11
	4 080	10.31	8.679 3	1.467 3	−7.43
雁山校区地下水	2 640	8.05	1.004 8	2.085 0	−8.23	−8.28
	3 360	8.01	0.964 1	1.886 9	−8.31	±0.05
	4 080	8.03	0.886 8	1.774 7	−8.30
桂林丫吉地下水	2 640	8.35	0.809 7	1.668 4	−8.10	−8.19
	3 360	8.32	0.747 5	1.498 8	−8.19	±0.09
	4 080	8.28	0.663 2	1.324 9	−8.28

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