Influence of lead and zinc on geological carbon sink under oxygen-rich conditions

doi:10.13745/j.esf.sf.2024.2.12

Abstract

Abstract:

Since the Industrial Revolution, the increasing demand for resources has led to the overexploitation of mineral resources, resulting in a series of geological and environmental problems. Research in mining has primarily focused on geological and environmental hazards, mine restoration technologies, and the health hazards posed by heavy metals exposure. However, few scholars have studied the relationship between heavy metals and geological carbon sinks. With the “dual-carbon” goal becoming a national strategy, research on the mechanisms of heavy metals and geological carbon sinks has significant scientific importance. This study investigates the influence of lead and zinc on geological carbon sinks under open system conditions by examining the dissolution characteristics of different rock samples in various concentrations of lead and zinc solutions. The findings are as follows: (1) With increasing experimental time, the pH value of all groups showed a decreasing trend, while the conductivity showed an increasing trend. (2) A 0.5 mg/L lead solution may inhibit rock dissolution, as the $\mathrm{HCO}_{3}^{-}$ concentration initially increased significantly on the 10th day before gradually decreasing. When lead-zinc ore powder from the Lingchuan County lead-zinc mine was added, the $\mathrm{HCO}_{3}^{-}$ concentration in the solution doubled. Data showed that the $\mathrm{HCO}_{3}^{-}$ concentration in the 0.1 mg/L lead solution with added lead-zinc ore powder was significantly lower than in the control group without the ore powder. This suggests that Pb²⁺ may act as an inhibitor, affecting the dissolution of rock samples in the solution. (3) In the 1 mg/L and 5 mg/L zinc solutions with added lead-zinc ore powder, the $\mathrm{HCO}_{3}^{-}$ concentrations in the limestone, hornfels, and limestone+hornfels groups were significantly higher than in the control groups without the ore powder, indicating that zinc may act as a catalyst. (4) Scanning non-in situ SEM images of the dried rock samples revealed that both low and high concentrations of lead solutions increased the number of dissolution pits compared to the lead-free solution. The dissolution steps were also more irregular in high-concentration lead solutions, accompanied by replacement reactions. From low to high concentrations of lead solutions, the development of porosity and the formation of cracks were observed.

Key words: mining, lead and zinc ions, geological carbon sink

CLC Number:

LI Liang, JIANG Zhiwei, WU Bingjin, WEI Dongwen, WANG Wenhai. Influence of lead and zinc on geological carbon sink under oxygen-rich conditions[J]. Earth Science Frontiers, 2024, 31(5): 421-429.

Figures/Tables 11

Fig.1 XRD diffractogram of test hornfels

Fig.2 XRD diffractogram of test limestones

Fig.3 The relationship between HCO 3 - concentration and time of rock samples in deionized water (a: With lead-zinc ore powder; b: Without lead-zinc ore powder)

Fig.4 The relationship between HCO 3 - concentration and time of rock samples in PbCl2 solution (a: 0.1 mg/L, b: 0.5 mg/L) a—0.1 mg/L;b—0.5 mg/L。

Fig.5 Microscopic model of Pb2+ adsorption on the surface of limestone. Adapted from [13]. (1: on the surface; 2: on the step; 3: kink; 4: within the step; 5: within the cavity)

Fig.6 The relationship between HCO 3 - concentration and time of rock samples in ZnCl2 solution (a: 1 mg/L, b: 5 mg/L) a—1 mg/L;b—5 mg/L。

Fig.7 The relationship between HCO 3 - concentration and time of rock samples in ZnCl2 solution (a: 1 mg/L, b: 5 mg/L)

Table 1 Dissolution of HCO 3 - in ore-bearing and non-ore-bearing rock samples in different concentrations of Pb solution

时间	不同浓度Pb溶液各岩样组的 $HCO 3 -$ 浓度/(mg·L^-1)
时间	灰岩+矿0.1 mg/L	角岩+矿0.1 mg/L	灰+角+矿0.1 mg/L	灰岩+矿0.5 mg/L	角岩+矿0.5 mg/L	灰+角+矿0.5 mg/L
第2天	9.58	20.44	39.05	45.76	48.81	58.27
第8天	14.94	32.95	49.42	61.02	75.05	106.17
第14天	21.35	44.84	62.54	78.71	103.73	125.70
时间	不同浓度Pb溶液各岩样组的 $HCO 3 -$ 浓度/(mg·L^-1)
时间	灰岩0.1 mg/L	角岩0.1 mg/L	灰+角0.1 mg/L	灰岩0.5 mg/L	角岩0.5 mg/L	灰+角0.5 mg/L
第2天	34.04	38.71	61.80	0	34.69	33.61
第8天	53.13	64.16	58.55	41.20	47.71	54.21
第14天	75.91	83.74	78.08	57.47	88.91	78.07

Table 1 Dissolution of HCO 3 - in ore-bearing and non-ore-bearing rock samples in different concentrations of Pb solution

时间	不同浓度Pb溶液各岩样组的 $HCO 3 -$ 浓度/(mg·L^-1)
时间	灰岩+矿0.1 mg/L	角岩+矿0.1 mg/L	灰+角+矿0.1 mg/L	灰岩+矿0.5 mg/L	角岩+矿0.5 mg/L	灰+角+矿0.5 mg/L
第2天	9.58	20.44	39.05	45.76	48.81	58.27
第8天	14.94	32.95	49.42	61.02	75.05	106.17
第14天	21.35	44.84	62.54	78.71	103.73	125.70
时间	不同浓度Pb溶液各岩样组的 $HCO 3 -$ 浓度/(mg·L^-1)
时间	灰岩0.1 mg/L	角岩0.1 mg/L	灰+角0.1 mg/L	灰岩0.5 mg/L	角岩0.5 mg/L	灰+角0.5 mg/L
第2天	34.04	38.71	61.80	0	34.69	33.61
第8天	53.13	64.16	58.55	41.20	47.71	54.21
第14天	75.91	83.74	78.08	57.47	88.91	78.07

Table 2 Dissolution of HCO 3 - in ore-bearing and non-ore-bearing rock samples in different concentrations of Zn solution

时间	不同浓度Zn溶液各岩样组的 $HCO 3 -$ 浓度/(mg·L^-1)
时间	灰岩+矿1 mg/L	角岩+矿1 mg/L	灰+角+矿1 mg/L	灰岩+矿5 mg/L	角岩+矿5 mg/L	灰+角+矿5 mg/L
第2天	68.34	76.88	88.47	97.63	110.44	118.37
第8天	120.51	137.60	155.29	176.34	190.38	212.95
第14天	145.53	166.27	188.55	207.16	227.29	248.96
时间	不同浓度Zn溶液各岩样组的 $HCO 3 -$ 浓度/(mg·L^-1)
时间	灰岩1 mg/L	角岩1 mg/L	灰+角1 mg/L	灰岩5 mg/L	角岩5 mg/L	灰+角5 mg/L
第2天	36.86	30.36	41.23	32.53	45.54	28.19
第8天	50.96	60.72	62.94	74.82	49.87	80.24
第14天	70.48	148.98	79.22	66.14	71.56	76.99

Table 2 Dissolution of HCO 3 - in ore-bearing and non-ore-bearing rock samples in different concentrations of Zn solution

时间	不同浓度Zn溶液各岩样组的 $HCO 3 -$ 浓度/(mg·L^-1)
时间	灰岩+矿1 mg/L	角岩+矿1 mg/L	灰+角+矿1 mg/L	灰岩+矿5 mg/L	角岩+矿5 mg/L	灰+角+矿5 mg/L
第2天	68.34	76.88	88.47	97.63	110.44	118.37
第8天	120.51	137.60	155.29	176.34	190.38	212.95
第14天	145.53	166.27	188.55	207.16	227.29	248.96
时间	不同浓度Zn溶液各岩样组的 $HCO 3 -$ 浓度/(mg·L^-1)
时间	灰岩1 mg/L	角岩1 mg/L	灰+角1 mg/L	灰岩5 mg/L	角岩5 mg/L	灰+角5 mg/L
第2天	36.86	30.36	41.23	32.53	45.54	28.19
第8天	50.96	60.72	62.94	74.82	49.87	80.24
第14天	70.48	148.98	79.22	66.14	71.56	76.99

Fig.8 Ex-situ SEM image of rock surface after 14 d dissolution in deionized water

Fig.9 (a) Dissolved in 0.1 mg/L PbCl2 solution for 14 d; (b) Dissolved in 0.5 mg/L PbCl2 solution for 14 d a—0.1 mg/L;b—0.5 mg/L。

References 29

[1]	TANG J, TANG X X, QIN Y M, et al. Karst rocky desertification progress: soil calcium as a possible driving force[J]. Science of the Total Environment, 2019, 649: 1250-1259.
[2]	刘丛强, 蒋颖魁, 陶发祥, 等. 西南喀斯特流域碳酸盐岩的硫酸侵蚀与碳循环[J]. 地球化学, 2008, 37(4): 404-414.
[3]	覃政教, 林玉石, 袁道先, 等. 西南岩溶区矿山与水污染问题探讨及建议[J]. 地球学报, 2012, 33(3): 341-348.
[4]	WANG H, ZHANG H, TANG H Y, et al. Heavy metal pollution characteristics and health risk evaluation of soil around a tungsten-molybdenum mine in Luoyang, China[J]. Environmental Earth Sciences, 2021, 80(7): 293.
[5]	QU S Y, WU W H, NEL W, et al. The behavior of metals/metalloids during natural weathering: a systematic study of the mono-lithological watersheds in the upper Pearl River Basin, China[J]. Science of the Total Environment, 2020, 708: 134572.
[6]	蒋忠诚. 中国南方表层岩溶系统的碳循环及其生态效应[J]. 第四纪研究, 2000, 20(4): 316.
[7]	王建成, 徐志明. 浅谈目前我国矿山地质环境问题与对策建议[J]. 中国新技术新产品, 2012(19): 117.
[8]	杨士海, 王西平. 河南省矿山地质环境问题治理对策研究[J]. 中国国土资源经济, 2013, 26(10): 11-14.
[9]	傅伯杰, 刘国华, 欧阳志云. 中国生态区划研究[M]. 北京: 科学出版社, 2013.
[10]	张进德, 郗富瑞. 我国废弃矿山生态修复研究[J]. 生态学报, 2020, 40(21): 7921-7930.
[11]	周家云, 李发斌, 朱创业. 四川省待复垦矿山分类及复垦对策研究[J]. 金属矿山, 2005(8): 63-66.
[12]	李亮, 曹建华, 黄芬, 等. 铅锌矿开采对河流水环境及地质碳汇的影响[J]. 矿业研究与开发, 2013, 33(3): 89-92.
[13]	LI L, WU B J, GUAN T Y, et al. Divalent lead in aqueous solution changes the surface morphology of dolomite and inhibits dissolution[J]. Water, 2022, 14(19): 2979.
[14]	华磊. 采矿活动对地质碳汇的影响: 以铅锌矿开采为例[J]. 水利科技与经济, 2013, 19(5): 1-4.
[15]	吕小溪, 颜翔琦, 胡晨鹏. 喀斯特关键带的地质碳汇及其影响因素研究进展[J]. 河北民族师范学院学报, 2020, 40(4): 107-115.
[16]	ASTILLEROS J M, FERNÁNDEZ-DÍAZ L, PUTNIS A. The role of magnesium in the growth of calcite: an AFM study[J]. Chemical Geology, 2010, 271(1/2): 52-58.
[17]	STURCHIO N C, CHIARELLO R P, CHENG L, et al. Lead adsorption at the calcite-water interface: synchrotron X-ray standing wave and X-ray reflectivity studies[J]. Geochimica et Cosmochimica Acta, 1997, 61(2): 251-263.
[18]	GODELITSAS A, ASTILLEROS J M, HALLAM K, et al. Interaction of calcium carbonates with lead in aqueous solutions[J]. Environmental Science and Technology, 2003, 37(15): 3351-3360. PMID
[19]	ROUFF A A, ELZINGA E J, REEDER R J, et al. The effect of aging and pH on Pb(II) sorption processes at the calcite-water interface[J]. Environmental Science and Technology, 2006, 40(6): 1792-1798. PMID
[20]	HENRY T H, LIANG Z. Surface Behavior of Calcite upon Uptake of Cd²⁺ and Pb²⁺[J]. Geological Journal of China Universities, 2012, 18(2): 193.
[21]	JURINAK J J, BAUER N. Thermodynamics of zinc adsorption on calcite, dolomite and magnesite-type minerals[J]. Soil Science Society of America Journal, 1956, 20(4): 466-471.
[22]	VALLEE B L, 汤立达. 锌的生物化学、生理学、毒理学及临床病理学[J]. 微量元素, 1988(3): 57-59.
[23]	LIU Z H. Role of carbonic anhydrase as an activator in carbonate rock dissolution and its implication for atmospheric CO₂ sink[J]. Acta Geologica Sinica - English Edition, 2001, 75(3): 275-278.
[24]	PUTNIS A, PUTNIS C V. The mechanism of reequilibration of solids in the presence of a fluid phase[J]. Journal of Solid State Chemistry, 2007, 180(5): 1783-1786.
[25]	PUTNIS A. 3. Mineral replacement reactions[M]//Thermodynamics and kinetics of Water-Rock Interaction. Chantilly, VA: De Gruyter, 2009: 87-124.
[26]	HARLOV D E, WIRTH R, FÖRSTER H J. An experimental study of dissolution-reprecipitation in fluorapatite: fluid infiltration and the formation of monazite[J]. Contributions to Mineralogy and Petrology, 2005, 150(3): 268-286.
[27]	SEYDOUX-GUILLAUME A M, MONTEL J M, BINGEN B, et al. Low-temperature alteration of monazite: fluid mediated coupled dissolution-precipitation, irradiation damage, and disturbance of the U-Pb and Th-Pb chronometers[J]. Chemical Geology, 2012, 330: 140-158.
[28]	TENAILLEAU C, PRING A, ETSCHMANN B, et al. Transformation of pentlandite to violarite under mild hydrothermal conditions[J]. American Mineralogist, 2006, 91(4): 706-709.
[29]	ZHAO J, BRUGGER J, GRUNDLER P V, et al. Mechanism and kinetics of a mineral transformation under hydrothermal conditions: calaverite to metallic gold[J]. American Mineralogist, 2009, 94(11/12): 1541-1555.