热化学硫酸盐还原作用(TSR)与贵州汞(金锑)矿床成因机制再探讨——从黔东锰矿古天然气渗漏沉积成矿理论得到的启示
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摘要
受黔东地区南华纪锰矿的古天然气渗漏成矿理论启示,在研究贵州典型汞矿成矿作用的地球化学机理的基础上,本文将热化学硫酸盐还原反应(TSR)引入成矿过程。提出富含汞(包括气态汞)、还原硫、Cl~-的含矿—运矿流体与含汞围岩相互作用,进一步论证推断深部油气藏的圈闭体系和围岩都可能是汞的重要来源。在较高温度条件下,有油气(烃类)参与的硫酸盐热化学还原作用是还原硫(H_2S、HS~-、S~(2-))的主要来源,而油气(烃类)在成矿作用中发挥了还原剂的重要作用。含矿的热流体(藏)渗漏或者喷溢,同时又溶解流经围岩中以辰砂、单质汞等形式存在的汞,转变为可溶解的汞—硫配合物而运移,在系统从封闭转为开放的构造作用下,气体组分逸失,在还原硫浓度m(S~(2-))降低、Eh升高、pH降低、压力和温度降低以及盐度降低等物理化学条件下成矿。类比研究显示,贵州一些金、锑等金属矿床具有与此类汞矿床类似的成矿机理。故20世纪80年代以来的这类(汞、金、锑)金属矿床的沉积—改造成因及作者提出的相关地球化学机理应当加以适当修正。
The study of sulfate thermochemical reduction reaction(TSR) was introduced into the mineralization process, inspired by the theory of paleo-gas percolation and sedimentary mineralization of the manganese ore in eastern Guizhou, based on the study of the geochemical mechanism of the mineralization of mercury depsides in Guizhou. It is further demonstrated that the source of mercury can be either the trap system of deep reservoirs or the surrounding rocks(such as Qingxudong Formation, which varies with specific deposits). The ore-forming fluid is transported by the ore-transporting fluid which is riched in mercury(including gaseous mercury), sulfur reduction and Cl~-, and also interacts with mercury in the surrounding rocks as the form of cinnabar and elemental mercury. The thermal chemical reduction of oil and gas(hydrocarbons) and sulfate at higher temperatures is the source of reducing sulfur(H_2S, HS~-, S~(2-)). Oil and gas(hydrocarbons) play an important role as reducing agent in mineralization. Due to leakage or spillage of the mineral bearing hot fluid(reservoir), the fluid also dissolves the mercury in the form of cinnabar and elemental mercury at flow through the surrounding rocks, by migration of mercury into soluble mercury—sulfur complexes. Mineralization occurred at geological conditions in the system from closed to open(structure), and gas composition nonvolatile, in m(S~(2-)) reduce elevated, Eh, pH, lower, lower pressure and temperature and salinity decrease such as physical and chemical conditions. The results show that the metallogenic mechanism of gold, antimony and other metal deposits in Guizhou is similar to that of mercury deposit. Therefore, the sedimentation—alteration origin of this kind of(mercury, gold and antimony) metal deposits since 1980 s, especially the geochemical mechanism proposed by the author should be improved.
The study of sulfate thermochemical reduction reaction(TSR) was introduced into the mineralization process, inspired by the theory of paleo-gas percolation and sedimentary mineralization of the manganese ore in eastern Guizhou, based on the study of the geochemical mechanism of the mineralization of mercury depsides in Guizhou. It is further demonstrated that the source of mercury can be either the trap system of deep reservoirs or the surrounding rocks(such as Qingxudong Formation, which varies with specific deposits). The ore-forming fluid is transported by the ore-transporting fluid which is riched in mercury(including gaseous mercury), sulfur reduction and Cl~-, and also interacts with mercury in the surrounding rocks as the form of cinnabar and elemental mercury. The thermal chemical reduction of oil and gas(hydrocarbons) and sulfate at higher temperatures is the source of reducing sulfur(H_2S, HS~-, S~(2-)). Oil and gas(hydrocarbons) play an important role as reducing agent in mineralization. Due to leakage or spillage of the mineral bearing hot fluid(reservoir), the fluid also dissolves the mercury in the form of cinnabar and elemental mercury at flow through the surrounding rocks, by migration of mercury into soluble mercury—sulfur complexes. Mineralization occurred at geological conditions in the system from closed to open(structure), and gas composition nonvolatile, in m(S~(2-)) reduce elevated, Eh, pH, lower, lower pressure and temperature and salinity decrease such as physical and chemical conditions. The results show that the metallogenic mechanism of gold, antimony and other metal deposits in Guizhou is similar to that of mercury deposit. Therefore, the sedimentation—alteration origin of this kind of(mercury, gold and antimony) metal deposits since 1980 s, especially the geochemical mechanism proposed by the author should be improved.
引文
陈履安. 1984.HgS—Cl—H2O体系中汞矿物的稳定场和其溶解类型的优势场的Eh—pH图及其地质意义.地质论评, 30(2):114～125.
陈履安. 1985.从HgS—NaCI—HCl—H2O体系的热力学分析——探讨辰砂以氯汞络合物运移成矿所需的物理化学条件.贵州地质, 2(3): 229～239.
陈履安.1989.碳酸盐建造中汞矿床形成过程中汞的存在形式及重金属分异的热力学分析.贵州地质, 6(2):175～186.
陈履安.1990.试论贵州碳酸盐建造中汞金锑砷成矿作用的地球化学机理.贵州地质, 7(3):196～208.
陈履安.2011.溶解运移与沉淀成矿——成矿作用的化学与地学交叉研究. 贵阳:贵州科技出版社.
丁康乐,李术元,岳长涛,钟宁宁. 2005。 硫酸盐热化学还原反应的研究进展. 石油大学学报(自然科学版), 29(1):150～154.
汞矿地质与普查探勘编写组.1978. 汞矿地质与普查探勘. 北京:地质出版社.
贵州省地质调查院. 2017. 中国区域地质志·贵州卷. 北京:地质出版社: 1067～1068.
何立贤, 曾若兰. 1989. 中国汞矿床. 见: 中国矿床编委会. 中国矿床(上册). 北京:地质出版社: 472～482.
花永丰. 1982. 中国汞矿成因及其找矿预测. 贵阳:贵州人民出版社.
花永丰. 1981. 贵州及其邻区汞矿成因的初步研究. 地质学报, 55(2): 139～148.
姜齐节,刘东升,陈民扬,冯建良,余大良,黄超,曾骥良.1980.论渗流热卤水成矿作用的意义和成因标志(上).地质与勘探, 16(1): 1～6.
林青,傅家谟,刘德汉,盛国英,卢家烂. 1993. 油气演化与一些金矿床成因的关系. 地球化学, 22(3):217～226.
饶纪龙. 1979. 地球化学中的热力学. 北京:科学出版社.
施继锡,余孝颖,王华云. 1995. 古油藏、沥青及沥青包裹体在金属成矿研究中的应用. 矿物学报,15(2):117～122.
沈治安. 1981. 热卤水成矿的水文地球化学机理. 地质论评, 27(3):237～242.
王华云,施继锡. 1997. 贵州丹寨、三都、都匀地区低温成矿系列的成矿物质来源和分异条件. 矿物学报,17(4):497～500.
武蔚文. 1989. 贵州东部若干古油藏的形成和破坏. 贵州地质, 6(1):9～22.
谢小峰,杨坤光,袁良军. 2015. 黔东地区“大塘坡式”锰矿研究现状及进展综述. 贵州地质, 32(3):171～176.
严钧平,王华云, 等. 1989. 贵州汞矿地质. 北京:地质出版社.
曾若兰,等. 1988. 中国汞矿. 成都:四川科学技术出版社.
周琦,杜远生.2012. 古天然气渗漏与锰矿成矿——以黔东地区南华纪“大塘坡式”锰矿为例.北京:地质出版社.
周琦,杜远生,覃英. 2013. 古天然气渗漏沉积型锰矿床成矿系统与成矿模式——以黔湘渝毗邻区南华纪“大塘坡式”锰矿为例. 矿床地质,32(3) :457～466.
周琦,杜远生,等. 2018. 华南古天然气渗漏沉积型锰矿. 北京:科学出版社.
Barnes H L and Czamanske G K. 1967. Solubility and transport of ore minerals: In: Barnes H L. ed. Geochemistry of Hydrothermal Ore Deposits: 1st ed.New York:Holt,Rinehart,and Winston: 334～381.
Barnes H L. 1979. Geochemistry of Hydrothermal Ore Deposits: 2nd ed. New York:Wiley-interscience: 404～454.
Chen L’an. 1984&. The Eh—pH diagram of the stability field of mercury minerals and the predominance field of their soluble species and HgS—Cl-—H2O versus 25～200 ℃ system and their geological significance. Geological Review, 30(2):114～125.
Chen L’an. 1984&. Research on the physical and chemical conditions required for the transporting and ore-forming of cinnabar as mercury as chloride complexes from thermodynamic analysis of the HgS—NaCI—HCl—H2O system. Guizhou Geology,2(3): 229～239.
Chen L’an. 1989&.Thermodynamical analysis of existing forms of mercury and differentiation mercury of heavy metals in the deposits in the formation process of forming of carbonate. Guizhou Geology, 6(2): 175～186.
Chen L’an. 1990&. A discussion on geochemical mechanism of mineralization of Hg,Sb,As and Au in carbonate formation in Guizhou. Guizhou Geology, 7(3): 196～208.
Chen L’an. 2011#. Dissolve—Transport and Sedimentation —Mineralization: Cross-Over Research of Chemistry and Geoscience in Mineralization. Guiyang: Guizhou Science and Technology Publishing House.
Ding Kangle, Li Shuyuan, Yue Changtao, Zhong Ningning. 2005&. Review of thermochemical sulfate reduction. Journal of China University of Petroleum, 29(1):150～154.
Guizhou Geological Survey Institute.2017#, Guizhou Volume, Regional Geology of China. Beijing: Geological Publishing House: 1067～1068.
He Lixian, Zeng Ruolan.1989#. China mercury deposit. In: China Mineral Deposit Editorial Committee. ed. China Mineral Deposit (Volume I). Beijing: Geological Publishing House: 472～482.
Helgeson H C. 1969. Thermodynamics of hydrothermal systems at elevated temperature and Pressures. Am. Jour. Sci., 267: 729～804.
Hua Yongfeng. 1982#, Genesis and Prospecting Prediction of Mercury Deposits in China. Guiyang: Guizhou People's Publishing House.
Hua Yongfeng.1981&. Preliminary study on the origin of mercury deposits in Guizhou and its neighboring areas. Acta Geologica Sinica, 55(2):139～148.
Jiang Qijie, Liu Dongsheng, Chen Minyang, Feng Jianliang, Yu Daliang, Huang Chao, Zeng Jiliang. 1980&. Significance and genetic markers of seepage hot brine mineralization (part I). Geology and Exploration, 16(1):1～6.
Johnson C A, Slack J F, Dumoulin J A, Kelley K D, Falck H. 2018. Sulfur isotopes of host strata for Howards Pass (Yukon–Northwest Territories) Zn—Pb deposits implicate anaerobic oxidation of methane, not basin stagnation. Geology, 46: 619～622.
Lin Qing, Fu Jiamu, Liu Dehan, Sheng Guoying, Lu Jialan. 1993&, The evolution of oil and gas and genesis of sedimentation reworked gold ore deposits. Geochemistry, 22(3): 217～226.
Machel H G. 2001. Bacterial and thermochemical sulfate reduction in digenetic settings: old and new insights. Sedimentary Geology, 140:143～175.
“Mercury Mine Geology,General Survey and Exploration” Compilation Group. 1978#. Mercury Mine Geology,General Survey and Exploration. Beijing: Geological Publishing House.
Rao Jilong. 1979#. Thermodynamics in Geochemistry. Beijing: Science Press.
Sangster D F. 2017. Toward an integrated genetic model for vent—distal SEDEX deposits. Mineralium Deposita, 53: 509～527.
Shi Jixi, Yu Xiaoying, Wang Huayun. 1995. The role of ancient oil reservoirs, bitumens and bitumen inclusions in metallogenic research. Acta Mineralogica Sinica, 15(2):117～122.
Shen Zhi'an. 1981& On the hydrogeochemical mechanism of the formation of hot brine ore deposits. Geological Review, 27(3):237～242.
Wang Huayun, Shi Jixi. 1997&. Sources of ore-forming materials and controls over depositional differentiation in the epithermal mineralization series in the Danzhai, Sandu and Duyun area of Guizhou Province. Acta Mineralogica Sinica, 17(4):497～500.
Wu Weiwen.1989&.The formation and destruction of palaeo-oil-reservoirs in the east of Guizhou Province. Guizhou Geology, 6(1):9～22.
Xie Xiaofeng,Yang Kunguang,Yuan Liangjun. 2015&. Research status and progress of “Datangpo” type manganese deposit in south Guizhou. Guizhou Geology, 32(3):171～176.
Yan Junping, Wang Huayun, et al.1989#, Geology of Mercury Deposits in Guizhou. Beijing: Geological Publishing House.
Zeng Ruolan, et al. 1988#. Mercury Deposits in China. Chengdu: Sichuan Science and Technology Press.
Zhou Qi, Du Yuansheng. 2012#. Ancient Natural Gas Seepage and Manganese Mineralization —— A Case Study of “Datangpo type” Manganese Ore in the Nanhua Period in Eastern Guizhou. Beijing: Geological Publishing House.
Zhou Qi, Du Yuansheng, Qin Ying. 2013&. Ancient natural gas seepage sedimentary-type manganese metallogenic system and ore-forming model: A case study of Datangpo type manganese deposits formed in rift basin of Nanhua Period along Guizhou—Hunan—Chongqing border area. Mineral Deposits, 32(3) :457～466.
Zhou Qi, Du Yuansheng, et al. 2017#. Ancient Natural Gas Seepage Sedimentary Manganese Deposits in South China. Beijing: Science Press.
陈履安. 1985.从HgS—NaCI—HCl—H2O体系的热力学分析——探讨辰砂以氯汞络合物运移成矿所需的物理化学条件.贵州地质, 2(3): 229～239.
陈履安.1989.碳酸盐建造中汞矿床形成过程中汞的存在形式及重金属分异的热力学分析.贵州地质, 6(2):175～186.
陈履安.1990.试论贵州碳酸盐建造中汞金锑砷成矿作用的地球化学机理.贵州地质, 7(3):196～208.
陈履安.2011.溶解运移与沉淀成矿——成矿作用的化学与地学交叉研究. 贵阳:贵州科技出版社.
丁康乐,李术元,岳长涛,钟宁宁. 2005。 硫酸盐热化学还原反应的研究进展. 石油大学学报(自然科学版), 29(1):150～154.
汞矿地质与普查探勘编写组.1978. 汞矿地质与普查探勘. 北京:地质出版社.
贵州省地质调查院. 2017. 中国区域地质志·贵州卷. 北京:地质出版社: 1067～1068.
何立贤, 曾若兰. 1989. 中国汞矿床. 见: 中国矿床编委会. 中国矿床(上册). 北京:地质出版社: 472～482.
花永丰. 1982. 中国汞矿成因及其找矿预测. 贵阳:贵州人民出版社.
花永丰. 1981. 贵州及其邻区汞矿成因的初步研究. 地质学报, 55(2): 139～148.
姜齐节,刘东升,陈民扬,冯建良,余大良,黄超,曾骥良.1980.论渗流热卤水成矿作用的意义和成因标志(上).地质与勘探, 16(1): 1～6.
林青,傅家谟,刘德汉,盛国英,卢家烂. 1993. 油气演化与一些金矿床成因的关系. 地球化学, 22(3):217～226.
饶纪龙. 1979. 地球化学中的热力学. 北京:科学出版社.
施继锡,余孝颖,王华云. 1995. 古油藏、沥青及沥青包裹体在金属成矿研究中的应用. 矿物学报,15(2):117～122.
沈治安. 1981. 热卤水成矿的水文地球化学机理. 地质论评, 27(3):237～242.
王华云,施继锡. 1997. 贵州丹寨、三都、都匀地区低温成矿系列的成矿物质来源和分异条件. 矿物学报,17(4):497～500.
武蔚文. 1989. 贵州东部若干古油藏的形成和破坏. 贵州地质, 6(1):9～22.
谢小峰,杨坤光,袁良军. 2015. 黔东地区“大塘坡式”锰矿研究现状及进展综述. 贵州地质, 32(3):171～176.
严钧平,王华云, 等. 1989. 贵州汞矿地质. 北京:地质出版社.
曾若兰,等. 1988. 中国汞矿. 成都:四川科学技术出版社.
周琦,杜远生.2012. 古天然气渗漏与锰矿成矿——以黔东地区南华纪“大塘坡式”锰矿为例.北京:地质出版社.
周琦,杜远生,覃英. 2013. 古天然气渗漏沉积型锰矿床成矿系统与成矿模式——以黔湘渝毗邻区南华纪“大塘坡式”锰矿为例. 矿床地质,32(3) :457～466.
周琦,杜远生,等. 2018. 华南古天然气渗漏沉积型锰矿. 北京:科学出版社.
Barnes H L and Czamanske G K. 1967. Solubility and transport of ore minerals: In: Barnes H L. ed. Geochemistry of Hydrothermal Ore Deposits: 1st ed.New York:Holt,Rinehart,and Winston: 334～381.
Barnes H L. 1979. Geochemistry of Hydrothermal Ore Deposits: 2nd ed. New York:Wiley-interscience: 404～454.
Chen L’an. 1984&. The Eh—pH diagram of the stability field of mercury minerals and the predominance field of their soluble species and HgS—Cl-—H2O versus 25～200 ℃ system and their geological significance. Geological Review, 30(2):114～125.
Chen L’an. 1984&. Research on the physical and chemical conditions required for the transporting and ore-forming of cinnabar as mercury as chloride complexes from thermodynamic analysis of the HgS—NaCI—HCl—H2O system. Guizhou Geology,2(3): 229～239.
Chen L’an. 1989&.Thermodynamical analysis of existing forms of mercury and differentiation mercury of heavy metals in the deposits in the formation process of forming of carbonate. Guizhou Geology, 6(2): 175～186.
Chen L’an. 1990&. A discussion on geochemical mechanism of mineralization of Hg,Sb,As and Au in carbonate formation in Guizhou. Guizhou Geology, 7(3): 196～208.
Chen L’an. 2011#. Dissolve—Transport and Sedimentation —Mineralization: Cross-Over Research of Chemistry and Geoscience in Mineralization. Guiyang: Guizhou Science and Technology Publishing House.
Ding Kangle, Li Shuyuan, Yue Changtao, Zhong Ningning. 2005&. Review of thermochemical sulfate reduction. Journal of China University of Petroleum, 29(1):150～154.
Guizhou Geological Survey Institute.2017#, Guizhou Volume, Regional Geology of China. Beijing: Geological Publishing House: 1067～1068.
He Lixian, Zeng Ruolan.1989#. China mercury deposit. In: China Mineral Deposit Editorial Committee. ed. China Mineral Deposit (Volume I). Beijing: Geological Publishing House: 472～482.
Helgeson H C. 1969. Thermodynamics of hydrothermal systems at elevated temperature and Pressures. Am. Jour. Sci., 267: 729～804.
Hua Yongfeng. 1982#, Genesis and Prospecting Prediction of Mercury Deposits in China. Guiyang: Guizhou People's Publishing House.
Hua Yongfeng.1981&. Preliminary study on the origin of mercury deposits in Guizhou and its neighboring areas. Acta Geologica Sinica, 55(2):139～148.
Jiang Qijie, Liu Dongsheng, Chen Minyang, Feng Jianliang, Yu Daliang, Huang Chao, Zeng Jiliang. 1980&. Significance and genetic markers of seepage hot brine mineralization (part I). Geology and Exploration, 16(1):1～6.
Johnson C A, Slack J F, Dumoulin J A, Kelley K D, Falck H. 2018. Sulfur isotopes of host strata for Howards Pass (Yukon–Northwest Territories) Zn—Pb deposits implicate anaerobic oxidation of methane, not basin stagnation. Geology, 46: 619～622.
Lin Qing, Fu Jiamu, Liu Dehan, Sheng Guoying, Lu Jialan. 1993&, The evolution of oil and gas and genesis of sedimentation reworked gold ore deposits. Geochemistry, 22(3): 217～226.
Machel H G. 2001. Bacterial and thermochemical sulfate reduction in digenetic settings: old and new insights. Sedimentary Geology, 140:143～175.
“Mercury Mine Geology,General Survey and Exploration” Compilation Group. 1978#. Mercury Mine Geology,General Survey and Exploration. Beijing: Geological Publishing House.
Rao Jilong. 1979#. Thermodynamics in Geochemistry. Beijing: Science Press.
Sangster D F. 2017. Toward an integrated genetic model for vent—distal SEDEX deposits. Mineralium Deposita, 53: 509～527.
Shi Jixi, Yu Xiaoying, Wang Huayun. 1995. The role of ancient oil reservoirs, bitumens and bitumen inclusions in metallogenic research. Acta Mineralogica Sinica, 15(2):117～122.
Shen Zhi'an. 1981& On the hydrogeochemical mechanism of the formation of hot brine ore deposits. Geological Review, 27(3):237～242.
Wang Huayun, Shi Jixi. 1997&. Sources of ore-forming materials and controls over depositional differentiation in the epithermal mineralization series in the Danzhai, Sandu and Duyun area of Guizhou Province. Acta Mineralogica Sinica, 17(4):497～500.
Wu Weiwen.1989&.The formation and destruction of palaeo-oil-reservoirs in the east of Guizhou Province. Guizhou Geology, 6(1):9～22.
Xie Xiaofeng,Yang Kunguang,Yuan Liangjun. 2015&. Research status and progress of “Datangpo” type manganese deposit in south Guizhou. Guizhou Geology, 32(3):171～176.
Yan Junping, Wang Huayun, et al.1989#, Geology of Mercury Deposits in Guizhou. Beijing: Geological Publishing House.
Zeng Ruolan, et al. 1988#. Mercury Deposits in China. Chengdu: Sichuan Science and Technology Press.
Zhou Qi, Du Yuansheng. 2012#. Ancient Natural Gas Seepage and Manganese Mineralization —— A Case Study of “Datangpo type” Manganese Ore in the Nanhua Period in Eastern Guizhou. Beijing: Geological Publishing House.
Zhou Qi, Du Yuansheng, Qin Ying. 2013&. Ancient natural gas seepage sedimentary-type manganese metallogenic system and ore-forming model: A case study of Datangpo type manganese deposits formed in rift basin of Nanhua Period along Guizhou—Hunan—Chongqing border area. Mineral Deposits, 32(3) :457～466.
Zhou Qi, Du Yuansheng, et al. 2017#. Ancient Natural Gas Seepage Sedimentary Manganese Deposits in South China. Beijing: Science Press.