An experimental study on metal precipitation driven by fluid mixing: implications for genesis of carbonate-hosted lead–zinc ore deposits
Abstract
A type of carbonate-hosted lead–zinc (Pb–Zn) ore deposits, known as Mississippi Valley Type (MVT) deposits, constitutes an important category of lead–zinc ore deposits. Previous studies proposed a fluid-mixing model to account for metal precipitation mechanism of the MVT ore deposits, in which fluids with metal-chloride complexes happen to mix with fluids with reduced sulfur, producing metal sulfide deposition. In this hypothesis, however, the detailed chemical kinetic process of mixing reactions, and especially the controlling factors on the metal precipitation are not yet clearly stated. In this paper, a series of mixing experiments under ambient temperature and pressure conditions were conducted to simulate the fluid mixing process, by titrating the metal-chloride solutions, doping with or without dolomite, and using NaHS solution. Experimental results, combined with the thermodynamic calculations, suggest that H2S, rather than HS− or S2−, dominated the reactions of Pb and/or Zn precipitation during the fluid mixing process, in which metal precipitation was influenced by the stability of metal complexes and the pH. Given the constant concentrations of metal and total S in fluids, the pH was a primary factor controlling the Pb and/or Zn metal precipitation. This is because neutralizing or neutralized processes for the ore-forming fluids can cause instabilities of Pb and/or Zn chloride complexes and re-distribution of sulfur species, and thus can facilitate the hydrolysis of Pb and Zn ions and precipitation of sulfides. Therefore, a weakly acidic to neutral fluid environment is most favorable for the precipitation of Pb and Zn sulfides associated with the carbonate-hosted Pb–Zn deposits.
Keywords
Metal precipitation Fluid mixing Sulfur species MVT lead–zinc ore deposits Carbonate-hosted lead–zinc depositsNotes
Acknowledgements
We thank two anonymous reviewers for their constructive comments. This work was supported jointly by the National Key R&D Program of China (No. 2016YFC0600408), the National Natural Science Foundation of China (Nos. 41572060, 41773054, U1133602, 41802089), China Postdoctoral Science Foundation (No. 2017M610614), projects of YM Lab (2011) and Innovation Team of Yunnan Province and KMUST (2008 and 2012), and Yunnan and Kunming University of Science and Technology Postdoctoral Sustentation Fund.
Supplementary material
References
- Akinfiev NN, Tagirov BR (2014) Zn in hydrothermal systems: thermodynamic description of hydroxide, chloride, and hydrosulfide complexes. Geochem Int 52:197–214Google Scholar
- And DJH, Brodholt JP, Sherman DM (2003) Zinc complexation in hydrothermal chloride brines: results from ab initio molecular dynamics calculations. J Phys Chem A 107:614–619Google Scholar
- Anderson GM (1973) The hydrothermal transport and deposition of galena and sphalerite near 100 °C. Econ Geol 68:480–492Google Scholar
- Anderson GM (1975) Precipitation of Mississippi Valley-type ores. Econ Geol 70:937–942Google Scholar
- Anderson GM (1991) Organic maturation and ore precipitation in southeast Missouri. Econ Geol 86:909–926Google Scholar
- Anderson CB (1997) Understanding carbonate equilibria by measuring alkalinity in experimental and natural systems. J Geosci Educ 50:389–403Google Scholar
- Anderson GM, Garven G (1987) Sulfate-sulfide-carbonate associations in Mississippi valley-type lead–zinc deposits. Econ Geol 82:482–488Google Scholar
- Appold MS, Garven G (2000) Reactive flow models of ore formation in the southeast Missouri district. Econ Geol 95:1605–1626Google Scholar
- Banks DA, Russell MJ (1992) Fluid mixing during ore deposition at the Tynagh base-metal deposit, Ireland. Eur J Miner 4:921–931Google Scholar
- Banks DA, Boyce AJ, Samson IM (2002) Constraints on the origins of fluids forming Irish Zn–Pb–Ba deposits: evidence from the composition of fluid inclusions. Econ Geol 97:471–480Google Scholar
- Barrett TJ, Anderson GM (1982) The solubility of sphalerite and galena in NaCl brines. Econ Geol 77:1923–1933Google Scholar
- Barrett TJ, Anderson GM (1988) The solubility of sphalerite and galena in 1–5 m NaCl solutions to 300 °C. Geochim Cosmochim Acta 52:813–820Google Scholar
- Barton PBJ (1967) Possible role of organic matter in the precipitation of the Mississippi Valley ores. Econ Geol 3:371–377Google Scholar
- Basuki NI (2002) A review of fluid inclusion temperatures and salinities in Mississippi Valley-type Zn–Pb deposits: identifying thresholds for metal transport. Explor Min Geol 11:1–17Google Scholar
- Beales FW (1975) Precipitation mechanisms for Mississippi valley-type ore deposits; a reply. Econ Geol 70:943–948Google Scholar
- Beales FW, Jackson SA (1966) Precipitation of lead–zinc ores in carbonate reservoirs as illustrated by Pine Point ore field, Canada. Inst Min Metall B 75:278–285Google Scholar
- Bottrell SH, Crowley S, Self C (2001) Invasion of a karst aquifer by hydrothermal fluids: evidence from stable isotopic compositions of cave mineralization. Geofluids 1:103–121Google Scholar
- Bourcier WL, Barnes HL (1987) Ore solution chemistry: VII. Stabilities of chloride and bisulphide complexes of zinc to 350 °C. Econ Geol 82:1839–1863Google Scholar
- Brown JS (1970) Mississippi valley type lead-zinc ores. Miner Deposita 5:103–119Google Scholar
- Carpenter AB, Trout ML, Pickett EE (1974) Preliminary report on the origin and chemical evolution of lead-and zinc-rich oil field brines in central Mississippi. Econ Geol 69:1191–1206Google Scholar
- Conliffe J, Wilton D, Blamey N, Archibald SM (2013) Paleoproterozoic Mississippi Valley type Pb–Zn mineralization in the Ramah Group, Northern Labrador: stable isotope, fluid inclusion and quantitative fluid inclusion gas analyses. Chem Geol 362:211–223Google Scholar
- Cooke DR (1996) Epithermal gold mineralization, Acupan, Baguio District, Philippines; geology, mineralization, alteration, and the thermochemical environment of ore deposition. Econ Geol 91:243–272Google Scholar
- Corbella M, Ayora C, Cardellach E (2004) Hydrothermal mixing, carbonate dissolution and sulfide precipitation in Mississippi Valley-type deposits. Miner Deposita 39:344–357Google Scholar
- Czamanske GK, Roedder E, Burns FC (1963) Neutron activation analysis of fluid inclusions for copper, manganese, and zinc. Science 140:401–403Google Scholar
- Daskalakis KD, Helz GR (1993) The solubility of sphalerite (ZnS) in sulfidic solutions at 25 °C and 1 atm pressure. Geochim Cosmochim Acta 57:4923–4931Google Scholar
- Emsbo P (2000) Gold in sedex deposits. SEG Rev 13:427–437Google Scholar
- Ewald AH, Hladky G (1980) Solubility measurements on sphalerite. CSIRO Div Miner Inv Rep 136:68Google Scholar
- Fan HR, Groves DI, Mikucki EJ, McNaughton NJ (2001) Fluid mixing in the generation of Nevoria gold mineralization in the Southern Cross greenstone belt, Western Australia. Miner Depos 20:37–43Google Scholar
- Fang WX, Li JX (2014) Metallogenic regulations, controlling factors, and evolutions of iron oxide copper and gold deposits in Chile. Adv Earth Sci 29:1011–1024Google Scholar
- Fraser DG, Feltham D, Whiteman M (1989) High-resolution scanning proton microprobe studies of micron-scale trace element zoning in a secondary dolomite: implications for studies of redox behaviour in dolomites. Sediment Geol 65:223–232Google Scholar
- Ganino C, Arndt N (2012) Metals and society: an introduction to economic geology. Springer, BerlinGoogle Scholar
- Gerdemann PE, Myers HE (1972) Relationships of carbonate facies patterns to ore distribution and to ore genesis in the southeast Missouri lead district. Econ Geol 67:426–433Google Scholar
- Giordano TH (2002) Transport of Pb and Zn by carboxylate complexes in basinal ore fluids and related petroleum-field brines at 100 C: the influence of pH and oxygen fugacity. Geochem Trans 3:56Google Scholar
- Giordano TH, Barnes HL (1979) Ore solution chemistry VI; PbS solubility in bisulfide solutions to 300 °C. Econ Geol 74:1637–1646Google Scholar
- Giordano TH, Barnes HL (1981) Lead transport in Mississippi Valley-type ore solutions. Econ Geol 76:2200–2211Google Scholar
- Grandia F, Canals A, Cardellach E, Banks DA, Perona J (2003) Origin of ore-forming brines in sediment-hosted Zn-Pb deposits of the Basque-Cantabrian Basin, Northern Spain. Econ Geol 98:1397–1411Google Scholar
- Gratz JF, Misra KC (1987) Fluid inclusion study of the Gordonsville zinc deposit, central Tennessee. Econ Geol 82:1790–1804Google Scholar
- Gregg JM (1985) Regional epigenetic dolomitization in the Bonneterre Dolomite (Cambrian), southeastern Missouri. Geology 13:503Google Scholar
- Han RS, Liu CQ, Huang ZL, Chen J, Ma DY, Lei L, Ma GS (2007) Geological features and origin of the Huize carbonate-hosted Zn–Pb–(Ag) District, Yunnan, South China. Ore Geol Rev 31:360–383Google Scholar
- Han RS, Li B, Ni P, Qiu WL, Wang XD, Wang TG (2016) Infrared micro-thermometry of fluid inclusions in sphalerite and geological significance of the huize super-large Zn–Pb–(Ge–Ag) deposit, Yunnan Province. J Jilin Univ Earth Sci Ed 46:91–104Google Scholar
- Hayashi K, Sugaki A, Kitakaze A (1990) Solubility of sphalerite in aqueous sulfide solutions at temperatures between 25 and 240 °C. Geochim Cosmochim Acta 54:715–725Google Scholar
- Haynes DW, Cross KC, Bills RT, Reed MH (1995) Olympic Dam ore genesis; a fluid-mixing model. Econ Geol 90:281–307Google Scholar
- Henley RW (1984) The geothermal framework of epithermal deposits. In: Berger BR, Bethke PM (eds) Geology and geochemistry of epithermal system: society of economic geologists. Rev Econ Geol, vol 2, pp 1–24Google Scholar
- Henley RW, Truesdell AH, Barton PB Jr, Whitney JA (1984) Fluid mineral equilibria in hydrothermal systems. Rev Econ Geol 1:267Google Scholar
- Hennig W (1971) Löslichkeit von Zinkblende unter hydrothermalen Bedingungen im System ZnS-NaC1-H2O. Neues Jahrb Mineralogie Abh 116:61–79Google Scholar
- Hofstra AH, Northrop HR, Rye RO, Landis GP, Birak DJ (1988) Origin of sediment-hosted disseminated gold deposits by fluid mixing: Evidence from jasperoids in the Jerritt Canyon gold district, Nevada, USA. In: Bicentennial gold ‘88, geological society of Australia, oral programme, vol 22, pp 284–289Google Scholar
- Jazi MA, Karimpour MH, Shafaroudi AM (2017) Nakhlak carbonate-hosted Pb (Ag) deposit, Isfahan province, Iran: a geological, mineralogical, geochemical, fluid inclusion, and sulfur isotope study. Ore Geol Rev 80:27–47Google Scholar
- Jiang SH, Nie FJ, Yi Z, Peng HU (2004) The latest advances in the research of epithermal deposits. Earth Sci Front 11:401–411Google Scholar
- Kendrick MA, Burgess R, Pattrick RAD, Turner G (2002) Hydrothemal fluid origins in a flourite-rich Mississippi Valley-type district: combined noble gas (He, Ar, Kr) and halogen (CI, Br, I) analysis of fluid inclusions from the South Pennine ore field, United Kingdom. Econ Geol 97:435–451Google Scholar
- Kesler SE, Friedman GM, Krstic D (1997) Mississippi valley-type mineralization in the Silurian paleoaquifer, central Appalachians. Chem Geol 138:127–134Google Scholar
- Leach DL, Rowan EL, Shelton KL, Bauer RM, Gregg JM (1993) Fluid-inclusion studies of regionally extensive epigenetic dolomites, Bonneterre Dolomite (Cambrian), southeast Missouri: evidence of multiple fluids during dolomitization and lead-zinc mineralization: alternative interpretation and reply. Geol Soc Am Bull 105:968–978Google Scholar
- Leach DD, Viets JG, Kozłowski A, Kibitlewski S (1996) Geology, geochemistry, and genesis of the Silesia-Cracow zinc–lead district, southern Poland. Econ Geol 4:144–170Google Scholar
- Leach DL, Bradley D, Lewchuk MT, Symons DT, Marsily GD, Brannon J (2001) Mississippi Valley-type lead–zinc deposits through geological time: implications from recent age-dating research. Miner Deposita 36:711–740Google Scholar
- Leach DL, Marsh E, Emsbo P, Rombach CS, Kelley KD, Anthony M (2004) Nature of hydrothermal fluids at the shale-hosted red dog Zn–Pb–Ag deposits, Brooks Range, Alaska. Econ Geol 99:1449–1480Google Scholar
- Leach DL, Sangster DF, Kelley KD, Large RR, Garven G, Allen CR, Gutzmer J, Walters S (2005) Sediment-hosted lead-zinc deposits: a global perspective. Econ Geol 100:561–607Google Scholar
- Leach D, Macquar JC, Lagneau V, Leventhal J, Emsbo P, Premo W (2006) Precipitation of lead–zinc ores in the Mississippi Valley-type deposit at Trèves, Cévennes region of southern France. Geofluids 6:24–44Google Scholar
- Li XJ, Liu W (2002) Fluid inclusion and stable isotope constraints on the genesis of the Mazhuangshan gold deposit, eastern Tianshan Mountains of China. Acta Petrol Sin 18:551–558Google Scholar
- Lin CX, Bai ZH, Zhang ZR (1985) The thermodynamic manual book of minerals and related compounds. Science Press, BeijingGoogle Scholar
- Lyle JR (1977) Petrography and carbonate diagenesis of the Bonneterre Formation in the Viburnum Trend area, southeast Missouri. Econ Geol 72:420–434Google Scholar
- Manning CE (2011) Sulfur surprises in deep geological fluids. Science 331:1018–1019Google Scholar
- Marie JS, Kesler SE (2000) Iron-rich and iron-poor Mississippi Valley-type mineralization, Metaline District, Washington. Econ Geol 95:1091–1106Google Scholar
- Melent’Yev BN, Ivanenko VV, Pamfilova LA (1969) Solubility of some ore-forming sulfides under hydrothermal conditions. Geochem Internet 6:416–460Google Scholar
- Misra KC (2000) Mississippi Valley-type (MVT) zinc–lead deposits. Springer, DordrechtGoogle Scholar
- Ohle EL (1985) Breccias in Mississippi Valley-type deposits. Econ Geol 80:1736–1752Google Scholar
- Oxtoby DW, Gillis HP, Campion A (2012) Principles of modern chemistry, 7th edn, Cengage learning, New York. Google Scholar
- Petrucci RH, Harwood WS (1977) General chemistry: principles and modern applications. Macmillan, New YorkGoogle Scholar
- Pinckney DM, Haffty J (1970) Content of zinc and copper in some fluid inclusions from the Cave-in-Rock District, southern Illinois. Econ Geol 65:451–458Google Scholar
- Pirajno F (1992) Hydrothermal mineral deposits. Springer, BerlinGoogle Scholar
- Plumlee GS (1994) Fluid chemistry evolution and mineral deposition in the main-stage Creede epithermal system. Econ Geol Bull Soc Econ Geol 89:1860–1882Google Scholar
- Plumlee GS, Leach DL, Hofstra AH, Landis GP, Rowan EL, Viets JG (1994) Chemical reaction path modeling of ore deposition in Mississippi Valley-type Pb-Zn deposits of the Ozark region, US midcontinent. Econ Geol 90:1346–1349Google Scholar
- Pokrovski GS, Dubrovinsky LS (2011) The S3-ion is stable in geological fluids at elevated temperatures and pressures. Science 331:1052–1054Google Scholar
- Reed MH (2006) Sulfide mineral precipitation from hydrothermal fluids. Rev Mineral Geochem 61:609–631Google Scholar
- Reed MH, Spycher NF (1985) Boiling, cooling, and oxidation in epithermal systems: a numerical modeling approach. Rev Econ Geol 61:249–272Google Scholar
- Robb L (2005) Introduction to ore-forming processes. Blackwell Publishing, OxfordGoogle Scholar
- Roedder E (1977) Fluid inclusion studies of ore deposits in the Viburnum Trend, Southeast Missouri. Econ Geol 72:474–479Google Scholar
- Rowan EL (1987) Homogenization temperatures and salinities of fluid inclusions from the Viburnum Trend, Southeast Missouri, and the northern Arkansas zinc distict. Endoscopy 30:69–87Google Scholar
- Samson IM, Russell MJ (1987) Genesis of the Silvermines zinc–lead-barite deposit, Ireland; fluid inclusion and stable isotope evidence. Econ Geol 82:371–394Google Scholar
- Sass-Gustkiewicz M, Dzulyński S (1998) On the origin of strata-bound Zn–Pb ores in the Upper Silesia, Poland. Ann Soc Geol Pol 68:267–278Google Scholar
- Savard MM, Chi G, Sami T, Williams-Jones AE, Leigh K (2000) Fluid inclusion and carbon, oxygen, and strontium isotope study of the Polaris Mississippi Valley-type Zn–Pb deposit, Canadian Arctic Archipelago: implications for ore genesis. Miner Deposita 35:495–510Google Scholar
- Seward TM (1984) The formation of lead (II) chloride complexes to 300 °C: a spectrophotometric study. Geochim Cosmochim Acta 48:121–134Google Scholar
- Seward TM, Barne HL (1997) Metal transport by hydrothermal ore fluids. In: Barnes HL (ed) Geochemistry of hydrothermal ore deposits, Wiley, New York, pp 435–486Google Scholar
- Stoffell B, Appold MS, Wilkinson JJ, Mcclean NA, Jeffries TE (2008) Geochemistry and evolution of Mississippi Valley-type mineralizing brines from the Tri-State and northern Arkansas districts determined by LA-ICP-MS microanalysis of fluid inclusions. Econ Geol 103:1411–1435Google Scholar
- Sverjensky DA (1986) Genesis of Mississippi Valley-type lead–zinc desposits. Annu Rev Earth Planet Sci 14:177Google Scholar
- Tagirov BR, Seward TM (2010) Hydrosulfide/sulfide complexes of zinc to 250 °C and the thermodynamic properties of sphalerite. Chem Geol 269:301–311Google Scholar
- Tagirov B, Zotov A, Schott J, Suleimenov O, Koroleva L (2007a) A potentiometric study of the stability of aqueous yttrium–acetate complexes from 25 to 175 °C and 1–1000 bar. Geochim Cosmochim Acta 71:1689–1708Google Scholar
- Tagirov BR, Suleimenov OM, Seward TM (2007b) Zinc complexation in aqueous sulfide solutions: determination of the stoichiometry and stability of complexes via ZnS (cr) solubility measurements at 100 °C and 150 bars. Geochim Cosmochim Acta 71:4942–4953Google Scholar
- Tossell JA (2012) Calculation of the properties of the S3—radical anion and its complexes with Cu+ in aqueous solution. Geochim Cosmochim Acta 95:79–92Google Scholar
- Wilkinson JJ (2001) Fluid inclusions in hydrothermal ore deposits. Lithos 55:229–272Google Scholar
- Wilkinson JJ, Stoffell B, Wilkinson CC, Jeffries TE, Appold MS (2009) Anomalously metal-rich fluids form hydrothermal ore deposits. Science 323:764–767Google Scholar
- Yardley BWD (2005) Metal concentrations in crustal fluids and their relationship to ore formation. Econ Geol 100:613–632Google Scholar
- Zhang CQ, Jinjie YU, Mao JW, Rui ZY (2009) Advances in the study of Mississippi Valley-type deposits. Miner Depos 28:195–210Google Scholar
- Zhang Y, Han R, Wei P, Qiu W (2014a) Thermodynamic study on paragenesis and separation of lead and zinc-taking the Zhaotong Pb–Zn deposit in Northeastern Yunnan, China as a case. Acta Geol Sin 88:247–248Google Scholar
- Zhang Y, Han R, Wu P, Zhou G, Wei P, Qiu W (2014b) The restrictions of fO2 and fS2 for lead–zinc paragenesis and separation of the Zhaotong Huize-type Pb–Zn deposit in Northeast Yunnan, China. Geotecton Et Metallog 38:898–907Google Scholar
- Zhong R, Brugger J, Chen Y, Li W (2015) Contrasting regimes of Cu, Zn and Pb transport in ore-forming hydrothermal fluids. Chem Geol 395:154–164Google Scholar