Abstract
Recent studies have identified gold nanoparticles in ores in a range of deposit types, but little is known about their formation processes. In this contribution, gold-bearing magnetite from the well-documented, world-class Beiya Au deposit, China, was investigated in terms of microstructure and crystallography at the nanoscale. We present the first three-dimensional (3D) focused ion beam/scanning electron microscopy (FIB/SEM) tomography of the distribution of gold nanoparticles in nanopores in the low-Si magnetite. The porous low-Si magnetite, which overprints an earlier generation of silician magnetite, was formed by a coupled dissolution-reprecipitation reaction (CDRR). The extrinsic changes in thermodynamic conditions (e.g., S content and temperature) of the hydrothermal fluids resulted in the CDRR in magnetite and the disequilibrium of Au-Bi melts. The gold nanoparticles crystallized from Au-supersaturated fluids originating from the disequilibrium of Au-Bi melts and grew in two ways depending on the intrinsic crystal structure and pore textures: (1) heteroepitaxial growth utilizing the (111) lattice planes of magnetite, and (2) randomly oriented nucleation and growth. Therefore, this study unravels how intrinsic and extrinsic factors drove the formation of gold nanoparticles at fluid-mineral interfaces.
Acknowledgments and Funding
We are grateful to Denis Fougerouse and three anonymous reviewers for their critical comments on the manuscript. The German Academic Exchange Service (DAAD) is thanked for funding Haoyang Zhou’s stay at GFZ. Sarah A. Gleeson and Sathish Mayanna acknowledge the financial support of the Helmholtz Recruiting Initiative (No. 0316 and I-044-16-01, respectively).
References cited
Acosta-Góngora, P., Gleeson, S.A., Samson, I.M., and Ootes, L.C. (2015) Gold refining by bismuth melts in the iron oxide-dominated NICO Au-Co-Bi (±Cu±W) deposit, NWT, Canada. Economic Geology, 110, 291–314.10.2113/econgeo.110.2.291Search in Google Scholar
Altree-Williams, A., Pring, A., Ngothai, Y., and Brugger, J. (2015) Textural and compositional complexities resulting from coupled dissolution–reprecipitation reactions in geomaterials. Earth-Science Reviews, 150, 628–651.10.1016/j.earscirev.2015.08.013Search in Google Scholar
Birski, Ł., Wirth, R., Słaby, E., Wudarska, A., Lepland, A., Hofmann, A., and Sch-reiber, A. (2018) (Ca-Y)-phosphate inclusions in apatite crystals from Archean rocks from the Barberton Greenstone Belt and Pilbara Craton: First report of natural occurrence. American Mineralogist, 103, 307–313.10.2138/am-2018-6150Search in Google Scholar
Ciobanu, C.L., Cook, N.J., Utsunomiya, S., Kogagwa, M., Green, L., Gilbert, S., and Wade, B. (2012) Gold-telluride nanoparticles revealed in arsenic-free pyrite. American Mineralogist, 97, 1515–1518.10.2138/am.2012.4207Search in Google Scholar
Cook, N.J., and Chryssoulis, S.L. (1990) Concentrations of invisible gold in the common sulfides. Canadian Mineralogist, 28, 1–16.Search in Google Scholar
Cook, N.J., Ciobanu, C.L., Meria, D., Silcock, D., and Wade, B. (2013) Arsenopyritepyrite association in an orogenic gold ore: Tracing mineralization history from textures and trace elements. Economic Geology, 108, 1273–1283.10.2113/econgeo.108.6.1273Search in Google Scholar
Dubacq, B., and Plunder, A. (2018) Controls on trace element distribution in oxides and silicates. Journal of Petrology, 59, 233–256.10.1093/petrology/egy027Search in Google Scholar
Fougerouse, D., Reddy, S.M., Saxey, D.W., Rickard, W.D.A., Riessen, A.V., and Micklethwaite, S. (2016) Nanoscale gold clusters in arsenopyrite controlled by growth rate not concentration: Evidence from atom probe microscopy. American Mineralogist, 101, 1916–1919.10.2138/am-2016-5781CCBYNCNDSearch in Google Scholar
Godel, B., Barnes, S.J., Barnes, S., and Maier, W.D. (2010) Platinum ore in three dimensions: Insights from high-resolution X‑ray computed tomography. Geology, 38, 1127–1130.10.1130/G31265.1Search in Google Scholar
Harlov, D.E., Wirth, R., and Förster, H. (2005) An experimental study of dissolution– reprecipitation in fluorapatite: fluid infiltration and the formation of monazite. Contributions to Mineralogy and Petrology, 150, 268–286.10.1007/s00410-005-0017-8Search in Google Scholar
He, W.Y., Yang, L.Q., Brugger, J., McCuaig, T.C., Lu, Y.J., Bao, X.S., Gao, X.Q., Lu, Y.G., and Xing, Y.L. (2017) Hydrothermal evolution and ore genesis of the Beiya giant Au polymetallic deposit, western Yunnan, China: Evidence from fluid inclusions and H–O–S–Pb isotopes. Ore Geology Reviews, 90, 847–862.10.1016/j.oregeorev.2016.10.035Search in Google Scholar
Hochella, M.F., Lower, S.K., Maurice, P.A., Penn, R.L., Sahai, N., Sparks, D.L., and Twining, B.S. (2008) Nanominerals, mineral nanoparticles, and Earth systems. Science, 319, 1631–1635.10.1126/science.1141134Search in Google Scholar PubMed
Hu, H., Lentz, D., Li, J.W., McCarron, T., Zhao, X.F., and Hall, D. (2015) Reequilibration processes in magnetite from iron skarn deposits. Economic Geology, 110, 1–8.10.2113/econgeo.110.1.1Search in Google Scholar
Jia, B.P., and Gao, L. (2008) Morphological transformation of Fe3O4 spherical aggregates from solid to hollow and their self-assembly under an external magnetic field. The Journal of Physical Chemistry C, 112, 666–671.10.1021/jp0763477Search in Google Scholar
Kusebauch, C., Gleeson, S.A., and Oelze, M. (2019) Coupled partitioning of Au and As into pyrite controls formation of giant Au deposits. Science Advances, 5, eaav5891.10.1126/sciadv.aav5891Search in Google Scholar PubMed PubMed Central
Large, R.R., Maslennikov, V.V., Robert, F., Danyushevsky, L.V., and Chang, Z. (2007) Multistage sedimentary and metamorphic origin of pyrite and gold in the giant Sukhoi Log deposit, Lena gold province, Russia. Economic Geology, 102, 1233–1267.10.2113/gsecongeo.102.7.1233Search in Google Scholar
Mao, J.W., Zhou, Y.M., Liu, H., Zhang, C.Q., Fu, D.G., and Liu, B. (2017) Metallogenic setting and ore genetic model for the Beiya porphyry-skarn polymetallic Au orefield, western Yunnan, China. Ore Geology Reviews, 86, 21–34.10.1016/j.oregeorev.2017.02.003Search in Google Scholar
Okamoto, H., and Massalski, T.B. (1983) The Au-Bi (gold-bismuth) system. Bulletin of Alloy Phase Diagrams, 4, 401–407.10.1007/BF02868093Search in Google Scholar
Palenik, C.S., Utsunomiya, S., Reich, M., Kesler, S.E., Wang, L., and Ewing, R.C. (2004) “Invisible” gold revealed: Direct imaging of gold nanoparticles in a Carlin-type deposit. American Mineralogist, 89, 1359–1366.10.2138/am-2004-1002Search in Google Scholar
Putnis, A. (2002) Mineral replacement reactions: from macroscopic observations to microscopic mechanisms. Mineralogical Magazine, 66, 689–708.10.1180/0026461026650056Search in Google Scholar
Reich, M., Kesler, S.E., Utsunomiya, S., Palenik, C.S., Chryssoulis, S.L., and Ewing, R.C. (2005) Solubility of gold in arsenian pyrite. Geochimica et Cosmochimica Acta, 69, 2781–2796.10.1016/j.gca.2005.01.011Search in Google Scholar
Reich, M., Utsunomiya, S., Kesler, S.E., Wang, L., Ewing, R.C., and Becker, U. (2006) Thermal behavior of metal nanoparticles in geologic materials. Geology, 34, 1033–1036.10.1130/G22829A.1Search in Google Scholar
Ruiz-Agudo, E., Putnis, C.V., and Putnis, A. (2014) Coupled dissolution and precipitation at mineral–fluid interfaces. Chemical Geology, 383, 132–146.10.1016/j.chemgeo.2014.06.007Search in Google Scholar
Scherer, G.W. (1999) Crystallization in pores. Cement and Concrete Research, 29, 1347–1358.10.1016/S0008-8846(99)00002-2Search in Google Scholar
Seo, J.H., Guillong, M., and Heinrich, C.A. (2009) The role of sulfur in the formation of magmatic–hydrothermal copper–gold deposits. Earth and Planetary Science Letters, 282, 323–328.10.1016/j.epsl.2009.03.036Search in Google Scholar
Simon, G., Huang, H., Penner-Hahn, J.E., Kesler, S.E., and Kao, L. (1999a) Oxidation state of gold and arsenic in gold-bearing arsenian pyrite. American Mineralogist, 84, 1071–1079.10.2138/am-1999-7-809Search in Google Scholar
Simon, G., Kesler, S.E., and Chryssoulis, S. (1999b) Geochemistry and textures of gold-bearing arsenian pyrite, Twin Creeks, Nevada; implications for deposition of gold in carlin-type deposits. Economic Geology, 94, 405–421.10.2113/gsecongeo.94.3.405Search in Google Scholar
Sung, Y.H., Brugger, J., Ciobanu, C.L., Pring, A., Skinner, W., and Nugus, M. (2009) Invisible gold in arsenian pyrite and arsenopyrite from a multistage Archaean gold deposit: Sunrise Dam, Eastern Goldfields Province, Western Australia. Mineralium Deposita, 44, 765–791.10.1007/s00126-009-0244-4Search in Google Scholar
Tooth, B., Brugger, J., Ciobanu, C., and Liu, W.H. (2008) Modeling of gold scavenging by bismuth melts coexisting with hydrothermal fluids. Geology, 36, 815–818.10.1130/G25093A.1Search in Google Scholar
Tooth, B., Ciobanu, C.L., Green, L., O’Neill, B., and Brugger, J. (2011) Bi-melt formation and gold scavenging from hydrothermal fluids: An experimental study. Geochimica et Cosmochimica Acta, 75, 5423–5443.10.1016/j.gca.2011.07.020Search in Google Scholar
Williams-Jones, A.E., Bowell, R.J., and Migdisov, A.A. (2009) Gold in solution. Elements, 5, 281–287.10.2113/gselements.5.5.281Search in Google Scholar
Wirth, R. (2004) Focused Ion Beam (FIB): A novel technology for advanced application of micro- and nanoanalysis in geosciences and applied mineralogy. European Journal of Mineralogy, 16, 863–876.10.1127/0935-1221/2004/0016-0863Search in Google Scholar
Wirth, R. (2009) Focused Ion Beam (FIB) combined with SEM and TEM: Advanced analytical tools for studies of chemical composition, microstructure and crystal structure in geomaterials on a nanometre scale. Chemical Geology, 261, 217–229.10.1016/j.chemgeo.2008.05.019Search in Google Scholar
Wu, Y.F., Fougerouse, D., Evans, K., Reddy, S.M., Saxey, D.W., Guagliardo, P., and Li, J.W. (2019) Gold, arsenic, and copper zoning in pyrite: A record of fluid chemistry and growth kinetics. Geology, 47, 641–644.10.1130/G46114.1Search in Google Scholar
Xing, Y.L., Brugger, J., Tomkins, A., and Shvarov, Y. (2019) Arsenic evolution as a tool for understanding formation of pyritic gold ores. Geology, 47, 335–338.10.1130/G45708.1Search in Google Scholar
Yin, S., Wirth, R., Ma, C.Q., and Xu, J.N. (2019) The role of mineral nanoparticles at a fluid-magnetite interface: Implications for trace-element uptake in hydrothermal systems. American Mineralogist, 104, 1180–1188.10.2138/am-2019-6996Search in Google Scholar
Zheleva, T., Jagannadham, K., and Narayan, J. (1994) Epitaxial growth in large-lattice-mismatch systems. Journal of Applied Physics, 75, 860–871.10.1063/1.356440Search in Google Scholar
Zhou, H.Y., Sun, X.M., Fu, Y., Lin, H., and Jiang, L.Y. (2016) Mineralogy and mineral chemistry of Bi-minerals: Constraints on ore genesis of the Beiya giant porphyryskarn gold deposit, southwestern China. Ore Geology Reviews, 79, 408–424.10.1016/j.oregeorev.2016.06.008Search in Google Scholar
Zhou, H.Y., Sun, X.M., Cook, N.J., Lin, H., Fu, Y., Zhong, R.C., and Brugger, J. (2017) Nano- to micrometer-scale particulate gold hosted by magnetite: A product of gold scavenging by bismuth melts. Economic Geology, 112, 993–1010.10.2113/econgeo.112.4.993Search in Google Scholar
Zhou, H.Y., Sun, X.M., Wu, Z.W., and Huang, Q. (2019) Timing of skarn gold deposition in the giant Beiya polymetallic gold deposit, southwest China: Constraints from in situ monazite SIMS U-Th-Pb geochronology. Ore Geology Reviews, 106, 226–237.10.1016/j.oregeorev.2019.01.028Search in Google Scholar
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Articles in the same Issue
- P-V-T equation of state of hydrous phase A up to 10.5 GPa
- Elastic properties and structures of pyrope glass under high pressures
- Effects of pH and Ca exchange on the structure and redox state of synthetic Na-birnessite
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- Origin, properties, and structure of breyite: The second most abundant mineral inclusion in super-deep diamonds
- Why Tolbachik diamonds cannot be natural
- Deciphering the enigmatic origin of Guyana’s diamonds
- Precipitation of low-temperature disordered dolomite induced by extracellular polymeric substances of methanogenic Archaea Methanosarcina barkeri: Implications for sedimentary dolomite formation
- Atomic-scale characterization of commensurate and incommensurate vacancy superstructures in natural pyrrhotites
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- New insights into the control of visible gold fineness and deposition: A case study of the Sanshandao gold deposit, Jiaodong, China
- A comment on “An evolutionary system of mineralogy: Proposal for a classification of planetary materials based on natural kind clustering”
- Reply to “A comment on ‘An evolutionary system of mineralogy: Proposal for a classification of planetary materials based on natural kind clustering’”
- New Mineral Names
Articles in the same Issue
- P-V-T equation of state of hydrous phase A up to 10.5 GPa
- Elastic properties and structures of pyrope glass under high pressures
- Effects of pH and Ca exchange on the structure and redox state of synthetic Na-birnessite
- A systematic assessment of the diamond trap method for measuring fluid compositions in high-pressure experiments
- Origin, properties, and structure of breyite: The second most abundant mineral inclusion in super-deep diamonds
- Why Tolbachik diamonds cannot be natural
- Deciphering the enigmatic origin of Guyana’s diamonds
- Precipitation of low-temperature disordered dolomite induced by extracellular polymeric substances of methanogenic Archaea Methanosarcina barkeri: Implications for sedimentary dolomite formation
- Atomic-scale characterization of commensurate and incommensurate vacancy superstructures in natural pyrrhotites
- Three-dimensional and microstructural fingerprinting of gold nanoparticles at fluid-mineral interfaces
- Seaborgite, LiNa6K2(UO2)(SO4)5(SO3OH)(H2O), the first uranyl mineral containing lithium
- Reheating and magma mixing recorded by zircon and quartz from high-silica rhyolite in the Coqen region, southern Tibet
- Crystal chemistry and thermal behavior of Fe-carpholite from the Pollino Massif, southern Italy
- New insights into the control of visible gold fineness and deposition: A case study of the Sanshandao gold deposit, Jiaodong, China
- A comment on “An evolutionary system of mineralogy: Proposal for a classification of planetary materials based on natural kind clustering”
- Reply to “A comment on ‘An evolutionary system of mineralogy: Proposal for a classification of planetary materials based on natural kind clustering’”
- New Mineral Names