Transport of colloidal Au-bearing nanoparticles driven by metamorphic decarbonization

Abstract

The genesis of bonanza-style gold deposits, characterized by weight-percent-level Au enrichment, challenges conventional models of chemical transport via aqueous complexes. Through high-pressure experiments (0.5-1.5 GPa, 600-1150 °C) combined with thermodynamic modeling and transmission electron microscopy (TEM) analyses, we demonstrate that CO₂-rich fluids generated by metamorphic decarbonization create overpressures exceeding ∼200 MPa. This initiates explosive upward migration of sulfide liquids containing Au-Ag nanoparticles (NPs) into porous peridotite at velocities up to 55.9 ± 12.9 µm/h. High-resolution TEM analyses furthermore confirm the mechanical entrainment of Au-Ag NPs within sulfides. Fractal analysis (FD = 1.55-1.62) of dendritic sulfide networks reveals that viscous fingering dominates fluid dynamics. We propose a unified model where gas-driven filter pressing extracts Au-bearing sulfides from subducted slabs, while viscous fingering further facilitates kilometer-scale transport through lithospheric faults. This novel mechanism bridges mantle-derived carbon fluxes with crustal mineralization, offering new insights into the formation of ultrahigh-grade gold deposits.

Keywords

Orogenic gold deposits / Au-Ag nanoparticles / Sulfides / Gas-driven filter pressing / Viscous fingering / Metamorphic decarbonization

CRediT authorship contribution statement

Zhenjiang Wang: Writing - review & editing, Writing - original draft, Visualization, Methodology, Investigation, Funding acquisition, Data curation, Conceptualization. Shaorui Zhao: Writing - review & editing, Conceptualization. Jingbo Li: Software, Formal analysis. Yanfei Zhang: Writing - review & editing, Methodology. Chao Wang: Writing - review & editing, Investigation. Dan Li: Resources, Conceptualization, Methodology, Writing - review & editing. Zhenmin Jin: Conceptualization.

Declaration of competing interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Acknowledgements

We are grateful to two anonymous reviewers for their useful suggestions and comments, and to Prof. Zhuosen Yao for discussions. We thank Prof. Fabin Pan for help with the EPMA analyses, Prof. Mingxing Gong, Dr. Jinyu Zheng, and Dr. Zhe Gong for their help with FIB and TEM analyses, Prof. Dan Liu and Dr. Sha Wang for their help with Raman analyses. In particular, I am grateful to my wife, Dr. Shasha Guo, for her support and assistance in my life. This work was supported by the DeepEarth Probe and Mineral Resources Exploration-National Science and Technology Major Project (2025ZD1007701), National Natural Science Foundation of China (No. 42102057), Hebei Natural Science Foundation (No. D2025402007), Science Research Project of Hebei Education Department (BJK2024051), and MOST Special Fund from State Key Laboratory of Geological Processes and Mineral Resources, China University of Geosciences (GPMR202413).

Appendix A. Supplementary data

Supplementary data to this article can be found online at https://doi.org/10.1016/j.gsf.2025.102240.

References

[1] Bajgain, S.K., Ashley, A.W., Mookherjee, M., Ghosh, D.B., Karki, B.B., 2022. Insights into magma ocean dynamics from the transport properties of basaltic melt. Nat. Commun. 13, 7590. https://doi.org/10.1038/s41467-022-35171-y.

[2] Bekaert, D.V., Turner, S.J., Broadley, M.W., Barnes, J.D., Halldórsson, S.A., Labidi, J., Wade, J., Walowski, K.J., Barry, P.H., 2021. Subduction-driven volatile recycling: a global mass balance. Annu. Rev. Earth Planet. Sci. 49, 37-70. https://doi.org/10.1146/annurev-earth-071620-055024.

[3] Beyer, C., Bissbort, T., Hartmann, R., Berndt, J., Klemme, S., Fonseca, R.O.C., 2022. High-pressure phase relations in the system Fe-Ni-Cu-S up to 14 GPa: Implications for the stability of sulfides in the earth’s upper mantle. Contrib. Mineral. Petrol. 177, 99. https://doi.org/10.1007/s00410-022-01966-x.

[4] Blanks, D.E., Holwell, D.A., Fiorentini, M.L., Moroni, M., Giuliani, A., Tassara, S., González-Jiménez, J.M., Boyce, A.J., Ferrari, E., 2020. Fluxing of mantle carbon as a physical agent for metallogenic fertilization of the crust. Nat. Commun. 11, 4342. https://doi.org/10.1038/s41467-020-18157-6.

[5] Botcharnikov, R.E., Linnen, R.L., Wilke, M., Holtz, F., Jugo, P.J., Berndt, J., 2011. High gold concentrations in sulphide-bearing magma under oxidizing conditions. Nat. Geosci. 4, 112-115. https://doi.org/10.1038/ngeo1042.

[6] Cano, N., González-Jiménez, J.M., Camprubí A., Morales-Casique, E., González-Partida, E., 2025. Transient non-soluble noble metal transport in hydrothermal ore systems. Nat. Commun. 16, 2521. https://doi.org/10.1038/s41467-025-57740-7.

[7] Cherdantseva, M., Anenburg, M., Fiorentini, M., Mavrogenes, J., 2024a. Carbonated magmatic sulfide systems: still or sparkling? Sci. Adv. 10, eadl3127. https://doi.org/10.1126/sciadv.adl3127.

[8] Cherdantseva, M., Vishnevskiy, A., Jugo, P.J., Martin, L.A.J., Aleshin, M., Roberts, M.P., Shaparenko, E., Langendam, A., Howard, D.L., Fiorentini, M.L., 2024b. Caught in the moment: Interaction of immiscible carbonate and sulfide liquids in mafic silicate magma—insights from the Rudniy intrusion (NW Mongolia). Mineral. Deposita 59, 733-755. https://doi.org/10.1007/s00126-023-01228-1.

[9] Chi, G., Dubé B., Williamson, K., Williams-Jones, A.E., 2006. Formation of the Campbell-Red Lake gold deposit by H₂O-poor, CO₂-dominated fluids. Mineral. Deposita 40, 726-741. https://doi.org/10.1007/s00126-005-0029-3.

[10] Connolly, J.A.D., 2009. The geodynamic equation of state: what and how. Geochem. Geophys. Geosyst. 10, Q10014. https://doi.org/10.1029/2009GC002540.

[11] Dasgupta, R., Buono, A., Whelan, G., Walker, D., 2009. High-pressure melting relations in Fe-C-S systems: Implications for formation, evolution, and structure of metallic cores in planetary bodies. Geochim. Cosmochim. Acta 73, 6678-6691. https://doi.org/10.1016/j.gca.2009.08.001.

[12] Degruyter, W., Parmigiani, A., Huber, C., Bachmann, O., 2019. How do volatiles escape their shallow magmatic hearth? Phil. Trans. r. Soc. Ser. a: Mathematical, Physical and Engineering Sciences 377, 20180017. https://doi.org/10.1098/rsta.2018.0017.

[13] Delpech, G., Lorand, J.P., Grégoire, M., Cottin, J.Y., O’Reilly, S.Y., 2012. In-situ geochemistry of sulfides in highly metasomatized mantle xenoliths from Kerguelen, southern Indian Ocean. Lithos 154, 296-314. https://doi.org/10.1016/j.lithos.2012.07.018.

[14] Deng, J., Yang, L.Q., Groves, D.I., Zhang, L., Qiu, K.F., Wang, Q.F., 2020. An integrated mineral system model for the gold deposits of the giant Jiaodong province, eastern China. Earth-Sci. Rev. 208, 103274. https://doi.org/10.1016/j.earscirev.2020.103274.

[15] Fan, G.H., Li, J.W., Wu, Y.F., Hu, S.Y., Deng, X.D., Zhou, H.Y., Li, Z.K., Liu, Y., 2024. Nanoparticle attachment promotes nugget effect of Au-rich metallic melts in hydrothermal ore deposits. Contrib. Mineral. Petrol. 179, 107. https://doi.org/10.1007/s00410-024-02184-3.

[16] Farsang, S., Zajacz, Z., 2024. Sulfur species and gold transport in arc magmatic fluids. Nat. Geosci. 18, 98-104. https://doi.org/10.1038/s41561-024-01601-3.

[17] Foley, S.F., Yaxley, G.M., Rosenthal, A., Buhre, S., Kiseeva, E.S., Rapp, R.P., Jacob, D.E., 2009. The composition of near-solidus melts of peridotite in the presence of CO₂ and H₂O between 40 and 60 kbar. Lithos 112, 274-283. https://doi.org/10.1016/j.lithos.2009.03.020.

[18] Gartman, A., Hannington, M., Jamieson, J.W., Peterkin, B., Garbe-Schönberg, D., Findlay, A.J., Fuchs, S., Kwasnitschka, T., 2018. Boiling-induced formation of colloidal gold in black smoker hydrothermal fluids. Geology 46, 39-42. https://doi.org/10.1130/G39492.1.

[19] Géraud, Y., Diraison, M., Orellana, N., 2006. Fault zone geometry of a mature active normal fault: a potential high permeability channel ( Pirgaki fault, Corinth rift, Greece). Tectonophysics 426, 61- 76. https://doi.org/10.1016/j.tecto.2006.02.023.

[20] Goldfarb, R.J., Groves, D.I., 2015. Orogenic gold: Common or evolving fluid and metal sources through time. Lithos 233, 2-26. https://doi.org/10.1016/j.lithos.2015.07.011.

[21] Groves, D.I., Santosh, M., 2016. The giant Jiaodong gold province: the key to a unified model for orogenic gold deposits? Geosci. Front. 7, 409-417. https://doi.org/10.1016/j.gsf.2015.08.002.

[22] Groves, D.I., Santosh, M., Deng, J., Wang, Q., Yang, L., Zhang, L., 2020. A holistic model for the origin of orogenic gold deposits and its implications for exploration. Mineral. Deposita 55, 275-292. https://doi.org/10.1007/s00126-019-00877-5.

[23] Hannington, M., Hardardóttir, V., Garbe-Schönberg, D., Brown, K.L., 2016. Gold enrichment in active geothermal systems by accumulating colloidal suspensions. Nat. Geosci. 9, 299-302. https://doi.org/10.1038/ngeo2661.

[24] Heinrich, C.A., Connolly, J.A.D., 2022. Physical transport of magmatic sulfides promotes copper enrichment in hydrothermal ore fluids. Geology 50, 1101-1105. https://doi.org/10.1130/G50138.1.

[25] Hochella, M.F., Lower, S.K., Maurice, P.A., Penn, R.L., Sahai, N., Sparks, D.L., Twining, B.S., 2008. Nanominerals, mineral nanoparticles, and earth systems. Science 319, 1631-1635. https://doi.org/10.1126/science.1141134.

[26] Holland, T.J.B., Powell, R., 2011. An improved and extended internally consistent thermodynamic dataset for phases of petrological interest, involving a new equation of state for solids. J. Metamorph. Geol. 29, 333-383. https://doi.org/10.1111/j.1525-1314.2010.00923.x.

[27] Huber, C., Bachmann, O., Vigneresse, J., Dufek, J., Parmigiani, A., 2012. A physical model for metal extraction and transport in shallow magmatic systems. Geochem. Geophys. Geosyst. 13, G08003. https://doi.org/10.1029/2012GC004042.

[28] Iacono-Marziano, G., Le Vaillant, M., Godel, B.M., Barnes, S.J., Arbaret, L., 2022. The critical role of magma degassing in sulphide melt mobility and metal enrichment. Nat. Commun. 13, 2359. https://doi.org/10.1038/s41467-022-30107-y.

[29] Kesharwani, P., Ma, R., Sang, L., Fatima, M., Sheikh, A., Abourehab, M.A.S., Gupta, N., Chen, Z.S., Zhou, Y., 2023. Gold nanoparticles and gold nanorods in the landscape of cancer therapy. Mol. Cancer 22, 98. https://doi.org/10.1186/s12943-023-01798-8.

[30] Kiseeva, E.S., Fonseca, R.O.C., Smythe, D.J., 2017. Chalcophile elements and sulfides in the upper mantle. Elements 13, 111-116. https://doi.org/10.2113/gselements.13.2.111.

[31] Kono, Y., Kenney-Benson, C., Shibazaki, Y., Park, C., Shen, G., Wang, Y., 2015. High-pressure viscosity of liquid Fe and FeS revisited by falling sphere viscometry using ultrafast X-ray imaging. Phys. Earth Planet. Inter. 241, 57-64. https://doi.org/10.1016/j.pepi.2015.02.006.

[32] Le Vaillant, M., Barnes, S.J., Mungall, J.E., Mungall, E.L., 2017. Role of degassing of the Noril’sk nickel deposits in the Permian-Triassic mass extinction event. Proc. Nat. Acad. Sci. 114, 2485-2490. https://doi.org/10.1073/pnas.1611086114.

[33] Lowenstern, J., 2001. Carbon dioxide in magmas and implications for hydrothermal systems. Mineral. Deposita 36, 490-502. https://doi.org/10.1007/s001260100185.

[34] Matsukage, K.N., Nishihara, Y., Karato, S.I., 2005. Seismological signature of chemical differentiation of Earth’s upper mantle. J. Geophys. Res. Solid Earth 110, B12305. https://doi.org/10.1029/2004JB003504.

[35] McKenzie, D., 1984. The generation and compaction of partially molten rock. J. Petrol. 25, 713-765. https://doi.org/10.1093/petrology/25.3.713.

[36] McLeish, D.F., Williams-Jones, A.E., Vasyukova, O.V., Clark, J.R., Board, W.S., 2021. Colloidal transport and flocculation are the cause of the hyperenrichment of gold in nature. Proc. Nat. Acad. Sci. 118, e2100689118. https://doi.org/10.1073/pnas.2100689118.

[37] McNab, R.R., Brugger, J., Voisey, C.R., Tomkins, A.G., 2024. Coprecipitation of amorphous silica and gold nanoparticles contributes to gold hyperenrichment. Geology 52, 737-741. https://doi.org/10.1130/g52138.1.

[38] Mernagh, T.P., Wygralak, A.S., 2007. Gold ore-forming fluids of the Tanami region, Northern Australia. Mineral. Deposita 42, 145-173. https://doi.org/10.1007/s00126-006-0098-y.

[39] Miller, J.M., Wilson, C.J.L., 2004. Stress controls on intrusion-related gold lodes: Wonga gold mine, Stawell, western Lachlan fold belt, southeastern Australia. Econ. Geol. 99, 941-963. https://doi.org/10.2113/gsecongeo.99.5.941.

[40] Miller, K.J., Montési, L.G.J., Zhu, W.L., 2015. Estimates of olivine-basaltic melt electrical conductivity using a digital rock physics approach. Earth Planet. Sci. Lett. 432, 332-341. https://doi.org/10.1016/j.epsl.2015.10.004.

[41] Miller, K.J., Zhu, W.L., Montési, L.G.J., Gaetani, G.A., Le Roux, V., Xiao, X., 2016. Experimental evidence for melt partitioning between olivine and orthopyroxene in partially molten harzburgite. J. Geophys. Res. [Solid Earth] 121, 5776- 5793. https://doi.org/10.1002/2016JB013122.

[42] Mungall, J., Brenan, J., 2014. Partitioning of platinum-group elements and Au between sulfide liquid and basalt and the origins of mantle-crust fractionation of the chalcophile elements. Geochim. Cosmochim. Acta 125, 265-289. https://doi.org/10.1016/j.gca.2013.10.002.

[43] Mungall, J.E., Brenan, J.M., Godel, B., Barnes, S.J., Gaillard, F., 2015. Transport of metals and sulphur in magmas by flotation of sulphide melt on vapour bubbles. Nat. Geosci. 8, 216-219. https://doi.org/10.1038/ngeo2373.

[44] Nishiyama, N., Sumino, H., Ujiie, K., 2020. Fluid overpressure in subduction plate boundary caused by mantle-derived fluids. Earth Planet. Sci. Lett. 538, 116199. https://doi.org/10.1016/j.epsl.2020.116199.

[45] Parmigiani, A., Degruyter, W., Leclaire, S., Huber, C., Bachmann, O., 2017. The mechanics of shallow magma reservoir outgassing. Geochem. Geophys. Geosyst. 18, 2887-2905. https://doi.org/10.1002/2017GC006912.

[46] Parmigiani, A., Faroughi, S., Huber, C., Bachmann, O., Su, Y., 2016. Bubble accumulation and its role in the evolution of magma reservoirs in the upper crust. Nature 532, 492-495. https://doi.org/10.1038/nature17401.

[47] Peterson, E.C., Mavrogenes, J.A., 2014. Linking high-grade gold mineralization to earthquake-induced fault-valve processes in the Porgera gold deposit, Papua New Guinea. Geology 42, 383-386. https://doi.org/10.1130/G35286.1.

[48] Petrella, L., Thebaud, N., Fougerouse, D., Tattitch, B., Martin, L., Turner, S., Suvorova, A., Gain, S., 2022. Nanoparticle suspensions from carbon-rich fluid make high-grade gold deposits. Nat. Commun. 13, 3795. https://doi.org/10.1038/s41467-022-31447-5.

[49] Pistone, M., Arzilli, F., Dobson, K.J., Cordonnier, B., Reusser, E., Ulmer, P., Marone, F., Whittington, A.G., Mancini, L., Fife, J.L., Blundy, J.D., 2015. Gas-driven filter pressing in magmas: Insights into in-situ melt segregation from crystal mushes. Geology 43, 699-702. https://doi.org/10.1130/G36766.1.

[50] Pokrovski, G.S., Akinfiev, N.N., Borisova, A.Y., Zotov, A.V., Kouzmanov, K., 2014. Gold speciation and transport in geological fluids: insights from experiments and physical-chemical modelling. Geol. Soc. London Spec. Pub. 402, 9-70. https://doi.org/10.1144/sp402.4.

[51] Primkulov, B.K., Pahlavan, A.A., Fu, X., Zhao, B., MacMinn, C.W., Juanes, R., 2021. Wettability and Lenormand’s diagram. J. Fluid Mech. 923, A34. https://doi.org/10.1017/jfm.2021.579.

[52] Qiu, K.F., Romer, R.L., Long, Z.Y., Williams-Jones, A.E., Yu, H.C., Turner, S., Wang, Q.F., Li, S.S., Zhang, J.Y., Duan, H.R., Deng, J., 2024. The role of an oxidized lithospheric mantle in gold mobilization. Sci. Adv. 10, eado6262. https://doi.org/10.1126/sciadv.ado6262.

[53] Saffer, D.M., Tobin, H.J., 2011. Hydrogeology and mechanics of subduction zone forearcs: Fluid flow and pore pressure. Annu. Rev. Earth Planet. Sci. 39, 157-186. https://doi.org/10.1146/annurev-earth-040610-133408.

[54] Simmons, S.F., Brown, K.L., 2006. Gold in magmatic hydrothermal solutions and the rapid formation of a giant ore deposit. Science 314, 288-291. https://doi.org/10.1126/science.1132866.

[55] Sibson, R.H., Robert, F., Poulsen, K.H., 1988. High-angle reverse faults, fluid-pressure cycling, and mesothermal gold-quartz deposits. Geology 16, 551-555. https://doi.org/10.1130/0091-7613(1988)0162.3.CO;2.

[56] Sisson, T.W., Bacon, C.R., 1999. Gas-driven filter pressing in magmas. Geology 27, 613-616. https://doi.org/10.1130/0091-7613(1999)0272.3.CO;2.

[57] Span, R., Wagner, W., 1996. A new equation of state for carbon dioxide covering the fluid region from the triple-point temperature to 1100 K at pressures up to 800 MPa. J. Phys. Chem. Ref. Data 25, 1509-1596. https://doi.org/10.1063/1.555991.

[58] Sundström, A.W., Eksteen, J.J., Georgalli, G.A., 2008. A review of the physical properties of base metal mattes. J. S. Afr. Inst. Min. 108, 431-448.

[59] Terasaki, H., Kato, T., Urakawa, S., Funakoshi, K., Suzuki, A., Okada, T., Maeda, M., Sato, J., Kubo, T., Kasai, S., 2001. The effect of temperature, pressure, and sulfur content on viscosity of the Fe-FeS melt. Earth Planet. Sci. Lett. 190, 93-101. https://doi.org/10.1016/S0012-821X(01)00374-0.

[60] von Bargen, N., Waff, H.S., 1986. Permeabilities, interfacial areas and curvatures of partially molten systems: results of numerical computations of equilibrium microstructures. J. Geophys. Res. Solid Earth 91, 9261-9276. https://doi.org/10.1029/jb091ib09p09261.

[61] Walter, M.J., 1998. Melting of garnet peridotite and the origin of komatiite and depleted lithosphere. J. Petrol. 39, 29-60. https://doi.org/10.1093/petroj/39.1.29.

[62] Wang, X., Wang, Z., Cheng, H., Zong, K., Wang, C.Y., Ma, L., Cai, Y.C., Foley, S., Hu, Z., 2022. Gold endowment of the metasomatized lithospheric mantle for giant gold deposits: Insights from lamprophyre dykes. Geochim. Cosmochim. Acta 316, 21-40. https://doi.org/10.1016/j.gca.2021.10.006.

[63] Wang, Z., Jin, Z., Mungall, J.E., Xiao, X., 2020. Transport of coexisting Ni-Cu sulfide liquid and silicate melt in partially molten peridotite. Earth Planet. Sci. Lett. 536, 116162. https://doi.org/10.1016/j.epsl.2020.116162.

[64] Wang, Z., Yao, Z., Jin, Z., Wang, Y., 2023. Experimental investigation on the transport of sulfide driven by melt-rock reaction in partially molten peridotite. J. Geophys. Res. Solid Earth 128, e2022JB026065. https://doi.org/10.1029/2022jb026065.

[65] Weatherley, D.K., Henley, R.W., 2013. Flash vaporization during earthquakes evidenced by gold deposits. Nat. Geosci. 6, 294-298. https://doi.org/10.1038/ngeo1759.

[66] Williams-Jones, A.E., Bowell, R.J., Migdisov, A.A., 2009. Gold in solution. Elements 5, 281-287. https://doi.org/10.2113/gselements.5.5.281.

[67] Wu, Y.F., Li, J.W., Evans, K., Koenig, A.E., Li, Z.K., O’Brien, H., Lahaye, Y., Rempel, K., Hu, S.Y., Zhang, Z.P., Yu, J.P., 2018. Ore-forming processes of the Daqiao epizonal orogenic gold deposit, west Qinling orogen, China: Constraints from textures, trace elements, and sulfur isotopes of pyrite and marcasite, and Raman spectroscopy of carbonaceous material. Econ. Geol. 113, 1093-1132. https://doi.org/10.5382/econgeo.2018.4583.

[68] Wu, Y.F., Evans, K., Williams-Jones, A.E., Fougerouse, D., Rempel, K., Guagliardo, P., Li, J.W., 2024. Efficient gold scavenging by iron sulfide colloids in an epizonal orogenic gold deposit. Geochim. Cosmochim. Acta 379, 111-123. https://doi.org/10.1016/j.gca.2024.06.039.

[69] Yao, Z., Mungall, J.E., 2020. Flotation mechanism of sulphide melt on vapour bubbles in partially molten magmatic systems. Earth Planet. Sci. Lett. 542, 116298. https://doi.org/10.1016/j.epsl.2020.116298.

[70] Zhang, Z., Hirschmann, M.M., 2016. Experimental constraints on mantle sulfide melting up to 8 GPa. Am. Mineral. 101, 181-192. https://doi.org/10.2138/am-2016-5308.

[71] Zhang, Z., von der Handt, A., Hirschmann, M.M., 2018. An experimental study of Fe-Ni exchange between sulfide melt and olivine at upper mantle conditions: Implications for mantle sulfide compositions and phase equilibria. Contrib. Mineral. Petrol. 173, 19. https://doi.org/10.1007/s00410-018-1444-7.

[72] Zou, Y., Chu, X., Mitchell, R.N., Li, Q., Zhao, L., Tang, Y., Guo, J., Zhai, M., 2025. Dehydration-induced supralithostatic fluid overpressure in metapelites from Northern Korea. Commun. Earth Environ. 6, 130. https://doi.org/10.1038/s43247-025-02125-3.