Skip to main content

Advertisement

SpringerLink
Log in

Formation of Mg-carbonates and Mg-hydroxides via calcite replacement controlled by fluid pressure

  • Original Paper
  • Published:
Contributions to Mineralogy and Petrology Aims and scope Submit manuscript

Abstract

Reactive fluid flow can control the mineralogical, mechanical and chemical evolution of the Earth’s crust. When rocks are exposed to differential stresses (i.e., vertical stress ≠ horizontal stress ≠ pore-fluid pressure (Pf)) during reactive fluid flow, effective pressure is usually assumed to control the overall reaction process. Here, we show that fluid pressure can play an important role in mineral replacement reactions. We conducted experiments in which calcite (CaCO3) grains (fraction size 53–150 µm) reacted with a Mg-rich solution at ~ 200 °C both in a closed system and under reactive fluid flow conditions with different fluid flow rates and fluid pore pressures, but with similar confining pressure (σn = 10 or 20 MPa) and effective pressure (Pe). Under closed system, vapor-saturated pressures, the magnesite formed with large pores between the magnesite and the calcite. In the open system flow-through experiments, however, brucite (Mg(OH)2) or magnesite (MgCO3) formed, depending on pore-fluid pressure. The main reaction product was brucite at low pore-fluid pressure (0.2 MPa), but magnesite at higher pore-fluid pressures (≥ 1 MPa). Calcite dissolution and precipitation of the product mineral increased concomitantly with flow rate, but the flow rate did not affect the nature of the products. The permeability of the reacting rock was related to the reaction pathway, i.e. the nature of the products. Magnesite replaced the pristine calcite in a pseudomorphic manner, and mantled the pristine calcite with 10–100 µm wide pores. In contrast, tabular and/or platy brucite blocked the porosity and resulted in a decrease in permeability. Our results show that the pore-fluid pressure can be a significant parameter controlling the reaction products and reaction processes in volatile-rich (e.g., CO2, HCl, H2S and SO2) systems at conditions close to phase separation; these conditions occur for example in epithermal and porphyry hydrothermal systems, and in carbonate-replacement and some metamorphic environments.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9

Similar content being viewed by others

References

  • Altree-Williams A, Pring A, Ngothai Y, Brugger J (2015) Textural and compositional complexities resulting from coupled dissolution–reprecipitation reactions in geomaterials. Earth Sci Rev 150:628–651

    Google Scholar 

  • Altree-Williams A, Pring A, Ngothai Y, Brugger J (2017) The carbonatation of anhydrite: kinetics and reaction pathways. ACS Earth Space Chem 1:89–100

    Google Scholar 

  • Arvidson RS, Mackenzie FT (1999) The dolomite problem; control of precipitation kinetics by temperature and saturation state. Am J Sci 299:257–288

    Google Scholar 

  • Bethke CM (1986) Inverse hydrologic analysis of the distribution and origin of Gulf Coast-type geopressured zones. J Geophys Res 91:6535–6545

    Google Scholar 

  • Bethke CM (2007) Geochemical and biogeochemical reaction modeling. Cambridge University Press, Cambridge

    Google Scholar 

  • Bish DL, Post JE (1993) Quantitative mineralogical analysis using the Rietveld full-pattern fitting method. Am Miner 78:932–940

    Google Scholar 

  • Brace W (1972) Pore pressure in geophysics, vol 16. American Geophysical Union Geophysical Monograph Series, Washington, pp 265–273

    Google Scholar 

  • Cartwright I, Weaver TR (1993) Fluid-rock interaction between syenites and marbles at Stephen Cross Quarry, Québec, Canada: petrological and stable isotope data. Contrib Miner Petrol 113:533–544

    Google Scholar 

  • Chang B, Li C, Liu D, Foster I, Tripati A, Lloyd M.K, Maradiaga I, Luo G, An Z, She Z, Xie S (2020) Massive formation of early diagenetic dolomite in the Ediacaran ocean: constraints on the “dolomite problem”. Proceedings of the National Academy of Sciences 117(25):14005–14014. https://doi.org/10.1073/pnas.1916673117

  • Coelho AA, Evans J, Evans I, Kern A, Parsons S (2011) The TOPAS symbolic computation system. Powder Diffr 26:S22–S25

    Google Scholar 

  • De Wolff PM, Walter-Levy L (1953) The crystal structure of Mg2(OH)3(Cl, Br).4H2O. Acta Crystallogr A 6:40–44

    Google Scholar 

  • Duan Z, Sun R, Zhu C, Chou IM (2006) An improved model for the calculation of CO2 solubility in aqueous solutions containing Na+, K+, Ca2+, Mg2+, Cl−, and SO42−. Mar Chem 98:131–139

    Google Scholar 

  • Etschmann B, Brugger J, Pearce M, Ta C, Brautigan D, Jung M, Pring A (2014) Grain boundaries as microreactors during reactive fluid flow: experimental dolomitization of a calcite marble. Contrib Miner Petrol 168:1045

    Google Scholar 

  • Ferry JM, Rumble D III (1997) Formation and destruction of periclase by fluid flow in two contact aureoles. Contrib Miner Petrol 128:313–334

    Google Scholar 

  • Gebauer D, Kellermeier M, Gale JD, Bergström L, Cölfen H (2014) Pre-nucleation clusters as solute precursors in crystallization. Chem Soc Rev 43:2348–2371

    Google Scholar 

  • Heinrich W (2007) Fluid immiscibility in metamorphic rocks. Rev Mineral Geochem 65:389–430

    Google Scholar 

  • Hellmann R, Renders PJ, Gratier J-P, Guiguet R (2002) Experimental pressure solution compaction of chalk in aqueous solutions. Part 1. Deformation behavior and chemistry. Water-rock Interact Ore Deposit Environ Geochem 7:129–152

    Google Scholar 

  • Huang F, Sverjensky DA (2019) Extended Deep Earth Water Model for predicting major element mantle metasomatism. Geochim Cosmochim Acta 254:192–230

    Google Scholar 

  • Jonas L, Müller T, Dohmen R, Baumgartner L, Putlitz B (2015) Transport-controlled hydrothermal replacement of calcite by Mg-carbonates. Geology 43:779–782

    Google Scholar 

  • Jonas L, Müller T, Dohmen R, Immenhauser A, Putlitz B (2017) Hydrothermal replacement of biogenic and abiogenic aragonite by Mg-carbonates–Relation between textural control on effective element fluxes and resulting carbonate phase. Geochim Cosmochim Acta 196:289–306

    Google Scholar 

  • Kaczmarek SE, Sibley DF (2011) On the evolution of dolomite stoichiometry and cation order during high-temperature synthesis experiments: an alternative model for the geochemical evolution of natural dolomites. Sed Geol 240:30–40

    Google Scholar 

  • Kaczmarek SE, Thornton BP (2017) The effect of temperature on stoichiometry, cation ordering, and reaction rate in high-temperature dolomitization experiments. Chem Geol 468:32–41

    Google Scholar 

  • Katz A, Matthews A (1977) The dolomitization of CaCO3: an experimental study at 252–295˚C. Geochim Cosmochim Acta 41:297–308

    Google Scholar 

  • Kessels LA, Sibley DF, Nordeng SH (2000) Nanotopography of synthetic and natural dolomite crystals. Sedimentology 47:173–186

    Google Scholar 

  • Land LS (1998) Failure to precipitate dolomite at 25 ˚C from dilute solution despite 1000-fold oversaturation after 32 years. Aquat Geochem 4:361–368

    Google Scholar 

  • Li Z, Chau CK (2007) Influence of molar ratios on properties of magnesium oxychloride cement. Cem Concr Res 37:866–870

    Google Scholar 

  • Lojka M, Jiříčková A, Lauermannová A-M, Pavlíková M, Pavlík Z, Jankovský O (2019) Kinetics of formation and thermal stability of Mg2(OH)3Cl.4H2O. In: AIP Conference Proceedings, Vol 2170, No 1. AIP Publishing LLC, p 020009. https://doi.org/10.1063/1.5132728

  • Matter JM, Kelemen PB (2009) Permanent storage of carbon dioxide in geological reservoirs by mineral carbonation. Nat Geosci 2:837–841

    Google Scholar 

  • Mei Y, Liu W, Sherman DM, Brugger J (2014) Metal complexation and ion hydration in low density hydrothermal fluids: ab initio molecular dynamics simulation of Cu (I) and Au (I) in chloride solutions (25–1000 C, 1–5000 bar). Geochim Cosmochim Acta 131:196–212

    Google Scholar 

  • Morrissey LJ, Tomkins AG (2020) Evaporite-bearing orogenic belts produce ligand-rich and diverse metamorphic fluids. Geochim Cosmochim Acta 275:163–187

    Google Scholar 

  • Müller T, Baumgartner LP, Foster CT Jr, Vennemann TW (2004) Metastable prograde mineral reactions in contact aureoles. Geology 32:821–824

    Google Scholar 

  • Oh KD, Morikawa H, Iwai SI, Aoki H (1973) The crystal structure of magnesite. Am Miner 58:1029–1033

    Google Scholar 

  • Okamoto A, Shimizu H (2015) Contrasting fracture patterns induced by volume-increasing and-decreasing reactions: implications for the progress of metamorphic reactions. Earth Planet Sci Lett 417:9–18

    Google Scholar 

  • Paquette J, Reeder RJ (1990) Single-crystal X-ray structure refinements of two biogenic magnesian calcite crystals. Am Miner 75:1151–1158

    Google Scholar 

  • Parkhurst DL, Appelo CAJ (2013) Description of input and examples for PHREEQC version 3: a computer program for speciation, batch-reaction, one-dimensional transport, and inverse geochemical calculations, No 6-A43. US Geological Survey. https://doi.org/10.3133/tm6A43

  • Poonoosamy J, Wanner C, Epping PA, Águila JF, Samper J, Montenegro L, Xie M, Su D, Mayer KU, Mäder U, Van Loon LR (2018) Benchmarking of reactive transport codes for 2D simulations with mineral dissolution–precipitation reactions and feedback on transport parameters. Comput Geosci. https://doi.org/10.1007/s10596-018-9793-x

    Article  Google Scholar 

  • Poonoosamy J, Westerwalbesloh C, Deissmann G, Mahrous M, Curti E, Churakov SV, Klinkenberg M, Kohlheyer D, von Lieres E, Bosbach D, Prasianakis NI (2019) A microfluidic experiment and pore scale modelling diagnostics for assessing mineral precipitation and dissolution in confined spaces. Chem Geol 528:119264

    Google Scholar 

  • Popov YA, Pevzner SL, Pimenov VP, Romushkevich RA (1999) New geothermal data from the Kola superdeep well SG-3. Tectonophysics 306:345–366

    Google Scholar 

  • Prasianakis NI, Curti E, Kosakowski G, Poonoosamy J, Churakov SV (2017) Deciphering pore-level precipitation mechanisms. Sci Rep 7:1–9

    Google Scholar 

  • Putnis A (2002) Mineral replacement reactions: from macroscopic observations to microscopic mechanisms. Mineral Mag 66:689–708

    Google Scholar 

  • Putnis A (2009) Mineral replacement reactions. Rev Mineral Geochem 70:87–124

    Google Scholar 

  • Putnis A (2014) Why mineral interfaces matter. Science 343:1441–1442

    Google Scholar 

  • Putnis A, Austrheim H (2010) Fluid-induced processes: metasomatism and metamorphism. Geofluids 10:254–269

    Google Scholar 

  • Putnis A, John T (2010) Replacement processes in the Earth’s crust. Elements 6:159–164

    Google Scholar 

  • Richards JP (2011) Magmatic to hydrothermal metal fluxes in convergent and collided margins. Ore Geol Rev 40:1–26

    Google Scholar 

  • Robin PYF (1973) Note on effective pressure. J Geophys Res 78:2434–2437

    Google Scholar 

  • Rodriguez-Navarro C, Burgos-Cara A, Di Lorenzo F, Ruiz-Agudo E, Elert K (2020) Nonclassical crystallization of calcium hydroxide via amorphous precursors and the role of additives. Cryst Growth Des 20:4418–4432

    Google Scholar 

  • Roehl PO, Choquette PW (2012) Carbonate petroleum reservoirs. Springer Science & Business Media, Berlin

    Google Scholar 

  • Seigneur N, Mayer KU, Steefel CI (2019) Reactive transport in evolving porous media. Rev Mineral Geochem 85:197–238

    Google Scholar 

  • Sibley DF, Nordeng SH, Borkowski ML (1994) Dolomitization kinetics of hydrothermal bombs and natural settings. J Sediment Res 64:630–637

    Google Scholar 

  • Simandl GJ, Paradis S, Irvine M (2007) Brucite-industrial mineral with a future. Geosci Can 34(2):57–64. https://journals.lib.unb.ca/index.php/GC/article/view/10236

  • Urwongse L, Sorrell CA (1980) The system MgO–MgCl2–H2O at 23 ˚C. J Am Ceram Soc 63:501–504

    Google Scholar 

  • Vandeginste V, Snell O, Hall MR, Steer E, Vandeginste A (2019) Acceleration of dolomitization by zinc in saline waters. Nat Commun 10:1851

    Google Scholar 

  • Vitaliano CJ, Callaghan E (1956) Geologic map of the Gabbs magnesite and brucite deposits, Nye County, Nevada. US Geological Survey, Carson

    Google Scholar 

  • Xia F, Brugger J, Chen G, Ngothai Y, O’Neill B, Putnis A, Pring A (2009) Mechanism and kinetics of pseudomorphic mineral replacement reactions: a case study of the replacement of pentlandite by violarite. Geochim Cosmochim Acta 73:1945–1969

    Google Scholar 

  • Xu J, Yan C, Zhang F, Konishi H, Xu H, Teng HH (2013) Testing the cation-hydration effect on the crystallization of Ca–Mg–CO3 systems. Proc Natl Acad Sci 110:17750–17755

    Google Scholar 

  • Yapparova A, Gabellone T, Whitaker F, Kulik DA, Matthäi SK (2017) Reactive transport modelling of dolomitisation using the new csmp++ gem coupled code: Governing equations, solution method and benchmarking results. Transp Porous Media 117:385–413

    Google Scholar 

  • Zang A, Stephansson O (2009) Stress field of the earth’s crust. Springer Science & Business Media, Berlin

    Google Scholar 

  • Zhang X, Spiers CJ, Peach CJ (2011) Effects of pore fluid flow and chemistry on compaction creep of calcite by pressure solution at 150 ˚C. Geofluids 11:108–122

    Google Scholar 

  • Zhao J, Brugger J, Chen G, Ngothai Y, Pring A (2014) Experimental study of the formation of chalcopyrite and bornite via the sulfidation of hematite: mineral replacements with a large volume increase. Am Miner 99:343–354

    Google Scholar 

  • Zhao J, Brugger J, Pring A (2019) Mechanism and kinetics of hydrothermal replacement of magnetite by hematite. Geosci Front 10:29–41

    Google Scholar 

  • Zhong X, Vrijmoed JC, Tajčmanová L (2017) Effect of grain-scale pressure variations on garnet growth: a numerical approach. J Metamorph Geol 35:19–33

    Google Scholar 

  • Zigan F, Rothbauer R (1967) Neutronenbeugungsmessungen am brucit. Neues Jahrbuch für Mineralogie Monatshefte 1967:137–214

    Google Scholar 

Download references

Acknowledgements

We thank the Australian Research Council (Grant DP170101893 to Joël Brugger) for supporting this research and Monash University for offering a scholarship during Gan’s Ph.D research. We acknowledge use of the facilities and the assistance of Xiya Fang at the Monash Centre for Electron Microscopy, Jisheng Ma from Monash X-ray platform and Nick Wilson from the Commonwealth Scientific and Industrial Research Organisation (CSIRO) Clayton. We thank Thibaut Gasst and others from Core Laboratories for helping build up and offer training for the tri-axial flow-through apparatus. We are grateful to two anonymous reviewers for helpful comments that improved the manuscript, and to associate editor Daniela Rubatto for handling this manuscript.

Author information

Authors and Affiliations

  1. School of Earth, Atmosphere and Environment, Monash University, Clayton, VIC, 3168, Australia

    Gan Duan, Joël Brugger, Barbara Etschmann, Rahul Ram, Andrew Frierdich & Steven Micklethwaite

Authors
  1. Gan Duan
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Joël Brugger
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Barbara Etschmann
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Rahul Ram
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Andrew Frierdich
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Steven Micklethwaite
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Joël Brugger.

Additional information

Communicated by Daniela Rubatto.

Publisher's Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary file1 (XLSX 670 KB)

Supplementary file2 (DOCX 2791 KB)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Duan, G., Brugger, J., Etschmann, B. et al. Formation of Mg-carbonates and Mg-hydroxides via calcite replacement controlled by fluid pressure. Contrib Mineral Petrol 176, 1 (2021). https://doi.org/10.1007/s00410-020-01755-4

Download citation

  • Received:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1007/s00410-020-01755-4

Keywords

Search

Navigation