Abstract
Limestone dolomitization is an example of a fluid-induced mineralogical transformation that commonly affects extensive rock volumes. To understand the mechanisms enabling these efficient replacement reactions, we investigated experimentally the dolomitization of a fractured calcite marble under flow-through conditions at mild hydrothermal conditions. Contrary to most earlier studies of coupled dissolution reprecipitation reactions that were conducted using small, individual grains, in this study, the integrity of the rock was preserved, so that the experiment explored the links between flow in a fracture and fluid–rock interaction. In these experiments, grain boundaries acted as microreactors, in which a Mg-poor ‘protodolomite’ formed initially, and then transformed into dolomite. The difficulty in nucleating dolomite played a key role in controlling the evolution of the porosity, by allowing for (1) initial dissolution along grain boundaries, and (2) formation of coarse porosity at the reaction interface. This porosity evolution not only enabled the reaction to progress efficiently, but also controlled the mineralogy of the system, as shown by brucite replacing calcite near the fracture once the fluid along calcite grain boundaries became sufficiently connected to the fluid flowing through the fracture. This study illustrates the role of grain boundaries, porosity evolution and nucleation in controlling reaction progress as well as the nature and textures of the products in pervasive mineralogical transformations.
Similar content being viewed by others
References
Al-Awadi M, Clark WJ, Moore WR, Herron M, Zhang T, Zhao W, Hurley N, Kho D, Montaron B, Sadooni F (2009) Dolomite: perspectives on a perplexing mineral. Oilfield Rev 21(3):32–45
Andreani M, Luquot L, Gouze P, Godard M, Hoise E, Gibert B (2009) Experimental study of carbon sequestration reactions controlled by the percolation of CO2-rich brine through peridotites. Environ Sci Technol 43(4):1226–1231
Antao SM, Mulder WH, Hassan I, Crichton WA, Parise JB (2004) Cation disorder in dolomite, CaMg(CO3)2, and its influence on the aragonite + magnesite − dolomite reaction boundary. Am Mineral 89:1142–1147
Arvidson RS, MacKenzie FT (1999) The dolomite problem: control of precipitation kinetics by temperature and saturation state. Am J Sci 299:257–288
Baker PA, Kaster M (1981) Constraints on the formation of sedimentary dolomite. Science 213:214–216
Bethke CM (2008) Geochemical and biogeochemical reaction modeling, 2nd edn. Cambridge University Press, New York, p 564
Bickle M, Baker J (1990) Migration of reaction and isotopic fronts in infiltration zones: assessments of fluid flux in metamorphic terrains. Earth Planet Sci Lett 98(1):1–13
Borg S, Liu W, Pearce M, Cleverley J, MacRae C (2014) Complex mineral zoning patterns caused by ultra-local equilibrium at reaction interfaces. Geology. Published on-line March 2014. doi:10.1130/G35287.1
Brady PV, Krumhansi JL, Papenguth HW (1996) Surface complexation clues to dolomite growth. Geochim Cosmochim Acta 60(4):727–731
Brugger J, McFadden A, Lenehan CE, Etschmann B, Xia F, Zhao J, Pring A (2010) A novel route for the synthesis of mesoporous and low-thermal stability materials by coupled dissolution–reprecipitation reactions: mimicking hydrothermal mineral formation. Chimia 64:693–698. doi:10.2533/chimia.2010.693
Chessin H, Hamilton WC, Post B (1965) Position and thermal parameters of oxygen atoms in calcite. Acta Cryst A 18:689–693
Dohmen R, Milke R (2010) Diffusion in polycrystalline materials grain boundaries, mathematical models, and experimental data. In: Zhang YX, Cherniak DJ (eds) Diffusion in minerals and melts. Reviews in Mineralogy & Geochemistry, 72:921–970
Goldsmith JR, Graf DL (1958) Structural and compositional variations in some natural dolomites. J Geol 66:678–693
Hardie LA (1987) Dolomitization: a critical view of some current views. J Sediment Petrol 57(1):166–183
Herzig C, Divinski S (2003) Grain boundary diffusion in metals: recent developments. Mater Trans 44:14–27
Holness MB, Graham CM (1991) Equilibrium dihedral angles in the system H2O–CO2–NaCl-calcite, and implications for fluid-flow during metamorphism. Contrib Miner Petrol 108(3):368–383
Hövelmann J, Putnis A, Geisler T, Schmidt BC, Golla-Schindler U (2010) The replacement of plagioclase feldspars by albite: observations from hydrothermal experiments. Contrib Miner Petrol 159(1):43–59
Hövelmann J, Austrheim H, Jamtveit B (2012) Microstructure and porosity evolution during experimental carbonation of a natural peridotite. Chem Geol 334:254–265
Janssen A, Putnis A, Geisler T, Putnis CV (2010) The experimental replacement of ilmenite by rutile in HCl solutions. Mineral Mag 74(4):633–644
Jonas L, John T, King HE, Geisler T, Putnis A (2014) The role of grain boundaries and transient porosity in rocks as fluid pathways for reaction front propagation. Earth Planet Sci Lett 386:64–74
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. Sediment Geol 240:30–40
Katz A, Matthews A (1977) The dolomitization of CaCO3: an experimental study at 252–295 °C. Geochim Cosmochim Acta 41:297–312
Lund LS (1998) Failure to precipitate dolomite at 25 °C from dilute solution despite 1000-fold oversaturation after 32 years. Aquat Geochem 4:361–368
Oliver NHS, Cleverley JS, Mark G, Pollard PJ, Fu B, Marshall LJ, Rubenach MJ, Williams PJ, Baker T (2004) Modeling the role of sodic alteration in the genesis of iron oxide-copper-gold deposits, Eastern Mount Isa block, Australia. Econ Geol 99:1145–1176
Pearce MA, Timms NE, Hough RM, Cleverley JS (2013) Reaction mechanism for the replacement of calcite by dolomite and siderite: implications for geochemistry, microstructure and porosity evolution during hydrothermal mineralisation. Contrib Miner Petrol 166:995–1009
Pilati T, Demartin F, Gramaccioli CM (1998) Lattice-dynamical estimation of atomic displacement parameters in carbonates: calcite and aragonite CaCO3, dolomite CaMg(CO3)2, and magnesite MgCO3. Acta Crystallographica B 54:515–523
Plümper O, Røyne A, Magraso A, Jamtveit B (2012) The interface-scale mechanism of reaction-induced fracturing during serpentinization. Geology 40:1103–1106
Putnis A (2009) Mineral replacement reactions. Rev Mineral Geochem 70:87–124
Putnis A, Austrheim H (2010) Fluid-induced processes: metasomatism and metamorphism. Geofluids 10:254–269. doi:10.1111/j.1468-8123.2010.00285.x
Qian G, Brugger J, Skinner WM, Chen G, Pring A (2010) An experimental study of the mechanism of the replacement of magnetite by pyrite up to 300 °C. Geochim Cosmochim Acta 74:5610–5630
Sibley DF (1982) The origin of common dolomite fabrics—clues from the Pliocene. J Sediment Petrol 52:1087–1100
Sibley DF, Dedoes RE, Bartlett TR (1987) Kinetics of dolomitization. Geology 15:1112–1114
Sibley DF, Nordeng SH, Borkowski ML (1994) Dolomitization kinetics in hydrothermal bombs and natural settings. J Sediment Res A64:630–637
Usdowski E (1994) Synthesis of dolomite and geochemical implications. In: Dolomites: a volume in honor of Dolomieu. International Association of Sedimentologists Special Publication, vol 21, pp 345–360
Van Noort R, Spiers CJ, Drury MR, Kandianis MT (2013) Peridotite dissolution and carbonation rates at fracture surfaces under conditions relevant for in situ mineralization of CO2. Geochim Cosmochim Acta 106:1–24
Warren J (2000) Dolomite: occurrence, evolution and economically important associations. Earth Sci Rev 52:1–81
Wolery TJ (1992) EQ3NR, a computer program for geochemical aqueous speciation-solubility calculations: theoretical manual, user’s guide, and related documentation (Version 7.0). Lawrence Livermore National Laboratory
Xia F, Brugger J, Ngothai Y, O’Neill B, Chen G, Pring A (2009a) Three-dimensional ordered arrays of zeolite nanocrystals with uniform size and orientation by a pseudomorphic coupled dissolution–reprecipitation replacement route. Cryst Growth Des 9(11):4902–4906
Xia F, Brugger J, Chen G, Ngothai Y, O’Neill B, Punis A, Pring A (2009b) Mechanism and kinetics of pseudomorphic mineral replacement reactions: a case study of the replacement of pentlandite by violarite. Geochim Cosmochim Acta 73:1945–1969
Zhao H, Jones B (2012) Genesis of fabric-destructive dolostones: a case study of the Brac formation (Oligocene), Cayman Brac, British New Indies. Sediment Geol 267–268:36–54
Zhao J, Brugger J, Grundler PV, Xia F, Chen GR, Pring A (2009) Mechanism and kinetics of a mineral transformation under hydrothermal conditions: calaverite to metallic gold. Am Mineral 94:1541–1555
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 Mineral 99:343–354
Zhukhlistov AP, Avilov AS, Ferraris D, Zvyagin BB, Plotnikov VP (1997) Statistical distribution of hydrogen over three positions in the brucite Mg(OH)2 structure from electron diffractometry data. Kristallografiya 22:200–206
Acknowledgments
The financial support of SACGER, University of Adelaide, ARENA and the Australian Research Council (DP1095069) is gratefully acknowledged. M.A.P. is funded by a CSIRO Office of the Chief Executive Postdoctoral Fellowship. The paper benefited from the suggestions of three anonymous reviewers.
Author information
Authors and Affiliations
Corresponding author
Additional information
Communicated by Prof. Jochen Hoefs.
Rights and permissions
About this article
Cite this article
Etschmann, B., Brugger, J., Pearce, M.A. et al. Grain boundaries as microreactors during reactive fluid flow: experimental dolomitization of a calcite marble. Contrib Mineral Petrol 168, 1045 (2014). https://doi.org/10.1007/s00410-014-1045-z
Received:
Accepted:
Published:
DOI: https://doi.org/10.1007/s00410-014-1045-z