Mineral growth in rocks: kinetic-rheological models of replacement, vein formation, and syntectonic crystallization

Fletcher, Robert J.; Merino, Enrique

doi:10.1016/s0016-7037(01)00726-8

Cited by 122 publications

(89 citation statements)

References 38 publications

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“…However, the rate of metasomatism is slower at low temperatures than the rate of metasomatism at high temperatures. The results of this study are consistent with those reported previously, which state that the rates of dissolution and precipitation of minerals during metasomatism are controlled by the reaction temperature (Merino et al, 1993(Merino et al, , 1994Wang et al, 1995;Merino, 1996, 1997;Merino and Dewers, 1998;Fletcher and Merino, 2001). William (1945) reported narrow rims of scheelite surrounding huebnerite in the tungsten deposit near Townsville.…”

Section: Discussionsupporting

confidence: 92%

Experimental study on metasomatism in huebnerite — CaCl2 solution system

Tamura

Shikazono

Nakata

2009

Journal of Mineralogical and Petrological Sciences

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Experiments on metasomatism in a system comprising huebnerite and aqueous CaCl 2 solution were performed at 130, 150, and 170 °C. SEM observations revealed the formation of euhedral crystals of scheelite replacing huebnerite in all experiments. The replacement texture of huebnerite by scheelite was classified as rim replacement texture. Although the molar volume ratio of replacing mineral to replaced mineral was 1.12 for the present study, huebnerite was replaced by scheelite. This suggests that the influence of molar volume ratio is small on the metasomatism of huebnerite to scheelite, which has not been expected in previous studies. Our results also suggest that the metasomatism of huebnerite to scheelite can be achieved if the CaCl 2 concentration in the solution and the reaction temperature are sufficiently high. The apparent rate constant k for huebnerite dissolution in the metasomatism is approximately 10 −9 -10 −6 mol l −1 s −1 ; the activation energies are 9.6, 20.7, and 31.2 kJ/mol for CaCl 2 concentrations of 0.01, 0.10, and 1.00 mol/l, respectively. The precipitation of scheelite can be the rate -determining process of the metasomatism during the initial stage when the W concentration in the solution is high.

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Section: Discussionsupporting

confidence: 92%

Experimental study on metasomatism in huebnerite — CaCl2 solution system

Tamura

Shikazono

Nakata

2009

Journal of Mineralogical and Petrological Sciences

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“…Examples of mineral reactions that have been shown or are believed to produce a FoC include (a) uptake of crystallisation water by thenardite to produce mirabilite [35,118], (b) delayed ettringite formation in concrete [37,54,116], (c) serpentinisation and possibly carbonation of peridotite [60,67,68,97,104], (d) replacement of leucite by analcime in low-silica rocks [61], (e) conversion of anhydrite into gypsum [70] and (f) the hydration of metal oxides such as quicklime (CaO) and periclase (MgO) [43,94]. In a geological context, development of a force of crystallisation is widely considered to play an important role in pseudomorphic replacement [40,89], as well as vein formation [40,47,87,114] and reaction-driven fracturing [61,97,100,104]. Despite this previous work on FoC-related processes, relatively few studies have been conducted where the magnitude of the FoC is determined directly.…”

Section: Force Of Crystallisation: Examples and Previous Measurementsmentioning

confidence: 99%

Reaction-driven casing expansion: potential for wellbore leakage mitigation

2017

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It is generally challenging to predict the postabandonment behaviour and integrity of wellbores. Leakage is, moreover, difficult to mitigate, particularly between the steel casing and outer cement sheath. Radially expanding the casing with some form of internal plug, thereby closing annular voids and fractures around it, offers a possible solution to both issues. However, such expansion requires development of substantial internal stresses. Chemical reactions that involve a solid volume increase and produce a force of crystallisation (FoC), such as CaO hydration, offer obvious potential. However, while thermodynamically capable of producing stresses in the GPa range, the maximum stress obtainable by CaO hydration has not been validated or determined experimentally. Here, we report uniaxial compaction/expansion experiments performed in an oedometer-type apparatus on precompacted CaO powder, at 65°C and at atmospheric pore fluid pressure. Using this set-up, the FoC generated during CaO hydration could be measured directly. Our results show FoC-induced stresses reaching up to 153 MPa, with reaction stopping or slowing down before completion. Failure to achieve the GPa stresses predicted by theory is attributed to competition between FoC development and its inhibiting effect on reaction progress. Microstructural observations indicate that reaction-induced stresses shut down pathways for water into the sample, hampering ongoing reaction and limiting the magnitude of stress build-up to the values observed. The results nonetheless point the way to understanding the behaviour of such systems and to finding engineering solutions that may allow large controlled stresses and strains to be achieved in wellbore sealing operations in future.

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“…Our discussion here, a summary from a review in progress, is based on four crucial papers: Bastin and others (1931), Maliva and Siever (1988), Dewers and Ortoleva (1989), and Nahon and Merino (1997). Others also relevant are those by Carmichael (1987), Merino and others (1993), Merino and Dewers (1998), Fletcher and Merino (2001), Merino and Banerjee (2008), and Banerjee and Merino (2011).…”

Section: Replacement Physicsmentioning

confidence: 97%

“…Dewers and Ortoleva (1989) applied the Navier-Stokes equation for momentum conservation to demonstrate that growth in a rigid rock must trigger other mineral reaction(s) such that volume is conserved; they thus demonstrated theoretically the existence of the replacement phenomenon. Fletcher and Merino (2001) showed that the correct coupling factor required for the equalization of volumetric rates in replacement was the crystallization stress or induced stress, which can enter into a feedback with the rates of guest growth and host dissolution, whereas the empirical force of crystallization cannot. Nahon and Merino (1997) showed how the rates are made to become mutually equal by the crystallization stress ( fig.…”

Section: Replacement Physicsmentioning

confidence: 99%

Self-accelerating dolomite-for-calcite replacement: Self-organized dynamics of burial dolomitization and associated mineralization

Merino¹,

Canals²

2011

American Journal of Science

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ABSTRACT. A new dynamic model of dolomitization predicts a multitude of textural, paragenetic, geochemical and other properties of burial dolomites. The model is based on two postulates, (1) that the dolomitizing brine is Mg-rich but undersaturated with both calcite and dolomite, and (2) that the dolomite-for-calcite replacement happens not by dissolution-precipitation as usually assumed, but by dolomite-growth-driven pressure solution of the calcite host. Crucially, the dolomitefor-calcite replacement turns out to be self-accelerating via Ca 2؉ : the Ca 2؉ released by each replacement increment accelerates the rate of the next, and so on. As a result, both pore-fluid Ca 2؉ and replacement rate grow exponentially. As brine enters and infiltrates a limestone, water/rock disequilibrium plus the self-accelerating feedback inevitably yield a process that is self-organized, both in time (as repeated dolomite growth pulses per slice of limestone) and in space (as successive slices). Self-organization in pulses and slices accounts for several properties of burial dolomites: (1) generation of dissolution porosity and its spatially periodic distribution; (2) dolomitization affects only limestones; (3) sharp field contacts between dolomitized and undolomitized limestone; (4) formation of both saddle dolomite and "late-stage" calcite near the end of each growth pulse, accompanied by MississippiValley-type ores if the brine also contains Zn, Pb, Ba, sulfate, and other relevant elements; (5) "sweeping" of ores downflow with accumulation in the last position of the dolomitization front.In addition, the combination of the self-accelerating feedback via Ca 2؉ with the known strain-rate-softening rheology of crystalline carbonates leads to another suite of predictions that are strikingly confirmed by observation. If the dolomite-for-calcite replacement becomes fast enough to lower the local rock viscosity sufficiently, then the dolomite growth will pass spontaneously from replacive to displacive. This is when thin, self-organized, displacive zebra veins form (Merino and others, 2006), indeed displaying seamless contacts with their replacive walls and consisting of curved, or saddle, dolomite crystals. Serendipitously, both the deformation of the dolomite crystals (produced by Ca-for-Mg substitution driven by the huge pore-fluid Ca 2؉ ) and the seamless rheological transition result from the self-accelerating feedback via Ca 2؉ itself; that is why they are always associated. This detail alone strongly suggests that the new model captures the chemistry, drives, mechanisms, and feedbacks that lend burial dolomitization and its often associated MVT ore deposits their geological uniqueness.

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Mineral growth in rocks: kinetic-rheological models of replacement, vein formation, and syntectonic crystallization

Cited by 122 publications

References 38 publications

Experimental study on metasomatism in huebnerite — CaCl2 solution system

Experimental study on metasomatism in huebnerite — CaCl2 solution system

Reaction-driven casing expansion: potential for wellbore leakage mitigation

Self-accelerating dolomite-for-calcite replacement: Self-organized dynamics of burial dolomitization and associated mineralization

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