Reaction mechanism for the replacement of calcite by dolomite and siderite: Implications for geochemistry, microstructure and porosity evolution during hydrothermal mineralisation

Carbonate reactions are common in mineral deposits due to CO2-rich mineralising fluids. This study presents the first in-depth, integrated analysis of microstructure and microchemistry of fluid-mediated carbonate reaction textures at hydrothermal conditions. In doing so, we describe the mechanisms by which carbonate phases replace one another, and the implications for the evolution of geochemistry, rock microstructures and porosity. The sample from the 1.95 Moz Junction gold deposit, Western Australia, contains calcite derived from carbonation of a metamorphic amphibole—plagioclase assemblage that has further altered to siderite and dolomite. The calcite is porous and contains iron-rich calcite blebs interpreted to have resulted from fluid-mediated replacement of compositionally heterogeneous amphiboles. The siderite is polycrystalline but nucleates topotactically on the calcite. As a result, the boundaries between adjacent grains are low-angle boundaries (<10°), which are geometrically similar to those formed by crystal–plastic deformation and recovery. Growth zoning within individual siderite grains shows that the low-angle boundaries are growth features and not due to deformation. Low-angle boundaries develop due to the propagation of defects at grain faces and zone boundaries and by impingement of grains that nucleated with small misorientations relative to each other during grain growth.The cores of siderite grains are aligned with the twin planes in the parent calcite crystal showing that the reactant Fe entered the crystal along the twin boundaries. Dolomite grains, many of which appear to in-fill space generated by the siderite replacement, also show alignment of cores along the calcite twin planes, suggesting that they did not grow into space but replaced the calcite. Where dolomite is seen directly replacing calcite, it nucleates on the Fe-rich calcite due to the increased compatibility of the Fe-bearing calcite lattice relative to the pure calcite. Both reactions are interpreted as fluid-mediated replacement reactions which use the crystallography and elemental chemistry of the calcite. Experiments of fluid-mediated replacement reactions show that they proceed much faster than diffusion-based reactions. This is important when considering the rates of reactions relative to fluid flow in mineralising systems

Microstructural records of multiple retrograde local H2O supplement in the pelitic gneiss, Lützow-Holm Complex at Akarui Point, East Antarctica

The alkali-feldspar and biotite in the sillimanite-biotite-garnet gneiss from East Antarctica preserves characteristic microstructural evidence of multi-stage H2O supplement during the retrograde metamorphism. The first microstructural evidence is the "zoned feldspar, " in which the mesoperthitic zone, the anti-perthitic zone, and lamella-free plagioclase zone coexist within a single crystal. They are occasionally found next to biotite, and are always depleted in orthoclase (Or) component toward the biotite. The formation process of this microstructure could be explained by the diffusion that oversteps the solvus. The second microstructural evidence is the serrate boundary between alkali-feldspar and biotite. The projections of biotite are selectively developed next to Or lamellae of alkali-feldspar every 3–5 μm. These two microstructures would have formed as the biotite grew by consuming potash in alkali-feldspar when H2O-bearing fluid locally passed through the grain boundaries. The former microstructure was formed at 825–900 °C before lamella formation, and the latter microstructure was formed after the lamella formation. These microstructures are the indicators of fluid pathways formed under two different temperature conditions. The common coexistence of these microstructures implies that the fluid used similar pathways during the retrograde metamorphism

Coexisting calderite and spessartine garnets in eclogite-facies Mn-rich metasediments of the Western Alps

International audienceThe coexistence of a colourless and a yellow garnet was observed in eclogite-facies manganese concentrations of the Mesozoic ophiolitic Zermatt-Saas Unit, at the Praborna mine near Saint-Marcel, Val d'Aoste, Italy, and in the upper Maurienne Valley, France. They occur both in oxidised metachert with hematite and braunite (þ minor Mn-pyroxenoid and tirodite, rare tiragalloite; with ardennite or piemontite in distinct layers), and in more reduced, carbonate-rich boudins included in it. The cooccurrence takes a variety of textural aspects, from coexisting euhedral garnets (10-100 mm in size for the calderite to mm-size for spessartine) to sharp overgrowths of yellow calderitic garnet on colourless spessartine, to yellow cauliflower-like masses (a few hundreds of mm in size) overgrowing colourless spessartine and showing evidence of oscillatory zoning, resorption stages and resumed growth. Sector zoning and anisotropy are common, although not consistent features. Compositions can be expressed to 95% in the quadrilateral system (Ca, Mn 2þ) 3 (Al, Fe 3þ) 2 Si 3 O 12 , with less than 1.0 wt% MgO and 0.8 wt% TiO 2 in colourless spessartine, and less than 0.2 wt% MgO and 1.6 wt% TiO 2 in yellow garnet. Calcium partitions into the ferric garnet. Coexisting pairs define two compositional gaps, bounded by values of the Fe 3þ =(Al þ Fe 3þ) ratio of 10 and 15% for the first one, of 40 and 65% for the other. The optically obvious discontinuity (colour change and Becke's line) corresponds to the narrower gap, between colourless spessartine and yellow spessartine, whereas the broad compositional gap occurs within yellow garnet, between yellow spessartine and yellow calderite, and is only revealed by back-scattered electron images. Only the latter can be a candidate for a miscibility gap, if any

Geochronology of Metasomatic Events

In order to date any geological event, suitable mineral geochronometers that record that and only that event must be identified and analyzed. In the case of metasomatism, recrystallisation is a key process that controls both the petrology and the isotopic record of minerals. It can occur both in the form of complete neocrystallisation (e.g. in a vein) and in the form of pseudomorphism, whereby dissolution/reprecipitation at the submicroscopic scale plays a central role. Recrystallisation may be complete or not, raising the possibility that relicts of a pre-metasomatic assemblage may be preserved. Because recrystallisation is energetically less costly at almost any temperature than diffusion, and because radiogenic isotopes (except 4He) never diffuse faster than major elements forming the mineral structure, there is a strong causal link between petrographic relicts and isotopic inheritance (as demonstrated for zircon, monazite, titanite, amphibole, K-feldspar, biotite, and muscovite). Metasomatic assemblages commonly contain such mixtures between relicts and newly formed phases, whose geochronology is slightly more complex than that of simple, ideal systems, but can be managed by techniques that have become routine in the last decade and which are described in this chapter. Because of its crucial role in controlling the isotope systematics, the petrogenesis of a mineral needs to be understood in extreme detail, especially using microchemical analyses and micro-imaging techniques, before mineral ages can be correctly interpreted. As the occurrence of recrystallization is limited by the availability of water, minerals act as “geohygrometers” that allow constraints to be placed on the nature and age of fluid circulation episodes, especially metasomatic events