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.     

Grain boundaries as microreactors during reactive fluid flow: experimental dolomitization of a calcite marble

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.     

Pb-Zn-Ag-bearing M anganoan Skarns of China

Manganoan skarns consist of special Mn (Ca, Mg, Fe, Al) silicate metasomatic minerals and are usually associated with Pb-Zn(Ag) mineralization. They occur chiefly along the lithologic contacts or faults and fractures of carbonate wall rocks distal from the intrusive contact zone, and are combined with Fe, Cu, W, Sn and Cu-bearing calcic or magnesian skarns occurring in the contact zones to constitute certain metasomatic zoning. Manganoan skarns are formed later than calcic or magnesian skarns. Their rock-forming temperatures are lower than those of calcic or magnesian skarns. The mineral assemblages of manganoan skarns occurring in different carbonate rocks (limestone or dolomite) are notably different.     

Microstructures in carbonates from the Alnø and Fen carbonatites

The nature of carbonates and related second phase minerals in carbonatite samples from the Alnø and Fen regions has been studied by optical and transmission electron microscopy, aided by X-ray diffraction and electron microprobe analysis.Calcite, dolomite and ankerite have been found to exhibit two phase microstructures. Coherent ribbons of calcitic material occur in dolomite and ankerite, while the calcite grains commonly contain a fine dispersion of plate-like and sometimes rod-like precipitates. Calcite and dolomite frequently occur in contact with the same crystallographic lattice orientation, the small lattice mismatch being indicated by moiré patterns at the grain boundaries and occasional misfit dislocations.The two-phase structure of calcite in dolomite reported for the first time in this paper is thought to be a high temperature analogue of the modulated microstructures reported recently in calcian sedimentary dolomites (Wenk et al. 1983).     

白云鄂博碳酸岩脉的显微共聚焦激光拉曼光谱分析

白云鄂博矿区发育的脉状稀土碳酸岩，由于其结晶迅速，矿物颗粒细微，其中的微小矿物的鉴定一直是一个难题。应用显微共聚焦激光拉曼光谱仪则能较好地解决这一问题。研究表明，白云鄂博地区存在富稀土白云质岩浆碳酸岩脉，早期阶段形成碱性长石和铁白云石，无稀土矿化；铁白云石常常出溶铁质而自身则形成方解石。霓石和方解石形成略晚，常常与氟碳铈矿等稀土矿物共生，出现强烈的稀土矿化；而无解理的方解石则形成于更晚的岩浆期后热液阶段，发育大量的流体包裹体，并出现强烈的铌、稀土矿化。铌铁矿分布在氟碳铈矿中和赤铁矿边缘，为热液交代作用的产物。早期结晶的矿物如碱性长石、铁白云石稀土矿化弱，岩浆晚期分异出大量的流体相，稀土元素和Sr等进入岩浆热液中，并在热液结晶矿物中富集，甚至在非平衡结晶的石英中产生强烈的稀土矿化。结合岩相学显微观察，显微拉曼探针很好的揭示了这一地质过程。同时为白云鄂博矿床铌、稀土矿化的热液交代成因提供了依据。     

Ca-Mg inter-diffusion in synthetic polycrystalline dolomite-calcite aggregate at elevated temperatures and pressure

This study measures the reaction rate of dolomite and aragonite (calcite) into Mg-calcite at 800, 850, and 900°C and 1.6 GPa. The dry synthetic dolomite-aragonite aggregate transformed very rapidly into dolomite-calcite polycrystalline aggregate while Mg-calcites formed at a relatively slow rate, becoming progressively richer in Mg with run time. We modeled the reaction progress semi-empirically by the first-order rate law. The temperature dependence of the overall transport rate of MgCO₃ into calcite can be described by the kinetic parameters (E?=?231.7 kJ/mol and A _o ?=?22.69 h^?1). Extrapolation using the Arrhenius equation to the conditions during exhumation of UHPM rocks indicates that the reaction of dolomite with aragonite into Mg-saturated calcite can be completed as the P-T path enters the Mg-calcite stability field in a geologically short time period (<1 Ky). On the other hand, the extrapolation of the rate to prograde metamorphic conditions reveals that the Mg-calcite formed from dolomitic marble in the absence of metamorphic fluid may not reach Mg-saturation until temperatures corresponding to high-grade metamorphism (e.g., >340°C and >10 My). SEM-EDS analysis of individual calcite grains shows compositional gradients of Mg in the calcite grains. The Mg-Ca inter-diffusion coefficient at 850°C is around 1.68?×?10^?14 m²/sec if diffusion is the major control of the reaction. The calculated closure temperatures for Ca-Mg inter-diffusion as a function of cooling rate and grain size reveal that Ca/Mg resetting in calcite in a dry polycrystalline carbonate aggregate (with grain size around 1 mm) may not occur at temperatures below 480°C at a geological cooling rate around 10°C/My, unless other processes, such as short-circuit interdiffusion along grain boundaries and dislocations, are involved.     

The dolomitization of CaCO3: an experimental study at 252–295°C

The results of experiments on the hydrothermal dolomitization of calcite (between 252 and 295°C) and aragonite (at 252°C) by a 2 M CaCl₂-MgCl₂ aqueous solution are reported and discussed. Dolomitization of calcite proceeds via an intermediate high (ca. 35 mole %) magnesian calcite, whereas that of aragonite is carried out through the conversion of the reactant into a low (5.6 mole %) magnesian calcite which in turn transforms into a high (39.6 mole %) magnesian calcite. Both the intermediate phases and dolomite crystallize through a dissolution-precipitation reaction. The intermediate phases form under local equilibrium within a reaction zone surrounding the dissolving reactant grains. The volume of the reaction zone solution can be estimated from Sr²⁺ and Mg²⁺ partitioning equations. In the case of low magnesian calcite growing at the expense of aragonite at 252°C, the total volume of these zones is in the range of 2 × 10^?5 to 2 × 10^?4 1., out of 5 × 10^?3 1., the volume of the bulk solution.The apparent activation energies for the initial crystallization of high magnesian calcite and dolomite are 48 and 49 kcal/mole, respectively.Calcite transforms completely into dolomite within 100 hr at 252°C. The overall reaction time is reduced to approximately 4 hr at 295°C. The transformation of aragonite to dolomite at 252°C occurs within 24 hr. The nature of the reactant dictates the relative rates of crystallization of the intermediate phases and dolomite. With calcite as reactant, dolomite growth is faster than that of magnesian calcite; this situation is reversed when aragonite is dolomitized.Coprecipitation of Sr²⁺ with dolomite is independent of temperature (within analytical error) between 252 and 295°C. Its partitioning, with respect to calcium, between dolomite and solution results in distribution coefficients in the range of 2.31 × 10^?2 to 2.78 × 10^?2.     

Petrographic and trace-element distribution studies on the dolomite-calcite in the regional metamorphic marble of the Griesscharte,Tyrol, Austria/Italy

Petrographic investigations on the light yellow marble outcrops in the Griesscharte, Tyrol, Austria/Italy revealed them to be dolomite. The white to blue-grey veins in these marbles were those of calcite. Inside these calcites and along the calcite-dolomite phase boundaries minute and microscopically unidentifiable crystallites (? 10 μ) were observed. These crystallites were recognised by X-ray diffractometry as dolomite and their form and distribution were established by scanning electron microscopy. Trace-element distributions on the calcite-dolomite neighbours were studied by neutron-activation method to elucidate the formation mechanism of these calcites in the marble.Genetic relationships of the dolomite crystallites, the calcite host and the surrounding dolomite marble have been discussed in the light of the petrographic and chemical studies. These findings substantiate a deposition of a new formed vein of calcite from the solution circulating in the fissures of the dolomite marble during prograde metamorphism rather than a simple deposition of mobilized sedimentary calcite. The dolomite crystallites in the calcite seem to have been formed post-tectonically, partly by the nucleation in the calcite cleavage planes during Mg-metasomatism and partly from the exsolutions during retrograde metamorphism.     

Microtexture of dolomite within exsolved magnesian calcite — examples from the Damara orogen (Namibia)

Exsolved magnesian calcite grains containing rods of dolomite were etched to remove the calcite matrix and investigated with a scanning electron microscope. The rods were found to be composed of small rhombohedral dolomite crystals. The single rhombohedrons are stacked with the threefold axis subparallel in all rods of the exsolved host crystal. The curvature of exsolution rods in the host is due to a step by step displacement of the single rhombohedrons.     

Compositional zoning of calcite in a high-pressure metamorphic calc-schist: clues to heterogeneous grain-scale fluid distribution during exhumation

Calcite in former aragonite–dolomite-bearing calc-schists from the ultrahigh-pressure metamorphic (UHPM) oceanic complex at Lago di Cignana, Valtournanche, Italy, preserved different kinds of zoning patterns at calcite grain and phase boundaries. These patterns are interpreted in terms of lattice diffusion and interfacial mass transport linked with a heterogeneous distribution of fluid and its response to a changing state of stress. The succession of events that occurred during exhumation is as follows: As the rocks entered the calcite stability field at T=530–550 °C, P ca. 1.2 GPa, aragonite occurring in the matrix and as inclusions in poikilitic garnet was completely transformed to calcite. Combined evidence from microstructures and digital element distribution maps (Mn-, Mg-, Fe- and Ca–Kα radiation intensity patterns) indicates that transformation rates have been much higher than rates of compositional equilibration of calcite (involving resorption of dolomite and grain boundary transport of Mg, Fe and Ca). This rendered the phase transformation an isochemical process. During subsequent cooling to T ca. 490 °C (where lattice diffusion effectively closed), grains of matrix calcite have developed diffusion-zoned rims, a few hundred micrometres thick, with Mg and Fe increasing and Ca decreasing towards the phase boundary. Composition profiles across concentrically zoned, large grains in geometrically simple surroundings can be successfully modelled with an error function describing diffusion into a semi-infinite medium from a source of constant composition. The diffusion rims in matrix calcite are continuous with quartz, phengite, paragonite and dolomite in the matrix. This points to an effective mass transport on phase boundaries over a distance of several hundred micrometres, if matrix dolomite has supplied the Mg and Fe needed for incorporation in calcite. In contrast, diffusion rims are lacking at calcite–calcite and most calcite–garnet boundaries, implying that only very minor mass transport has occurred on these interfaces over the same T–t interval. From available grain boundary diffusion data and experimentally determined fluid–solid grain boundary structures, inferred large differences in transport rates can be best explained by the discontinuous distribution of aqueous fluid along grain/phase boundaries. Observed patterns of diffusion zoning indicate that fluid was distributed not only along grain-edge channels, but spread out along most calcite–white mica and calcite–quartz two-grain junctions. On the other hand, the inferred non-wetting of calcite grain boundaries in carbonate-rich domains is compatible with fluid–calcite–calcite dihedral angles >60° determined by Holness and Graham (1995) for a wide range of fluid compositions under the P–T conditions of interest. Whereas differential stress has been very low at the stage of diffusion zoning (T > 490 °C), it increased as the rocks were cooling below 440 °C (at 0.3–0.5 GPa). Dislocation creep and the concomitant increase of strain energy in matrix calcite induced migration recrystallisation of high-angle grain boundaries. For that stage, the compositional microstructure of recrystallised calcite grain boundary domains indicates significant mass transport along calcite two-grain junctions, which at the established low temperatures is likely to have been accomplished by ionic diffusion within a hydrous grain boundary fluid film (“dynamic wetting” of migrating grain boundaries). Received: 10 January 2000 / Accepted: 10 April 2000     

中国镁质碳酸盐岩型温石棉矿床的成矿规律

镁质碳酸盐岩型温石棉矿床是成矿热液交代镁质碳酸盐岩生成的,一般均产于地台环境。按地台稳定性不同,成矿环境分为地台隆起区的基底建造类型和地台拗陷区的盖层建造类型。产于地台隆起区的矿床,以前震旦纪镁质碳酸盐岩为控矿层位。产于太古代及早、中元古代深变质结晶基底中的矿床,由区域变质及混合岩化过程中的变质热液交代碳酸盐岩成矿。产于晚元古代浅变质褶皱基底(扬子准地台)中的矿床,以岩浆期后热液或接触交代(湿矽卡岩)热液为成矿热液来源。产于地台拗陷区的矿床,均以震旦纪镁质碳酸盐岩为控矿层位。其成矿时期较晚,一般与拗陷区内岩浆活动同期,由岩浆期后热液或接触交代(湿矽卡岩)热液对镁质碳酸盐岩进行交代成矿。     

Mineralogical and geochemical characterization of listwaenite from the Semail Ophiolite, Oman

The late Cretaceous-lower Tertiary hydrothermal alteration of serpentinized peridotite in the Semail ophiolite has formed two distinct types of listwaenite. Type I is characterized by the presence of calcite (Type IA) or dolomite (Type IB)+fuchsite±spinel. Type II is dominated by silicate minerals (quartz, chlorite, fuchsite)±calcite+dolomite±magnetite±apatite±plagioclase. Most listwaenites occur as veins along thrust fault zones within the ophiolite mélange. High Cr and Ni contents, abundant occurrence of Cr-spinel within a matrix of red-brown ferruginous carbonates within a micro-vein network of goethite, and the relics of mesh texture indicate an ultramafic protolith. Type I and II listwaenites represent different stages of hydrothermal alteration. The mineralogical and chemical distinctions of both types are the response to the extent of the reactions between the protoliths and the solutions leading to different stages of metasomatic replacement. The hydrothermal fluids involved in the formation of Type I listwaenite were enriched in Ca, Mg, and CO₂, whereas Type II listwaenite bodies were formed from a hydrothermal fluid enriched in SiO₂. REE and trace elements in both listwaenite types were extracted in part from adjoining peridotite. No Au anomaly in the study areas has been detected.     

Metamorphic temperature determined by means of the dolomite-calcite solvus geothermometer-examples from the central Damara Orogen (South West Africa)

Using a marble sample from the central Damara Orogen (South West Africa) the determination of the temperature of metamorphism was undertaken with the help of the dolomite-calcite solvus geothermometer for unmixed magnesian calcite crystals. There is good agreement between the results obtained by electron microprobe analysis and by point count analysis of the surface area of exsolved dolomite grains in magnesian calcite. Accordingly, the temperature reached during metamorphism of the investigated marble occurence, based on the dolomite-calcite solvus determination of Goldsmith and Newton (1969), was 620 ° C.     

Cracking mechanisms during galena mineralization in a sandstone-hosted lead–zinc ore deposit: case study of the Jinding giant sulfide deposit, Yunnan, SW China

There are two types of lead–zinc ore bodies, i.e., sandstone-hosted ores (SHO) and limestone-hosted ores (LHO), in the Jinding giant sulfide deposit, Yunnan, SW China. Structural analysis suggests that thrust faults and dome structures are the major structural elements controlling lead–zinc mineralization. The two types of ore bodies are preserved in two thrust sheets in a three-layered structural profile in the framework of the Jinding dome structure. The SHO forms the cap of the dome and LHO bodies are concentrated beneath the SHO cap in the central part of the dome. Quartz, feldspar and calcite, and sphalerite, pyrite, and galena are the dominant mineral components in the sandstone-hosted lead–zinc ores. Quartz and feldspar occur as detrital clasts and are cemented by diagenetic calcite and epigenetic sulfides. The sulfide paragenetic sequence during SHO mineralization is from early pyrite to galena and late sphalerite. Galena occurs mostly in two types of cracks, i.e., crescent-style grain boundary cracks along quartz–pyrite, or rarely along pyrite–pyrite boundaries, and intragranular radial cracks in early pyrite grains surrounding quartz clasts. The radial cracks are more or less perpendicular to the quartz–pyrite grain boundaries and do not show any overall (whole rock) orientation pattern. Their distribution, morphological characteristics, and geometrical relationships with quartz and pyrite grains suggest the predominant role of grain-scale cracking. Thermal expansion cracking is one of the most important mechanisms for the generation of open spaces during galena mineralization. Cracking due to heating or cooling by infiltrating fluids resulted from upwelling fluid phases through fluid passes connecting the SHO and LHO bodies, provided significant spaces for crystallization of galena. The differences in coefficients of thermal expansion between pyrite and quartz led to a difference in volume changes between quartz grains and pyrite grains surrounding them and contributed to cracking of the pyrite grains when temperature changed. Combined thermal expansion and elastic mismatch due to heating and subsequent cooling resulted in the radial and crescent cracking in the pyrite grains and along the quartz–pyrite grain boundaries.     

Holocene carbonate sedimentation in Lake Manitoba, Canada

The carbonate mineral suite of the modern offshore bottom sediment of the South Basin of Lake Manitoba consists mainly of high magnesian calcite and dolomite with minor amounts of low-Mg calcite and aragonite. The high-Mg calcite is derived from inorganic precipitation within the water column in response to supersaturation brought about by high levels of organic productivity in the basin. Both dolomite and pure calcite are detrital in origin, derived from erosion of the surrounding carbonate-rich glacial deposits. Aragonite, present only in trace amounts in the offshore sediments, is bioclastic in origin. The upward increase in the amount of magnesian calcite in the post-glacial sediment record is attributed to increasing photosynthetic utilization of CO₂ in the lake. Stratigraphic variation in the amount of magnesium incorporated into the calcite lattice is interpreted as reflecting a variable magnesium input to the lake from ground water and surface runoff, and possibly variable calcium removal in the precipitating lake water. The effects of long-term chemical weathering at the source and size segregation explain the changes in dolomite content throughout the section.     

Disseminated ‘jigsaw piece’ dolomite in Upper Jurassic shelf sandstones,Central North Sea: an example of cement growth during bioturbation?

Unusual textural and chemical characteristics of disseminated dolomite in Upper Jurassic shelf sediments of the North Sea have provided the basis for a proposed new interpretation of early diagenetic dolomite authigenesis in highly bioturbated marine sandstones. The dolomite is present throughout the Franklin Sandstone Formation of the Franklin and Elgin Fields as discrete, non‐ferroan, generally unzoned, subhedral to highly anhedral ‘jigsaw piece’ crystals. These are of a similar size to the detrital silicate grains and typically account for ≈5% of the rock volume. The dolomite crystals are never seen to form polycrystalline aggregates or concretions, or ever to envelop the adjacent silicate grains. They are uniformly dispersed throughout the sandstones, irrespective of detrital grain size or clay content. Dolomite authigenesis predated all the other significant diagenetic events visible in thin section. The dolomite is overgrown by late diagenetic ankerite, and bulk samples display stable isotope compositions that lie on a mixing trend between these components. Extrapolation of this trend suggests that the dolomite has near‐marine δ¹⁸O values and low, positive δ¹³C values. The unusual textural and chemical characteristics of this dolomite can all be reconciled if it formed in the near‐surface zone of active bioturbation. Sea water provided a plentiful reservoir of Mg and a pore fluid of regionally consistent δ¹⁸O. Labile bioclastic debris (e.g. aragonite, Mg‐calcite) supplied isotopically positive carbon to the pore fluids during shallow‐burial dissolution. Such dissolution took place in response to the ambient ‘calcite sea’ conditions, but may have been catalysed by organic matter oxidation reactions. Bioturbation not only ensured that the dissolving carbonate was dispersed throughout the sandstones, but also prohibited coalescence of the dolomite crystals and consequent cementation of the grain framework. Continued exchange of Mg²⁺ and Ca²⁺ with the sea‐water reservoir maintained a sufficient Mg/Ca ratio for dolomite (rather than calcite) to form. Irregular crystal shapes resulted from dissolution, of both the dolomite and the enclosed fine calcitic shell debris, before ankerite precipitation during deep‐burial diagenesis.     

中国辽东地区超大型菱镁矿矿床的地球化学特征和成因模式

我国辽东地区早元古代大石桥组镁质碳酸盐-泥质岩建造中赋存有多个超大型菱镁矿矿床。在这些矿床中,菱铁矿矿体均只限定在大石桥组三段岩层中。该层岩石主要由白云质大理岩、菱镁质大理岩、菱镁矿和少量泥质板岩薄层组成。赋矿层位之下地层为大石桥组二段的云母片岩;其下为大石桥组一段的白云质大理岩与云母片岩夹层。在大石桥组一段中未见菱铁矿体产出。研究表明,菱铁矿的δ18O值为5.2‰~13.8‰,低于围岩大理岩的δ18O值(11.2‰~22.8‰)。但两音的δ13C值大多接近零值,其中菱镁矿δ13C值变化为-1.4‰~1.2‰,大理岩δ13C值变化为-4.5‰~4 4‰。在菱镁矿层位中发现有石膏成层和脉状产出,其δ34S值为23.9‰~26.5‰,显示海相蒸发沉积特征。菱镁矿的稀土元素分析表明存在三种不同页岩标准化配分模式。类型Ⅰ显示中稀土富集特征,类型Ⅲ显示重稀土富集和正铕异常特征,它们可能反映了不同时期成矿热液的特征。而类型Ⅱ显示与围岩大理岩相同的平坦型,反映继承了原岩沉积碳酸盐岩的特征。本文认为,辽东地区的镁质碳酸盐岩(镁方解石和白云石)可能是从蒸发的泻湖盆地中沉积的,而菱镁矿石则主要是沉积后富镁卤水下渗交代原岩碳酸盐岩形成的。由于大石桥组二段云母片岩渗透率低隔水性强,因此菱铁矿的矿化交代作用只发     

The mechanical and microstructural behaviour of calcite-dolomite composites: An experimental investigation

The styles and mechanisms of deformation associated with many variably dolomitized limestone shear systems are strongly controlled by strain partitioning between dolomite and calcite. Here, we present experimental results from the deformation of four composite materials designed to address the role of dolomite on the strength of limestone. Composites were synthesized by hot isostatic pressing mixtures of dolomite (Dm) and calcite powders (% Dm: 25%-Dm, 35%-Dm, 51%-Dm, and 75%-Dm). In all composites, calcite is finer grained than dolomite. The synthesized materials were deformed in torsion at constant strain rate (3 × 10⁻⁴ and 1 × 10⁻⁴ s⁻¹), high effective pressure (262 MPa), and high temperature (750 °C) to variable finite shear strains. Mechanical data show an increase in yield strength with increasing dolomite content. Composites with <75% dolomite (the remaining being calcite), accommodate significant shear strain at much lower shear stresses than pure dolomite but have significantly higher yield strengths than anticipated for 100% calcite. The microstructure of the fine-grained calcite suggests grain boundary sliding, accommodated by diffusion creep and dislocation glide. At low dolomite concentrations (i.e. 25%), the presence of coarse-grained dolomite in a micritic calcite matrix has a profound effect on the strength of composite materials as dolomite grains inhibit the superplastic flow of calcite aggregates. In high (>50%) dolomite content samples, the addition of 25% fine-grained calcite significantly weakens dolomite, such that strain can be partially localized along narrow ribbons of fine-grained calcite. Deformation of dolomite grains by shear fracture is observed; there is no intracrystalline deformation in dolomite irrespective of its relative abundance and finite shear strain.     

湖北省南漳县红星磷矿磷块岩特征与物质组分研究

湖北省南漳县震旦系沉积型红星磷矿矿体P_2O_5平均含量23.91%,矿石自然类型主要为角砾状磷块岩,其次为白云质磷块岩、泥质纹层状和条带状致密块状磷块岩。工业类型主要为钙(镁)质和硅钙(镁)质磷矿,其次为硅质磷矿。矿石矿物为胶状磷灰石和微晶磷灰石,经x-射线衍射物相分析,其种属为含碳氟磷灰石。嵌布粒度以细-中粒为主。脉石矿物主要为白云石、伊利石、高岭石、铁质。经测定当磷块岩磨矿粒度小于0.1mm,其磷酸盐矿物单体解离率可达92.53％,这为确定合理的选矿流程具有实际意义。     

Exsolution of dolomite and application of calcite–dolomite solvus geothermometry in high‐grade marbles: an example from Skallevikshalsen,East Antarctica

Calcite–dolomite solvus geothermometry is a versatile method for the estimation of metamorphic temperature because of its simplicity. However, in medium‐ to high‐grade metamorphic rocks the accuracy of estimating temperature by the integration of unmixed dolomite and calcite is hampered by the heterogeneous distribution of unmixed dolomite, difficulties in distinguishing between preexisting and exsolved dolomite and demarcating grain boundaries. In this study, it is shown that calcite–dolomite solvus thermometry can be applied to calcite inclusions in forsterite and spinel for the estimation of peak metamorphic temperature in granulite facies marbles from Skallevikshalsen, East Antarctica. The marbles are comprised of a granoblastic mineral assemblage of calcite + dolomite + forsterite + diopside + spinel + phlogopite ± apatite, characteristic of granulite facies metamorphic conditions. Forsterite, spinel and apatite frequently contain ‘negative crystal’ inclusions of carbonates that display homogeneously distributed dolomite lamellae. On the basis of narrow ranges of temperature (850–870 °C) recorded from carbonate inclusions compared with the range from matrix carbonate it is regarded that the inclusion carbonates represent a closed system. Furthermore, this estimate is consistent with dolomite–graphite carbon isotope geothermometry, and is considered to be the best estimate of peak metamorphic temperature for this region. Matrix calcite records different stages of retrograde metamorphism and re‐equilibration of calcite that continued until Mg diffusion ceased at ～460 °C. Electron backscattered diffraction (EBSD) results together with morphological features of unmixed coarse tabular dolomite suggest anisotropic diffusion and mineral growth are influenced by crystallographic orientation. Identification of sub‐grain boundaries and formation of fine‐grained unmixing in calcite rims suggest the presence of grain boundary fluids in the late retrograde stages of metamorphic evolution. These results, thus, demonstrate the usefulness of carbonate inclusion geothermometry in estimating the peak metamorphic temperatures of high‐grade terranes and the application of EBSD in understanding the unmixing behaviour of minerals with solid solutions.