Grain coarsening in polymineralic contact metamorphic carbonate rocks: The role of different physical interactions during coarsening

The microstructural evolution of polymineralic contact metamorphic calcite marbles (Adamello contact aureole) with variable volume fractions of second-phase minerals were quantitatively analyzed in terms of changes in grain size and nearest neighbor relations, as well as the volume fractions, dispersion and occurrences of the second phases as a function of changing metamorphic conditions. In all samples, the calcite grain size is controlled by pinning of grain boundaries by second phases, which can be expressed by the Zener parameter (Z), i.e., the ratio between size and volume fraction of the second phases. With increasing peak metamorphic temperature, both the sizes of matrix grains and second phases increase in dependence on the second-phase volume fraction. Two distinct coarsening trends are revealed: trend I with coupled grain coarsening limited by the growth of the second phases is either characterized by large-sized or a large number of closely spaced-second phase particles, and results finally in a dramatic increase in the calcite grain size with Z. Trend II is manifest by matrix controlled grain growth, which is retarded by the presence of single second-phase particles that are located on calcite grain boundaries. It is supported by grain boundary pinning induced by triple junctions, and the calcite grain size increases moderately with Z. The two different grain coarsening trends manifest the transition between relatively pure polymineralic aggregates (trend II) and microstructures with considerable second-phase volume fractions of up to 0.5. The variations might be of general validity for any polymineralic rock, which undergoes grain coarsening during metamorphism. The new findings are important for a better understanding of the initiation of strain localization based on the activation of grain size dependent deformation mechanisms.     

Grain growth kinetics of dolomite,magnesite and calcite: a comparative study

The rates of grain growth of stoichiometric dolomite [CaMg(CO₃)₂] and magnesite (MgCO₃) have been measured at temperatures T of 700–800°C at a confining pressure P _c of 300 MPa, and compared with growth rates of calcite (CaCO₃). Dry, fine-grained aggregates of the three carbonates were synthesized from high purity powders by hot isostatic pressing (HIP); initial mean grain sizes of HIP-synthesized carbonates were 1.4, 1.1, and 17 μm, respectively, for CaMg(CO₃)₂, MgCO₃, and CaCO₃, with porosities of 2, 28, and 0.04% by volume. Grain sizes of all carbonates coarsened during subsequent isostatic annealing, with mean values reaching 3.9, 5.1, and 27 μm for CaMg(CO₃)₂, MgCO₃, and CaCO₃, respectively, in 1 week. Grain growth of dolomite is much slower than the growth rates of magnesite or calcite; assuming normal grain growth and n = 3 for all three carbonates, the rate constant K for dolomite (≃5 × 10⁻⁵ μm³/s) at T = 800°C is less than that for magnesite by a factor of ~30 and less than that for calcite by three orders of magnitude. Variations in carbonate grain growth may be affected by differences in cation composition and densities of pores at grain boundaries that decrease grain boundary mobility. However, rates of coarsening correlate best with the extent of solid solution; K is the largest for calcite with extensive Mg substitution for Ca, while K is the smallest for dolomite with negligible solid solution. Secondary phases may nucleate at advancing dolomite grain boundaries, with implications for deformation processes, rheology, and reaction kinetics of carbonates.     

Polycrystalline calcite to aragonite transformation kinetics: experiments in synthetic systems

The kinetics of the calcite to aragonite transformation have been investigated using synthetic polycrystalline calcite aggregates, with and without additional minerals present. The reaction progresses as a function of time were measured at four temperature/pressure conditions: (1) 550 °C/1.86 GPa; (2) 600 °C/2.11 GPa; (3) 650 °C/2.11 GPa, and (4) 700 °C/2.29 GPa. Experiments reveal that Mg-calcite and Fe-calcite transforms to aragonite at considerably slower rates than pure calcite, and that Sr-bearing calcite and calcite + quartz aggregates transform at significantly higher rates than pure calcite. The reaction progresses vs. time data for pure calcite were fitted to Cahns grain-boundary nucleation and interface-controlled growth model. Evidence for interface-controlled growth is provided by petrographic observations of grain boundaries. The activation energy for aragonite growth from the synthetic polycrystalline calcite determined in this study is significantly lower than that previously determined from a natural marble. The discrepancy in rates and activation energy may be attributed to the nature of grain boundaries, to deformational strain or the presence of impurities in the studied samples, and likely to uncertainties in experimental conditions. The results of this study imply that the variation of local petrologic conditions, in addition to temperature, pressure and grain size, may play an important role in determining the rates for the calcite to aragonite transformation in nature.Editorial responsibility: W. Schreyer     

The role of carbonate-fluoride melt immiscibility in shallow REE deposit evolution

The Lugiin Gol nepheline syenite intrusion, Mongolia, hosts a range of carbonatite dikes mineralized in rare-earth elements(REE). Both carbonatites and nepheline syenite-fluorite-calcite veinlets are host to a previously unreported macroscale texture involving pseudo-graphic intergrowths of fluorite and calcite. The inclusions within calcite occur as either pure fluorite, with associated REE minerals within the surrounding calcite, or as mixed calcite-fluorite inclusions, with associated zirconosilicate minerals. Consideration of the nature of the texture, and the proportions of fluorite and calcite present(～29 and 71 mol%,respectively), indicates that these textures most likely formed either through the immiscible separation of carbonate and fluoride melts, or from cotectic crystallization of a carbonatefluoride melt. Laser ablation ICP-MS analyses show the pure fluorite inclusions to be depleted in REE relative to the calcite. A model is proposed, in which a carbonate-fluoride melt phase enriched in Zr and the REE, separated from a phonolitic melt, and then either unmixed or underwent cotectic crystallization to generate an REE-rich carbonate melt and an REE-poor fluoride phase. The separation of the fluoride phase(either solid or melt) may have contributed to the enrichment of the carbonate melt in REE, and ultimately its saturation with REE minerals. Previous data have suggested that carbonate melts separated from silicate melts are relatively depleted in the REE, and thus melt immiscibility cannot result in the formation of REE-enriched carbonatites. The observations presented here provide a mechanism by which this could occur, as under either model the textures imply initial separation of a mixed carbonate-fluoride melt from a silicate magma. The separation of an REEenriched carbonate-fluoride melt from phonolitic magma is a hitherto unrecognized mechanism for REE-enrichment in carbonatites, and may play an important role in the formation of shallow magmatic REE deposits.     

The normal grain growth behaviour of nominally pure calcitic aggregates

The normal grain growth behaviour of four different, but all nominally pure, calcite powders (99%+ analytic grade calcite, 99.7% chalk, 99.97% crushed Iceland Spar, 99.95%+ chelometric grade calcite) has been investigated as a function of temperature (550, 600, 650, 700 °C) and confining pressure (100, 190 MPa) under both “dry” and hydrostatic (P _fluid = P _total) conditions. The initial particle size of both the analytic grade and chelometric grade calcite was about 5 μm, and that of the chalk was about 3 μm, while the experiments on the Iceland Spar were conducted on powders of three different initial particle sizes (3.4, 7.5, 38.5 μm). On each material, at each pressure/temperature condition 6 to 15 experiments, equally spaced in log time from 15 minutes to 50 days, were conducted. Under dry conditions all four materials recrystallized to aggregates which contained less than 2% porosity and which had a grain size of between 4 and 20 μm (depending on the initial particle size). Subsequently the aggregates coarsened by normal grain growth, with the kinetics of the growth process being controlled by the rate at which the grain boundaries could drag the residual pores with them as they migrated. Under nominally identical conditions both the mechanism and rates of pore drag differed greatly for the different materials, implying that this process is highly sensitive to trace solute impurity concentrations. This sensitivity renders the task of providing a systematic account of dry calcite grain growth kinetics highly problematic. Under hydrostatic conditions all the powders followed the same normal grain growth kinetics in which the growth process was rate-controlled by diffusion through the pore fluid on the grain boundaries. An activation enthalpy of 162.6 kJ mol⁻¹ and an activation volume of 34.35 cm³ mol⁻¹ was obtained for this process. Received: 23 May 1996 / Accepted: 8 July 1997     

Compositions of magmas,formation conditions,and genesis of carbonate-bearing ijolites and carbonatites of the Belaya Zima alkaline carbonatite complex,eastern Sayan

Based on the investigation of melt inclusions using electron and ion microprobe analysis, we estimated the composition, evolution, and formation conditions of magmas responsible for the calcite-bearing ijolites and carbonatites of the Belaya Zima alkaline carbonatite complex (eastern Sayan, Russia). Primary melt and coexisting crystalline inclusions were found in the nepheline and calcite of these rocks. Diopside, amphibole (?), perovskite, potassium feldspar, apatite, calcite, pyrrhotite, and titanomagnetite were identified among the crystalline inclusions. The melt inclusions in nepheline from the ijolites are completely crystallized. The crystalline daughter phases of these inclusions are diopside, phlogopite, apatite, calcite, magnetite, and cuspidine. During thermometric experiments with melt inclusions in nepheline, the complete homogenization of the inclusions was attained through the dissolution of a gas bubble at temperatures of 1120–1130°C. The chemical analysis of glasses from the homogenized melt inclusions in nepheline of the ijolites revealed significant variations in the content of components: from 36 to 48 wt % SiO₂, from 9 to 21 wt % Al₂O₃, from 8 to 25 wt % CaO, and from 0.6 to 7 wt % MgO. All the melts show very high contents of alkalis, especially sodium. According to the results of ion microprobe analysis, the average content of water in the melts is no higher than a few tenths of a percent. The most salient feature of the melt inclusions is the extremely high content of Nb and Zr. The glasses of melt inclusions are also enriched in Ta, Th, and light rare earth elements but depleted in Ti and Hf. Primary melt inclusions in calcite from the carbonatites contain a colorless glass and daughter phlogopite, garnet, and diopside. The silicate glass from the melt inclusions in calcite of the carbonatite is chemically similar to the glasses of homogenized melt inclusions in nepheline from the ijolites. An important feature of melt inclusions in calcite of the carbonatites is the presence in the glass of carbonate globules corresponding to calcite in composition. The investigation of melt inclusions in minerals of the ijolites and carbonatites and the analysis of the alkaline and ore-bearing rocks of the Belaya Zima Massif provided evidence for the contribution of crystallization differentiation and silicate-carbonate liquid immiscibility to the formation of these rocks. Using the obtained trace-element compositions of glasses of homogenized melt inclusions and various alkaline rocks and carbonatites, we determined to a first approximation the compositions of mantle sources responsible for the formation of the rock association of the Belaya Zima alkaline-carbonatite complex. The alkaline rocks and carbonatites were derived from the depleted mantle affected by extensive metasomatism. It is supposed that carbonate melts enriched in sodium and calcium were the main agents of mantle metasomatism.     

Thin amorphous films (1–2 nm) at olivine grain boundaries in mantle xenoliths from San Carlos,Arizona

 Olivine grain boundaries and phase boundaries in xenoliths from San Carlos have been investigated by high-resolution transmission electron microscopy (HREM) and analytical electron microscopy (AEM). Thin amorphous intergranular layers with variable width (1–2 nm) were detected along olivine grain boundaries. The Al₂O₃, TiO₂ and CaO concentrations of the amorphous layers increase with increasing width of the layer. The composition of the amorphous intergranular layers depends on the interface type – grain or phase boundary. Morphology, amorphous state and chemical composition of the intergranular layer suggest the presence of a melt film at olivine grain boundaries. Since the composition of the amorphous phase strongly depends on the type of interface, the melt must have been generated at the grain boundary. Also, the melt chemistry is different from the composition of partial melts produced from possible hydrous phases, such as phlogopite or amphibole, and from the host basanite. The mobility of very thin melt films is assumed to be very limited due to the strong interface forces between the melt and the grain boundary. It is concluded that grain boundary melting occurred at the interfaces due to decompression during uplift. The melt wetted olivine grain boundaries as well as olivine-opx phase boundaries. The thin amorphous layers formed melt microsystems. Mixing of melts from different microsystems is suggested to occur in wider melt films, melt veins or melt pockets thus creating a magmatic melt that could be extracted from its source. Received: 6 November 1995 / Accepted: 24 January 1996     

Low melting temperature for calcite at 1000 bars on the join CaCO3‐H2O – some geological implications

Melting experiments of calcite were performed on the join CaCO₃‐H₂O at a pressure of 1000 bars. The system evolves to the ternary CaO‐H₂O‐CO₂ system during melting experiments. Our experiments show that partial melting of calcite begins at a low temperature, below 650 °C. Such a low partial melting temperature for carbonates revives the debate about the presence of carbonate melts in the upper crust. More specifically, the conditions for carbonate partial melting are present in carbonate host rocks undergoing contact metamorphism at high temperatures in the presence of water‐rich fluid. The presence of carbonate melts influences physical parameters such as viscosity and permeability in contact aureoles, and, furthermore, decarbonation reactions release massive amounts of CO₂.     

Caco3 precipitation kinetics in waters from the great Bahama bank:: Implications for the relationship between bank hydrochemistry and whitings

The source of whitings on the Great Bahama Bank and their relationship to major changes in the chemistry of Bank waters have been among the longest and most hotly debated topics in carbonate geochemistry. In this paper, we demonstrate that the reaction kinetics of calcite with Bank waters for a given saturation state are similar to, but somewhat slower (2 to 3 times) than with Gulf Stream water. The interpretation of the reaction kinetics of suspended Bank sediment with Bank water requires that the precipitating phase be about twice as soluble as aragonite. Good agreement at equivalent saturation states was found between experimental precipitation rates and those calculated for the rate of change of Bank water chemistry in the region of whitings. These results indicate that the dominant mode of carbonate removal is via precipitation on resuspended sediments rather than the rapid pseudo-homogeneous precipitation of calcium carbonate in the water column resulting in the formation of a whiting. Estimates indicate that single aragonite needles may be resuspended many times over a period of decades during which they experience repeated overgrowth. A major portion (>98%) of suspended calcium carbonate is outside the visually dramatic whitings. Thus, as visually spectacular as they are, whitings do not represent a short-term locally massive precipitation of carbonate on the Great Bahama Bank, nor are they even likely to be the dominant sites of carbonate removal in this region. Although future refinements are needed that include seafloor processes, we have at this point arrived at a mechanistic kinetic model that provides a reasonably quantitative explanation for the hydrochemistry of the carbonate system on the northern Great Bahama Bank.     

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.     

Immiscibility between calciocarbonatitic and silicate melts and related wall rock reactions in the upper mantle: a natural case study from Romanian mantle xenoliths

This paper presents the textural, mineralogical and chemical study of veinlets cross-cutting peridotite xenoliths from the lithospheric mantle and brought to the surface by alkaline basalts (Persani Mountains, Romania). The veinlets utilized pre-existing zones of weakness in the host rocks or display a random distribution, lining grain boundaries or cross-cutting any mineral, and always forming an interconnected network. They are filled with carbonate patches included in a silicate matrix. Both products are holocrystalline. Carbonate products have alkali-poor calciocarbonatitic to sövitic compositions, while the silicate matrix composition ranges from monzodioritic to monzonitic and alkali feldspar syenitic, depending on the host-sample, i.e., within a rather alkaline silica-saturated series. The mineral phases present in the silicate matrix (F-apatite, armalcolite, chromite, diopside–enstatite series, plagioclase–sanidine series) are usually present in the carbonate zones, where forsterite is also found. Some minerals cross-cut the interface between both types of zones. Only the matrix is different, feldspathic (oligoclase to sanidine) in the former and pure calcite in the latter. Thus, mineralogical and textural relationships between both products are consistent with an origin with equilibrium liquid immiscibility. Mantle minerals cross-cut by veinlets are sometimes resorbed at grain boundaries, and at the contact of the most alkaline silicate and carbonate melts, subhedral diopside/augite formed at the expense of mantle enstatite or olivine. In terms of mineral chemistry, the compositional variations recorded by vein minerals vary along a continuous trend. They generally superpose to those observed from lherzolites to harzburgites, and exhibit the same range of composition as that observed between rims and cores of mantle minerals cross-cut by veinlets. In detail, the Ca-rich pyroxenes of veinlets are Al-poor and Mg-rich; cpx in the carbonate zones are slightly more Ca-rich than those in the silicate matrix; spinels are relatively Al- and Mg-poor but rather Cr- and Fe-rich. Existence of only one titanium oxide (armalcolite) and various pairs of pyroxenes suggest crystallization temperatures in the range 1100–1200°C and pressures between 10–15 kb. Feldspar compositions in silicate materials, which vary continuously from labradorite to sanidine, are consistent with hypersolvus and dry crystallization conditions. All of these results provide evidence that immiscibility occurred at mantle depth as the liquid was forcibly injected during hydraulic fracturing of the mantle. The compositions of conjugate melts suggest a very large miscibility gap, as expected at high pressure in a dry environment from the experiments of Kjarsgaard and Hamilton [Kjarsgaard, B.A., Hamilton, D.L., 1988. Liquid immiscibility and the origin of alkali-poor carbonatites. Mineral. Mag. 52, 43–55; Kjarsgaard, B.A., Hamilton, D.L., 1989. The genesis of carbonatites by immiscibility. In: Bell, K. (Ed.), Carbonatites: Genesis and Evolution. Unwyn Hyman, London, pp. 388–404.]. The parental melt was carbonate, silica-undersaturated and rich in F, Cl and CO₂. Both immiscible melts were water-undersaturated. The cooling rate until total crystallization in veinlets was very slow, limited and necessarily occurred at mantle depth. Wall rock reactions leading to the formation of Ca-rich pyroxene at the expense of mantle enstatite or olivine occurred only at the contact with somewhat alkali-rich carbonatitic or silicate melts. Calcite, always anhedral, is the last mineral to crystallize. It is a differentiation product formed by magmatic crystallization or wall rock reaction. In some cases, given the rarity of any other minerals, it may be the product of the crystallization of a pure sövite immiscible melt.     

Effects of melt viscosity and silica activity on the rate and mechanism of quartz dissolution in melts of the CMAS and CAS systems

The dissolution rate of quartz in melts of the CMAS and CAS systems at 1,600°C and 1.5 GPa is a function of both the silica activity of the melt and its viscosity. In melts with low silica activity quartz dissolves more quickly than in higher aSiO₂ melts regardless of viscosity. For melts with equal aSiO₂, dissolution is faster in the low viscosity melt. Quartz dissolution is controlled by interface kinetics in three of the four melts used in this study for times much greater than predicted by the model of Zhang et al. (in Contrib Mineral Petrol 102:492–513 1989). One melt which was previously shown to adhere to the predicted behaviour at lower temperature shows a significant activation time at higher temperature. All the dissolution data indicate that there are likely to be three distinct domains of dissolution behaviour, although the details of why a particular melt falls in any one domain require further study. Although the current database is small, the relationship between quartz solubility and the dissolution constant indicate that solubility may be a useful parameter for predicting dissolution rates, particularly if silica activity and melt viscosity are also known.     

The solubility of calcite in seawater solutions of various magnesium concentration, It = 0.697 m at 25 °C and one atmosphere total pressure

Stoichiometric solubility constants of calcite in initially supersaturated solutions of various magnesium to calcium concentration ratios but identical ionic strength were determined at 25°C and one atmosphere total pressure.The thermodynamic solubility constant of calcite is used with ion pairing equations to interpret the data reported in this study. Results indicate that even though magnesian calcites, rather than pure calcite, precipitate from seawater solutions containing magnesium ions, the incorporation of MgCO₃ in the calcite crystal lattice does not extensively alter the equilibrium calcium carbonate activity product.The equilibrium activity of the ionic species in solution and the composition of magnesian calcite overgrowths precipitated from solutions of similar composition are used to calculate the solubility of magnesian calcites. The values for magnesian calcite solubilities obtained by this approach are lower than those obtained from the dissolution kinetics of biogenic carbonates.     

Carbonate xenoliths in La Palma: Carbonatite or alteration product?

Carbonate xenoliths containing olivine and rimmed by kaersutitic amphibole were collected in basaltic rocks of the Basal Complex of La Palma. The mineralogical composition and microscopic appearance may suggest a relationship with carbonatites in general, thus a major element, trace element and stable isotope study was conducted to investigate the origin of the carbonate formation. Based on electron microprobe analyses, the carbonate is calcite with up to 6.3 wt% MgO and 7.2 wt% SiO₂. The elevated SiO₂ content may suggest a melt origin for the carbonate. However, the C and O isotope compositions of the carbonate xenoliths (δ¹³C and δ¹⁸O around −1‰ and 13‰, respectively) are similar to those of calcite veins and amygdales in basaltic rocks of the Basal Complexes of La Palma and Fuerteventura and are interpreted as produced by fluid degassing and metasomatism by CO₂-H₂O fluid derived from mobilization of sedimentary material. Trace element contents determined by laser-ablation ICP-MS analyses support the assumed origin, thus, the relationship with carbonatitic melts can be excluded. Based on trace element compositions, the amphibole surrounding the xenoliths is not related genetically to the carbonate. The elevated SiO₂ content of the calcite can be attributed to submicron relics of pyroxene, thus, the use of this feature as an evidence for melt origin is questionable.     

Reactions of iron with calcium carbonate at 6 GPa and 1273–1873 K: implications for carbonate reduction in the deep mantle

Experimental data on Fe-CaCO₃ interaction at 6 GPa and 1273–1873 K are presented. The system models the hypothetical redox interaction in subducting slabs at the contact with the reduced mantle and a putative process at the core-mantle boundary. The reaction is accompanied by carbonatite melt formation. It also produces Fe3C and calcium wustite, which form solid or liquid phases depending on experimental conditions. In iron-containing systems at 6 GPa, calcium carbonate melts in the range 1473–1573 K, which is consistent with aragonite disappearance from complex carbonate systems. The composition of calcium carbonate liquid is not influenced by metallic Fe. It corresponds to nearly pure CaCO₃. Along the mantle adiabat or at slightly higher temperatures, nearly pure CaCO₃ coexists with metallic iron or calcium wustite. This hypothesis explains the coexistence of metallic iron and carbonate inclusions in lithospheric and superdeep diamonds.     

Genesis of carbonate aggregates in lamprophyres from the northeastern Transdanubian Central Range, Hungary: Magmatic or hydrothermal origin?

Summary Carbonate aggregates in Late Cretaceous lamprophyre dikes of the northeastern Transdanubian Central Range (TCR) in Northwest Hungary have been classified into three genetic groups. Type-I dolomite + calcite ± magnesite aggregates have petrographic and geochemical features similar to ocelli described by other workers. Fluid inclusions in Type-I aggregates homogenize between 77 and 204 °C and are of hydrothermal origin. Type-II aggregates are characterized by a polygonal shape and are mostly dolomite. Based on their shape and primary fluid inclusions which homogenize between 95 and 172 °C, these carbonate aggregates are interpreted to fill vugs produced by the dissolution of olivine phenocrysts. Type-III carbonate aggregates show an irregular to polygonal shape and distinct compositional zonation and contain secondary aqueous fluid inclusions. Homogenization temperatures of fluid inclusions are below 104 °C, and zonation patterns suggest partial recrystallization. These carbonate aggregates are most likely xenoliths and xenocrysts from the wall rocks of the lamprophyre melt conduits.     

基于石灰石粉钙源的微生物固化砂土试验研究

微生物诱导碳酸钙沉积（MICP）作用是一种新型的土体改良技术。钙源作为MICP反应中重要的反应物,对微生物诱导碳酸钙沉积的效果有重要的影响。目前应用最广泛的钙源——氯化钙（CaCl2）,具有成本高,环境污染性大的缺点。为此,文章提出利用石灰石粉提取钙源,通过在石灰石粉中加入乙酸溶液,释放钙离子用于微生物固化土体。通过开展无侧限抗压强度试验以及微观结构的扫描电镜观测、碳酸钙含量测定等分析,验证利用石灰石粉提取的钙源用于微生物诱导碳酸钙沉积作用固化土体的可行性,同时与醋酸钙和氯化钙固化砂柱进行了对比分析。研究结果表明：（1）石灰石粉用于微生物固化土体具有可行性,固化后砂柱的强度和碳酸钙含量较高,结构完整性高;（2）不同钙源固化砂柱的力学特性不同但均呈典型的脆性破坏模式,其中醋酸钙固化砂柱的无侧限抗压强度略高于石灰石钙源固化砂柱,氯化钙固化砂柱的无侧限抗压强度则远低于前两者且表面更加粗糙,孔隙更多,破坏后的完整性更低;（3）不同钙源固化砂柱的碳酸钙含量不同。醋酸钙和石灰石钙源固化砂柱的碳酸钙含量相近,而氯化钙固化砂柱中碳酸钙含量较低。不同钙源固化砂柱的碳酸钙含量和无侧限抗压强度基本呈正相关关系;（4）醋酸钙和石灰石钙源固化砂柱中砂土颗粒的表面和接触点间均沉积大量碳酸钙,碳酸钙晶体主要为薄片状堆叠的方解石。氯化钙固化砂柱中碳酸钙沉积量低于前两者,碳酸钙晶体主要为六面体状的方解石;（5）不同钙源主要通过影响微生物成矿过程的晶型、晶貌、晶体含量、晶体分布及胶结特征来改变固化效果。     

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.     

Pressure dependence of viscosity of rhyolitic melts

Viscosity of silicate melts is a critical property for understanding volcanic and igneous processes in the Earth. We investigate the pressure effect on the viscosity of rhyolitic melts using two methods: indirect viscosity inference from hydrous species reaction in melts using a piston cylinder at pressures up to 2.8 GPa and direct viscosity measurement by parallel-plate creep viscometer in an internally-heated pressure vessel at pressures up to 0.4 GPa. Comparison of viscosities of a rhyolitic melt with 0.8 wt% water at 0.4 GPa shows that both methods give consistent results. In the indirect method, viscosities of hydrous rhyolitic melts were inferred based on the kinetics of hydrous species reaction in the melt upon cooling (i.e., the equivalence of rheologically defined glass transition temperature and chemically defined apparent equilibrium temperature). The cooling experiments were carried out in a piston-cylinder apparatus using hydrous rhyolitic samples with 0.8-4 wt% water. Cooling rates of the kinetic experiments varied from 0.1 K/s to 100 K/s; hence the range of viscosity inferred from this method covers 3 orders of magnitude. The data from this method show that viscosity increases with increasing pressure from 1 GPa to 3 GPa for hydrous rhyolitic melts with water content ?0.8 wt% in the high viscosity range. We also measured viscosity of rhyolitic melt with 0.13 wt% water using the parallel-plate viscometer at pressures 0.2 and 0.4 GPa in an internally-heated pressure vessel. The data show that viscosity of rhyolitic melt with 0.13 wt% water decreases with increasing pressure. Combining our new data with literature data, we develop a viscosity model of rhyolitic melts as a function of temperature, pressure and water content.     

Structure and chemistry of grain boundaries in deformed, olivine + basalt and partially molten lherzolite aggregates: evidence of melt-free grain boundaries

Olivine grain boundaries in deformed aggregates of olivine + basalt and partially molten lherzolite were analyzed with various electron microscopy techniques to test for the presence of thin (0.5-10 nm) intergranular melt films. High-resolution transmission electron microscopy (HREM) observations reveal that most of the boundaries do not contain a thin amorphous phase, although a small fraction of grains are separated by relatively thick (~1 µm) layers of melt. However, due to the anisotropy of the olivine-melt interfacial energy, melt often tapers from a triple junction into an adjoining grain boundary over a length of 1 to 2 µm, giving an effective dihedral angle of only ~2°. The chemistry of olivine-olivine grain boundaries was analyzed using energy dispersive X-ray (EDX) profiling by scanning transmission electron microscopy (STEM) with a probe size of <1.5 nm. Ca, Al and Ti segregate to grain boundaries forming enriched regions of <7 nm width. Although these elements are concentrated in the glass phases, the presence of glass films with the same chemical composition as the bulk glass phases cannot explain concentrations of other elements such as Si and Al at the boundaries. Combined with the HREM results, the STEM/EDX profiling demonstrates the existence of chemical segregation between solid grains but the absence of thin, grain boundary melt films. Additionally, if melt films exist along all of the grain boundaries, as reported for similar samples by other groups, the rock should be substantially weakened. Creep experiments on the partially molten rocks analyzed in this study reveal little weakening at small melt contents, consistent with our observations of melt-free grain boundaries.