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1.
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.  相似文献   

2.
Kuh-I-Mond field in the Zagros foreland basin is a conventional heavy oil resource and is composed of fractured carbonates whose fractures were filled by calcite, dolomite, and anhydrite cements. Oil inclusions occurred within the fracture-fill cements indicate that fractures were open and played an active role during oil migration and charge. The highest measured values for secondary porosities belong to fractures in Asmari Formation, which is characterized by significant amounts of vug- and fracture-filling cements. Fractures facilitated fluid circulation and subsequently dissolution of allochems and high Mg carbonates. In contrast, fine-grained carbonate facies were less cemented, and thus, porosity enhancement by cement dissolution was insignificant. Temperature profiles of oil inclusions in the dolomite, calcite, and anhydrite minerals characterized by distinct variations in the homogenization temperatures (Th) that are divided into two ranges below 50°C in anhydrites and from 45°C to 125°C in dolomites and calcites. The lower Th ranges for anhydrite suggests that it may have formed at shallower burial depths during early to middle diagenesis. The oil inclusions display trend for increasing temperature downward which conform to Formation geothermal gradient. In other word, the decreasing trend of Th temperatures upward within Asmari Formation that can be observed in Th versus depth plot is consistent with the uplift events at Late Miocene time and later that caused removal of about 1,300 m of the crest of the Kuh-I-Mond anticline. Vitrinite reflectance data from source rock intervals in the field area do not support vertical migration of locally generated hydrocarbons into the Kuh-I-Mond accumulation, and long-distance lateral oil migration and charge from a source kitchen to the southwest is proposed. Vitrinite reflectance data from this dolomite and limestone reservoir suggest low maturation levels corresponding to paleotemperatures less than 50°C. The observed maturation level (<0.5% Ro) does not exceed values for simple burial maturation based on the estimated burial history. Also, homogenization temperatures from fluid inclusion populations in calcite and dolomites show expected good correlation with reflectance-derived temperatures. The Th data represent pore fluids became warmer and more saline during burial. As aqueous fluid inclusions in calcite veins were homogenized between 22°C and 90°C with a decrease in salinity from 22 to 18 eq.?wt.% NaCl. The Th values suggest a change in water composition and that dolomite and calcite cements might have precipitated from petroleum-derived fluids. The hydrocarbon fluid inclusions microthermometry data suggest that the reservoir was being filled by heavy black oils in reservoir during Cenozoic. Aqueous fluid inclusions hosted by calcite equant sparry/fossil cavity fills suggest low cementation temperatures (<45°C) and high salinities (19 eq.?wt.% NaCl), while those in dolostones are characterized by highly variable homogenization temperature (52°C to 125°C) and salinities (6.5 to 20 eq.?wt.% NaCl).  相似文献   

3.
Metasediments in the southern Grossvenediger area (Tauern Window, Austria) were studied along a cross-section through rocks of increasing metamorphic grade from the margin of the Tauern Window in the south to the base of the Upper Schieferhülle, including the Eclogite Zone, in the north. In the southern part of the cross-section there is no evidence for a pre-late Alpine metamorphic history in the form of high-pressure relics or pseudomorphs. Mineral assemblages are characterized by the stability of tremolite + calcite, biotite + calcite and biotite + chlorite + calcite. In the northern part a more complete Alpine metamorphic evolution is preserved. Primary high-pressure assemblages are dolomite + quartz, tremolite + zoisite, zoisite + dolomite + quartz + phengite I and probably tremolite + dolomite + phengite I. Secondary, post-kinematic assemblages [tremolite + calcite, talc + calcite, phengite II + chlorite + calcite (+ quartz), biotite + chlorite + calcite, biotite + zoisite + calcite] formed as a result of the dominant late Alpine metamorphic overprint. The occurrence of biotite + zoisite + calcite is confined to the northernmost area and defines a biotite–zoisite–calcite isograd. P–T estimates based on standard thermobarometric techniques and on stability relationships of tremolite + calcite + dolomite + quartz and zoisite give consistent results. P–T conditions of the main Tertiary metamorphic overprint were 525° C, P= 7.5 ± 1 kbar in the northern part of the cross-section. The southern part was metamorphosed at lower temperatures of 430–470° C. The Si-content of phengites from this area is almost as high as that of phengites from the Eclogite Zone (Simax= 3.4 pfu). Pressures > 10 kbar at 420° C are suggested by phengite barometry according to Massone & Schreyer (1987). In the absence of high-pressure relics or pseudomorphs, these phengites, which lack late Alpine re-equilibration, are the only record that rocks of the southern part probably also experienced an early non-eclogitic high-pressure metamorphism.  相似文献   

4.
This study presents calcite–graphite carbon isotope fractionations for 32 samples from marble in the northern Elzevir terrane of the Central Metasedimentary Belt, Grenville Province, southern Ontario, Canada. These results are compared with temperatures calculated by calcite–dolomite thermometry (15 samples), garnet–biotite thermometry (four samples) and garnet–hornblende thermometry (three samples). Δcal‐gr values vary regularly across the area from >6.5‰ in the south to 4.0‰ in the north, which corresponds to temperatures of 525 °C in the south to 650 °C in the north. Previous empirical calibration of the calcite–graphite thermometer agrees very well with calcite–dolomite, garnet–biotite and garnet–hornblende thermometry, whereas, theoretical calibrations compare less well with the independent thermometry. Isograds in marble based on the reactions rutile + calcite + quartz =titanite and tremolite + calcite + quartz = diopside, span temperatures of 525–600 °C and are consistent with calculated temperature–X(CO2) relations. Results of this study compare favourably with large‐scale regional isotherms, however, local variation is greater than that revealed by large‐scale sampling strategies. It remains unclear whether the temperature–Δcal‐gr relationship observed in natural materials below 650 °C represents equilibrium fractionations or not, but the regularity and consistency apparent in this study demonstrate its utility for thermometry in amphibolite facies marble.  相似文献   

5.
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.  相似文献   

6.
Dolomitic marble on the island of Naxos was deformed at variable temperatures ranging from 390 °C to >700 °C. Microstructural investigations indicate two end-member of deformation mechanisms: (1) Diffusion creep processes associated with small grain sizes and weak or no CPO (crystallographic preferred orientation), whereas (2) dislocation creep processes are related with larger grain sizes and strong CPO. The change between these mechanisms depends on grain size and temperature. Therefore, sample with dislocation and diffusion creep microstructures and CPO occur at intermediate temperatures in relative pure dolomite samples. The measured dolomite grain size ranges from 3 to 940 μm. Grain sizes at Tmax >450 °C show an Arrhenius type evolution reflecting the stabilized grain size in deformed and relative pure dolomite. The stabilized grain size is five times smaller than that of calcite at the same temperature and shows the same Arrhenius-type evolution. In addition, the effect of second phase particle influences the grain size evolution, comparable with calcite. Calcite/dolomite mixtures are also characterized by the same difference in grain size, but recrystallization mechanism including chemical recrystallization induced by deformation may contribute to apparent non-temperature equilibrated Mg-content in calcite.  相似文献   

7.
Small dolomite marble lenses and bands occur in the vast Caledonian migmatite and gneiss area of NW Spitsbergen (Svalbard archipelago). The fine-banded marbles contain numerous assemblages of minerals: calcite, dolomite, olivine, clinohumite, diopside, amphibole, chlorite, spiner and phologopite. The coexistence of calcite + dolomite + olivine + chlorite + spinel over the entire area indicates metamorphic temperatures of 600 to 680° at an estimated pressure of 4 kilobars. A temperature of near 600°C for the peak of metamorphism is suggested by mineral assemblages at the southernmost locality, Jäderinfjellet. Calcite-dolomite geothermometry indicated 595°C at the same locality. The spatial distribution of the marble assemblages suggests that metamorphism occurred under nearly isothermal conditions over an area of at least 25 by 30 kilometres.  相似文献   

8.
The partitioning of Sr between calcite, dolomite and liquids is essentially independent of temperature between 150° and 350° C. The partition coefficients corrected for number of cation sites are b calc=0.096 and b dol= 0.048 for 1 mol cations/6 mol H2O liquid. Upon dilution the partition coefficients increase, but their ratio stays constant at about 2∶1. This ratio is due to the fact that calcite has twice as many Ca-sites for Sr-substitution as dolomite. The 2∶1 relationship is also observed in natural calcite and dolomite which have undergone diagenesis. The temperature independence of partitioning is caused by the relatively small thermal expansion of calcite and dolomite. Thermal expansion between 25° and 400° C was found to follow the equations V calc=7.0·10−4 T(°C)+36.95 and V dol=6.9·10−4 T(°C)+32.24, V: cm3/mol. Therefore calcite and dolomite cannot serve as a temperature indicator. To have an ideal geothermometer a mineral pair with high and low thermal expansion is required. Literature date demonstrate that wurtzite, sphalerite, and galena are such minerals.  相似文献   

9.
Kuh-e Mond Field is a conventional heavy oil resource in the Zagros foreland Basin, Iran, produced from the fractured carbonates partially filled by dolomite, calcite, and anhydrite cement. Vitrinite reflectance data from carbonate reservoir suggest low-maturation levels corresponding to paleotemperatures as low as 50 °C. The observed maturation level (< 0.5% Rmax) does not exceed values for simple burial maturation based on the estimated burial history. Oil inclusions within fracture-filled calcite and dolomite cement indicate the key role of these fractures in oil migration.The fluid inclusion temperature profiles constructed from the available data revealed the occurrence of petroleum in dolomite, calcite, and anhydrite and characterize the distinct variations in the homogenization temperatures (Th). Fluid inclusions in syntectonic calcite veins homogenize between 22 °C and 90 °C, showing a salinity decrease from 22 to 18 eq. wt.% NaCl. Fluid inclusions in anhydrite homogenize at < 50 °C, showing that the pore fluids became warmer and more saline during burial. The Th range in the calcite-dolomite cement depicts a change in water composition; therefore, we infer these cements precipitated from petroleum-derived fluids. The microthermometry data on the petroleum fluid inclusions suggest that the reservoir was filled with heavy black oils and high-salinity waters and indicate that undersaturated oil was present in a hydrostatically pressured reservoir.The Th data do not support vertical migration of hot fluids througout the section, but extensive lateral fluid migration, most likely, drove tectonically dewatering in the south or west of the pool.  相似文献   

10.
In laboratory experiments, the precipitation of dolomite at ambient temperature is virtually impossible due to strong solvation shells of magnesium ions in aqueous media and probably also due to the existence of a more intrinsic crystallization barrier that prevents the formation of long-range ordered crystallographic structures at ambient surface conditions. Conversely, dolomite can easily form at high temperature (>100 °C), but its precipitation and growth requires several days or weeks depending on experimental conditions. In the present study, experiments were performed to assess how a single heat-ageing step promotes the formation of dolomite under high-carbonate alkaline conditions via dissolution-precipitation reactions. This reaction pathway is relevant for the so-called hydrothermal dolomite frequently observed in carbonate platforms, but still ill-defined and understood. Our precipitation route is summarized by two main sequential reactions: (1) precipitation of Mg-calcite at low temperature (∼20 °C) by aqueous carbonation of synthetic portlandite (Ca(OH)2) in a highly alkaline medium (1 M of NaOH and 1 M of MgCl2), leading to precipitation of oriented nanoparticles of low- and high-Mg calcite (∼79 wt%) coexisting with aragonite (∼18 wt%) and brucite (∼3 wt%) after 24 h; (2) fast dolomitization process starting from 1 h of reaction by a single heat-ageing step from ∼20 to 200, 250 and 300 °C. Here, the Mg-calcite acts as a precursor that lowers the overall kinetics barrier for dolomite formation. Moreover, it is an important component in some bio-minerals (e.g. corals and seashells). Quantitative Rietveld refinements of XRD patterns, FESEM observations and FTIR measurements on the sequentially collected samples suggest fast dolomite precipitation coupled with dissolution of transient mineral phases such as low-Mg calcite (Mg < 4 mol%), high-Mg calcite (Mg > 4 mol%), proto-dolomite (or disordered dolomite; Mg > 40 mol%) and Ca-magnesite. In this case, the dolomite formation rate and the time-dependent mineral composition strongly depend on reaction temperature. For example, high-purity dolomitic material (87 wt% of dolomite mixed with 13 wt% of magnesite) was obtained at 300 °C after 48 h of reaction. Conversely, a lower proportion of dolomite (37 wt%), mixed with proto-dolomite (43 wt%), Ca-magnesite (16 wt%) and high-Mg calcite (4 wt%), was obtained at 200 °C after 72 h. The present experiments provide an additional mechanism for the massive dolomite formation in sedimentary environments (ex. deep sea organic-rich carbonate-sediments) if such sediments are subjected to significant temperature variations, for example by hot fluid circulations related to volcanic activity. In such systems, organic degradation increases the carbonate alkalinity (HCO3−) necessary to induce the dolomitization process at low and high temperature.  相似文献   

11.
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.  相似文献   

12.
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.  相似文献   

13.
The carbonate platforms of the Wetterstein Formation of the Eastern Alps (Drau Range and Northern Calcareous Alps) show a distinct facies zonation of reefs and lagoons. While some lagoonal areas were episodically emerged and formed lagoonal islands, others remained permanently flooded. The scale of near surface, meteoric or marine diagenesis was related to this lagoonal topography. At shallow burial depth, cementation was dominated by altered marine solutions, which additionally caused recrystallization of metastable constituents of the sediment and earlier marine cements (high magnesian calcite, aragonite) connected with a carbon and oxygen isotopic change to more negative values. Deeper burial cementation shows a succession with two types of saddle dolomite and three types of blocky calcite. Carbon and oxygen isotopic values of these cements show a trend towards more negative values from the first to the last generation, in the following succession: clear saddle dolomite—zoned blocky calcite—cloudy saddle dolomite—post-corrosion blocky calcite—replacive blocky calcite. Fluid inclusion studies of the carbonate cements are interpreted to indicate a deeper burial temperature development that first increases from 175 to 317°C, followed by a temperature decrease to 163–260°C, and subsequent increase up to 316°C, whereby the samples of the Drau Range always show the lowest values. Calculations of the isotopic composition of the water, from which the carbonate cements were precipitated, yielded positive δ18O values from 6.66 to 17.81%o (SMOW), which are characteristic for formation and/or metamorphic waters. Also, the isotopic compositions of the palaeofluids probably changed during deeper burial diagenesis, following the temperature development.  相似文献   

14.
Reactive-transport models are developed here that produce dolomite via two scenarios: primary dolomite (no CaCO3 dissolution involved) versus secondary dolomite (dolomitization, involving CaCO3 dissolution). Using the available dolomite precipitation rate kinetics, calculations suggest that tens of meters of thick dolomite deposits cannot form at near room temperature (25-35°C) by inorganic precipitation mechanism, though this mechanism will provide dolomite aggregates that can act as the nuclei for dolomite crystallization during later dolomitization stage. Increase in supersaturation, Mg+2/Ca+2 ratio and CO3-2 on the formation of dolomite at near room temperature are subtle except for temperature.This study suggests that microbial mediation is needed for appreciable amount of primary dolomite formation. On the other hand, reactive-transport models depicting dolomitization (temperature range of 40 to 200°C) predicts the formation of two adjacent moving coupled reaction zones (calcite dissolution and dolomite precipitation) with sharp dolomitization front, and generation of >20% of secondary porosity. Due to elevated temperature of formation, dolomitization mechanism is efficient in converting existing calcite into dolomite at a much faster rate compared to primary dolomite formation.  相似文献   

15.
The solid‐state reaction magnesite (MgCO3) + calcite (aragonite) (CaCO3) = dolomite (CaMg(CO3)2) has been identified in metapelites from western Tianshan, China. Petrological studies show that two metamorphic stages are recorded in the metapelites: (1) the peak mineral assemblage of magnesite and calcite pseudomorphs after aragonite which is only preserved as inclusions within dolomite; and (2) the retrograde glaucophane‐chloritoid facies mineral assemblage of glaucophane, chloritoid, dolomite, garnet, paragonite, chlorite and quartz. The peak metamorphic temperatures and pressures are calculated to be 560–600 °C, 4.95–5.07 GPa based on the calcite–dolomite geothermometer and the equilibrium calculation of the reaction dolomite = magnesite + aragonite, respectively. These give direct evidence in UHP metamorphic rocks from Tianshan, China, that carbonate sediments were subducted to greater than 150 km depth. This UHP metamorphism represents a geotherm lower than any previously estimated for subduction metamorphism (< 3.7 °C km?1) and is within what was previously considered a ‘forbidden’ condition within Earth. In terms of the carbon cycle, this demonstrates that carbonate sediments can be subducted to at least 150 km depth without releasing significant CO2 to the overlying mantle wedge.  相似文献   

16.
An extensive humite‐bearing marble horizon within a supracrustal sequence at Ambasamudram, southern India, was studied using petrological and stable isotopic techniques to define its metamorphic history and fluid characteristics. At peak metamorphic temperatures of 775±73°C, based on calcite‐graphite carbon isotope thermometry, the mineral assemblages suggest layer‐by‐layer control of fluid compositions. Clinohumite + calcite‐bearing assemblages suggest XCO2 < 0.4 (at 700°C and 5 kbar), calcite + forsterite + K‐feldspar‐bearing assemblages suggest XCO2>0.9 (at 790°C); and local wollastonite + scapolite + grossular‐bearing zones formed at XCO2 of c. 0.3. Retrograde reaction textures such as scapolite + quartz symplectites after feldspar and calcite and replacement of dolomite + diopside or tremolite+dolomite after calcite+forsterite or calcite+clinohumite are indicative of retrogression under high XCO2 conditions. Calcite preserves late Proterozoic carbon and oxygen isotopic signatures and the marble lacks evidence for extensive retrograde fluid infiltration, while during prograde metamorphism the possible infiltration of aqueous fluids did not produce significant isotopic resetting. Isotopic zonation of calcite and graphite grains was likely produced by localized CO2 fluid infiltration during retrogression. Contrary to the widespread occurrence of humite‐marbles related to retrograde aqueous fluid infiltration, the Ambasamudram humite‐marbles record a prograde‐to‐peak metamorphic humite formation and retrogression under conditions of low XH2O.  相似文献   

17.
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  相似文献   

18.
The early Pliocene Shirahama Limestone is a grainstone-packstone principally composed of fragments of algae, bryozoa, and echinoderm and subordinate volcanic rocks. The limestone was variously dolomitized and the regional distribution of dolomite is patchy. Dolomite occurs as isolated crystals filling pores, moulds, and solution vugs, and mosaic aggregates replacing bioclasts. Calcite occurs as rim and pore-filling sparry cements, and as calcareous skeletons. Isotopically, the dolomites are classified into a heavy oxygen group (?2 to ? 3.5%0 PDB) and a light oxygen group (?5.5 to ? 7.5%0 PDB). Calcite associated with heavy oxygen dolomite has δ18O of ? 6.5 to ?8.5%0 PDB, whereas those associated with light oxygen dolomite have a wide range from ?7.5 to ?14%0 PDB. Calcite in dolomite-free limestone has an oxygen isotopic composition of ?2 to ?8.5%0 PDB. Textures, chemistry, and isotopic evidence indicate that heavy oxygen calcite formed in freshwater, and heavy oxygen dolomite in a meteoric-marine mixture of 10–30% seawater. Light oxygen calcite and dolomite precipitated from modified hydrothermal fluids at approximately 30–65°C. Petrographic features, and both isotopic and chemical evidence suggest that the Shirahama Limestone was exposed to freshwater soon after deposition. Subsequently blocky calcite precipitated (Stage I). The limestone was locally submerged in the meteoric-marine mixture due to gradual subsidence or eustatic movement. This led to the precipitation of heavy oxygen, zoned dolomite and dolospar (Stage II). Hydrothermal alterations occurred in the area a few Myr ago, and related hydrothermal fluids and mixed meteoric-hydrothermal waters caused dedolomitization of some zoned dolomite, partial dissolution of vuggy dolomite, precipitation of limpid dolomite and recrystallization of some earlier dolomites (Stage III). Zeolites were also precipitated from these fluids. Finally, the Shirahama Limestone was exposed again to freshwater and sparry calcite precipitated to plug some of the remaining pores (Stage IV).  相似文献   

19.
During an experimental investigation of the metamorphism of siliceous dolomites the equilibrium data of the heterogeneous bivariant reaction 1 $$3{\text{ dolomite + 4 quartz + 1 H}}_{\text{2}} O \rightleftharpoons + 3 calcite + 3 CO_2 $$ were determined for the total fluid pressures of 1,000, 3,000 and 5,000 bars. The equilibrium conditions were found by experiments in which dolomite, quartz and water react to form talc, calcite and CO2, as well as by experiments with reversible reaction direction. Results are shown on the temperature- \(X_{CO_2 } \) -diagram of Fig. 3. The temperature of formation of talc and calcite depends to a considerable extent on the composition of the CO2-H2O-gas phase; this can be read straight off the isobaric (P f =const.) equilibrium curves in Fig. 3. In addition a strong dependence of the equilibrium temperature on the total pressure P f was established (see Fig. 5). At a total gas pressure of 1,000 bars dolomite and quartz can react, according to the composition of the CO2-H2O-gas phase, to talc and calcite over the whole of the temperature range between about 350° and 490° C. This indicates that at low pressures the formation of talc and calcite takes place in the field of the albite-epidote-hornfels facies. At a pressure of 3,000 bars dolomite and quartz are stable up to about 550° C if the fluid phase is rich in carbon dioxide and correspondingly poor in water. Thus, this paragenesis can occur up to the stability field of staurolite [see annotation (5)] if the partial pressure of CO2 is large. At the higher total gas pressure of 5,000 bars dolomite and quartz react even at medium CO2-concentrations only at about 580° C to give talc and calcite. Therefore it is expected that in regional metamorphism at about 5,000 bars pressure or more the paragenesis dolomite plus quartz exists up to and within the stability field of staurolite and reacts only here to form talc and calcite after reaction (1) or tremolite and calcite after the following reaction (2)1: $$5 dolomite + 8 quartz + 1 H_2 O \rightleftharpoons 1 tremolite + 3 calcite + 7 CO_2 $$ . The exact physico-chemical conditions under which dolomite, quartz and water react on the one hand to form talc, calcite and CO2, and on the other hand to form tremolite, calcite and carbon dioxide, will be discussed later when our experimental investigations on the formation of tremolite are completed. First results were already published in a short note by Metz, Puhan and Winkler (1968).  相似文献   

20.
《Applied Geochemistry》1991,6(5):509-521
Bands of calcite and dolomite cements alternating with zones of nearly carbonate-free sand occur in the Stevens sandston aat North Coles Levee, San Joaquin, Valley, California. Temperatures calculated from O isotopes suggest that the calcite cement bands were emplaced episodically as a result of repeated injections of hot water from deeper in the section. Burial analysis suggests that these cements precipitated from 7 Ma to the present over the temperature range of 45 to ∼95°C.Carbon isotope data suggest that the C in the cements is a mixture derived from two sources, detrital shell material (δ13C(PDB)≈) and CO2 liberated from maturing kerogen (δ13C ≈ −24). Plots of δ13C vs time and depth of crystallization show that the cementation sequence was: (1) dolomite cements, possibly concretionary, precipitated at depths <1–2 km and at temperatures <45°C; (2) calcite cements with δ13C(PDB) values as low as −13, crystallized from depths between 1220 and 1820 m (4000 and 6000 ft) and at temperatures between 45 and 80°C; (3) calcite cements with δ13C(PDB) values approaching zero and calculated temperatures of crystallization up to the present reservoir temperature of 95±3°C.A log of δ13C vs calculated depth of crystallization correlates with the stratigraphic column at North Coles Levee. If the correlation is valid the light δ13 in each cement sample can be tied to its source. A model based on this interpretation suggests that the early, light C was derived from maturing kerogen in the Kreyenhagen Formation (Eocene) as it passed through the oil window between 4 and 5 Ma. The subsequent passage of younger sediments with less organic material produced correspondingly smaller amounts of light CO2 which was reflected in the relatively heavier C isotopes in the later cements.It is suggested that the epidsodic injections of hot water carried dissolved gases and minerals, principally calcite, upward from rocks as deep as 2–3 km below the Stevens sandstone and reprecipitated the calcite in more permeable zones in the rock. Degassing of CO2 from rising pore waters likely triggered the precipitation and accounts for the relatively large volumes of cement. The Sibson model for seismic pumping of pore fluids is considered a likely explanation for the observed cementation.  相似文献   

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