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1.
The well‐known Erzberg site represents the largest siderite (FeCO3) deposit in the world. It consists of various carbonates accounting for the formation of prominent CaCO3 (dominantly aragonite) precipitates filling vertical fractures of different width (centimetres to decimetres) and length (tens of metres). These commonly laminated precipitates are known as ‘erzbergite’. This study focuses on the growth dynamics and environmental dependencies of these vein fillings. Samples recovered on‐site and from mineral collections were analyzed, and these analyses were further complemented by modern water analyses from different Erzberg sections. Isotopic signatures support meteoric water infiltration and sulphide oxidation as the principal hydrogeochemical mechanism of (Ca, Mg and Fe) carbonate host rock dissolution, mobilization and vein mineralization. Clumped isotope measurements revealed cool formation temperatures of ca 0 to 10°C for the aragonite, i.e. reflecting the elevated altitude Alpine setting, but unexpectedly low for aragonite nucleation. The 238U–234U–230Th dating yielded ages from 285·1 ± 3·9 to 1·03 ± 0·04 kyr bp and all samples collected on‐site formed after the Last Glacial Maximum. The observed CaCO3 polymorphism is primarily controlled by the high aqueous Mg/Ca ratios resulting from dissolution of Mg‐rich host rocks, with Mg/Ca further evolving during prior CaCO3 precipitation and CO2 outgassing in the fissured aquifer. Aragonite represents the ‘normal’ mode of erzbergite formation and most of the calcite is of diagenetic (replacing aragonite) origin. The characteristic lamination (millimetre‐scale) is an original growth feature and mostly associated with the deposition of stained (Fe‐rich) detrital particle layers. Broader zonations (centimetre‐scale) are commonly of diagenetic origin. Petrographic observations and radiometric dating support an irregular nature for most of the layering. Open fractures resulting from fault tectonics or gravitational mass movements provide water flow routes and fresh chemical reaction surfaces of the host rock carbonates and accessory sulphides. If these prerequisites are considered, including the hydrogeochemical mechanism, modern water compositions, young U‐Th ages and calculated precipitation rates, it seems unlikely that the fractures had stayed open over extended time intervals. Therefore, it is most likely that they are geologically young.  相似文献   

2.
This study explores the effects of cation composition on mass bias (i.e., the matrix effect), which is a major component of instrumental mass fractionation (IMF) in the microanalyses of δ13C and δ18O by SIMS in carbonates of the magnesite–siderite solid‐solution series (MgCO3–FeCO3). A suite of twelve calibration reference materials (RMs) was developed and documented (calibrated range: Fe# = 0.002–0.997, where Fe# = molar Fe/[Mg + Fe]), along with empirical expressions for regressing calibration data (affording residuals < 0.5‰ relative to certified reference material NIST‐19). The calibration curves of both isotope systems are non‐linear and have, over a 2‐year period, fallen into one of two distinct but largely self‐consistent shape categories (data from ten measurement sessions), despite adherence to well‐established analytical protocols for carbonate δ13C and δ18O analyses at WiscSIMS (CAMECA IMS 1280). Mass bias was consistently most sensitive to changes in composition near the magnesite end‐member (Fe# 0–0.2), deviating by up to 4.5‰ (δ13C) and 14‰ (δ18O) with increasing Fe content. The cause of variability in calibration curve shapes is not well understood at present and demonstrates the importance of having available a sufficient number of well‐characterised RMs so that potential complexities of curvature can be adequately delineated and accounted for on a session‐by‐session basis.  相似文献   

3.
The interaction between CO2-rich waters and basaltic glass was studied using reaction path modeling in order to get insight into the water-rock reaction process including secondary mineral composition, water chemistry and mass transfer as a function of CO2 concentration and reaction progress (ξ). The calculations were carried out at 25-90 °C and pCO2 to 30 bars and the results were compared to recent experimental observations and natural systems. A thermodynamic dataset was compiled from 25 to 300 °C in order to simulate mineral saturations relevant to basalt alteration in CO2-rich environment including revised key aqueous species for mineral dissolution reactions and apparent Gibbs energies for clay and carbonate solid solutions observed to form in nature. The dissolution of basaltic glass in CO2-rich waters was found to be incongruent with the overall water composition and secondary mineral formation depending on reaction progress and pH. Under mildly acid conditions in CO2 enriched waters (pH <6.5), SiO2 and simple Al-Si minerals, Ca-Mg-Fe smectites and Ca-Mg-Fe carbonates predominated. Iron, Al and Si were immobile whereas the Mg and Ca mobility depended on the mass of carbonate formed and water pH. Upon quantitative CO2 mineralization, the pH increased to >8 resulting in Ca-Mg-Fe smectite, zeolites and calcite formation, reducing the mobility of most dissolved elements. The dominant factor determining the reaction path of basalt alteration and the associated element mobility was the pH of the water. In turn, the pH value was determined by the concentration of CO2 and extent of reaction. The composition of the carbonates depended on the mobility of Ca, Mg and Fe. At pH <6.5, Fe was in the ferrous oxidation state resulting in the formation of Fe-rich carbonates with the incorporation of Ca and Mg. At pH >8, the mobility of Fe and Mg was limited due to the formation of clays whereas Ca was incorporated into calcite, zeolites and clays. Competing reactions between clays (Ca-Fe smectites) and carbonates at low pH, and zeolites and clays (Mg-Fe smectites) and carbonates at high pH, controlled the availability of Ca, Mg and Fe, playing a key role for low temperature CO2 mineralization and sequestration into basalts. Several problems of the present model point to the need of improvement in future work. The determinant factors linking time to low temperature reaction path modeling may not only be controlled by the primary dissolving phase, which presents challenges concerning non-stoichiometric dissolution, the leached layer model and reactive surface area, but may include secondary mineral precipitation kinetics as rate limiting step for specific reactions such as retrieved from the present reaction path study.  相似文献   

4.
This study is Part II of a series that documents the development of a suite of calibration reference materials for in situ SIMS analysis of stable isotope ratios in Ca‐Mg‐Fe carbonates. Part I explored the effects of Fe2+ substitution on SIMS δ18O bias measured from the dolomite–ankerite solid solution series [CaMg(CO3)2–CaFe(CO3)2], whereas this complementary work explores the compositional dependence of SIMS δ13C bias (calibrated range: Fe# = 0.004–0.789, where Fe# = molar Fe/(Mg+Fe)). Under routine operating conditions for carbonate δ13C analysis at WiscSIMS (CAMECA IMS 1280), the magnitude of instrumental bias increased exponentially by 2.5–5.5‰ (session‐specific) with increasing Fe‐content in the dolomite structure, but appeared insensitive to minor Mn substitution [< 2.6 mole % Mn/(Ca+Mg+Fe+Mn)]. The compositional dependence of bias (i.e., the matrix effect) was expressed using the Hill equation, yielding calibration residual values ≤ 0.3‰ relative to CRM NBS‐19 for eleven carbonate reference materials (6‐μm‐diameter spot size measurements). Based on the spot‐to‐spot repeatability of a drift monitor material that ‘bracketed’ each set of ten sample‐spot analyses, the analytical precision was ± 0.6–1.2‰ (2s, standard deviations). The analytical uncertainty for individual sample analyses was approximated by combining the precision and calibration residual values (propagated in quadrature), suggesting an uncertainty of ± 1.0–1.5‰ (2s).  相似文献   

5.
Long-chain amines, used in potash ore flotation as collectors, are insoluble in NaCl–KCl saturated brine. In commercial applications, these amines are melted at 70–90 °C, dispersed in acidic solution of hydrochloric or acetic acids, and such emulsions are then introduced to the flotation pulp.To model the commercial potash ore flotation process, dodecyl amine, used in this study, was melted at 70 °C, dispersed in hydrochloric acid aqueous solution and was added to a KCl–NaCl saturated brine at room temperature. This results in the precipitation of the amine. The present study summarizes the influence of the conditions on the particle size and morphology of the precipitating amine particles. Methyl isobutyl carbinol (MIBC), common frother in flotation processes, was shown to affect amine dispersion when added into a hot amine emulsion prior to mixing with a saturated brine. This study demonstrates that the precipitating amine particles are selectively abstracted by KCl particles, but not by NaCl particles.  相似文献   

6.
Carbonate concretions, lenses and bands in the Pleistocene, Palaeogene and Upper Triassic coalfields of Japan consist of various carbonate minerals with varied chemical compositions. Authigenic carbonates in freshwater sediments are siderite > calcite > ankerite > dolomite >> ferroan magnesite; in brackish water to marine sediments in the coal measures, calcite > dolomite > ankerite > siderite >> ferroan magnesite; and in the overlying marine deposits, calcite > dolomite >> siderite. Most carbonates were formed progressively during burial within a range of depths between the sediment-water interface and approximately 3 km. The mineral species and the chemical composition of the carbonates are controlled primarily by the initial sedimentary facies of the host sediments and secondarily by the diagenetic evolution of pore water during burial. Based on the regular sequence and burial depth of precipitation of authigenic carbonates in a specific sedimentary facies, three diagenetic stages of carbonates are proposed. Carbonates formed during Stage I (< 500 m) strongly reflect the initial sedimentary facies, e.g. low Ca-Mg siderite in freshwater sediments which are initially rich in iron derived from lateritic soil on the nearby landmass, and Mg calcite and dolomite in brackish-marine sediments whose pore waters abound in Ca2+ and Mg2+ originating in seawater and calcareous shells. Carbonates formed during Stage II (500–2000 m) include high Ca-Mg siderite, ankerite, Fe dolomite and Fe–Mg calcite in freshwater sediments. The assemblage of Stage II carbonates in brackish-marine sediments in the coal measures is similar to that in freshwater sediments. This suggests similar diagenetic environments owing to an effective migration and mixing of pore water due to the compaction of host sediments. Carbonates formed during Stage III (> 2000 m) are Fe calcite and extremely high Ca-Mg siderite; the latter is exclusively in marine mudstones. The supply of Ca is partly from the alteration of silicates in the sediments at elevated burial temperatures. After uplift, calcite with low Mg content precipitates from percolating groundwater and fills extensional cracks.  相似文献   

7.
Magnesite, siderite and dolomite are characteristic alteration minerals occurring in Miocene hanging wall rocks of dacitic composition which host the Kuroko orebodies. These carbonates generally occur in a more stratigraphically upper horizon than chlorite alteration zone surrounding the orebodies. The Mg/(Mg+Fe) ratios of the carbonates decrease from the central alteration zone to marginal zone. The Mg/(Mg+Fe) ratios of carbonates and chlorite positively correlate. The δ18O and δ13C values of magnesite, siderite and dolomite positively correlate with each other and lie between the igneous and marine carbonate values. The petrographic, isotopic and fluid inclusion characteristics and thermochemical modelling calculations indicate that magnesite and dolomite formed in the central zone close to the orebodies due to the interaction of hydrothermal solutions with the biogenic marine carbonates. Calcite formed further from the orebodies from hydrothermal fluids which did not contain a biogenic marine carbon component. The compositional and textural relationships indicate that superimposed alterations (chlorite alteration and carbonate alteration) occurred in hanging wall rocks. The mode of occurrences and the Mg/(Mg+Fe) ratios of magnesite and dolomite occurring in hanging wallrocks are useful in the exploration for concealed volcanogenic massive sulfide-sulfate deposits. Received: 9 September 1997 / Accepted: 23 September 1997  相似文献   

8.
The spinel–quartz-bearing Al–Fe granulites from Ihouhaouene (In Ouzzal, West Hoggar) have a migmatitic appearance with quartzo-feldspathic layers intercalated with restitic layers. These granulites are characterized by a hercynitic spinel–quartz assemblage typical of high grade terranes. The stability of the spinel–quartz assemblage is attributed to an elevation of temperature (from 800 to >1100 °C) at high pressures (10–11 kbar), followed by an isothermal decompression from 9 to 5 kbar, an evolution typical of the In Ouzzal clockwise P–T path. The Al–Fe granulites’ history can be subdivided into different successive crystallisation stages. During the first stage, the spinel–quartz assemblage formed, probably following a prograde event that also produced partial melting. During a second stage, the primary spinel–garnet–sillimanite–quartz paragenesis broke-down to give rise to the secondary assemblage. The metamorphic evolution and phase relations during this stage are shown in P–T–X pseudosections calculated for the simple FMASH system. These pseudosections show that the orthopyroxene–cordierite–spinel symplectite appeared during a high temperature decompression, as a product of destabilisation of garnet in sillimanite-free microdomains with high XMg values. At the same time, the spinel–quartz association broke-down into cordierite in Fe-rich microdomains. Average pressure and temperature estimates for the orthopyroxene–spinel–garnet–cordierite–quartz association are close to the thermal peak of metamorphism (1000 ± 116 °C at 6.3 ± 0.5 kbar). With decreasing temperatures garnet–sillimanite corona developed from the breakdown of the primary spinel–quartz assemblage in the Fe-rich microdomains, whereas cordierite–spinel formed at the expense of primary sillimanite and garnet in the Mg-rich microdomains.  相似文献   

9.
Keilite (Fe>0.5,Mg<0.5)S, the iron-dominant cubic analog of niningerite, (Mg>0.5,Fe<0.5)S, occurs in enstatite chondrites [Shimizu, M., Yoshida, H., Mandarino, J.A., 2002. The new mineral species keilite, (Fe,Mg)S, the iron-dominant analog of niningerite. Can. Mineral. 40, 1687–1692]. I find that keilite occurs only in enstatite chondrite impact-melt rocks and impact-melt breccias. Based on the phase relations in the system MgS–MnS–CaS–FeS [Skinner, B.J., Luce, F.D., 1971. Solid solutions of the type (Ca,Mg,Mn,Fe)S and their use as geothermometers for the enstatite chondrites. Am. Mineral. 56, 1269–1296], I conclude that keilite formed from niningerite or alabandite (Mn>0.5,Fe<0.5)S by reaction with troilite (FeS) at elevated temperatures of well above 500 °C (the lowest equilibration temperature of keilite), but it is likely that the maximum temperatures during melting experienced by keilite-bearing impact-melt rocks and impact-melt breccias were considerably higher, perhaps >1500 °C, as indicted by the occurrence of euhedral enstatite that formed from a melt [McCoy, T.J., Dickinson, T.L., Lofgren, G.E., 1999. Partial melting of the Indarch (EH4) meteorite: a textural, chemical, and phase relations view of melting and melt migration. Meteorit. Planet. Sci. 34, 735–746]. Based on the classifications of the keilite-bearing meteorites as impact-melt rocks and impact-melt breccias and my own textural observations, I conclude that this elevated temperature was reached as a result of impact and not internal heating and melting, followed by fast cooling, thus, quenching in keilite. Enstatite chondrite impact-melt rocks and impact-melt breccias that do not contain keilite may have been more deeply buried after impact and, hence, cooled slowly and were annealed so that FeS exsolved from keilite, concomitant with the formation of niningerite, alabandite or various (Mn,Mg,Fe) mixed sulfides.  相似文献   

10.
The isotopic composition of Fe was determined in water, Fe-oxides and sulfides from the Tinto and Odiel Basins (South West Spain). As a consequence of sulfide oxidation in mine tailings both rivers are acidic (1.45 < pH < 3.85) and display high concentrations of dissolved Fe (up to 420 mmol l− 1) and sulphates (up to 1190 mmol l− 1).The δ56Fe of pyrite-rich samples from the Rio Tinto and from the Tharsis mine ranged from − 0.56 ± 0.08‰ to + 0.25 ± 0.1‰. δ56Fe values for Fe-oxides precipitates that currently form in the riverbed varied from − 1.98 ± 0.10‰ to 1.57 ± 0.08‰. Comparatively narrower ranges of values (− 0.18 ± 0.08‰ and + 0.21 ± 0.14‰) were observed in their fossil analogues from the Pliocene–Pleistocene and in samples from the Gossan (the oxidized layer that formed through exposure to oxygen of the massive sulfide deposits) (− 0.36 ± 0.12‰ to 0.82 ± 0.07‰). In water, δ56Fe values ranged from − 1.76 ± 0.10‰ to + 0.43 ± 0.05‰.At the source of the Tinto River, fractionation between aqueous Fe(III) and pyrite from the tailings was less than would be expected from a simple pyrite oxidation process. Similarly, the isotopic composition of Gossan oxides and that of pyrite was different from what would be expected from pyrite oxidation. In rivers, the precipitation of Fe-oxides (mainly jarosite and schwertmannite and lesser amounts of goethite) from water containing mainly (more than 99%) Fe(III) with concentrations up to 372 mmol l− 1 causes variable fractionation between the solid and the aqueous phase (− 0.98‰ < Δ56Fesolid–water < 2.25‰). The significant magnitude of the positive fractionation factor observed in several Fe(III) dominated water may be related to the precipitation of Fe(III) sulphates containing phases.  相似文献   

11.
Abstract. The distribution of Na, K, Ca, Mg, Mn and Fe between the granodiorite JG-la, one of the geochemical standard rocks, and 2M NaCl aqueous solution was experimentally determined at temperatures of 300 to 800C and a pressure of 1 kb using standard cold seal-type pressure vessels. The solid run products melted partially at 800C. Only K shows a significantly different behavior from the experiments using the basalt JB-la (Uchida and Tsutsui, 2000) due to the presence of ortho-clase in the JG-la. The transition elements tend to be preferably partitioned into the aqueous chloride solutions with increasing temperature. At 800C and 1 kb, the Fe concentration of the aqueous chloride solutions reached up to 5,000 ppm, and the Mn concentration up to 350 ppm. The distribution coefficient, KD, i = Ci, sol/Ci, rock, is in the order of Na>K>Mn>Ca> Fe>Mg at 300C, but changed in the order of Mn>N>K>Fe>Ca>Mg at 800C. The distribution coefficients of the divalent cations for the JG-la are higher than those for the JB-1a. The distribution coefficient of the transition elements, Fe and Mn, increases significantly with increasing temperature. The thermodynamic analysis for aqueous speciation revealed that this is attributable to the formation of the tri-chloro complexes of the transition elements at higher temperatures.  相似文献   

12.
Crystallization of authigenic carbonates in mud volcanoes at Lake Baikal   总被引：1，自引：0，他引：1  
This paper presents data on authigenic siderite first found in surface sediments from mud volcanoes in the Central (K-2) and Southern (Malen’kii) basins of Lake Baikal. Ca is the predominant cation, which substitutes Fe in the crystalline lattice of siderite. The enrichment of the carbonates in the 13C isotope (from +3.3 to +6.8‰ for the Malen’kii volcano and from +17.7 to +21.9‰ for K-2) results from the crystallization of the carbonates during methane generation via the bacterial destruction of organic matter (acetate). The overall depletion of the carbonates in 18O is mainly inherited from the isotopic composition of Baikal water.  相似文献   

13.
A shale split in the well-studied Foord Seam (Upper Carboniferous), Stellarton Basin, Nova Scotia, provides a rare opportunity to study little known siderite concretions with anatomically preserved plants from a limnic basin. Siderite concretions occur throughout the split, commonly as sheet-like, inter-connected lepidodendrid logs, or less frequently as spherical masses; they are typically vuggy. A sample of 14 stratigraphically oriented concretions in the split shows that primary siderite varies from 45% to 80% (wt.%) due to selective replacement by 5% to 40% ferroan dolomite or ankerite in plant tissues. These two minerals show large Mg/Fe and Mg/Ca variability and are Fezoned. Clay content ranges from trace to 20%, and quartz from 5% to 10%. Partial cell-wall destruction by erosion and changeable oxic/anoxic conditions, prior to siderite permineralization, resulted in preservation mainly of the more resistant plant tissues. On average, carbon from siderite is isotopically heavier (+4.8±1.9 0/00) than that from ‘dolomite' (−7.2±1.1 0/00). The distribution of and the positive correlation between δ13C and δ18O probably reflects the two fractionation processes associated with methanogenesis and ‘dolomitization', respectively, in the genetic history of the siderite concretions in the split. Siderite concretions formed diagenetically early from bicarbonate under reducing conditions in a slightly alkaline freshwater environment that precluded calcite deposition.  相似文献   

14.
Dissolution of the synthetic hydroxylapatite (HAP) and fluorapatite (FAP) in pure water was studied at 25 °C and 45 °C in a series of batch experiments. The XRD, FT-IR and SEM analyses indicated that the synthetic, microcrystalline HAP and FAP with apatite structure used in the experiments were found to have no obvious variation after dissolution except that the existence of OH groups in FT-IR spectra for FAP after 2880 h dissolution was observed. During the HAP dissolution (0–4320 h), the aqueous calcium and phosphate concentrations reached the maxima after 120 h and then decreased slowly with time. For the FAP dissolution in pure water, after a transient time of 1440 h (< 60 d), element concentrations and pH became constant suggesting attainment of a steady-state between the solution and solid. During early stages of the FAP dissolution reaction (< 72–120 h), mineral components were released in non-stoichiometric ratios with reacted solution ratios of dissolved Ca:P, Ca:F and P:F being lower than mineral stoichiometric ratios of Ca5(PO4)3F, i.e., 1.67, 5.0 and 3.0, respectively. This indicated that F were preferentially released compared to Ca from the mineral structure. The mean Ksp values were calculated by using PHREEQC for HAP of 10− 53.28 (10− 53.02–10− 53.51) and for FAP of 10− 55.71 (10− 55.18–10− 56.13) at 25 °C, the free energies of formation ΔGfo[HAP] and ΔGfo[FAP] were calculated to be − 6282.82 kJ/mol and − 6415.87 kJ/mol, respectively.  相似文献   

15.
The metamorphic evolution of the Garzón Massif, Colombia, is established on the basis of the textural, goethermobarometric, and geochronological relationships of the metamorphic minerals. The geothermobarometric data define a clockwise, nearly isothermal decompression path (ITD) for rocks from Las Margaritas migmatites, constrained by four P–T areas: 780–826 °C and 6.3–8.0 kbar, 760–820 °C and 8.0–8.8 kbar, 680–755 °C and 6.6–9.0 kbar, and 630 °C and 4 kbar. For the a garnet-bearing charnockitic gneiss from the Vergel granulites, the path is counterclockwise, constrained by geothermobarometric data of 5.3–6.2 kbar and 700–780 °C and 6.2–7.2 kbar and 685–740 °C. The clockwise ITD path represents a loop followed by the orogen during the transitional granulite–amphibolite metamorphic conditions, probably associated with a subduction process followed by a collisional tectonic event. This subduction framework produced continental crust thickening between 1148 and 1034 Ma and later collision with another continental block approximately 1000 Ma ago. The orogenic exhumation occurred with moderate uplift rate. The counterclockwise trajectory and two metamorphic events suggest a vertical displacement between the Vergel granulites and Las Margaritas migmatites units, because there is no isotopic difference that indicates the existence of different terranes. The data confirm that the metamorphic evolution for this domain was more dynamic than previously believed and includes: (1) metamorphic processes with the generation of new crust with a possible mixture of old material and (2) metamorphic recycling of continental crust. These geological processes characterize a complex Mesoproterozoic orogenic event that shares certain features with the Grenvillian basement rocks participating in the formation of Rodinia.  相似文献   

16.
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17.
The carbonate-hosted Kabwe Pb–Zn deposit, Central Zambia, has produced at least 2.6 Mt of Zn and Pb metal as well as minor amounts of V, Cd, Ag and Cu. The deposit consists of four main epigenetic, pipe-like orebodies, structurally controlled along NE–SW faults. Sphalerite, galena, pyrite, minor chalcopyrite, and accessory Ge-sulphides of briartite and renierite constitute the primary ore mineral assemblage. Cores of massive sulphide orebodies are surrounded by oxide zones of silicate ore (willemite) and mineralized jasperoid that consists largely of quartz, willemite, cerussite, smithsonite, goethite and hematite, as well as numerous other secondary minerals, including vanadates, phosphates and carbonates of Zn, Pb, V and Cu.Galena, sphalerite and pyrite from the Pb–Zn rich massive orebodies have homogeneous, negative sulphur isotope ratios with mean δ34SCDT permil (‰) values of − 17.75 ± 0.28 (1σ), − 16.54 ± 0.0.27 and − 15.82 ± 0.25, respectively. The Zn-rich and Pb-poor No. 2 orebody shows slightly heavier ratios of − 11.70 ± 0.5‰ δ34S for sphalerite and of − 11.91 ± 0.71‰ δ34S for pyrite. The negative sulphur isotope ratios are considered to be typical of sedimentary sulphides produced through bacterial reduction of seawater sulphate and suggest a sedimentary source for the sulphur.Carbon and oxygen isotope ratios of the host dolomite have mean δ13CPDB and δ18OSMOW values of 2.89‰ and 27.68‰, respectively, which are typical of marine carbonates. The oxygen isotope ratios of dolomite correlate negatively to the SiO2 content introduced during silicification of the host dolomite. The depletion in 18O in dolomite indicates high temperature fluid/rock interaction, involving a silica- and 18O-rich hydrothermal solution.Two types of secondary fluid inclusions in dolomite, both of which are thought to be related to ore deposition, indicate temperatures of ore deposition in the range of 257 to 385 and 98 to 178 °C, respectively. The high temperature fluid inclusions contain liquid + vapour + solid phases and have salinities of 15 to 31 eq. wt.% NaCl, whereas the low temperature inclusions consist of liquid + vapour with a salinity of 11.5 eq. wt.% NaCl.Fluid transport may have been caused by tectonic movements associated with the early stages of the Pan-African Lufilian orogeny, whereas ore deposition within favourable structures occurred due to changes in pressure, temperature and pH in the ore solution during metasomatic replacement of the host dolomite. The termination of the Kabwe orebodies at the Mine Club fault zone and observed deformation textures of the ore sulphides as well as analysis of joint structures in the host dolomite, indicate that ore emplacement occurred prior to the latest deformation phase of the Neoproterozoic Lufilian orogeny.  相似文献   

18.
Garnet–biotite and garnet–cordierite geothermometers have been consistently calibrated, using the results of Fe2+–Mg cation exchange experiments and utilizing recently evaluated nonideal mixing properties of garnet. Nonideal mixing parameters of biotite (including Fe, Mg, AlVI, and Ti) and of cordierite (involving Fe and Mg) are evaluated in terms of iterative multiple least-square regressions of the experimental results. Assuming the presence of ferric Fe in biotite in relation to the coexisting Fe-oxide phases (Case A), and assuming the absence of ferric Fe in biotite (Case B), two formulae of garnet–biotite thermometer have been derived. The garnet–cordierite geothermometer was constructed using Margules parameters of garnet adopted in the garnet–biotite geothermometers. The newly calibrated garnet–biotite and garnet–cordierite thermometers clearly show improved conformity in the calculated temperatures. The thermometers give temperatures that are consistent with each other using natural garnet–biotite–cordierite assemblages within ±50 °C. The effects of ferric Fe in biotite on garnet–biotite thermometry have been evaluated comparing the two calibrations of the thermometer. The effects are significant; it is clarified that taking ferric Fe content in biotite into account leads to less dispersion of thermometric results.  相似文献   

19.
Subduction carries atmospheric and crustal carbon hosted in the altered oceanic crystalline basement and in pelagic sediments back into the mantle. Reactions involving complex carbonate solid solutions(s) lead to the transfer of carbon into the mantle, where it may be stored as graphite/diamond, in fluids or melts, or in carbonates. To constrain the thermodynamics and thus reactions of the ternary Ca–Mg–Fe carbonate solid solution, piston cylinder experiments have been performed in the system CaCO3–MgCO3–FeCO3 at a pressure of 3.5 GPa and temperatures of 900–1,100°C. At 900°C, the system has two miscibility gaps: the solvus dolomite–calcite, which closes at X MgCO3 ~0.7, and the solvus dolomite–magnesite, which ranges from the Mg to the Fe side of the ternary. With increasing temperature, the two miscibility gaps become narrower until complete solid solutions between CaCO3–Ca0.5Mg0.5CO3 is reached at 1,100°C and between CaCO3–FeCO3 at 1,000°C. The solvi are characterized by strong compositional asymmetry and by an order–disorder mechanism. To deal with these features, a solid solution model based on the van Laar macroscopic formalism has been calculated for ternary carbonates. This thermodynamic solid solution model is able to reproduce the experimentally constrained phase relations in the system CaCO3–MgCO3–FeCO3 in a broad P–T range. To test our model, calculated phase equilibria were compared with experiments performed in carbonated mafic protolithes, demonstrating the reliability of our solid solution model at pressures up to 6 GPa in complex systems.  相似文献   

20.
Steady-state element release rates from crystalline basalt dissolution at far-from-equilibrium were measured at pH from 2 to 11 and temperatures from 5 to 75 °C in mixed-flow reactors. Steady-state Si and Ca release rates exhibit a U-shaped variation with pH where rates decrease with increasing pH at acid condition but increase with increasing pH at alkaline conditions. Silicon release rates from crystalline basalt are comparable to Si release rates from basaltic glass of the same chemical composition at low pH and temperatures ?25 °C but slower at alkaline pH and temperatures ?50 °C. In contrast, Mg and Fe release rates decrease continuously with increasing pH at all temperatures. This behaviour is interpreted to stem from the contrasting dissolution behaviours of the three major minerals comprising the basalt: plagioclase, pyroxene, and olivine. Calcium is primarily present in plagioclase, which exhibits a U-shaped dissolution rate dependence on pH. In contrast, Mg and Fe are contained in pyroxene and olivine, minerals whose dissolution rates decrease monotonically with pH. As a result, crystalline basalt preferentially releases Mg and Fe relative to Ca at acidic conditions. The injection of acidic CO2-charged fluids into crystalline basaltic terrain may, therefore, favour the formation of Mg and Fe carbonates rather than calcite. Element release rates estimated from the sum of the volume fraction normalized dissolution rates of plagioclase, pyroxene, and olivine are within one order of magnitude of those measured in this study.  相似文献   

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