A geochemical clogging model with carbonate precipitation rates under hydrothermal conditions     

《Applied Geochemistry》2013

A step-wise numerical calculation method was developed to provide predictions of when and where carbonate deposits might be found through reservoirs during CO₂ sequestration. Flow experiments through porous media using a supersaturated carbonate fluid were also performed in order to observe flow rates. In order to evaluate precipitation rates and permeability change in the formation, calculated flow rates based on the proposed geochemical clogging model were compared with the experimentally observed data. Both high and low temperature cases were studied to understand how hydrothermal conditions can affect precipitation rates of carbonate. According to chemical kinetics, growth rates of minerals are generally proportional to the saturation index (S.I.) that depends on temperature. Thus, a supersaturated fluid has the advantage of improving the filtration and the amount of C fixation (σ). However, when the ratio of filtration coefficient (λ) to pore fluid velocity (u) increases, the permeability around the injection point tends to be significantly reduced by carbonate accumulation, and thus, this might result in insufficient injection of CO₂. Therefore, it is essential to understand how to control both λ and u so that the precipitation of carbonate can be located as far away from the inlet as possible.  相似文献   

Late Paleocene–early Eocene Tethyan carbonate platform evolution — A response to long- and short-term paleoclimatic change     

C. Scheibner  R.P. Speijer   《Earth》2008,90(3-4):71-102

The early Paleogene experienced the most pronounced long-term warming trend of the Cenozoic, superimposed by transient warming events such as the Paleocene–Eocene Thermal Maximum (PETM). The consequences of climatic perturbations and associated changes on the evolution of carbonate platforms are relatively unexplored. Today, modern carbonate platforms, especially coral reefs are highly sensitive to environmental and climatic change, which raises the question how (sub)tropical reef systems of the early Paleogene reacted to gradual and sudden global warming, eutrophication of shelf areas, enhanced CO₂ levels in an ocean with low Mg/Ca ratios. The answer to this question may help to investigate the fate of modern coral reef systems in times of global warming and rising CO₂ levels.Here we present a synthesis of Tethyan carbonate platform evolution in the early Paleogene (~ 59–55 Ma) concentrating on coral reefs and larger foraminifera, two important organism groups during this time interval. We discuss and evaluate the importance of the intrinsic and extrinsic factors leading to the dissimilar evolution of both groups during the early Paleogene. Detailed analyses of two carbonate platform areas at low (Egypt) and middle (Spain) paleolatitudes and comparison with faunal patterns of coeval platforms retrieved from the literature led to the distinction of three evolutionary stages in the late Paleocene to early Eocene Tethys: Stage I, late Paleocene coralgal-dominated platforms at low to middle paleolatitudes; stage II, a transitional latest Paleocene platform stage with coralgal reefs dominating at middle paleolatitudes and larger foraminifera-dominated (Miscellanea, Ranikothalia, Assilina) platforms at low paleolatitudes; and stage III, early Eocene larger foraminifera-dominated (Alveolina, Orbitolites, Nummulites) platforms at low to middle paleolatitudes. The onset of the latter prominent larger foraminifera-dominated platform correlates with the Paleocene/Eocene Thermal Maximum.The causes for the change from coral-dominated platforms to larger foraminifera-dominated platforms are multilayered. The decline of coralgal reefs in low latitudes during platform stage II is related to overall warming, leading to sea-surface temperatures in the tropics beyond the maximum temperature range of corals. The overall low occurrence of coral reefs in the Paleogene might be related to the presence of a calcite sea. At the same time larger foraminifera started to flourish after their near extinction at the Cretaceous/Paleogene boundary. The demise of coralgal reefs at all studied paleolatitudes in platform stage III can be founded on the effects of the PETM, resulting in short-term warming, eutrophic conditions on the shelves and acidification of the oceans, hampering the growth of aragonitic corals, while calcitic larger foraminifera flourished. In the absence of other successful carbonate-producing organisms, larger foraminifera were able to take over the role as the dominant carbonate platform inhabitant, leading to a stepwise Tethyan platform stage evolution around the Paleocene/Eocene boundary. This szenario might be also effective for threatened coral reef sites.  相似文献   

The control of Phanerozoic atmosphere and seawater composition by basalt–seawater exchange reactions     

Rolf S. Arvidson  Michael Guidry  Fred T. Mackenzie   《Journal of Geochemical Exploration》2006,88(1-3):412

We present results from a long term geochemical cycling model, with a focus on the sensitivity of atmospheric carbon dioxide, oxygen, and the major element composition of seawater to seafloor spreading rates. This model incorporates rock weathering, basalt–seawater exchange reactions, and the formation and destruction of chemical sediments and organic matter. Hydrothermal reactions between seafloor and seawater involving calcium, magnesium, sodium, potassium, sulfate and carbon are the high temperature counterparts to low temperature redox, weathering, precipitation and diagenetic reactions. A major source of uncertainty is the extent to which these exchange fluxes are controlled by seafloor spreading rate. In addition, the return fluxes of these components to the atmospheric and primary silicate reservoirs reflect not only the overall rates of subduction and metamorphism, but the distribution of the overlying sedimentary burden and authigenic minerals formed during basalt alteration as well. In particular, we show how the stoichiometry of exchange fluxes (Mg/Ca and SO₄/Ca) may buffer atmospheric CO₂ and O₂ concentrations.  相似文献   

Carbonatization of oceanic crust by the seafloor hydrothermal activity and its significance as a CO₂ sink in the Early Archean     

Kentaro Nakamura 《Geochimica et cosmochimica acta》2004,68(22):4595-4618

Early Archean (3.46 Ga) hydrothermally altered basaltic rocks exposed near Marble Bar, eastern Pilbara Craton, have been studied in order to reveal geological and geochemical natures of seafloor hydrothermal carbonatization and to estimate the CO₂ flux sunk into the altered oceanic crust by the carbonatization. The basaltic rocks are divided into basalt and dolerite, and the basalt is further subdivided into type I, having original igneous rock textures, and type II, lacking these textures due to strong hydrothermal alteration. Primary clinopyroxene phenocrysts are preserved in some part of the dolerite samples, and the alteration mineral assemblage of dolerite (chlorite + epidote + albite + quartz ± actinolite) indicates that the alteration condition was typical greenschist facies. In other samples, all primary minerals were completely replaced by secondary minerals, and the alteration mineral assemblage of the type I and type II basalts (chlorite + K-mica + quartz + carbonate minerals ± albite) is characterized by the presence of K-mica and carbonate minerals and the absence of Ca-Al silicate minerals such as epidote and actinolite, suggesting the alteration condition of high CO₂ fugacity. The difference of the alteration mineral assemblages between basalt and dolerite is probably attributed to the difference of water/rock ratio that, in turn, depends on their porosity.Carbonate minerals in the carbonatized basalt include calcite, ankerite, and siderite, but calcite is quite dominant. The δ¹³C values of the carbonate minerals are −0.3 ± 1.2‰ and mostly within the range of marine carbonate, indicating that the carbonate minerals were formed by seafloor hydrothermal alteration and that carbonate carbon in the altered basalt was derived from seawater. Whole-rock chemical composition of the basaltic rocks is essentially similar to that of modern mid-ocean ridge basalt (MORB) except for highly mobile elements such as K₂O, Rb, Sr, and Ba. Compared to the least altered dolerite, all altered basalt samples are enriched in K₂O, Rb, and Ba, and are depleted in Na₂O, reflecting the presence of K-mica replacing primary plagioclase. In addition, noticeable CO₂ enrichment is recognized in the basalt due to the ubiquitous presence of carbonate minerals, but there was essentially neither gain nor loss of CaO. This suggests that the CO₂ in the hydrothermal fluid (seawater) was trapped by using Ca originally contained in the basalt. The CaO/CO₂ ratios of the basalt are generally the same as that of pure calcite, indicating that Ca in the basalt was almost completely converted to calcite during the carbonatization, although Mg and Fe were mainly redistributed into noncarbonate minerals such as chlorite.The carbon flux into the Early Archean oceanic crust by the seafloor hydrothermal carbonatization is estimated to be 3.8 × 10¹³ mol/yr, based on the average carbon content of altered oceanic crust of 1.4 × 10^-3 mol/g, the alteration depth of 500 m, and the spreading rate of 1.8 × 10¹¹ cm²/yr. This flux is equivalent to or greater than the present-day total carbon flux. It is most likely that the seafloor hydrothermal carbonatization played an important role as a sink of atmospheric and oceanic CO₂ in the Early Archean.  相似文献   

Thermal metamorphism and H2O-CO2-NaCl immiscibility at Patapedia,Quebec: evidence from fluid inclusions     

Anthony E. Williams-Jones  Dexter R. Ferreira 《Contributions to Mineralogy and Petrology》1989,102(2):247-254

The methamorphic history of the Patapedia thermal zone, Gaspé, Quebec, is re-evaluated in the light of results obtained from a study of fluid inclusions contained in quartz phenocrysts of felsic dyke rocks. The thermal zone is characterised by calc-silicate bodies that have outwardly telescoping prograde metamorphic isograds and display extensive retrograde metamorphism with associated copper mineralization. Three distinct fluid inclusion types are recognized: a low to moderate salinity, high density aqueous fluid (Type I); a low density CO₂ fluid (Type II); and a high salinity, high density aqueous fluid (Type III). Fluid inclusion Types I and II predominate whereas Type III inclusions form <10% of the fluid inclusion population. All three fluid types are interpreted to have been present during prograde metamorphism. Temperatures and pressures of metamorphism estimated from fluid inclusion microthermometry and isochore calculations are 450°–500° C and 700–1000 bars, respectively. A model is proposed in which the metamorphism at Patapedia was caused by heat transferred from a low to moderate salinity fluid of partly orthomagmatic origin (Type I inclusions). During the early stages, and particularly in the deeper parts of the system, CO₂ produced by metamorphism was completely miscible in the aqueous hydrothermal fluid and locally resulted in high XCO₂ fluids. On cooling and/or migrating to higher levels these latter fluids exsolved high salinity aqueous fluids represented by the Type III inclusions. Most of the metamorphism, however, took place at temperature-pressure conditions consistent with the immiscibility of CO₂ and the hydrothermal fluid and was consequently accompanied by the release of large volumes of CO₂ vapour which is represented by Type II inclusions. The final stage of the history of the Patapedia aureole was marked by retrograde metamorphism and copper mineralization of a calcite-free calc-silicate hornfels in the presence of a low XCO₂ fluid.  相似文献   

接触变质条件下变碳酸岩CO₂释放与定量计算——以郯庐断裂南段肥东县双山为例     

孙占强  刘德良  郑德山  杨晓勇  王佰长  陈永见  张交东  谈迎  李振生 《地质力学学报》2001,7(2):144-150

为了探讨接触变质带内变碳酸盐岩变质过程CO₂释放的数量和排放CO₂的物理、化学及地质条件,根据递进变质反应和时间积分流体通量模型,定量分析和定量计算了双山地区变碳酸盐岩在接触变质作用中释放CO₂的通量。计算结果得到CO₂的通量值为0.729×104~2.446×104 mol/cm2,CO₂的来源以接触变质反应释放为主;CO₂的生成释放与变质程度呈正相关关系。自白云石带至方解石带变质流体中X_CO2不断升高,但钙铝榴石带由于岩浆水影响,流体通量最高而X_CO2急剧下降。   相似文献   

Can the long-term potential for carbonatization and safe long-term CO2 storage in sedimentary formations be predicted?     

《Applied Geochemistry》2013

A sedimentary formation perturbated by supercritical CO₂ reacts by dissolving primary minerals and forming new secondary phases. In this process CO₂ may be trapped in stable carbonate minerals and may thereby be immobilized for long time spans. The potential for mineral trapping can be estimated by solving kinetic expressions for the reservoir minerals and possible secondary phases. This is, however, not trivial as kinetic data are uncertain or even lacking for the minerals of interest. Here, the rate equations most commonly used for CO₂ storage simulations have been solved, and the rate parameters varied, to obtain sensitivity on the total amount of CO₂ stored as mineral carbonate. As various expressions are in use to estimate growth rates of secondary carbonates, three formulations were compared, including one taking into account mineral nucleation preceding growth. The sensitivity studies were done on two systems, the Utsira Sand being representative for a cold quartz-rich sand (37 °C, 100 bar CO₂), and the Gulf Coast Sediment, being representative for a medium temperature quartz–plagioclase-rich system (75 °C, 300 bar CO₂).The simulations showed that the total predicted CO₂ mineral storage is especially sensitive to the choice of growth rate model and the reactive surface area. The largest sensitivity was found on α, fraction of total surface area available for reactions, with a reduction of one order of magnitude for all reacting phases leading to 3–4 times lower predicted CO₂ mineral storage. Because the reactive surface area is highly uncertain for natural systems, the range in predicted results may be even larger. The short-term predictions (<100–1000 a), such as the onset of carbonate growth, were highly sensitive to nucleation and growth rates. Moreover, the type of carbonate minerals formed was shown to be model dependent, with the simplest model predicting an unlikely carbonate assemblage at low temperature (i.e., formation of dolomite at 37 °C). Therefore, to use kinetic models to upscale short-term (<months) laboratory experiments in time, to identify the past reactions and physical conditions of natural CO₂ storage analogues, and finally to predict the potential for CO₂ trapping in existing and future storage projects, more knowledge has to be collected, especially on the reactive surface area of CO₂ storage reservoirs, and on the rate of secondary carbonate nucleation and growth.  相似文献   

History of carbonate ion concentration over the last 100 million years     

Toby Tyrrell  Richard E. Zeebe 《Geochimica et cosmochimica acta》2004,68(17):3521-3530

Instead of having been more or less constant, as once assumed, it is now apparent that the major ion chemistry of the oceans has varied substantially over time. For instance, independent lines of evidence suggest that calcium concentration ([Ca²⁺]) has approximately halved and magnesium concentration ([Mg²⁺]) approximately doubled over the last 100 million years. On the other hand, the calcite compensation depth, and hence the CaCO₃ saturation, has varied little over the last 100 My as documented in deep sea sediments. We combine these pieces of evidence to develop a proxy for seawater carbonate ion concentration ([CO₃²⁻]) over this period of time. From the calcite saturation state (which is proportional to the product of [Ca²⁺] times [CO₃²⁻], but also affected by [Mg²⁺]), we can calculate seawater [CO₃²⁻]. Our results show that [CO₃²⁻] has nearly quadrupled since the Cretaceous. Furthermore, by combining our [CO₃²⁻] proxy with other carbonate system proxies, we provide calculations of the entire seawater carbonate system and atmospheric CO₂. Based on this, reconstructed atmospheric CO₂ is relatively low in the Miocene but high in the Eocene. Finally, we make a strong case that seawater pH has increased over the last 100 My.  相似文献   

The application of P–T–X(CO2) modelling in constraining metamorphism and hydrothermal alteration at the Damang gold deposit,Ghana     

A. J. R. White  D. J. Waters  L. J. Robb 《Journal of Metamorphic Geology》2013,31(9):937-961

Orogenic gold mineralization at the Damang deposit, Ghana, is associated with hydrothermal alteration haloes around gold‐bearing quartz veins, produced by the infiltration of a H₂O–CO₂–K₂O–H₂S fluid following regional metamorphism. Alteration assemblages are controlled by the protoliths with sedimentary rocks developing a typical assemblage of muscovite, ankerite and pyrite, while intrusive dolerite bodies contain biotite, ankerite and pyrrhotite, accompanied by the destruction of hornblende. Mineral equilibria modelling was undertaken with the computer program thermocalc , in subsets of the model system MnO–Na₂O–CaO–K₂O–FeO–MgO–Al₂O₃–SiO₂–CO₂–H₂O–TiO₂–Fe₂O₃, to constrain conditions of regional metamorphism and the subsequent gold mineralization event. Metapelites with well‐developed amphibolite facies assemblages reliably constrain peak regional metamorphism at ~595 °C and 5.5 kbar. Observed hydrothermal alteration assemblages associated with gold mineralization in a wide compositional range of lithologies are typically calculated to be stable within P–T–X(CO₂) arrays that trend towards lower temperatures and pressures with increasing equilibrium fluid X(CO₂). These independent P–T–X(CO₂) arrays converge and the region of overlap at ~375–425 °C and 1–2 kbar is taken to represent the conditions of alteration approaching equilibrium with a common infiltrating fluid with an X(CO₂) of ~0.7. Fluid‐rock interaction calculations with M–X(CO₂) diagrams indicate that the observed alteration assemblages are consistent with the addition of a single fluid phase requiring minimum fluid/rock ratios on the order of 1.  相似文献   

Subduction metamorphism of serpentinite‐hosted carbonates beyond antigorite‐serpentinite dehydration (Nevado‐Filábride Complex,Spain)     

Manuel D. Menzel  Carlos J. Garrido  Vicente Lpez Snchez‐Vizcaíno  Kroly Hidas  Claudio Marchesi 《Journal of Metamorphic Geology》2019,37(5):681-715

At sub‐arc depths, the release of carbon from subducting slab lithologies is mostly controlled by fluid released by devolatilization reactions such as dehydration of antigorite (Atg‐) serpentinite to prograde peridotite. Here we investigate carbonate–silicate rocks hosted in Atg‐serpentinite and prograde chlorite (Chl‐) harzburgite in the Milagrosa and Almirez ultramafic massifs of the palaeo‐subducted Nevado‐Filábride Complex (NFC, Betic Cordillera, S. Spain). These massifs provide a unique opportunity to study the stability of carbonate during subduction metamorphism at P–T conditions before and after the dehydration of Atg‐serpentinite in a warm subduction setting. In the Milagrosa massif, carbonate–silicate rocks occur as lenses of Ti‐clinohumite–diopside–calcite marbles, diopside–dolomite marbles and antigorite–diopside–dolomite rocks hosted in clinopyroxene‐bearing Atg‐serpentinite. In Almirez, carbonate–silicate rocks are hosted in Chl‐harzburgite and show a high‐grade assemblage composed of olivine, Ti‐clinohumite, diopside, chlorite, dolomite, calcite, Cr‐bearing magnetite, pentlandite and rare aragonite inclusions. These NFC carbonate–silicate rocks have variable CaO and CO₂ contents at nearly constant Mg/Si ratio and high Ni and Cr contents, indicating that their protoliths were variable mixtures of serpentine and Ca‐carbonate (i.e., ophicarbonates). Thermodynamic modelling shows that the carbonate–silicate rocks attained peak metamorphic conditions similar to those of their host serpentinite (Milagrosa massif; 550–600°C and 1.0–1.4 GPa) and Chl‐harzburgite (Almirez massif; 1.7–1.9 GPa and 680°C). Microstructures, mineral chemistry and phase relations indicate that the hybrid carbonate–silicate bulk rock compositions formed before prograde metamorphism, likely during seawater hydrothermal alteration, and subsequently underwent subduction metamorphism. In the CaO–MgO–SiO₂ ternary, these processes resulted in a compositional variability of NFC serpentinite‐hosted carbonate–silicate rocks along the serpentine‐calcite mixing trend, similar to that observed in serpentinite‐hosted carbonate‐rocks in other palaeo‐subducted metamorphic terranes. Thermodynamic modelling using classical models of binary H₂O–CO₂ fluids shows that the compositional variability along this binary determines the temperature of the main devolatilization reactions, the fluid composition and the mineral assemblages of reaction products during prograde subduction metamorphism. Thermodynamic modelling considering electrolytic fluids reveals that H₂O and molecular CO₂ are the main fluid species and charged carbon‐bearing species occur only in minor amounts in equilibrium with carbonate–silicate rocks in warm subduction settings. Consequently, accounting for electrolytic fluids at these conditions slightly increases the solubility of carbon in the fluids compared with predictions by classical binary H₂O–CO₂ fluids, but does not affect the topology of phase relations in serpentinite‐hosted carbonate‐rocks. Phase relations, mineral composition and assemblages of Milagrosa and Almirez (meta)‐serpentinite‐hosted carbonate–silicate rocks are consistent with local equilibrium between an infiltrating fluid and the bulk rock composition and indicate a limited role of infiltration‐driven decarbonation. Our study shows natural evidence for the preservation of carbonates in serpentinite‐hosted carbonate–silicate rocks beyond the Atg‐serpentinite breakdown at sub‐arc depths, demonstrating that carbon can be recycled into the deep mantle.  相似文献   

Low melting temperature for calcite at 1000 bars on the join CaCO3‐H2O – some geological implications          下载免费PDF全文

Cyril Durand  Lukas P. Baumgartner  Didier Marquer 《地学学报》2015,27(5):364-369

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.  相似文献   

Carbon Sequestration and Release from Antarctic Lakes: Lake Vida and West Lake Bonney (McMurdo Dry Valleys)     

G. M. Marion  A. E. Murray  B. Wagner  C. H. Fritsen  F. Kenig  P. T. Doran 《Aquatic Geochemistry》2013,19(2):135-145

Perennial ice covers on many Antarctic lakes have resulted in high lake inorganic carbon contents. The objective of this paper was to evaluate and compare the brine and CO₂ chemistries of Lake Vida (Victoria Valley) and West Lake Bonney (Taylor Valley), two lakes of the McMurdo Dry Valleys (East Antarctica), and their potential consequences during global warming. An existing geochemical model (FREZCHEM-15) was used to convert measured molarity into molality needed for the FREZCHEM model, and this model added a new algorithm that converts measured DIC into carbonate alkalinity needed for the FREZCHEM model. While quite extensive geochemical information exists for ice-covered Taylor Valley lakes, such as West Lake Bonney, only limited information exists for the recently sampled brine of >25 m ice-thick Lake Vida. Lake Vida brine had a model-calculated pCO₂ = 0.60 bars at the field pH (6.20); West Lake Bonney had a model-calculated pCO₂ = 5.23 bars at the field pH (5.46). Despite the high degree of atmospheric CO₂ supersaturation in West Lake Bonney, it remains significantly undersaturated with the gas hydrate, CO₂·6H₂O, unless these gas hydrates are deep in the sediment layer or are metastable having formed under colder temperatures or greater pressures. Because of lower temperatures, Lake Vida could start forming CO₂·6H₂O at lower pCO₂ values than West Lake Bonney; but both lakes are significantly undersaturated with the gas hydrate, CO₂·6H₂O. For both lakes, simulation of global warming from current subzero temperatures (?13.4 °C in Lake Vida and ?4.7 °C in West Lake Bonney) to 10 °C has shown that a major loss of solution-phase carbon as CO₂ gases and carbonate minerals occurred when the temperatures rose above 0 °C and perennial ice covers would disappear. How important these Antarctic CO₂ sources will be for future global warming remains to be seen. But a recent paper has shown that methane increased in atmospheric concentration due to deglaciation about 10,000 years ago. So, CO₂ release from ice lakes might contribute to atmospheric gases in the future.  相似文献   

Far from equilibrium enstatite dissolution rates in alkaline solutions at earth surface conditions     

Sougata Halder  John V. Walther 《Geochimica et cosmochimica acta》2011,75(23):7486-7493

Far from equilibrium enstatite dissolution rates both open to atmospheric CO₂ and CO₂ purged were measured as a function of solution pH from 8 to 13 in batch reactors at room temperature. Congruent dissolution was observed after an initial period of incongruent dissolution with preferential Si release from the enstatite. Steady-state dissolution rates in open to atmospheric CO₂ conditions decrease with increase in solution pH from 8 to 12 similar to the behavior reported by other investigators. Judging from the pH 13 dissolution rate, rates increase with pH above pH 12. This is thought to occur because of the increase in overall negative surface charges on enstatite as Mg surface sites become negative above pH 12.4, the pH of zero surface charge of MgO.Steady-state dissolution rates of enstatite increase above pH 10 when CO₂ was purged by performing the experiments in a N₂ atmosphere. This suggests inhibition of dissolution rates above pH 10 when experiments were open to the atmosphere. The dissolved carbonate in these solutions becomes dominantly CO₃²⁻ above pH 10.33. It is argued that CO₃²⁻ forms a >Mg₂-CO₃ complex at positively charged Mg surface sites on enstatite, resulting in stabilization of the surface Si-O bonds. Therefore, removal of solution carbonate results in an increase in dissolution rates of enstatite above pH 10. The log rate of CO₂-purged enstatite dissolution in moles per cm² per s as a function of increasing pH above pH 10 is equal to 0.35. This is consistent with the model of silicate mineral dissolution in the absence of surface carbonation in alkaline solutions proposed earlier in the literature.  相似文献   

Prograde and retrograde fluid flow during contact metamorphism of siliceous carbonate rocks from the Ballachulish aureole,Scotland     

John M. Ferry 《Contributions to Mineralogy and Petrology》1996,124(3-4):235-254

 Siliceous dolomites and limestones contain abundant retrograde minerals produced by hydration-carbonation reactions as the aureole cooled. Marbles that contained periclase at the peak of metamorphism bear secondary brucite, dolomite, and serpentine; forsterite-dolomite marbles have retrograde tremolite and serpentine; wollastonite limestones contain secondary calcite and quartz; and wollastonite-free limestones have retrograde tremolite. Secondary tremolite never appears in marbles where brucite has replaced periclase or in wollastonite-bearing limestones. A model for infiltration of siliceous carbonates by CO₂-H₂O fluid that assumes (a) vertical upwardly-directed flow, (b) fluid flux proportional to cooling rate, and (c) flow and reaction under conditions of local equilibrium between peak temperatures and ≈400 °C, reproduces the modes of altered carbonate rocks, observed reaction textures, and the incompatibility between tremolite and brucite and between tremolite and wollastonite. Except for samples from a dolomite xenolith, retrograde time-integrated flux recorded by reaction progress is on the order of 1000 mol fluid/cm² rock. Local focusing of flow near the contact is indicated by samples from the xenolith that record values an order of magnitude greater. Formation of periclase, forsterite, and wollastonite at the peak of metamorphism also required infiltration with prograde time-integrated flux approximately 100–1000 mol/cm². The comparatively small values of prograde and retrograde time-integrated flux are consistent with lack of stable isotope alteration of the carbonates and with the success of conductive thermal models in reproducing peak metamorphic temperatures recorded by mineral equilibria. Although isobaric univariant assemblages are ubiquitous in the carbonates, most formed during retrograde metamorphism. Isobaric univariant assemblages observed in metacarbonates from contact aureoles may not record physical conditions at the peak of metamorphism as is commonly assumed. Received: 19 September 1995 / Accepted: 14 March 1996  相似文献   

Secondary siderite-oxide-sulphide and carbonate-andalusite assemblages in cordierite granulites from Sri Lanka: post-granulite facies fluid evolution during uplift     

D. J. Ellis  Yoshikuni Hiroi 《Contributions to Mineralogy and Petrology》1997,127(4):315-335

We report here that some of the pelitic rocks from the Wanni and Highland Complexes of Sri Lanka reacted with CO₂-rich fluids to produce a wide range of unusual secondary carbonate-silicate-oxide-sulphide assemblages. These enable the depth, temperature and fluid compositions of CO₂ reactions to be calculated more rigorously than is generally possible for the patches of arrested charnockite that have been described from Sri Lanka. Magnesite-andalusite-quartz has partially replaced primary cordierite, and siderite-rutile replaced ilmenite. Paragenetic sequences involving primary pyrrhotite, ilmenite and magnetite and secondary pyrite-siderite-rutile-magnetite-(hematite) demonstrate the control which carbonate equilibria have upon evolving fluid compositions during cooling. Direct evidence for the role of graphite as a source of CO₂ is found in the Highland Complex where primary graphite partially reacted with silicates to form secondary siderite assemblages. It is proposed that following peak metamorphism, continued uplift along a clockwise P-T-t path was accompanied by a series of devolatilization reactions involving breakdown of graphite and the continuous production of secondary CO₂-rich fluids. The limited extent of disseminated secondary carbonate reflects the small amount of graphite inferred to have been present in the source rocks. These rocks demonstrate that CO₂-rich fluids, as found in disseminated fluid inclusions, need not form during peak granulite metamorphism but may be an inevitable consequence of continued uplift along a clockwise P-T-t path. The arrested charnockite which overprinted some of the hornblende-bearing felsic-intermediate composition rocks in Sri Lanka most likely formed by the same process. Received: 4 May 1994 / Accepted: 25 October 1996  相似文献   

Tracing high-pressure metamorphism in marbles: Phase relations in high-grade aluminous calcite–dolomite marbles from the Greek Rhodope massif in the system CaO–MgO–Al₂O₃–SiO₂–CO₂ and indications of prior aragonite     

A. Proyer  E. Mposkos  I. Baziotis  G. Hoinkes 《Lithos》2008,104(1-4):119-130

Four different types of parageneses of the minerals calcite, dolomite, diopside, forsterite, spinel, amphibole (pargasite), (Ti–)clinohumite and phlogopite were observed in calcite–dolomite marbles collected in the Kimi-Complex of the Rhodope Metamorphic Province (RMP). The presence of former aragonite can be inferred from carbonate inclusions, which, in combination with an analysis of phase relations in the simplified system CaO–MgO–Al₂O₃–SiO₂–CO₂ (CMAS–CO₂) show that the mineral assemblages preserved in these marbles most likely equilibrated at the aragonite–calcite transition, slightly below the coesite stability field, at ca. 720 °C, 25 kbar and a_CO2 ~ 0.01. The thermodynamic model predicts that no matter what activity of CO₂, garnet has to be present in aluminous calcite–dolomite-marble at UHP conditions.  相似文献   

A Comparative geochemical study of pelitic schists and metamorphosed carbonate rocks from south-central Maine,USA     

J. M. Ferry 《Contributions to Mineralogy and Petrology》1982,80(1):59-72

Whole-rock major element chemical analyses of progressively metamorphosed impure carbonate rocks and pelitic schists, collected from the same metamorphic terrain, reveal similarities and differences in the chemical response of these rock types to the metamorphic event. Relative to a constant aluminum reference frame, both schist and carbonate exhibit no detectable change in their contents of Fe, Mg, Ti, Si, and Ca with change in metamorphic grade. Carbonate rocks become progressively depleted in K and Na with increasing grade of metamorphism, while schists exhibit no statistically significant change in their contents of K and Na. Both rock types become depleted in volatiles (principally CO₂ and H₂O) with increasing grade.Whole-rock chemical data permit two mechanisms for migration of K and Na from the carbonate rocks during metamorphism: (a) diffusion of alkalis from carbonate to adjacent schist; (b) transport of alkalis by through-flowing metamorphic fluid (infiltration). Mineral equilibria in schist and metacarbonate rock from the same outcrops allow calculation of the affinity for cation exchange between the two rock types during metamorphism. Measured affinities indicate that if mass transport of K and Na occurred by diffusion, chemical potential gradients would have driven the alkalis from schist into carbonate rock. Because diffusion cannot produce the observed chemical trends in the metacarbonates, K and Na are believed to have been removed during metamorphism by infiltration.The disparity in chemical behavior between the pelitic schists and metacarbonate rocks may be a result of enhanced fluid flow through the carbonates. The carbonate rocks may have acted as metamorphic aquifers; the greater flow of fluid through them would then have had a correspondingly greater effect on their whole-rock chemistry.  相似文献   

Fluid infiltration and regional metamorphism of the Waits River Formation, north-east Vermont, USA   总被引：2，自引：0，他引：2  

A. LÉGER  J. M. FERRY 《Journal of Metamorphic Geology》1993,11(1):3-29

Abstract The Siluro-Devonian Waits River Formation of north-east Vermont was deformed, intruded by plutons and regionally metamorphosed during the Devonian Acadian Orogeny. Five metamorphic zones were mapped based on the mineralogy of carbonate rocks. From low to high grade, these are: (1) ankerite-albite, (2) ankerite-oligoclase, (3) biotite, (4) amphibole and (5) diopside zones. Pressure was near 4.5kbar and temperature varied from c. 450° C in the ankerite-albite zone to c. 525° C in the diopside zone. Fluid composition for all metamorphic zones was estimated from mineral equilibria. Average calculated χ_co2[= CO₂/(CO₂+ H₂O)] of fluid in equilibrium with the marls increases with increasing grade from 0.05 in the ankerite-oligoclase zone, to 0.25 in the biotite zone and to 0.44 in the amphibole zone. In the diopside zone, χ_CO2 decreases to 0.06. Model prograde metamorphic reactions were derived from measured modes, mineral chemistry, and whole-rock chemistry. Prograde reactions involved decarbonation with an evolved volatile mixture of χ_CO2 > 0.50. The χ_CO2 of fluid in equilibrium with rocks from all zones, however, was generally <0.40. This difference attests to the infiltration of a reactive H₂O-rich fluid during metamorphism. Metamorphosed carbonate rocks from the formation suggests that both heat flow and pervasive infiltration of a reactive H₂O-rich fluid drove mineral reactions during metamorphism. Average time-integrated volume fluxes (cm³ fluid/cm² rock), calculated from the standard equation for coupled fluid flow and reaction in porous media, are (1) ankerite-oligoclase zone: c. 1 × 10⁴; (2) biotite zone: c. 3 × 10⁴; (3) amphibole zone: c. 10 × 10⁴; and diopside zone: c. 60 × 10⁴. The increase in calculated flux with increasing grade is at least in part the result of internal production of volatiles from prograde reactions in pelitic schists and metacarbonate rocks within the Waits River Formation. The mapped pattern of time-integrated fluxes indicates that the Strafford-Willoughby Arch and the numerous igneous intrusions in the field area focused fluid flow during metamorphism. Many rock specimens in the diopside zone experienced extreme alkali depletion and also record low χ_CO2. Metamorphic fluids in equilibrium with diopside zone rocks may therefore represent a mixture of acid, H₂O-rich fluids given off by the crystallizing magmas, and CO₂-H₂O fluids produced by devolatilization reactions in the host marls. Higher fluxes and different fluid compositions recorded near the plutons suggest that pluton-driven hydrothermal cells were local highs in the larger regional metamorphic hydrothermal system.  相似文献   

Reactions between olivine and CO2-rich seawater at 300 °C: Implications for H2 generation and CO2 sequestration on the early Earth     

《地学前缘(英文版)》2017,8(2):387-396

To understand the influence of fluid CO₂ on ultramafic rock-hosted seafloor hydrothermal systems on the early Earth, we monitored the reaction between San Carlos olivine and a CO₂-rich NaCl fluid at 300 °C and 500 bars. During the experiments, the total carbonic acid concentration (ΣCO₂) in the fluid decreased from approximately 65 to 9 mmol/kg. Carbonate minerals, magnesite, and subordinate amount of dolomite were formed via the water-rock interaction. The H₂ concentration in the fluid reached approximately 39 mmol/kg within 2736 h, which is relatively lower than the concentration generated by the reaction between olivine and a CO₂-free NaCl solution at the same temperature. As seen in previous hydrothermal experiments using komatiite, ferrous iron incorporation into Mg-bearing carbonate minerals likely limited iron oxidation in the fluids and the resulting H₂ generation during the olivine alteration. Considering carbonate mineralogy over the temperature range of natural hydrothermal fields, H₂ generation is likely suppressed at temperatures below approximately 300 °C due to the formation of the Mg-bearing carbonates. Nevertheless, H₂ concentration in fluid at 300 °C could be still high due to the temperature dependency of magnetite stability in ultramafic systems. Moreover, the Mg-bearing carbonates may play a key role in the ocean-atmosphere system on the early Earth. Recent studies suggest that the subduction of carbonated ultramafic rocks may transport surface CO₂ species into the deep mantle. This process may have reduced the huge initial amount of CO₂ on the surface of the early Earth. Our approximate calculations demonstrate that the subduction of the Mg-bearing carbonates formed in komatiite likely played a crucial role as one of the CO₂ carriers from the surface to the deep mantle, even in hot subduction zones.  相似文献   

Activity of water during granulite metamorphism around Anakapalle,Vishakhapatnam District,A.P.     

S. N. Lal 《Journal of Earth System Science》1995,104(1):79-84

A refined mathematical equation is proposed to quantify the ambient activity of water during granulite fades metamorphism. The thermodynamic calculations point to the low activity of water during metamorphism in the area around Anakapalle, Vishakhapatnam district, A.P. Carbonic metamorphism seems to be responsible for the low activity of water during this metamorphism. Calc-silicate rocks in the area, could have been the source of the CO₂.  相似文献