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1.
Hydrated Portland cement was reacted with CO2 in supercritical, gaseous and aqueous phases to understand the potential cement alteration processes along the length of a wellbore, extending from a deep CO2 storage reservoir to the shallow subsurface during geologic carbon sequestration. The 3-D X-ray microtomography (XMT) images showed that the cement alteration was significantly more extensive with CO2-saturated synthetic groundwater than dry or wet supercritical CO2 at high P (10 MPa)-T (50 °C) conditions. Scanning electron microscopy with energy dispersive spectroscopy (SEM–EDS) analysis also exhibited a systematic Ca depletion and C enrichment in cement matrix exposed to CO2-saturated groundwater. Integrated XMT, XRD and SEM–EDS analyses identified the formation of an extensive carbonated zone filled with CaCO3(s), as well as a porous degradation front and an outermost silica-rich zone in cement after exposure to CO2-saturated groundwater. Cement alteration by CO2-saturated groundwater for 2–8 months overall decreased the porosity from 31% to 22% and the permeability by an order of magnitude. Cement alteration by dry or wet supercritical CO2 was slow and minor compared to CO2-saturated groundwater. A thin single carbonation zone was formed in cement after exposure to wet supercritical CO2 for 8 months or dry supercritical CO2 for 15 months. An extensive calcite coating was formed on the outside surface of a cement sample after exposure to wet gaseous CO2 for 1–3 months. The chemical–physical characterization of hydrated Portland cement after exposure to various phases of CO2 indicates that the extent of cement carbonation can be significantly heterogeneous depending on the CO2 phase present in the wellbore environment. Both experimental and geochemical modeling results suggest that wellbore cement exposure to supercritical, gaseous and aqueous phases of CO2 during geologic C sequestration is unlikely to damage the wellbore integrity because cement alteration by all phases of CO2 is dominated by carbonation reactions. This is consistent with previous field studies of wellbore cement with extensive carbonation after exposure to CO2 for three decades. However, XMT imaging indicates that preferential cement alteration by supercritical CO2 or CO2-saturated groundwater can occur along the cement–steel or cement–rock interfaces. This highlights the importance of further investigation of cement degradation along the interfaces of wellbore materials to ensure permanent geologic carbon storage. 相似文献
2.
Composite Portland cement–basalt caprock cores with fractures, as well as neat Portland cement columns, were prepared to understand the geochemical and geomechanical effects on the integrity of wellbores with defects during geologic carbon sequestration. The samples were reacted with CO2–saturated groundwater at 50 °C and 10 MPa for 3 months under static conditions, while one cement–basalt core was subjected to mechanical stress at 2.7 MPa before the CO2 reaction. Micro-XRD and SEM–EDS data collected along the cement–basalt interface after 3-month reaction with CO2–saturated groundwater indicate that carbonation of cement matrix was extensive with the precipitation of calcite, aragonite, and vaterite, whereas the alteration of basalt caprock was minor. X-ray microtomography (XMT) provided three-dimensional (3-D) visualization of the opening and interconnection of cement fractures due to mechanical stress. Computational fluid dynamics (CFD) modeling further revealed that this stress led to the increase in fluid flow and hence permeability. After the CO2-reaction, XMT images displayed that calcium carbonate precipitation occurred extensively within the fractures in the cement matrix, but only partially along the fracture located at the cement–basalt interface. The 3-D visualization and CFD modeling also showed that the precipitation of calcium carbonate within the cement fractures after the CO2-reaction resulted in the disconnection of cement fractures and permeability decrease. The permeability calculated based on CFD modeling was in agreement with the experimentally determined permeability. This study demonstrates that XMT imaging coupled with CFD modeling represent a powerful tool to visualize and quantify fracture evolution and permeability change in geologic materials and to predict their behavior during geologic carbon sequestration or hydraulic fracturing for shale gas production and enhanced geothermal systems. 相似文献
3.
The interaction of groundwater with cement in a geological disposal facility (GDF) for intermediate level radioactive waste will produce a high pH leachate plume. Such a plume may alter the physical and chemical properties of the GDF host rock. However, the geochemical and mineralogical processes which may occur in such systems over timescales relevant for geological disposal remain unclear. This study has extended the timescale for laboratory experiments and shown that, after 15 years two distinct phases of reaction may occur during alteration of a dolomite-rich rock at high pH. In these experiments the dissolution of primary silicate minerals and the formation of secondary calcium silicate hydrate (C–S–H) phases containing varying amounts of aluminium and potassium (C–(A)–(K)–S–H) during the early stages of reaction (up to 15 months) have been superseded as the systems have evolved. After 15 years significant dedolomitisation (MgCa(CO3)2 + 2OH− → Mg(OH)2 + CaCO3 + CO32−(aq)) has led to the formation of magnesium silicates, such as saponite and talc, containing variable amounts of aluminium and potassium (Mg–(Al)–(K)–silicates), and calcite at the expense of the early-formed C–(A)–(K)–S–H phases. This occured in high pH solutions representative of two different periods of cement leachate evolution with little difference in the alteration processes in either a KOH and NaOH or a Ca(OH)2 dominated solution but a greater extent of alteration in the higher pH KOH/NaOH leachate. The high pH alteration of the rock over 15 years also increased the rock’s sorption capacity for U(VI). The results of this study provide a detailed insight into the longer term reactions occurring during the interaction of cement leachate and dolomite-rich rock in the geosphere. These processes have the potential to impact on radionuclide transport from a geodisposal facility and are therefore important in underpinning any safety case for geological disposal. 相似文献
4.
Calcium carbonate scaling poses highly challenging tasks for its prediction and preventative action. Here an elemental, isotopic and modelling approach was used to decipher the evolution of alkaline tunnel drainage solutions and sinter formation mechanisms for 3 sites in Austria. Drainage solutions originate from local groundwater and form their characteristic chemical composition by interaction with shotcrete/concrete. This interaction is indicated by a positive correlation of dissolved K+ and pH (up to 12.3), and a decrease of aqueous Mg2+ by the formation of brucite (pH > 10.5). Variability in Ca2+ and DIC is strongly attributed to portlandite dissolution, calcite precipitation and CO2 exchange with the atmosphere, where the 13C/12C and 18O/16O signatures of calcite can be traced back to the source of carbonate. The internal PCO2 value is a reliable proxy to evaluate whether uptake of CO2 results in an increase or decrease of the degree of calcite saturation with a threshold value of 10−6.15 atm at 25 °C (pH ≈ 11). Precipitation rates of calcite are highest at pH ≈ 10. Mixing of groundwater-like solutions with strong alkaline drainage solutions has to be considered as a crucial factor for evaluating apparent composition of drainage solutions and calcite precipitation capacities. 相似文献
5.
《Chemie der Erde / Geochemistry》2016,76(4):643-657
Chemical interaction processes among injected CO2, saline fluids and potential reservoir materials are experimentally simulated to derive dissolution rates of natural materials (minerals) that can be used as input parameters for modeling of CO2 storage in deep saline formations and risk analyses. In order to study dissolution processes, mineral aliquots were exposed to CO2-bearing brines at elevated temperature (60, 100, 150 °C) and pressure (85 bar) and at various run durations. Several potential reservoir rocks include carbonates as cement. Calcite and dolomite grains were therefore mainly used as solid starting material. Experiments with the two feldspar varieties alkali feldspar and almost pure anorthite were performed in addition. Grain sizes of the mineral starting materials varied between <63 μm and 500 μm with most experiments performed at grain size fractions of 160 – 250 μm and 250 – 500 μm. All experiments run with a complex synthetic brine (total dissolved solids: ∼156 g/l) according to a natural upper cretaceous formation water. Dry ice was used as CO2-source. All experiments were done in closed batch reactors. These reactors allow mimicking reservoir conditions far from the injection site as well as reservoir conditions after finishing the CO2 injection. The concentration changes during the experiment were monitored by ICP-OES measurements of the initial and the post-run fluids. Dissolution rates were derived based on the concentration changes of the brine.Most of the studied experimental variables and parameters (temperature, run duration, grain size, brine composition – expressed as pH-value and ionic strength) impact alteration of the reacting agents, i.e. they change the chemical composition of the brine, change the surfaces of the mineral aliquots exposed to the CO2-bearing brine, and induce formation of secondary minerals. Hence, all influencing parameters on dissolution processes have to be considered and time-resolved changes of the dissolution behavior have to be implemented in numerical simulations of processes at CO2 injection sites and CO2 storage reservoirs. 相似文献
6.
《Ore Geology Reviews》2008,33(3-4):629-650
In the Raposos orogenic gold deposit, hosted by banded iron-formation (BIF) of the Archean Rio das Velhas greenstone belt, the hanging wall rocks to BIF are hydrothermally-altered ultramafic schists, whereas metamafic rocks and their hydrothermal schistose products represent the footwall. Planar and linear structures at the Raposos deposit define three ductile to brittle deformational events (D1, D2 and D3). A fourth group of structures involve spaced cleavages that are considered to be a brittle phase of D3. The orebodies constitute sulfide-bearing D1-related shear zones of BIF in association with quartz veins, and result from the sulfidation of magnetite and/or siderite. Pyrrhotite is the main sulfide mineral, followed by lesser arsenopyrite and pyrite. At level 28, the hydrothermal alteration of the mafic and ultramafic wall rocks enveloping BIF define a gross zonal pattern surrounding the ore zones. Metabasalt comprises albite, epidote, actinolite and lesser Mg/Fe–chlorite, calcite and quartz. The incipient stage includes the chlorite and chlorite-muscovite alteration zone. The least-altered ultramafic schist contains Cr-bearing Mg-chlorite, actinolite and talc, with subordinate calcite. The incipient alteration stage is subdivided into the talc–chlorite and chlorite–carbonate zone. For both mafic and ultramafic wall rocks, the carbonate–albite and carbonate–muscovite zones represent the advanced alteration stage.Rare earth and trace element analyses of metabasalt and its alteration products suggest a tholeiitic protolith for this wall rock. In the case of the ultramafic schists, the precursor may have been peridotitic komatiite. The Eu anomaly of the Raposos BIF suggests that it was formed proximal to an exhalative hydrothermal source on the ocean floor. The ore fluid composition is inferred by hydrothermal alteration reactions, indicating it to having been H2O-rich containing CO2 + Na+ and S. Since the distal alteration halos are dominated by hydrated silicate phases (mainly chlorite), with minor carbonates, fixation of H2O is indicated. The CO2 is consumed to form carbonates in the intermediate alteration stage, in halos around the chlorite-dominated zones. These characteristics suggest variations in the H2O to CO2-ratio of the sulfur-bearing, aqueous-carbonic ore fluid, which interacted at varying fluid to rock ratios with progression of the hydrothermal alteration. 相似文献
7.
《Chemie der Erde / Geochemistry》2016,76(3):327-352
Soils act as sources and sinks for greenhouse gases (GHG) such as carbon dioxide (CO2), methane (CH4), and nitrous oxide (N2O). Since both storage and emission capacities may be large, precise quantifications are needed to obtain reliable global budgets that are necessary for land-use management (agriculture, forestry), global change and for climate research. This paper discusses exclusively the soil emission-related processes and their influencing parameters. It reviews soil emission studies involving the most important land-cover types and climate zones and introduces important measuring systems for soil emissions. It addresses current shortcomings and the obvious bias towards northern hemispheric data.When using a conservative average of 300 mg CO2e m−2 h−1 (based on our literature review), this leads to global annual net soil emissions of ≥350 Pg CO2e (CO2e = CO2 equivalents = total effect of all GHG normalized to CO2). This corresponds to roughly 21% of the global soil C and N pools. For comparison, 33.4 Pg CO2 are being emitted annually by fossil fuel combustion and the cement industry. 相似文献
8.
The response to CO2 exposure of a variety of carbonate cemented rocks has been investigated using pressurised batch experiments conducted under simulated reservoir conditions, 70 °C and 20 MPa, and with a durations of up to14 months. Calcite, dolomite, ankerite and siderite cement were present in the unreacted reservoir rocks and caprocks. Core plugs of the reservoir rocks were used in order to investigate the alterations in situ. Crushing of the caprock samples was necessary to maximise reactions within the relatively short duration of the laboratory experiments. Synthetic brines were constructed for each batch experiment to match the specific formation water composition known from the reservoir and caprock formations in each well. Chemical matched synthetic brines proved crucial in order to avoid reactions due to non-equilibra of the fluids with the rock samples, for example observations of the dissolution of anhydrite, which were not associated with the CO2 injection, but rather caused by mismatched brines.Carbonate dissolution as a response to CO2 injection was confirmed in all batch experiments by both petrographical observations and geochemical changes in the brines. Increased Ca and Mg concentrations after 1 month reaction with CO2 and crushed caprocks are ascribed to calcite and dolomite dissolution, respectively, though not verified petrographically. Ankerite and possible siderite dissolution in the sandstone plugs are observed petrographically after 7 months reaction with CO2; and are accompanied by increased Fe and Mn contents in the reacted fluids. Clear evidence for calcite dissolution in sandstone plugs is observed petrographically after 14 months of reaction with CO2, and is associated with increased amounts of Ca (and Mg) in the reacted fluid. Dolomite in sandstones shows only minor dissolution features, which are not clearly supported by increased Mg content in the reacted fluid.Silicate dissolution cannot be demonstrated, either by chemical changes in the fluids, as Si and Al concentrations remain below the analytical detection limits, nor by petrographical changes, as partly dissolved feldspar grains and authigenic analcime are present in the sediments prior to the experiments. It is noteworthy, that authigenic K-feldspar and authigenic albite in sandstones show no signs of dissolution and consequently seem to be stable under the experimental conditions. 相似文献
9.
A prognosis of the geochemical effects of CO2 storage induced by the injection of CO2 into geologic reservoirs or by CO2 leakage into the overlaying formations can be performed by numerical modelling (non-invasive) and field experiments. Until now the research has been focused on the geochemical processes of the CO2 reacting with the minerals of the storage formation, which mostly consists of quartzitic sandstones. Regarding the safety assessment the reactions between the CO2 and the overlaying formations in the case of a CO2 leakage are of equal importance as the reactions in the storage formation. In particular, limestone formations can react very sensitively to CO2 intrusion. The thermodynamic parameters necessary to model these reactions are not determined explicitly through experiments at the total range of temperature and pressure conditions and are thus extrapolated by the simulation code. The differences in the calculated results lead to different calcite and CO2 solubilities and can influence the safety issues.This uncertainty study is performed by comparing the computed results, applying the geochemical modelling software codes The Geochemist’s Workbench, EQ3/6, PHREEQC and FactSage/ChemApp and their thermodynamic databases. The input parameters (1) total concentration of the solution, (2) temperature and (3) fugacity are varied within typical values for CO2 reservoirs, overlaying formations and close-to-surface aquifers. The most sensitive input parameter in the system H2O–CO2–NaCl–CaCO3 for the calculated range of dissolved calcite and CO2 is the fugacity of CO2. Hence, the largest range of dissolved calcite is calculated at high fugacities and is 210 mmol/kgw. The average deviation of the results using the databases phreeqc.dat and wateq4f.dat in combination with the code PHREEQC is lowest in comparison to the results of the specific model of Duan and Li, which represents the experimental values at best. Still, the solubility of CO2 is overestimated in the formation water using these two databases. Therefore, the model results calculate a larger retention capacity, defined as the quantity of CO2 dissolved in the formation water, than the Duan and Li model would do. 相似文献
10.
《Applied Geochemistry》2005,20(6):1131-1157
The Weyburn Oil Field is a carbonate reservoir in south central Saskatchewan, Canada and is the site of a large CO2 injection project for purposes of enhanced oil recovery. The Weyburn Field, in the Mississippian Midale Formation, was discovered in 1954 and was under primary production until secondary recovery by water flood began in 1964. The reservoir comprises two units, the Vuggy and the Marly, and primary and secondary recovery are thought to only have significantly depleted the Vuggy zone, leaving the Marly with higher oil saturations. In 2000, PanCanadian Resources (now EnCana), the operator of the field, began tertiary recovery by injection of CO2 and water, primarily into the Marly. The advent of this project was an opportunity to study the potential for geological storage of CO2.Using 43 Baseline samples collected in August 2000, before CO2 injection at Weyburn, and 44 monitoring samples collected in March 2001, changes in the fluid chemistry and isotope composition have been tracked. The initial fluid distribution showed water from discovery through water flood in the Midale Formation with Cl ranging from 25,000 to 60,000 mg/L, from the NW to the SE across the Phase 1A area. By the time of Baseline sampling the produced water had been diluted to Cl of 25,000–50,000 mg/L as a result of the addition of make up water from the low TDS Blairmore Formation, but the pattern of distribution was still present. The Cl distribution is mimicked by the distribution of other dissolved ions and variables, with Ca (1250–1500 mg/L) and NH3 (aq) increasing from NW to SE, and alkalinity (700–300 mg/L), resistivity, and H2S (300–100 mg/L) decreasing. Based on chemical and isotopic data, the H2S is interpreted to result from bacterial SO4 reduction. After 6 months of injection of CO2, the general patterns are changed very little, except that the pH has decreased by 0.5 units and alkalinity has increased, with values over 1400 mg/L in the NW, decreasing to 500 mg/L in the SE. Calcium has increased to range from 1250 to 1750 mg/L, but the pattern of NW–SE distribution is altered. Chemical and isotopic data suggest this change in distribution is caused by the dissolution of calcite due to water–rock reactions driven by CO2. The Baseline samples varied from −22 to −12‰ δ13C (V-PDB) for CO2 gas. The injected CO2 has an isotope ratio of −20‰. The Monitor-1 samples of produced CO2 ranged from −18 to −13‰, requiring a heavy source of C, most easily attributed to dissolution of carbonate minerals. Field measured pH had increased and alkalinity had decreased by the second monitoring trip (July 2001) to near Baseline values, suggesting continued reaction with reservoir minerals.Addition of CO2 to water–rock mixtures comprising carbonate minerals causes dissolution of carbonates and production of alkalinity. Geochemical modeling suggests dissolution is taking place, however more detail on water–oil–gas ratios needs to be gathered to obtain more accurate estimates of pH at the formation level. Geological storage of CO2 relies on the potential that, over the longer term, silicate minerals will buffer the pH, causing any added CO2 to be precipitated as calcite. Some initial modeling of water–rock reactions suggests that silica sources are available to the water resident in the Midale Formation, and that clay minerals may well be capable of acting as pH buffers, allowing injected CO2 to be stored as carbonate minerals. Further work is underway to document the mineralogy of the Midale Formation and associated units so as to define more accurately the potential for geological storage. 相似文献
11.
We use a reactive diffusion model to investigate what happens to CO2 injected into a subsurface sandstone reservoir capped by a chlorite- and illite-containing shale seal. The calculations simulate reaction and transport of supercritical (SC) CO2 at 348.15 K and 30 MPa up to 20,000 a. Given the low shale porosity (5%), chemical reactions mostly occurred in the sandstone for the first 2000 a with some precipitation at the ss/sh interface. From 2000 to 4000 a, ankerite, dolomite and illite began replacing Mg–Fe chlorite at the sandstone/shale interface. Transformation of chlorite to ankerite is the dominant reaction occluding the shale porosity in most simulations: from 4000 to 7500 a, this carbonation seals the reservoir and terminates reaction. Overall, the carbonates (calcite, ankerite, dolomite), chlorite and goethite all remain close to local chemical equilibrium with brine. Quartz is almost inert from the point of its dissolution/precipitation. However, the rate of quartz reaction controls the long-term decline in aqueous silica activity and its evolution toward equilibrium. The reactions of feldspars and clays depend strongly on their reaction rate constants (microcline is closer to local equilibrium than albite). The timing of porosity occlusion mostly therefore depends on the kinetic constants of kaolinite and illite. For example, an increase in the kaolinite kinetic constant by 0.25 logarithmic units hastened porosity closure by 4300 a. The earliest simulated closure of porosity occurred at approximately 108 a for simulations designed as sensitivity tests for the rate constants.These simulations also emphasize that the rate of CO2 immobilization as aqueous bicarbonate (solubility trapping) or as carbonate minerals (mineral trapping) in sandstone reservoirs depends upon reaction kinetics – but the relative fraction of each trapped CO2 species only depends upon the initial chemical composition of the host sandstone. For example, at the point of porosity occlusion the fraction of bicarbonate remaining in solution depends upon the initial Na and K content in the host rock but the fraction of carbonate mineralization depends only on the Ca, Mg, Fe content. Since ankerite is the dominant mineral that occludes porosity, the dissolved concentration of ferrous iron is also an important parameter. Future efforts should focus on cross-comparisons and ground-truthing of simulations made for standard case studies as well as laboratory measurements of the reactivities of clay minerals. 相似文献
12.
《Ore Geology Reviews》2010,37(4):333-349
Gold mineralization at Jonnagiri, Dharwar Craton, southern India, is hosted in laminated quartz veins within sheared granodiorite that occur with other rock units, typical of Archean greenstone–granite ensembles. The proximal alteration assemblage comprises of muscovite, plagioclase, and chlorite with minor biotite (and carbonate), which is distinctive of low- to mid-greenschist facies. The laminated quartz veins that constitute the inner alteration zone, contain muscovite, chlorite, albite and calcite. Using various calibrations, chlorite compositions in the inner and proximal zones yielded comparable temperature ranges of 263 to 323 °C and 268 to 324 °C, respectively. Gold occurs in the laminated quartz veins both as free-milling native metal and enclosed within sulfides. Fluid inclusion microthermometry and Raman spectroscopy in quartz veins within the sheared granodiorite in the proximal zone and laminated auriferous quartz veins in inner zone reveal the existence of a metamorphogenic aqueous–gaseous (H2O–CO2–CH4 + salt) fluid that underwent phase separation and gave rise to gaseous (CO2–CH4), low saline (~ 5 wt.% NaCl equiv.) aqueous fluids. Quartz veins within the mylonitized granodiorites and the laminated veins show broad similarity in fluid compositions and P–T regime. Although the estimated P–T range (1.39 to 2.57 kbar at 263 to 323 °C) compare well with the published P–T values of other orogenic gold deposits in general, considerable pressure fluctuation characterize gold mineralization at Jonnagiri. Factors such as fluid phase separation and fluid–rock interaction, along with a decrease in f(O2), were collectively responsible for gold precipitation, from an initial low-saline metamorphogenic fluid. Comparison of the Jonnagiri ore fluid with other lode gold deposits in the Dharwar Craton and major granitoid-hosted gold deposits in Australia and Canada confirms that fluids of low saline aqueous–carbonic composition with metamorphic parentage played the most dominant role in the formation of the Archean lode gold systems. 相似文献
13.
R. Prez-Lpez G. Montes-Hernandez J.M. Nieto F. Renard L. Charlet 《Applied Geochemistry》2008,23(8):2292-2300
The global warming of Earth’s near-surface, air and oceans in recent decades is a direct consequence of anthropogenic emission of greenhouse gases into the atmosphere such as CO2, CH4, N2O and CFCs. The CO2 emissions contribute approximately 60% to this climate change. This study investigates experimentally the aqueous carbonation mechanisms of an alkaline paper mill waste containing about 55 wt% portlandite (Ca(OH)2) as a possible mineralogical CO2 sequestration process. The overall carbonation reaction includes the following steps: (1) Ca release from portlandite dissolution, (2) CO2 dissolution in water and (3) CaCO3 precipitation. This CO2 sequestration mechanism was supported by geochemical modelling of final solutions using PHREEQC software, and observations by scanning electron microscope and X-ray diffraction of final reaction products. According to the experimental protocol, the system proposed would favour the total capture of approx. 218 kg of CO2 into stable calcite/ton of paper waste, independently of initial CO2 pressure. The final product from the carbonation process is a calcite (ca. 100 wt%)-water dispersion. Indeed, the total captured CO2 mineralized as calcite could be stored in degraded soils or even used for diverse industrial applications. This result demonstrates the possibility of using the alkaline liquid–solid waste for CO2 mitigation and reduction of greenhouse effect gases into the atmosphere. 相似文献
14.
Olivier Regnault Vincent Lagneau Hubert Catalette Hélène Schneider 《Comptes Rendus Geoscience》2005,337(15):1331-1339
Carbon dioxide sequestration in deep aquifers and depleted oilfields is a potential technical solution for reducing green-house gas release to the atmosphere: the gas containment relies on several trapping mechanisms (supercritical CO2, CO2(sc), dissolution together with slow water flows, mineral trapping) and on a low permeability cap-rock to prevent CO2(sc), which is less dense than the formation water, from leaking upwards. A leakproof cap-rock is thus essential to ensure the sequestration efficiency. It is also crucial for safety assessment to identify and assess potential alteration processes that may damage the cap-rock properties: chemical alteration, fracture reactivation, degradation of injection borehole seals, etc. The reactivity of the host-rock minerals with the supercritical CO2 fluid is one of the potential mechanisms, but it is altogether unknown. Reactivity tests have been carried out under such conditions, consisting of batch reactions between pure minerals and anhydrous supercritical CO2, or a two-phase CO2/H2O fluid at 200?°C and 105/160 bar. After 45 to 60 days, evidence of appreciable mineral-fluid reactivity was identified, including in the water-free experiments. For the mixed H2O/CO2 experiments, portlandite was totally transformed into calcite; anorthite displayed many dissolution patterns associated with calcite, aragonite, tridymite and smectite precipitations. For the anhydrous CO2 experiments, portlandite was totally carbonated to form calcite and aragonite; anorthite also displayed surface alteration patterns with secondary precipitation of fibrous calcite. To cite this article: O. Regnault et al., C. R. Geoscience 337 (2005). 相似文献
15.
Vein-type gold deposits in the Atud area are related to the metagabbro–diorite complex that occurred in Gabal Atud in the Central Eastern Desert of Egypt. This gold mineralization is located within quartz veins and intense hydrothermal alteration haloes along the NW–SE brittle–ductile shear zone, as well as along the contacts between them. By using the mass balance calculations, this work is to determine the mass/volume gains and losses of the chemical components during the hydrothermal alteration processes in the studied deposits. In addition, we report new data on the mineral chemistry of the alteration minerals to define the condition of the gold deposition and the mineralizing fluid based on the convenient geothermometers. Two generations of quartz veins include the mineralized grayish-to-white old vein (trending NW–SE), and the younger, non-mineralized milky white vein (trending NE–SW). The ore minerals associated with gold are essentially arsenopyrite and pyrite, with chalcopyrite, sphalerite, enargite, and goethite forming during three phases of mineralization; first, second (main ore), and third (supergene) phases. Three main hydrothermal alteration zones of mineral assemblages were identified (zones 1–3), placed around mineralized and non-mineralized quartz veins in the underground levels. The concentrations of Au, Ag, and Cu are different from zone to zone having 25–790 ppb, 0.7–69.6 ppm, and 6–93.8 ppm; 48.6–176.1 ppb, 0.9–12.3 ppm, and 39.6–118.2 ppm; and 53.9–155.4 ppb, 0.7–3.4 ppm, and 0.2–79 ppm for zones 1, 2, and 3, respectively.The mass balance calculations and isocon diagrams (calculated using the GEOISO-Windows program) revealed the gold to be highly associated with the main mineralized zone as well as sericitization/kaolinitization and muscovitization in zone 1 more than in zones 2 and 3. The sericite had a higher muscovite component in all analyzed flakes (average XMs = 0.89), with 0.10%–0.55% phengite content in wall rocks and 0.13%–0.29% phengite content in mineralized quartz veins. Wall rocks had higher calcite (CaCO3) contents and lower MgCO3 and FeCO3 contents than the quartz veins. The chlorite flakes in the altered wall rocks were composed of pycnochlorite and ripidolite, with estimated formation temperatures of 289–295 °C and 301–312 °C, respectively. Albite has higher albite content (95.08%–99.20%) which occurs with chlorite in zone 3. 相似文献
16.
The Dongping gold deposit hosted in syenites is one of the largest hydrothermal gold deposits in China and composed of ore veins in the upper parts and altered zones in the lower parts of the ore bodies. Pervasive potassic alteration and silicification overprint the wall rocks of the ore deposit. The alteration minerals include orthoclase, microcline, perthite, quartz, sericite, epidote, calcite, hematite and pyrite, with the quartz, pyrite and hematite assemblages closely associated with gold mineralization. The phases of hydrothermal alteration include: (i) potassic alteration, (ii) potassic alteration - silicification, (iii) silicification - epidotization - hematitization, (iv) silicification - sericitization - pyritization and (v) carbonation. Mass-balance calculations in potassic altered and silicified rocks reveal the gain of K2O, Na2O, SiO2, HFSEs and transition elements (TEs) and the loss of REEs. Most major elements were affected by intense mineral reactions, and the REE patterns of the ore are consistent with those of the syenites. Gold, silver and tellurium show positive correlation and close association with silicification. Fluid inclusion homogenization temperatures in quartz veins range from 154 °C to 382 °C (peak at 275 °C–325 °C), with salinities of 4–9 wt.% NaCl equiv. At temperatures of 325 °C the fluid is estimated to have pH = 3.70–5.86, log fO2 = − 32.4 to − 28.1, with Au and Te transported as Au (HS)2− and Te22 − complexes. The ore forming fluids evolved from high pH and fO2 at moderate temperatures into moderate-low pH, low fO2 and low temperature conditions. The fineness of the precipitated native gold and the contents of the oxide minerals (e.g., magnetite and hematite) decreased, followed by precipitation of Au- and Ag-bearing tellurides. The hydrothermal system was derived from an alkaline magma and the deposit is defined as an alkaline rock-hosted hydrothermal gold deposit. 相似文献
17.
The Yangla Cu deposit is the largest Cu skarn deposit in the Jinshajiang tectonic belt. Based on the detailed observation of crosscutting relationships, three mineralization stages (i.e., pre-ore, ore and supergene) have been identified in the Yangla deposit. The pre-ore stage is dominated by prograde skarn. The ore stage is characterized by the precipitation of hydrous silicate minerals, Fe-oxides, Fe-Cu-Mo-sulfides, quartz and calcite, whose mineral assemblages were formed in the early and late sub-ore stages. The early sub-ore stage is marked by retrograde alteration with the deposition of hydrous silicate minerals (e.g., actinolite, epidote and chlorite), Fe-oxides, abundant Fe-Cu-Mo-sulfides, quartz and minor calcite. Whilst, the late sub-ore stage, associated with silicic and carbonate alteration, is represented by widespread thick quartz or calcite veins with disseminated pyrite, chalcopyrite, galena and sphalerite. We present new carbon-oxygen (C-O) isotopic compositions of the ore-hosting marble and hydrothermal calcite of this deposit. The hydrothermal calcite in the Yangla deposit was precipitated from both the early and late sub-ore stages. Calcite I from the early sub-ore stage is anhedral, and occurs as spot in the skarn or locally replaces the skarn minerals. Calcite II from the late sub-ore stage is distinguished by being coarse-grained, subhedral to euhedral and its occurrence in thick veins. Calcite I contains lower δ13CPDB (−7.0‰ to −5.0‰) and δ18OSMOW (7.2‰ to 12.7‰) than Calcite II (δ13CPDB = −4.5‰ to −2.3‰; δ18OSMOW = 10.7‰ to 19.4‰). In the δ13CPDB vs. δ18OSMOW diagram, the Calcite I and Calcite II data fall close to the igneous carbonatite field and between the fields of igneous carbonatite and marine carbonates, respectively. This suggests a dominantly magmatic origin for the early sub-ore fluids, and there might have been increasing carbonate wall rock involvement towards the late sub-ore stage. The ore-hosting marble (δ13CPDB = −4.8‰ to −0.3‰; δ18OSMOW = 10.2‰ to 23.9‰) also shows a positive δ13CPDB vs. δ18OSMOW correlation, which is interpreted to reflect the decreasing alteration intensity during the interactions between the hydrothermal fluids and ore-hosting carbonates. Simulated calculation suggests that both the Calcite I and Calcite II precipitated at 350 °C to 250 °C and 250 °C to 150 °C, respectively. We proposed that CO2 degassing and water/rock interactions were likely the two major processes that precipitated the calcite and led to the observed C-O isotopic features of the Yangla Cu deposit. 相似文献
18.
The Qianfanling Mo deposit, located in Songxian County, western Henan province, China, is one of the newly discovered quartz-vein type Mo deposits in the East Qinling–Dabie orogenic belt. The deposit consists of molybdenite in quartz veins and disseminated molybdenite in the wall rocks. The alteration types of the wall rocks include silicification, K-feldspar alteration, pyritization, carbonatization, sericitization, epidotization and chloritization. On the basis of field evidence and petrographic analysis, three stages of hydrothermal mineralization could be distinguished: (1) pyrite–barite–quartz stage; (2) molybdenite–quartz stage; (3) quartz–calcite stage.Two types of fluid inclusions, including CO2-bearing fluid inclusions and water-rich fluid inclusions, have been recognized in quartz. Homogenization temperatures of fluid inclusions vary from 133 °C to 397 °C. Salinity ranges from 1.57 to 31.61 wt.% NaCl eq. There are a large number of daughter mineral-CO2-bearing inclusions, which is the result of fluid immiscibility. The ore-forming fluids are medium–high temperature, low to moderate salinity H2O–NaCl–CO2 system. The δ34S values of pyrite, molybdenite, and barite range from − 9.3‰ to − 7.3‰, − 9.7‰ to − 7.3‰ and 5.9‰ to 6.8‰, respectively. The δ18O values of quartz range from 9.8‰ to 11.1‰, with corresponding δ18Ofluid values of 1.3‰ to 4.3‰, and δ18D values of fluid inclusions of between − 81‰ and − 64‰. The δ13CV-PDB values of fluid inclusions in quartz and calcite have ranges of − 6.7‰ to − 2.9‰ and − 5.7‰ to − 1.8‰, respectively. Sulfur, hydrogen, oxygen and carbon isotope compositions show that the sulfur and ore-forming fluids derived from a deep-seated igneous source. During the peak collisional period between the North China Craton and the Yangtze Craton, the ore-forming fluids that derived from a deep igneous source extracted base and precious metals and flowed upwards through the channels that formed during tectonism. Fluid immiscibility and volatile exsolution led to the crystallization of molybdenite and other minerals, and the formation of economic orebodies in the Qianfanling Mo deposit. 相似文献
19.
The Shapinggou porphyry Mo deposit, one of the largest Mo deposits in Asia, is located in the Dabie Orogen, Central China. Hydrothermal alteration and mineralization at Shapinggou can be divided into four stages, i.e., stage 1 ore-barren quartz veins with intense silicification, followed by stage 2 quartz-molybdenite veins associated with potassic alteration, stage 3 quartz-polymetallic sulfide veins related to phyllic alteration, and stage 4 ore-barren quartz ± calcite ± pyrite veins with weak propylitization. Hydrothermal quartz mainly contains three types of fluid inclusions, namely, two-phase liquid-rich (type I), two- or three-phase gas-rich CO2-bearing (type II) and halite-bearing (type III) inclusions. The last two types of fluid inclusions are absent in stages 1 and 4. Type I inclusions in the silicic zone (stage 1) display homogenization temperatures of 340 to 550 °C, with salinities of 7.9–16.9 wt.% NaCl equivalent. Type II and coexisting type III inclusions in the potassic zone (stage 2), which hosts the main Mo orebodies, have homogenization temperatures of 240–440 °C and 240–450 °C, with salinities of 34.1–50.9 and 0.1–7.4 wt.% NaCl equivalent, respectively. Type II and coexisting type III inclusions in the phyllic zone (stage 3) display homogenization temperatures of 250–345 °C and 220–315 °C, with salinities of 0.2–6.5 and 32.9–39.3 wt.% NaCl equivalent, respectively. Type I inclusions in the propylitization zone (stage 4) display homogenization temperatures of 170 to 330 °C, with salinities lower than 6.5 wt.% NaCl equivalent. The abundant CO2-rich and coexisting halite-bearing fluid inclusion assemblages in the potassic and phyllic zones highlight the significance of intensive fluid boiling of a NaCl–CO2–H2O system in deep environments (up to 2.3 kbar) for giant porphyry Mo mineralization. Hydrogen and oxygen isotopic compositions indicate that ore-fluids were gradually evolved from magmatic to meteoric in origin. Sulfur and lead isotopes suggest that the ore-forming materials at Shapinggou are magmatic in origin. Re–Os dating of molybdenite gives a well-defined 187Re/187Os isochron with an age of 112.7 ± 1.8 Ma, suggesting a post-collisional setting. 相似文献
20.
The active acid gas (H2S–CO2 mixture) injection operations in North America provide practical experience for the operators in charge of industrial scale CO2 geological storage sites. Potential leakage via wells and their environmental impacts make well construction durability an issue for efficiency/safety of gas geological storage. In such operations, the well cement is in contact with reservoir brines and the injected gas, meaning that gas–water–solid chemical reactions may change the physical properties of the cement and its ability to confine the gas downhole. The cement-forming Calcium silicate hydrates carbonation (by CO2) and ferrite sulfidation (by H2S) reactions are expected. The main objective of this study is to determine their consequences on cement mineralogy and transfer ability. Fifteen and 60 days duration batch experiments were performed in which well cement bars were immersed in brine itself caped by a H2S–CO2 phase at 500 bar–120 °C. Scanning electron microscopy including observations/analyses and elemental mapping, mineralogical mapping by micro-Raman spectroscopy, X-ray diffraction and water porosimetry were used to characterize the aged cement. Speciation by micro-Raman spectroscopy of brine trapped within synthetic fluid inclusions were also performed. The expected calcium silicate hydrates carbonation and ferrite sulfidation reactions were evidenced. Furthermore, armouring of the cement through the fast creation of a non-porous calcite coating, global porosity decrease of the cement (clogging) and mineral assemblage conservation were demonstrated. The low W/R ratio of the experimental system (allowing the cement to buffer the interstitial and external solution pH at basic values) and mixed species diffusion and chemical reactions are proposed to explain these features. This interpretation is confirmed by reactive transport modelling performed with the HYTEC code. The observed cement armouring, clogging and mineral assemblage conservation suggest that the tested cement has improved transfer properties in the experimental conditions. This work suggests that in both acid gas and CO2 geological storage, clogging of cement or at least mineral assemblage conservation and slowing of carbonation progress could occur in near-well zones where slight water flow occurs e.g. in the vicinity of caprock shales. 相似文献