Brucite [Mg(OH2)] carbonation in wet supercritical CO2: An in situ high pressure X-ray diffraction study

Understanding mechanisms and kinetics of mineral carbonation reactions relevant to sequestering carbon dioxide as a supercritical fluid (scCO₂) in geologic formations is crucial to accurately predicting long-term storage risks. Most attention so far has been focused on reactions occurring between silicate minerals and rocks in the aqueous dominated CO₂-bearing fluid. However, water-bearing scCO₂ also comprises a reactive fluid, and in this situation mineral carbonation mechanisms are poorly understood. Using in situ high-pressure X-ray diffraction, the carbonation of brucite [Mg(OH)₂] in wet scCO₂ was examined at pressure (82 bar) as a function of water concentration and temperature (50 and 75 °C). Exposing brucite to anhydrous scCO₂ at either temperature resulted in little or no detectable reaction over three days. However, addition of trace amounts of water resulted in partial carbonation of brucite into nesquehonite [MgCO₃·3H₂O] within a few hours at 50 °C. By increasing water content to well above the saturation level of the scCO₂, complete conversion of brucite into nesquehonite was observed. Tests conducted at 75 °C resulted in the conversion of brucite into magnesite [MgCO₃] instead, apparently through an intermediate nesquehonite step. Raman spectroscopy applied to brucite reacted with ¹⁸O-labeled water in scCO₂ show it was incorporated into carbonate at a relatively high concentration. This supports a carbonation mechanism with at least one step involving a direct reaction between the mineral and water molecules without mediation by a condensed aqueous layer.     

Carbonation of lignite fly ash at ambient T and P in a semi-dry reaction system for CO2 sequestration

The global rise in atmospheric greenhouse gas concentrations calls for practicable solutions to capture CO₂. In this study, a mineral carbonation process was applied in which CO₂ reacts with alkaline lignite ash and forms stable carbonate solids. In comparison to previous studies, the assays were conducted at low temperatures and pressures and under semi-dry reaction conditions in an 8 L laboratory mixing device. In order to find optimum process conditions the pCO₂ (10-20%), stirring rate (500-3000 rpm) and the liquid to solid ratio (L/S = 0.03-0.36 L kg⁻¹) were varied. In all experiments a considerable CO₂ uptake from the gas phase was observed. Concurrently the solid phase contents of Ca and Mg (hydr)oxides decreased and CaCO₃ and MgCO₃ fractions increased throughout the experiments, showing that CO₂ was stabilized as a solid carbonate. The carbonation reaction depends on three factors: Dissolution of CO₂ in the liquid phase, mobilization of Ca and Mg from the mineral surface and precipitation of the carbonate solids. Those limitations were found to depend strongly on the variation of the process parameters. Optimum reaction conditions could be found for L/S ratios between 0.12 and 0.18, medium stirring velocities and pCO₂ between 10% and 20%.Maximum CO₂ uptake by the solid phase was 4.8 mmol g⁻¹ after 120 min, corresponding to a carbonation efficiency for the alkaline material of 53% of the theoretical CO₂ binding capacity. In comparison to previous studies both CO₂ uptake and carbonation efficiencies were in a similar range, but the reaction times in the semi-dry process were considerably shorter. The proposed method additionally allows for a more simple carbonation setup due to low T and P, and produces an easier to handle product with low water content.     

Quantifying carbon fixation in trace minerals from processed kimberlite: A comparative study of quantitative methods using X-ray powder diffraction data with applications to the Diavik Diamond Mine,Northwest Territories,Canada

The capacity of mine waste to trap CO₂ is, in some cases, much larger than the greenhouse gas production of a mining operation. In mine tailings, the presence of secondary carbonate minerals that trap CO₂ can therefore represent substantial fixation of this greenhouse gas. The abilities of three methods of quantitative phase analysis to measure trace nesquehonite (MgCO₃·3H₂O) in samples of processed kimberlite have been assessed: the method of reference intensity ratios (RIR), the internal standard method, and the Rietveld method with X-ray powder diffraction data. Tests on synthetic mixtures made to resemble processed kimberlite indicate that both the RIR and Rietveld methods can be used accurately to quantify nesquehonite to a lower limit of approximately 0.5 wt.% for conditions used in the laboratory. Below this value, estimates can be made to a limit of approximately 0.1 wt.% using a calibration curve according to the internal standard method. The RIR method becomes increasingly unreliable with decreasing abundance of nesquehonite, primarily as a result of an unpredictable decline in preferred orientation of crystallites. For Rietveld refinements, structureless pattern fitting was used to account for planar disorder in lizardite by considering it as an amorphous phase. Rietveld refinement of data collected from specimens that were serrated to minimize preferred orientation of crystallites gives rise to systematic overestimates of refined abundances for lizardite and underestimates for other phases. The resulting pattern of misestimates may be mistaken for the effect of amorphous and/or nanocrystalline material in samples. This effect is mitigated by collecting data from non-serrated specimens, which typically give relative errors on refined abundances for major and minor phases in the range of 5–20%. However, relative error can increase rapidly for abundances less than 5 wt.%. Nonetheless, absolute errors are sufficiently small that estimates can be made for the amount of CO₂ stored in secondary nesquehonite using the RIR method or the Rietveld method for abundances ?0.5 wt.% and a calibration curve for abundances <0.5 wt.%. The extent to which C is being mineralized in an active mine setting at the Diavik Diamond Mine, Northwest Territories, Canada, has been investigated. Rietveld refinement results and calibrated abundances for trace nesquehonite are used to estimate the amount of CO₂ trapped in Diavik tailings. Results of quantitative phase analysis are also used to calculate neutralization potentials for the kimberlite mine tailings and to estimate the contribution made by secondary nesquehonite.     

CO2-water-basalt interaction. Numerical simulation of low temperature CO2 sequestration into basalts

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.     

Investigation of the accelerated carbonation of a MgO-based binder used to treat contaminated sediment

A MgO-based binder developed to simultaneously solidify/stabilize contaminated sediment and store CO₂ has been described previously. The objectives of the study presented here were to investigate the kinetics of the carbonation reactions of the binder and the extent to which carbonation occurred and to identify the optimal conditions for using the binder. The carbonation reaction was clearly faster and the degree of carbonation higher at CO₂ concentrations of 50 and 100% than in the ambient atmosphere (which contains 0.04% CO₂). A modified unreactive core model adequately described the kinetics. The rate constants were 0.0217–0.319 h^?1 and were proportional to the degree of carbonation. A high degree of carbonation, 93.8%, was achieved at a CO₂ concentration of 100%. The water to sediment ratio strongly affected carbonation, the optimal ratio being around 0.7. The relative humidity did not strongly affect the carbonation performance. The carbonation products were magnesite (MgCO₃) and nesquehonite (MgCO₃·3H₂O). X-ray diffraction analysis showed that brucite (Mg(OH)₂) was not present, suggesting that brucite was very quickly transformed into magnesium carbonates, the presence of which was confirmed by thermal gravimetric analysis. The results indicated that, in 7 d, 1 kg of binder could sequester up to 0.507 kg of CO₂ in a 100% CO₂ atmosphere. The results indicate that the MgO-based binder has great potential to be used to sequester CO₂ under accelerated carbonation conditions.     

The hydromagnesite playas of Atlin, British Columbia, Canada: A biogeochemical model for CO2 sequestration

Anthropogenic greenhouse gas emissions may be offset by sequestering carbon dioxide (CO₂) through the carbonation of magnesium silicate minerals to form magnesium carbonate minerals. The hydromagnesite [Mg₅(CO₃)₄(OH)₂·4H₂O] playas of Atlin, British Columbia, Canada provide a natural model to examine mineral carbonation on a watershed scale. At near surface conditions, CO₂ is biogeochemically sequestered by microorganisms that are involved in weathering of bedrock and precipitation of carbonate minerals. The purpose of this study was to characterize the weathering regime in a groundwater recharge zone and the depositional environments in the playas in the context of a biogeochemical model for CO₂ sequestration with emphasis on microbial processes that accelerate mineral carbonation.Regions with ultramafic bedrock, such as Atlin, represent the best potential sources of feedstocks for mineral carbonation. Elemental compositions of a soil profile show significant depletion of MgO and enrichment of SiO₂ in comparison to underlying ultramafic parent material. Polished serpentinite cubes were placed in the organic horizon of a coniferous forest soil in a groundwater recharge zone for three years. Upon retrieval, the cube surfaces, as seen using scanning electron microscopy, had been colonized by bacteria that were associated with surface pitting. Degradation of organic matter in the soil produced chelating agents and acids that contributed to the chemical weathering of the serpentinite and would be expected to have a similar effect on the magnesium-rich bedrock at Atlin. Stable carbon isotopes of groundwater from a well, situated near a wetland in the southeastern playa, indicate that  12% of the dissolved inorganic carbon has a modern origin from soil CO₂.The mineralogy and isotope geochemistry of the hydromagnesite playas suggest that there are three distinct depositional environments: (1) the wetland, characterized by biologically-aided precipitation of carbonate minerals from waters concentrated by evaporation, (2) isolated wetland sections that lead to the formation of consolidated aragonite sediments, and (3) the emerged grassland environment where evaporation produces mounds of hydromagnesite. Examination of sediments within the southeastern playa–wetland suggests that cyanobacteria, sulphate reducing bacteria, and diatoms aid in producing favourable geochemical conditions for precipitation of carbonate minerals.The Atlin site, as a biogeochemical model, has implications for creating carbon sinks that utilize passive microbial, geochemical and physical processes that aid in mineral carbonation of magnesium silicates. These processes could be exploited for the purposes of CO₂ sequestration by creating conditions similar to those of the Atlin site in environments, artificial or natural, where the precipitation of magnesium carbonates would be suitable. Given the vast quantities of Mg-rich bedrock that exist throughout the world, this study has significant implications for reducing atmospheric CO₂ concentrations and combating global climate change.     

Aqueous mineral carbonation of serpentinite on a pilot scale: The effect of liquid recirculation on CO2 sequestration and carbonate precipitation

Following the promising results obtained on the laboratory scale, an aqueous mineral carbonation process was tested under industrial conditions as part of a pilot project conducted in a cement plant in Quebec. Experiments were conducted using a Parr 18.7 L reactor with cement plant flue gas (14–18 vol.%CO₂) and serpentinite tailings as a source of magnesium. The gas was not concentrated or separated before use. The reactions occurred at a solid/liquid ratio of 150 g/L, 22 ± 3 °C and a total pressure between 2 and 10 bar. To decrease water consumption, the effect of liquid recirculation on the rates of CO₂ sequestration, Mg leaching and carbonate precipitation were studied. The solid reacted with 6 successive batches of gas (15 min each), and the liquid was recovered for the carbonate precipitation after every two batches. For the recirculation assays, after carbonate filtration, the liquid was reused with subsequent batches.The results showed that the dissolution of CO₂ was not affected by the liquid recirculation since 72.5% of the CO₂ introduced was dissolved; in comparison to 77% when fresh liquid was used. The captured CO₂ resulted in 0.215 and 0.211 g CO₂/g of residue in the experiments with and without liquid recirculation, respectively. This result corresponds to approximately 45% of serpentinite's total capacity for CO₂ sequestration, which is 0.47 g CO₂/g of residue. The carbonate precipitation experiments were conducted in a separate system at low temperatures (32–40 °C) and included 2 h of stirring. When the liquid was recirculated, supersaturation was reached more quickly because of the accumulation of Mg²⁺ and HCO₃⁻/CO²⁻₃ ions. Therefore, the rate of precipitation and the amount of carbonate formed were significantly more important when the liquid was recirculated. However, the overall efficiency corresponding to the captured CO₂ under carbonate form does not exceed 9% even with liquid recirculation.     

CO2 mineral sequestration by wollastonite carbonation

In this paper, we demonstrated a new approach to CO₂ mineral sequestration using wollastonite carbonation assisted by sulfuric acid and ammonia. Samples were characterized by X-ray diffraction, scanning electron microscopy, Fourier transform infrared spectroscopy, and ²⁹Si nuclear magnetic resonance. The change in Gibbs free energy from ?223 kJ/mol for the leaching reaction of wollastonite to ?101 kJ/mol for the carbonation reaction indicated that these two reactions can proceed spontaneously. The leached and carbonated wollastonite showed fibrous bassanite and granular calcium carbonate, respectively, while the crystal structure of pristine wollastonite was destroyed and the majority of the Ca²⁺ in pristine wollastonite leached. The chemical changes in the phases were monitored during the whole process. A high carbonation rate of 91.1 % could be obtained under the action of sulfuric acid and ammonia at 30 °C at normal atmospheric pressure, indicating its potential use for CO₂ sequestration.     

Carbonate and carbon isotopic evolution of groundwater contaminated by produced water brine with hydrocarbons

The major ionic and dissolved inorganic carbon (DIC) concentrations and the stable carbon isotope composition of DIC (δ¹³C_DIC) were measured in a freshwater aquifer contaminated by produced water brine with petroleum hydrocarbons. Our aim was to determine the effects of produced water brine contamination on the carbonate evolution of groundwater. The groundwater was characterized by three distinct anion facies: HCO₃⁻-rich, SO₄²⁻-rich and Cl⁻-rich. The HCO₃⁻-rich groundwater is undergoing closed system carbonate evolution from soil CO_2(g) and weathering of aquifer carbonates. The SO₄²⁻-rich groundwater evolves from gypsum induced dedolomitization and pyrite oxidation. The Cl⁻-rich groundwater is contaminated by produced water brine and undergoes common ion induced carbonate precipitation. The δ¹³C_DIC of the HCO₃⁻-rich groundwater was controlled by nearly equal contribution of carbon from soil CO_2(g) and the aquifer carbonates, such that the δ¹³C of carbon added to the groundwater was −11.6‰. In the SO₄²⁻-rich groundwater, gypsum induced dedolomitization increased the ¹³C such that the δ¹³C of carbon added to the groundwater was −9.4‰. In the produced water brine contaminated Cl⁻-rich groundwater, common ion induced precipitation of calcite depleted the ¹³C such that the δ¹³C of carbon added to the groundwater was −12.7‰. The results of this study demonstrate that produced water brine contamination of fresh groundwater in carbonate aquifers alters the carbonate and carbon isotopic evolution.     

富CO2深部流体对碳酸盐岩的溶蚀-充填作用的热力学分析

由于广泛而强烈的岩浆作用,我国东部的松辽、渤海湾、莺歌海以及西部的塔里木等盆地中都有富CO₂深部流体的活动。富CO₂深部流体与碳酸盐岩相互作用可用Duan and Li(2008)所建立的CO₂-H₂O-CaCO₃-NaCl体系的热力学模型来进行模拟计算。计算结果表明,富CO₂深部流体在自深部向浅部运移过程中对CaCO₃的溶解度会逐渐增加,到达一定深度后溶解度达到最大值,再向浅部溶解度开始逐渐降低; 也就是深部流体具有深部溶蚀碳酸盐岩-浅部沉淀碳酸盐矿物的规律。与浅部地层中的流体发生混合会使流体的CO₂含量和盐度降低,会导致CaCO₃的沉淀充填; 深部流体进入开启性断裂/裂缝体系中时,由于压力的降低,也会发生CaCO₃的沉淀充填。深部流体的CO₂含量、盐度、温度和压力的变化影响着实际的溶蚀-充填过程。塔中地区钻井也揭示了深部下奥陶统碳酸盐岩中发育有丰富的溶蚀孔隙,而在相对浅部的奥陶系灰岩和志留系砂岩中见有大量方解石的充填,这是富CO₂流体深部溶蚀-浅部充填的一个较好的实例。基于理论和实际分析,本文认为在岩浆火山作用广泛发育的塔里木等盆地中下古生界深部优质碳酸盐岩储层存在的可能性。     

Experiments and geochemical modelling of CO2 sequestration by olivine: Potential,quantification

Aqueous solutions equilibrated with supercritical CO₂ (150 °C and total pressure of 150 bar) were investigated in order to characterize their respective conditions of carbonation. Dissolution of olivine and subsequent precipitation of magnesite with a net consumption of CO₂ were expected. A quantified pure mineral phase (powders with different olivine grain diameter [20–80 μm], [80–125 μm], [125–200 μm] and [>200 μm]), and CO₂ (as dried ice) were placed in closed-batch reactors (soft Au tubes) in the presence of solutions. Different salinities (from 0 to 3400 mM) and different ratios of solution/solid (mineral phase) (from 0.1 to 10) were investigated. Experiments were performed over periods from 2 to 8 weeks. Final solid products were quantified by the Rock-Eval 6 technique, and identified using X-ray diffraction, Raman spectroscopy, electron microprobe and scanning electron microscopy. Gaseous compounds were quantified by a vacuum line equipped with a Toepler pump and identified and measured by gas chromatography (GC). Carbon mass balances were calculated.     

The CO2 system in rivers of the Australian Victorian Alps: CO2 evasion in relation to system metabolism and rock weathering on multi-annual time scales

The patterns of dissolved inorganic C (DIC) and aqueous CO₂ in rivers and estuaries sampled during summer and winter in the Australian Victorian Alps were examined. Together with historical (1978–1990) geochemical data, this study provides, for the first time, a multi-annual coverage of the linkage between CO₂ release via wetland evasion and CO₂ consumption via combined carbonate and aluminosilicate weathering. δ¹³C values imply that carbonate weathering contributes ∼36% of the DIC in the rivers although carbonates comprise less than 5% of the study area. Baseflow/interflow flushing of respired C3 plant detritus accounts for ∼50% and atmospheric precipitation accounts for ∼14% of the DIC. The influence of in river respiration and photosynthesis on the DIC concentrations is negligible. River waters are supersaturated with CO₂ and evade ∼27.7 × 10⁶ mol/km²/a to ∼70.9 × 10⁶ mol/km²/a CO₂ to the atmosphere with the highest values in the low runoff rivers. This is slightly higher than the global average reflecting higher gas transfer velocities due to high wind speeds. Evaded CO₂ is not balanced by CO₂ consumption via combined carbonate and aluminosilicate weathering which implies that chemical weathering does not significantly neutralize respiration derived H₂CO₃. The results of this study have implications for global assessments of chemical weathering yields in river systems draining passive margin terrains as high respiration derived DIC concentrations are not directly connected to high carbonate and aluminosilicate weathering rates.     

Determination of carbon fractionation factor between aqueous carbonate and CO2(g) in two-direction isotope equilibration

The experiments were conducted in the open CO₂ system to find out the equilibrium fractionation between the carbonate ion and CO₂(g). The existence of isotopic equilibrium was checked using the two-direction approach by passing the CO₂−N₂ gases with different δ¹³C compositions (− 1.5‰ and − 23‰) through the carbonate solution with δ¹³C = − 4.2‰. The Δ_{CO3T²⁻−CO2(g)} equilibrium fractionation is given as 6.03 ± 0.17‰ at 25 °C. Discussion is provided about the significance of carbonate complexing in determination of Δ_{CO3T²⁻−CO2(g)} and Δ_{HCO3T⁻−CO2(g)} fractionations. Finally, an isotope numerical model of flow and kinetics of hydration and dehydroxylation is built to predict the isotopic behaviour of the system with time.     

苏北盆地黄桥地区富CO_2流体对二叠系龙潭组砂岩储层的改造与意义

富CO_2流体-砂岩相互作用是砂岩储层次生孔隙的重要形成机制。苏北黄桥地区作为中国重要的CO_2气产区,富CO_2流体对上二叠统龙潭组砂岩储层的改造问题备受关注。为揭示富CO_2流体的作用特征及其对储层的影响,对黄桥地区典型钻井开展了系统的岩心描述和岩矿鉴定,并进行了微区原位观测和相关地球化学分析。结果表明,在靠近CO_2流体活动强烈的断裂带部位(特别是断层上盘),砂岩中碳酸盐胶结物基本溶蚀殆尽,仅存少量交代成因菱铁矿,同时钾长石类碎屑溶蚀非常强烈,并伴随高岭石等矿物沉淀,以及石英次生加大,还发育片钠铝石等指示高浓度CO_2作用的特征矿物,形成与CO_2流体作用相关的特征矿物组合(片钠铝石+高岭石+次生石英+菱铁矿);而在远离断裂的部位,受CO_2流体影响较弱,溶蚀作用也较弱,有较多的次生方解石沉淀,形成了以方解石+菱铁矿为主的自生矿物组合。前者次生孔隙发育,后者则更加致密。据此提出了深源断裂主控下与富CO_2流体作用相关的储层发育模式,为油气勘探和开发提供了新的思路。     

Coal seam gas distribution and hydrodynamics of the Sydney Basin,NSW, Australia

This paper reviews various coal seam gas (CSG) models that have been developed for the Sydney Basin, and provides an alternative interpretation for gas composition layering and deep-seated CO₂ origins. Open file CSG wells, supplemented by mine-scale information, were used to examine trends in gas content and composition at locations from the margin to the centre of the basin. Regionally available hydrochemistry data and interpretations of hydrodynamics were incorporated with conventional petroleum well data on porosity and permeability. The synthesised gas and groundwater model presented in this paper suggests that meteoric water flow under hydrostatic pressure transports methanogenic consortia into the subsurface and that water chemistry evolves during migration from calcium-rich freshwaters in inland recharge areas towards sodium-rich brackish water down-gradient and with depth. Groundwater chemistry changes result in the dissolution and precipitation of minerals as well as affecting the behaviour of dissolved gases such as CO₂. Mixing of carbonate-rich waters with waters of significantly different chemistries at depth causes the liberation of CO₂ gas from the solution that is adsorbed into the coal matrix in hydrodynamically closed terrains. In more open systems, excess CO₂ in the groundwater (carried as bicarbonate) may lead to precipitation of calcite in the host strata. As a result, areas in the central and eastern parts of the basin do not host spatially extensive CO₂ gas accumulations but experience more widespread calcite mineralisation, with gas compositions dominated by hydrocarbons, including wet gases. Basin boundary areas (commonly topographic and/or structural highs) in the northern, western and southern parts of the basin commonly contain CO₂-rich gases at depth. This deep-seated CO₂-rich gas is generally thought to derive from local to continental scale magmatic intrusions, but could also be the product of carbonate dissolution or acetate fermentation.     

New constraints on carbonation associated with brecciation in hyperextended margins (example of Iberia and Newfoundland margins)

The sequestration of CO₂ occurs naturally in (ultra)‐mafic rocks by carbonation processes and is commonly noted in areas of the seafloor where mantle lithologies are exhumed. As well as carbonation, mantle exhumation is also responsible for rock brecciation. The relationship between carbonation and brecciation is not well constrained. A temporal evolution from syn‐ to post‐tectonic carbonation and brecciation is proposed in line with progressive mantle exhumation. Using a petrological study of brecciated material from IODP drill cores of the Iberia–Newfoundland conjugated margins, we relate crack–seal veins to tectonic brecciation, authigenic calcite with scalenohedral structure to hydraulic brecciation and reworked clasts within cement to (tectono)‐sedimentary processes. Oxygen isotope compositions reveal late‐staged < 50°C carbonate generation in the proximal part of the ocean–continent transition, which have followed an earlier phase of sub‐seafloor carbonate generation. The results are crucial to understand CO₂ exchange within the reworked sub‐seafloor in passive margins and oceanic systems.     

Rare earth partitioning between immiscible carbonate and silicate liquids and CO2 vapor: Results and implications for the formation of light rare earth-enriched rocks

Melting relations at 5 and 20 kbar on the composition join sanidine-potassium carbonate are dominated by a two-liquid region that covers over 60% of the join at 1,300 ° C. At this temperature, the silicate melt contains approximately 19 wt% carbonate component at 5 kbar and 32 wt% carbonate component at 20 kbar. The conjugate carbonate melt contains less than 5 wt% silicate component, and it varies less as a function of temperature than does the silicate melt.Partition coefficients for Ce, Sm, and Tm between the immiscible carbonate and silicate melts at 1,200 ° and 1,300 ° C at 5 and 20 kbar are in favor of the carbonate melt by a factor of 2–3 for light REE and 5–8 for heavy REE. The effect of pressure on partitioning cannot be evaluated independently because of complementary changes in melt compositions.Minimum REE partition coefficients for CO₂ vapor/carbonate melt and CO₂ vapor/silicate melt can be calculated from the carbonate melt/silicate melt partition coefficients, the known proportions of melt, and maximum estimates of the proportion of CO₂ vapor. The vapor phase is enriched in light REE relative to both melts at 20 kbar and enriched in all REE, especially the light elements, at 5 kbar. The enrichment of REE in CO₂ vapor relative to both melts is 3–4 orders of magnitude in excess of that in water vapor (Mysen, 1979) at 5 kbar and is approximately the same as that in water vapor at 20 kbar.Mantle metasomatism by a CO₂-rich vapor enriched in light REE, occurring as a precursor to magma genesis, may explain the enhanced REE contents and light REE enrichment of carbonatites, alkali-rich silicate melts, and kimberlites. Light REE enrichment in fenites and the granular suite of nodules from kimberlites attests to the mobility of REE in CO₂-rich fluids under both mantle and crustal conditions.     

Fixation of CO2 by chrysotile in low-pressure dry and moist carbonation: Ex-situ and in-situ characterizations

A detailed study of low-pressure gas-solid carbonation of chrysotile in dry and humid environments has been carried out. The evolving structure of chrysotile and its reactivity as a function of temperature (300-1200 °C), humidity (0-10 mol %) and CO₂ partial pressure (20-67 mol %), thermal preconditioning, and alkali metal doping (Li, Na, K, Cs) have been monitored through in-situ X-ray photoelectron spectroscopy, isothermal thermogravimetry/mass spectrometry, ex-situ X-ray powder diffraction, and water and nitrogen adsorption/desorption. Based on chrysotile crystalline structure and its nanofibrilar orderliness, a multistep carbonation mechanism was elaborated to explain the role of water during chrysotile partial amorphisation, formation of periclase, brucite, and hydromagnesite crystalline phases, and surface passivation thereof, during humid carbonation. The weak carbonation reactivity was rationalized in terms of incongruent CO₂ van der Waals molecular diameters with the octahedral-tetrahedral lattice constants of chrysotile. This lack of reactivity appeared to be relatively indifferent to the facilitated water crisscrossing during chrysotile core dehydroxylation/pseudo-amorphisation and surface hydroxylation induced product stabilization during humid carbonation. Thermodynamic stability domains of the species observed at low pressure have been thoroughly discussed on the basis of X-ray powder diffraction patterns and X-ray photoelectron spectroscopy evidence. The highest carbon dioxide uptake occurred at 375 °C in moist atmospheres. On the basis of chrysotile fresh N₂ BET area, nearly 15 atoms out of 100 of the surface chrysotile brucitic Mg moiety have been carbonated at this temperature which was tantamount to the carbonation of about 2.5 at. % of the total brucitic Mg moiety in chrysotile. The carbonation of brucite (Mg(OH)₂) impurities coexisting in chrysotile was minor and estimated to contribute by less than 17.6 at. % of the total converted magnesium. The presence of cesium traces (3 Cs atoms per 100 Mg atoms) was found to boost chrysotile carbonation capacity by a factor 2.7.     

Chemical evolution of the Mt. Hekla,Iceland, groundwaters: A natural analogue for CO2 sequestration in basaltic rocks

A detailed study of the chemical composition of the groundwater surrounding the Mt. Hekla volcano in south Iceland was performed to assess fluid evolution and toxic metal mobility during CO₂-rich fluid basalt interaction. These fluids provide a natural analogue for evaluating the consequences of CO₂ sequestration in basalt. The concentration of dissolved inorganic C in these groundwaters decreases from 3.88 to 0.746 mmol/kg with increasing basalt dissolution while the pH increases from 6.9 to 9.2. This observation provides direct evidence of the potential for basalt dissolution to sequester CO₂. Reaction path calculations suggest that dolomite and calcite precipitation is largely responsible for this drop in groundwater dissolved C concentration. The concentrations of toxic metal(loid)s in the waters are low, for example the maximum measured concentrations of Cd, As and Pb were 0.09, 22.8 and 0.06 nmol/kg, respectively. Reaction path modelling indicates that although many toxic metals may be initially liberated by the dissolution of basalt by acidic CO₂-rich solutions, these metals are reincorporated into solid phases as the groundwaters are neutralized by continued basalt dissolution. The identity of the secondary toxic metal bearing phases depends on the metal. For example, calculations suggest that Sr and Ba are incorporated into carbonates, while Pb, Zn and Cd are incorporated into Fe (oxy)hydroxide phases.