On the potential for CO2 mineral storage in continental flood basalts – PHREEQC batch- and 1D diffusion–reaction simulations

Continental flood basalts (CFB) are considered as potential CO₂ storage sites because of their high reactivity and abundant divalent metal ions that can potentially trap carbon for geological timescales. Moreover, laterally extensive CFB are found in many place in the world within reasonable distances from major CO₂ point emission sources. Based on the mineral and glass composition of the Columbia River Basalt (CRB) we estimated the potential of CFB to store CO₂ in secondary carbonates. We simulated the system using kinetic dependent dissolution of primary basalt-minerals (pyroxene, feldspar and glass) and the local equilibrium assumption for secondary phases (weathering products). The simulations were divided into closed-system batch simulations at a constant CO₂ pressure of 100?bar with sensitivity studies of temperature and reactive surface area, an evaluation of the reactivity of H₂O in scCO₂, and finally 1D reactive diffusion simulations giving reactivity at CO₂ pressures varying from 0 to 100?bar. Although the uncertainty in reactive surface area and corresponding reaction rates are large, we have estimated the potential for CO₂ mineral storage and identified factors that control the maximum extent of carbonation. The simulations showed that formation of carbonates from basalt at 40?C may be limited to the formation of siderite and possibly FeMg carbonates. Calcium was largely consumed by zeolite and oxide instead of forming carbonates. At higher temperatures (60 ?C 100?C), magnesite is suggested to form together with siderite and ankerite. The maximum potential of CO₂ stored as solid carbonates, if CO₂ is supplied to the reactions unlimited, is shown to depend on the availability of pore space as the hydration and carbonation reactions increase the solid volume and clog the pore space. For systems such as in the scCO₂ phase with limited amount of water, the total carbonation potential is limited by the amount of water present for hydration of basalt.     

Secondary Silicates as a Barrier to Carbon Capture and Storage in Deccan Basalt

Investigating the immobilization of CO2, previous basalt-water-CO2 interaction studies revealed the formation of carbonates over a short period, but with the extensive formation of secondary silicates (SS). The mechanisms involved in these processes remain unresolved, so the present study was undertaken to understand secondary mineral formation mechanisms. XRPD and Rietveld refinement data for neo-formed minerals show a drastic decrease in the Ca-O bond length, with the calcite structure degenerating after 80 h (hours). However, SEM images and EDS data revealed that a longer interaction time resulted in the formation of chlorite and smectite, adjacent to basalt grains which prevent basalt-water-CO2 interaction to form carbonates, thus restricting carbonate formation. As a result of this, the CO2 mineralization rate is initially high (till 80 h), but it later reduces drastically. It is evident that, for such temperature-controlled transformations, low temperature is conducive to minimizing SS surface coating at the time of mineral carbonation.     

海拉尔盆地贝尔凹陷含片钠铝石沉凝灰岩的成岩作用

以海拉尔盆地贝尔凹陷大磨拐河组-伊敏组的含片钠铝石火山碎屑岩为研究对象,采用偏光显微镜、扫描电镜及配套能谱、茜素红 S染色、阴极发光和X 射线衍射分析等技术手段,对研究样品的岩石类型、自生矿物种类及共生序列进行了详细研究。贝尔凹陷发育片钠铝石的宿主岩石类型为沉凝灰岩,自生矿物以发育片钠铝石、铁白云石和菱铁矿三种碳酸盐矿物为主,片钠铝石含量高达25%。成岩共生序列为菱铁矿Ⅰ→高岭石、石英次生加大→片钠铝石→微晶石英→方解石→铁白云石→菱铁矿Ⅱ→沥青。不同于国内外其它地区发现片钠铝石的主要产状为充填孔隙,本区内发育的片钠铝石以交代长石、石英、岩屑颗粒和高岭石基质为赋存特征,表明沉凝灰岩中的长石、岩屑、高岭石基质可以为其提供金属离子物质来源,并在CO2参与下,与成岩流体反应生成片钠铝石。大量碳酸盐矿物（15-44%）的发育证明了火山碎屑岩具有较高的CO2矿物捕获能力。     

Origin and diagenetic evolution of Ca–Mg–Fe carbonates in some coalfields of Japan

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

Potential for offsetting diamond mine carbon emissions through mineral carbonation of processed kimberlite: an assessment of De Beers mine sites in South Africa and Canada

De Beers kimberlite mine operations in South Africa (Venetia and Voorspoed) and Canada (Gahcho Kué, Victor, and Snap Lake) have the potential to sequester carbon dioxide (CO₂) through weathering of kimberlite mine tailings, which can store carbon in secondary carbonate minerals (mineral carbonation). Carbonation of ca. 4.7 to 24.0 wt% (average = 13.8 wt%) of annual processed kimberlite production could offset 100% of each mine site’s carbon dioxide equivalent (CO₂e) emissions. Minerals of particular interest for reactivity with atmospheric or waste CO₂ from energy production include serpentine minerals, olivine (forsterite), brucite, and smectite. The most abundant minerals, such as serpentine polymorphs, provide the bulk of the carbonation potential. However, the detection of minor amounts of highly reactive brucite in tailings from Victor, as well as the likely presence of brucite at Venetia, Gahcho Kué, and Snap Lake, is also important for the mineral carbonation potential of the mine sites.

     

活性MgO碳化固化土的抗硫酸盐侵蚀性研究

既有研究表明,活性MgO固化土经CO2碳化几小时后其强度能达到甚至超过28 d的水泥固化土强度,碳化反应生成镁的碳酸化合物能有效降低固化土的含水率和孔隙率,提高土颗粒胶结能力。通过室内试验进一步研究碳化固化土的抗硫酸盐侵蚀特性。采用硫酸钠溶液、硫酸镁溶液浸泡碳化固化土,对浸泡不同龄期后的碳化固化土进行无侧限抗压强度试验和微观测试（XRD,SEM和MIP）,并与硫酸盐侵蚀后的水泥固化土进行试验对比。结果表明：活性MgO固化粉土碳化3 h,试样的无侧限抗压强度可达5 MPa左右,经硫酸盐溶液浸泡28 d后其强度基本保持不变,试样质量变化也不大;而水泥土试样的早期强度（7 d）则有一定增长,随龄期增长,强度大大降低,质量则明显增长。通过对硫酸盐侵蚀前后的碳化土的微观机制分析,发现活性MgO碳化固化土中的镁碳酸化合物的化学成分并未发生明显变化,孔隙结构也未明显改变,从而保证其强度稳定。因此,活性MgO固化粉土碳化后具有比水泥固化土更强的抗硫酸盐侵蚀能力。     

CO2矿化封存条件下玄武岩溶解反应速率模型

实施CO2补集与地质封存是目前降低大气中CO2含量、减轻温室效应的有效途径。在所能利用的封存方式中,CO2矿化封存最为安全、稳定。在能实施矿化封存的岩石介质中,玄武岩封存潜力巨大,且岩石溶解反应过程是矿化沉淀过程的基础;因此,研究玄武岩溶解反应速率十分必要。在构成玄武岩的单一矿物与缓冲溶剂的反应速率模型的基础上,提出不同温度下玄武岩样品在超临界CO2水溶液中的溶解速率模型,并通过室内实验,利用采自山东省临朐县的玄武岩岩心样品,在45~100 ℃、10 MPa条件下,与超临界CO2－纯水反应,并运用最小二乘法确定模型中相关参数。同时利用57 ℃、72 ℃、92 ℃ 3个温度下的模型计算值与实验值对模型进行验证,结果证明了模型的准确性和可靠性,研究结果可直接应用于CO2地质封存条件下玄武岩溶解速率的计算。     

武汉东湖淤泥碳化-固化试验研究

引入活性MgO-粉煤灰固化材料,采用碳化-固化联合技术处理武汉东湖疏浚淤泥,通过无侧限抗压强度、扫描电镜和压汞试验,研究加压碳化模式、碳化时间、MgO-粉煤灰配比和固化剂掺量等因素下CO2碳化作用对固化淤泥力学性质和微观结构的影响。结果表明：活性MgO-粉煤灰固化淤泥碳化后抗压强度进一步增长,应力-应变关系曲线压密阶段应变缩小;不同固化剂配比的东湖淤泥试样具有不同的最佳加压模式,而加压模式决定了相同碳化时间下固化淤泥CO2吸入量,从而影响碳化-固化淤泥试样抗压强度;活性MgO掺量低时试样抗压强度整体较低,强度随碳化时间增加先增大后减小;MgO掺量较高时,碳化试样强度随碳化时间快速达到较高值,随后增长缓慢。微观分析表明：水碳镁石、球碳镁石和碳酸镁石等镁碳酸盐是碳化-固化联合技术增强淤泥强度的主要原因,其膨胀性和胶结作用促使土体中团粒内孔隙向颗粒间孔隙转化,土体更密实,抗压强度增加。     

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.     

基性、超基性岩: 二氧化碳地质封存的新途径

CO₂地质封存是控制全球CO₂净排放量的有效手段.自然界存在大量基性、超基性岩石的碳酸盐风化作用, 与CO₂反应生成稳定的碳酸盐矿物.影响基性、超基性岩石与CO₂反应速率的因素有温度、压力、pH值、流体流动速率以及与矿物接触的表面积等.矿物在反应过程中放热可以使碳酸盐化体系进入自我加热的良性循环, 同时控制流体的流动速率可以保持最佳温度并使反应速率最大化.蛇绿岩中的橄榄岩、大陆玄武岩和深海玄武岩在地球表层广泛分布, 可贮存大量CO₂.目前研究表明此方法在技术上可行, 经济成本上有优势.因此, 基性、超基性岩石具有封存CO₂的巨大潜力, 可以作为地质封存CO₂的新途径.      

Numerical simulation of CO2 disposal by mineral trapping in deep aquifers

Carbon dioxide disposal into deep aquifers is a potential means whereby atmospheric emissions of greenhouse gases may be reduced. However, our knowledge of the geohydrology, geochemistry, geophysics, and geomechanics of CO₂ disposal must be refined if this technology is to be implemented safely, efficiently, and predictably. As a prelude to a fully coupled treatment of physical and chemical effects of CO₂ injection, the authors have analyzed the impact of CO₂ immobilization through carbonate mineral precipitation. Batch reaction modeling of the geochemical evolution of 3 different aquifer mineral compositions in the presence of CO₂ at high pressure were performed. The modeling considered the following important factors affecting CO₂ sequestration: (1) the kinetics of chemical interactions between the host rock minerals and the aqueous phase, (2) CO₂ solubility dependence on pressure, temperature and salinity of the system, and (3) redox processes that could be important in deep subsurface environments. The geochemical evolution under CO₂ injection conditions was evaluated. In addition, changes in porosity were monitored during the simulations. Results indicate that CO₂ sequestration by matrix minerals varies considerably with rock type. Under favorable conditions the amount of CO₂ that may be sequestered by precipitation of secondary carbonates is comparable with and can be larger than the effect of CO₂ dissolution in pore waters. The precipitation of ankerite and siderite is sensitive to the rate of reduction of Fe(III) mineral precursors such as goethite or glauconite. The accumulation of carbonates in the rock matrix leads to a considerable decrease in porosity. This in turn adversely affects permeability and fluid flow in the aquifer. The numerical experiments described here provide useful insight into sequestration mechanisms, and their controlling geochemical conditions and parameters.     

氯化铵浸取纤蛇纹石动力学研究

较低的矿物溶解率和反应剂的不可循环利用是CO2矿物封存发展的两大难题。针对这些问题,本文提出了一种新的以可循环的NH4Cl溶液作为中间媒介的CO2矿物封存工艺,并系统地研究了蛇纹石在氯化铵溶液中的液-固两相的反应动力学。实验研究发现:(1)纤蛇纹石的浸取符合Elovich模型,浸取过程基本在1h左右完成,在100℃、5mol/L氯化铵溶液中,纤蛇纹石的浸取率达到12.67%;(2)温度对纤蛇纹石初始反应速率的影响显著,温度越高,反应速率越快;(3)当氯化铵浓度在1~5mol/L范围内变化时,它对镁离子浸取率的影响不明显,反应速率随着浓度的升高而有所增加;(4)本实验反应表现出来的活化能大小为129.56kJ/mol。      

四川省峨边县玄武岩特征及开发利用前景

四川省峨边县玄武岩矿资源丰富,但尚无开发利用纤维用玄武岩的矿山。从玄武岩的矿石组构、化学成分和玄武岩拉丝性能判别指标3个方面开展纤维用玄武岩评价工作。研究结果显示: 研究区致密块状玄武岩和杏仁状玄武岩多属拉斑系列与碱性系列的过渡型岩石,玻基玄武岩均为碱性系列; 拉斑玄武岩系列矿石的化学成分具有SiO₂含量较高、(K₂O+Na₂O)和TiO₂含量较低、FeO/MgO值较大的特征; 区内致密块状玄武岩适合连续玄武岩纤维生产,而杏仁状玄武岩的杏仁中含有石英和方解石等次矿物,玻基玄武岩具有火山玻璃成分含量高、杏仁状构造及酸度系数过高等特征,均不宜作为生产玄武岩纤维的原料。研究区玄武岩矿具备纤维用玄武岩资源储备地的潜力,建议采用综合开发的方式利用玄武岩矿资源。     

Secular variations in seawater chemistry controlling dolomitization in shallow reflux systems: insights from reactive transport modelling

Dolomitization often plays a critical role in the pore network development of platform carbonates, with implications for reservoir quality distribution. Understanding both the hydrological system driving dolomitization and the chemistry of the fluids involved is fundamental to constrain predictions of the geometry and the petrophysical properties of dolomite bodies. Here, the role of secular variations in seawater Mg/Ca as a control on dolomitization and early porosity modification was evaluated using one‐dimensional reactive transport models and fluids based on modern (aragonite sea), Mississippian and Aptian (calcite sea) seawaters. The sensitivity of dolomitization to a range of extrinsic controls (brine salinity, temperature, fluid flow rate and pCO₂) and to intrinsic reactivity of the sediments (effective reactive surface area) was also explored. Simulations suggest faster calcite replacement by dolomite for seawaters with higher Mg/Ca, indicating that dolomitization potential is determined more by Mg/Ca rather than saturation index. Increasing evaporative concentration enhances reaction rate independent of the effect of enhanced density‐driven fluid flux. In addition to brine composition, effective surface area of precursor sediments and temperature exert a critical control on replacement rate, while secular variations of pH and carbonate alkalinity associated with changes in pCO₂ are only secondary controls. Above flow rates of 0·01 m yr^?1 replacive dolomitization is reaction‐limited rather than flux limited, favouring alteration of fine‐grained carbonates and suggesting that preferential alteration of grainstone units is rare unless head gradients are low. Post‐replacement dolomite cementation is flux dependent, and thus favoured in areas of high head gradient and high permeability sediments and, contrary to replacement, supersaturation is a more important driver than Mg/Ca. While uncertainties remain regarding low‐temperature dolomitization kinetics, the capability of numerical simulations to decouple individual controls provides new insights which can be used, in conjunction with traditional comparative sedimentology, to generate more rigorous conceptual models for individual reservoir settings.     

A reactive-transport model for weathering rind formation on basalt

Saprolite formation rates influence many important geological and environmental issues ranging from agricultural productivity to landscape evolution. Here we investigate the chemical and physical transformations that occur during weathering by studying small-scale “saprolites” in the form of weathering rinds, which form on rock in soil or saprolite and grow in thickness without physical disturbance with time. We compare detailed observations of weathered basalt clasts from a chronosequence of alluvial terraces in Costa Rica to diffusion-reaction simulations of rind formation using the fully coupled reactive transport model CrunchFlow. The four characteristic features of the weathered basalts which were specifically used as criteria for model comparisons include (1) the mineralogy of weathering products, (2) weathering rind thickness, (3) the coincidence of plagioclase and augite reaction fronts, and (4) the thickness of the zones of mineral reaction, i.e. reaction fronts. Four model scenarios were completed with varying levels of complexity and degrees of success in matching the observations. To fit the model to all four criteria, however, it was necessary to (1) treat diffusivity using a threshold in which it increased once porosity exceeded a critical value of 9%, and (2) treat mineral surface area as a fitting factor. This latter approach was presumably necessary because the mineral-water surface area of the connected (accessible) porosity in the Costa Rica samples is much less than the total porosity (Navarre-Sitchler et al., 2009). The model-fit surface area, here termed reacting surface area, was much smaller than the BET-measured surface area determined for powdered basaltic material. In the parent basalt, reacting surface area and diffusivity are low due to low pore connectivity, and early weathering is therefore transport controlled. However, as pore connectivity increases as a result of weathering, the reacting surface area and diffusivity also increase and weathering becomes controlled by mineral reaction kinetics. The transition point between transport and kinetic control appears to be related to a critical porosity (9%) at which pore connectivity is high enough to allow rapid transport. Based on these simulations, we argue that the rate of weathering front advance is controlled by the rate at which porosity is created in the weathering interface, and that this porosity increases because of mineral dissolution following a rate that is largely surface-reaction controlled.     

活性氧化镁碳化固化粉质黏土微观机制

以活性氧化镁碳化固化粉质黏土为研究对象,通过无侧限抗压强度试验、酸碱度测试、X射线衍射试验、压汞试验和扫描电镜试验,研究了不同初始含水率和碳化时间影响下活性氧化镁碳化加固粉质黏土的强度、pH值、碳化产物和微观结构等变化。根据碳化固化土强度与碳化产物含量及累积孔隙体积间的内在联系,提出了粉质黏土的碳化反应微观模型。结果表明：随碳化时间增加和初始含水率减小,碳化固化土的碳化产物含量增加、累积孔隙体积减小,同时氧化镁碳化加固土的强度提高;碳化固化土的pH值随碳化时间不断减小,而随初始含水率变化不大;最后提出了粉质黏土的碳化反应微观模型,确定了活性氧化镁固化粉质黏土在碳化约6.0 h时可获得最高强度。     

Reactivity of micas and cap-rock in wet supercritical CO2 with SO2 and O2 at CO2 storage conditions

Seal or cap-rock integrity is a safety issue during geological carbon dioxide capture and storage (CCS). Industrial impurities such as SO₂, O₂, and NOx, may be present in CO₂ streams from coal combustion sources. SO₂ and O₂ have been shown recently to influence rock reactivity when dissolved in formation water. Buoyant water-saturated supercritical CO₂ fluid may also come into contact with the base of cap-rock after CO₂ injection. Supercritical fluid-rock reactions have the potential to result in corrosion of reactive minerals in rock, with impurity gases additionally present there is the potential for enhanced reactivity but also favourable mineral precipitation.The first observation of mineral dissolution and precipitation on phyllosilicates and CO₂ storage cap-rock (siliciclastic reservoir) core during water-saturated supercritical CO₂ reactions with industrial impurities SO₂ and O₂ at simulated reservoir conditions is presented. Phyllosilicates (biotite, phlogopite and muscovite) were reacted in contact with a water-saturated supercritical CO₂ containing SO₂, or SO₂ and O₂, and were also immersed in the gas-saturated bulk water. Secondary precipitated sulfate minerals were formed on mineral surfaces concentrated at sheet edges. SO₂ dissolution and oxidation resulted in solution pH decreasing to 0.74 through sulfuric acid formation. Phyllosilicate dissolution released elements to solution with ∼50% Fe mobilized. Geochemical modelling was in good agreement with experimental water chemistry. New minerals nontronite (smectite), hematite, jarosite and goethite were saturated in models. A cap-rock core siltstone sample from the Surat Basin, Australia, was also reacted in water-saturated supercritical CO₂ containing SO₂ or in pure supercritical CO₂. In the presence of SO₂, siderite and ankerite were corroded, and Fe-chlorite altered by the leaching of mainly Fe and Al. Corrosion of micas in the cap-rock was however not observed as the pH was buffered by carbonate dissolution. Ca-sulfate, and Fe-bearing precipitates were observed post SO₂-CO₂ reaction, mainly centered on surface cracks and an illite rich illite-smectite precipitate quantified. Water saturated impure supercritical CO₂ was observed to have reactivity to rock-forming biotite, muscovite and phlogopite mineral separates. In the cap-rock core however carbonates and chlorite were the main reacting minerals showing the importance of assessing actual whole core.     

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 influence of submarine weathering of basalts on their partial melting during subduction

Compositional changes beyond that of simple hydration are present in most of the analyzed examples of submarine weathering of basalt. Recalculations of 278 analyses from the literature of altered basalts to simplified basalt, amphibolite and eclogite mineral assemblages result in significant increases of the quartz contents of the rock relative to fresh basalt in most examples. The increased quartz contents result in mineral assemblages that have enhanced potentials to generate andesitic partial melts from the basalt or amphibolite forms of most altered basalts and trondhjemitic partial melts from the eclogite form of most altered basalts.     

Origin of high manganese concentrations in coal mine drainage, eastern Tennessee

The origin of high dissolved manganese concentrations in slightly acidic mine runoff from a surface mine operated by the Cumberland Coal Company in eastern Tennessee was investigated. Mineralogical and chemical analyses were performed on 31 samples of sandstone, shale, coal, and mudstone from the mine to identify the sources and stratigraphic distribution of high extractable manganese contents in the spoil materials. The samples were analyzed for their bulk mineral content by X-ray diffraction, net acid-base potential, and reaction to 2 or 4 chemical extraction procedures. A limited number of samples were analyzed for petrographic characteristics, clay mineral composition by X-ray diffraction, and mineral compositions by electron microprobe. Analysis of the data and consideration of the geochemical conditions at the mine were used to identify probable sources for the high extractable manganese contents.The results indicate 2 prominent, independent sources of extractable manganese. The first source is exchangeable manganese on clay minerals (mainly illite + muscovite and chlorite) and is concentrated in shale and mudstone rock types. The second and more significant source is manganese in siderite concretions and cement, mainly in shale and mudstone. Comparison to other coal-bearing strata indicates that manganese-rich siderite is common in fresh- to brackish-water subaqueous sediments that overlie coal. This is especially the case for coals formed in wet, tropical environments.Ratios of manganese to calcium and magnesium in mine runoff suggest that manganese from siderite is the major cause of the high dissolved manganese contents. A conceptual model is developed to explain the high manganese contents of the mine runoff. Oxidation of pyrite creates mildly acidic waters that are subsequently partially neutralized by reaction with impure siderite. Solubilized manganese remains dissolved in the slightly acidic runoff water, whereas dissolved iron precipitates as ferric hydroxide or goethite. Consideration of data from other coal mining regions suggests that similar reactions involving impure siderite may be responsible for high manganese concentrations in acidic to slightly acidic mine runoff. Geochemical reaction path modeling of pyrite and impure siderite with rainwater illustrate how resulting water compositions may vary depending on pyrite to siderite ratios in spoil materials. Spoil water compositions from the Cumberland mine are largely consistent with reaction of pyrite and impure siderite in proportions observed in the sediments; however, deviations may be explained by minor mixing with waters that reacted only with impure siderite or clay mineral exchange reactions.