Experimental study of potential wellbore cement carbonation by various phases of carbon dioxide during geologic carbon sequestration

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.     

Generation of homologous porphyrins under simulated geochemical conditions

Crude oils generally contain at least one symmetrical homologous series of porphyrins, which is usually centered at m/e 476 (DPEP) or m/e 478 (etioporphyrin). Simulated geochemical conditions in the present study resulted in decarboxylations and alkylations which ultimately led to the synthesis of homologous porphyrins from a single porphyrin. In several series of closed tube experiments, mesoporphyrin IX dimethylester (MPDME) was mixed with a variety of constituents including benzene, acetic acid, propionic acid, water and clay; the experiments were performed at temperatures between 135°C and 400°C at time intervals up to 80 days. Dealkylation, alkylation, hydrolysis, decarboxylation and metallation products were observed. An unsymmetrical homologous series of porphyrins was produced from MPDME. The dominant mass was m/e 478 (corresponding to a double deoarboxylation). Dealkylation products in multiples of 14 amu below the m/e 478 peak comprised the other members of the series. Cu-MPDME also produced homologous porphyrins. These, however, exhibited symmetry about the dominant members, similar to the symmetry found for the porphyrins of most petroleums and oil shales.     

A geochemical clogging model with carbonate precipitation rates under hydrothermal conditions

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

硫酸盐侵蚀环境下水泥土的力学行为研究

针对含硫酸盐介质的环境水服役条件,通过室内模拟试验手段,研究了不同配合比参数和不同条件下水泥土的无侧限强度、弹性模量以及应力-应变的变化规律,分析了硫酸盐侵蚀环境下水泥土力学性能的劣化机理。结果表明,配合比参数以及环境条件对水泥土的无侧限抗压强度、弹性模量、应力-应变曲线有显著的影响;硫酸盐溶液中的水、硫酸根离子与水泥土之间的复杂物理、化学作用,影响水泥土内部微细观结构,从而对水泥土的力学性能存在显著劣化作用;且这种侵蚀作用在90d龄期内最为显著。     

Geochemical effects of CO2 sequestration in sandstones under simulated in situ conditions of deep saline aquifers

The geochemical effects of brine and supercritical CO₂ (SCCO₂) on reservoir rocks from deep (1500–2000 m) saline aquifers were examined via experimental simulation at in situ conditions. Dry sandstone samples were mounted in a triaxial cell and autoclave system, evacuated, and saturated with 1 M NaCl solution. The brine-rock system was allowed to react at 30 MPa confining pressure, 15 MPa pore fluid pressure, and 60 °C while SCCO₂ was injected at a pressure gradient of 1–2 MPa. The experiment was conducted for a period of 1496 h, during which fluids were periodically sampled and analyzed. The pH measured in partially degassed fluid samples at 25 °C decreased from a starting value of 7.0–4.3 (9 days) and finally 5.1 after saturation with SCCO₂.     

Dissolution-precipitation reactions controlling fast formation of dolomite under hydrothermal conditions

In laboratory experiments, the precipitation of dolomite at ambient temperature is virtually impossible due to strong solvation shells of magnesium ions in aqueous media and probably also due to the existence of a more intrinsic crystallization barrier that prevents the formation of long-range ordered crystallographic structures at ambient surface conditions. Conversely, dolomite can easily form at high temperature (>100 °C), but its precipitation and growth requires several days or weeks depending on experimental conditions. In the present study, experiments were performed to assess how a single heat-ageing step promotes the formation of dolomite under high-carbonate alkaline conditions via dissolution-precipitation reactions. This reaction pathway is relevant for the so-called hydrothermal dolomite frequently observed in carbonate platforms, but still ill-defined and understood. Our precipitation route is summarized by two main sequential reactions: (1) precipitation of Mg-calcite at low temperature (∼20 °C) by aqueous carbonation of synthetic portlandite (Ca(OH)₂) in a highly alkaline medium (1 M of NaOH and 1 M of MgCl₂), leading to precipitation of oriented nanoparticles of low- and high-Mg calcite (∼79 wt%) coexisting with aragonite (∼18 wt%) and brucite (∼3 wt%) after 24 h; (2) fast dolomitization process starting from 1 h of reaction by a single heat-ageing step from ∼20 to 200, 250 and 300 °C. Here, the Mg-calcite acts as a precursor that lowers the overall kinetics barrier for dolomite formation. Moreover, it is an important component in some bio-minerals (e.g. corals and seashells). Quantitative Rietveld refinements of XRD patterns, FESEM observations and FTIR measurements on the sequentially collected samples suggest fast dolomite precipitation coupled with dissolution of transient mineral phases such as low-Mg calcite (Mg < 4 mol%), high-Mg calcite (Mg > 4 mol%), proto-dolomite (or disordered dolomite; Mg > 40 mol%) and Ca-magnesite. In this case, the dolomite formation rate and the time-dependent mineral composition strongly depend on reaction temperature. For example, high-purity dolomitic material (87 wt% of dolomite mixed with 13 wt% of magnesite) was obtained at 300 °C after 48 h of reaction. Conversely, a lower proportion of dolomite (37 wt%), mixed with proto-dolomite (43 wt%), Ca-magnesite (16 wt%) and high-Mg calcite (4 wt%), was obtained at 200 °C after 72 h. The present experiments provide an additional mechanism for the massive dolomite formation in sedimentary environments (ex. deep sea organic-rich carbonate-sediments) if such sediments are subjected to significant temperature variations, for example by hot fluid circulations related to volcanic activity. In such systems, organic degradation increases the carbonate alkalinity (HCO₃⁻) necessary to induce the dolomitization process at low and high temperature.     

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.     

Effect of the water/cement ratio on concrete behavior under extreme loading

This study focuses on identifying concrete behavior under severe triaxial loadings (near field detonation or ballistic impacts). In order to reproduce high stress levels with well‐controlled loading paths, static tests have been carried out on concrete samples by mean of a very high‐capacity triaxial press (stress levels on the order of 1 GPa). It is a longstanding fact that the water/cement ratio (W/C), upon entering the concrete composition, is a major parameter affecting the porosity and strength of the cement matrix of hardened concrete. The objective of this article is to quantify the effect of this ratio on concrete behavior under conditions of high confinement. From the composition of a reference ‘ordinary’ concrete (i.e. W/C=0.6), two other concretes have been produced with W/C ratios equal to 0.4 and 0.8, respectively. This article presents experimental results and their analysis regarding the effect of water/cement ratio (W/C) on concrete behavior under high confinement. It shows that when placed under high confinement, concrete behaves like a granular stacking composed of concrete without any influence from the level of cement matrix strength. Copyright © 2009 John Wiley & Sons, Ltd.     

Effect of geochemical conditions on fate of organic compounds in groundwater

In situ microcosms were successfully used to study the degradation of a range of organic compounds in two pristine aquifers, one aerobic (Vejen) and one anaerobic (Villa Farm). Degradation and sorption behavior in the laboratory column microcosms packed with Villa Farm sediment was very similar to that in the in situ microcosms. However, when the columns were packed with quartz and equilibrated with aerated Villa Farm groundwater, behavior mirrored that at Vejen, indicating that oxygen rather than sediment or groundwater composition was the critical parameter. The aromatic and polyaromatic compounds (benzene, toluene,o-xylene, naphthalene) degraded under aerobic conditions only. The organochlorine compounds (trichloroethylene, tetrachloroethylene, 1,1,1-trichloroethane, 1,4-dichlorobenzene and 1,2-dichlorobenzene) showed little or no sign of degradation either aerobically or anaerobically. Interpretation of the data was complicated by strong sorption to the Villa Farm sediment but tetrachloromethane, nitrobenzene, ando-nitrophenol appeared to degrade under anaerobic conditions only. Phenol degraded rapidly under both sets of conditions.     

不同法向边界条件接触面三维力学特性的试验研究

运用最新研制的80 t三维多功能土工试验机对粗粒土与结构接触面在3种典型法向边界条件下的三维力学特性进行了试验研究。结果表明,接触面法向边界条件对其力学特性有重要影响,不同法向边界条件下接触面表现出了一些相似和不同的力学响应：(1)接触面总体上剪缩或有剪缩趋势,但数值不同;(2)除常应力条件外,接触面切向应力-切向位移关系曲线同一循环内一般不闭合,不同循环也不重合;(3)3种法向边界条件下接触面应力比-切向位移关系曲线同一循环内基本闭合,不同循环也基本重合,且形状较为相似,均呈椭圆形;(4)接触面静、动抗剪强度指标随法向边界条件变化不大,但动抗剪强度则差别很大。     

Reaction and diffusion at the reservoir/shale interface during CO2 storage: Impact of geochemical kinetics

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.     

Arsenic enrichment in groundwater of West Bengal,India: geochemical evidence for mobilization of As under reducing conditions

The mechanism of As release and source(s) of As has been investigated in a small part of a watershed in the Murshidabad district of West Bengal. Analyses include major ion and trace element concentrations, as well as O, H and S isotope ratios of groundwater, surface water and a thermal spring. The results indicate that all water samples belong to the Ca–HCO₃ type, except for the thermal spring which is of the Na–HCO₃ type. Shallow and deeper groundwaters have distinct hydrochemical features. High As contents were registered only in the deeper groundwater horizon. Factor analysis and the distribution pattern of major and trace elements indicate that As is present in the aquifer as a scavenged phase by Fe(III) and to a lesser extent by Mn(IV) phases. The release of As into the groundwater occurs gradually in successive stages, corresponding to the actual redox state in the aquifer. The main stage of As release is related to the bacterial reduction of Fe(III) to Fe(II) (i.e. to the simultaneous dissolution of Fe oxyhydroxides). Low redox conditions in highly polluted areas are indicated by low SO₄ concentration and high δ³⁴S values. During bacterial SO₄ reduction, residual SO₄ in groundwater is depleted in the lighter S isotope (³²S). However, the cause of the gradual decrease of the redox state in the groundwater is still not well understood.     

新疆巴什布拉克铀矿床成矿地球化学环境分析

从地球化学角度,利用古气候条件和相关地球化学指标分析,指出研究区赋矿岩石形成于干旱的氧化环境;通过分析与铀矿化常见伴生元素组合结果,指出目的层曾遭受过不同程度还原性流体的改造,并在构造抬升期,地表氧化性流体顺层对目的层进行了再次改造,铀矿化则发生于两种不同性质流体混合改造部位。     

Identifying oceanographic conditions conducive to coastal impacts on temperate open coastal beaches

Natural Hazards - Warnings issued by meteorological or oceanographic agencies are a common means of allowing people to prepare for likely impactful events. Quantifying the relationships between...     

Mineralogy and geochemical behaviour during weathering of greenstone belt under tropical dry conditions in the extreme North Cameroon (Central Africa)

Mineralogy, major, trace and rare earth elements of a weathering profile developed on tertiary greenstone belt in the extreme North Cameroon are reported. The aim of which was to investigate mineralogical evolution and element mobilization and redistribution during weathering under dry tropical climate. The weathering profile consists of four main horizons: (1) a spheroidal weathering zone constituted by a corestone–shell complex, (2) a C horizon, (3) a Bw horizon and an Ah horizon. The results indicate that nontronite, a Fe-rich smectite, is the exclusive clay mineral formed in the exfoliated shells and the C horizon. It is associated with kaolinite in the upper horizons. The coexistence of these two clay minerals induced a decrease of CEC and pH which becomes neutral. The weathering index (WI) values reveal that weathering becomes more and more intensive from the corestone up to Bw horizon, which is the most weathered horizon in the weathering profile. Mass balance calculations, using Th as immobile element, indicate that Ti is quite mobile and that Al and Fe are relatively enriched at the bottom and strongly leached at the top of the profile. Alkalis and alkaline earth elements are strong leached through out the profile, except Ca which displays similar trend as Al and Fe. The same goes for LILE (Cs, Sr), TTE (Cr, Co, Ni) and HSFE (Y, Nb, Hf). In opposite, REE are depleted at the bottom and enriched in the upper horizons, with more enrichment for LREE than for HREE. It appears that weathering of greenstone belt causes a fractionation of HREE and induces a concentration of LREEs. Ce and Eu anomalies display opposite behaviour.     

深厚砂黏分界处不同工况下多圈管冻结温度场特性

多圈管冻结壁设计方案是解决深冻结问题的有效方法,为研究深厚砂黏层分界处不同工况下多圈管冻结温度场特性,采取分界处原黏性土XRD试验结果,利用ANSYS数值模拟冻结三圈管,对比分析了细砂土与膨胀性黏土在冻结管偏斜与不偏斜工况下温度场冻结壁形成与发展特性。研究表明：多圈管不偏斜冻结,细砂层与膨胀性黏土层冻结壁温度场均呈规则、对称、有序发展,主冻结中圈管间、内圈管间、中-内圈管间、中-外圈管间、外圈管依次形成交圈过程,随着冻结时间增加,中-内圈、中-外圈管间冻结温度由抛物线型发展为梯形降温形状,且温差减少,内、外圈管外侧呈倒八字型发展形态,内圈管内侧降温效果明显好于外圈管外侧。偏斜时,冻结壁温度场交圈降温不规则,冻结冷锋交圈叠加具有随机性和离散性。膨胀性黏土冻结壁形成时间严重滞后,偏斜、土性差异对冻结壁温度影响均较大,偏斜对膨胀性黏土影响尤其明显,与某矿冻结法凿井在地层-400 m以上砂黏分界处发生的多根冻结管断管事件较为吻合,研究成果可以为类似深层矿井冻结施工提供参考。     

冻结作用下粉土-混凝土接触面抗拉强度试验研究

为探究冻结作用下土与结构接触面抗拉强度的影响因素及变化规律, 开展了冻结状态下多种含水率、 温度及干密度的粉土-混凝土接触面抗拉强度正交试验研究。试验结果表明： 在试验温度下,粉土-混凝土接触面的冻结抗拉强度约为饱和黄土的1/10, 粉质黏土的1/10 ~ 1/7; 含水率对接触面的冻结抗拉强度影响最大, 其次是温度、 干密度; 在试验含水率范围内, 接触面的冻结抗拉强度与含水率正相关; 温度降低会增大接触面冻结抗拉强度, 在-2 ℃至-6 ℃, 冻结抗拉强度迅速增长, 在-6 ℃以后, 冻结抗拉强度的增长速率显著减小。结果证明： 低温、 高含水率、 低干密度条件下, 接触面冻结抗拉强度达到最佳; 三种因素对接触面冻结抗拉强度具有不同的影响程度, 其中含水率、 温度影响显著, 干密度影响不显著; 在试验含水率区间内, 接触面冻结抗拉强度随含水率增长呈线性增长态势, 且含水率、 温度之间存在交互作用; 随温度降低, 存在一临界负温, 接触面冻结抗拉强度由迅速增长转为缓慢增长。     

Dissolution of Columbia River Basalt under mildly acidic conditions as a function of temperature: Experimental results relevant to the geological sequestration of carbon dioxide

Increasing attention is being focused on the rapid rise of CO₂ levels in the atmosphere, which many believe to be the major contributing factor to global climate change. Sequestering CO₂ in deep geological formations has been proposed as a long-term solution to help stabilize CO₂ levels. However, before such technology can be developed and implemented, a basic understanding of H₂O–CO₂ systems and the chemical interactions of these fluids with the host formation must be obtained. Important issues concerning mineral stability, reaction rates, and carbonate formation are all controlled or at least significantly impacted by the kinetics of rock–water reactions in mildly acidic, CO₂-saturated solutions. Basalt has recently been identified as a potentially important host formation for geological sequestration. Dissolution kinetics of the Columbia River Basalt (CRB) were measured for a range of temperatures (25–90 °C) under mildly acidic to neutral pH conditions using the single-pass flow-through test method. Under anaerobic conditions, the normalized dissolution rates for CRB decrease with increasing pH (3 ? pH ? 7) with a slope, η, of −0.15 ± 0.01. Activation energy, E_a, has been estimated at 32.0 ± 2.4 kJ mol⁻¹. Dissolution kinetics measurements like these are essential for modeling the rate at which CO₂-saturated fluids react with basalt and ultimately drive conversion rates to carbonate minerals in situ.