Kinetic fractionation of carbon-13 during calcium carbonate precipitation

Kinetic isotope fractionation of ¹³C during precipitation of CaCO₃ under open system conditions has been investigated. The isotope enrichment factor ?_HCO3^?-CaCO₃ varies between ?0.35 ± 0.23 and ?3.37 ± 0.36%. at 25°C depending on the rate of precipitation and mineralogy, the enrichment of ¹³C in the solid carbonate phase decreasing with increasing precipitation rate. An estimate of equilibrium ?_HCO3-Calcite of between ?1.83 ± 0.32 and ?2.26 ± 0.31%. is calculated from slow precipitation runs. A surface diffusion crystal growth model is used to describe the combination of kinetic isotope effects on thermodynamic isotope fractionation during rapid diffusion controlled crystal growth. Under slow precipitation conditions ?_{Calcite-Aragonite} was estimated as ?1.4%.; however, during rapid precipitation this fractionation appears to diminish and aragonite becomes less enriched in ¹³C.     

Effect of multiple precipitation inhibitors on calcium carbonate nucleation

Understanding the factors which affect the precipitation of calcium carbonate is important to the study of most natural waters. The effect of blends of precipitation inhibitors on calcium carbonate nucleation is investigated via a new test apparatus. Results indicate that the behavior of mixed inhibitors at minimum concentration levels is strictly additive, as predicted theoretically. The potential existence of a “super effective” inhibitor in nature or in industry is therefore precluded; this may have significant consequences for water-processing industries. The possibility of extending the upper limit of inhibitor effectiveness, imposed by the solubility of the calcium-inhibitor salts, through the use of mixed inhibitors is discussed. It is also possible that the notion of additive effects of mixed inhibitors may be valid in other systems, such as geochemical environments, potable water treatment systems, and industrial waters in which naturally occurring calcium carbonate inhibitors exist.     

微生物沉积碳酸钙固化砂土试验研究

砂土固化对增加砂土强度、减小渗透性极为有利,可提高和改善砂土的力学特性。通过培养基L进行菌种繁殖,研究了不同条件下的细菌生长特性;分析流出液的pH值和Ca~(2+)浓度的内在关系,揭示了固化砂柱的渗透性、无侧限抗压强度变化规律;通过微观结构阐释微生物固化效果,并研究了Ca~(2+)浓度与试样强度的关系。结果表明:2mL细菌母液加入100mL培养液并在30℃、pH为6,150rpm振动速度的条件下最适宜菌种生长;固化过程中,pH值逐渐降低,而Ca~(2+)浓度则增大;采用0.5mol/L胶凝液固化效果较好且固化周期短;固化后砂土颗粒间孔隙被生成的碳酸钙填充;试样渗透性最终降低3~4个数量级;流速越小,固化时间越长,固化效果越好;且固化试样破坏模式都是脆性破坏;采用尿素和醋酸钙混合溶液作为胶凝液,更能提高Ca~(2+)利用率。     

基于生物诱导碳酸钙沉淀的土体固化研究进展

基于微生物或脲酶诱导碳酸钙沉淀（MICP/EICP）的土体固化技术是近年来岩土和地质工程领域的研究热点之一。在系统回顾基于生物诱导碳酸钙沉淀的土体固化技术发展历程的基础上,重点阐述了MICP/EICP固化机制、土体孔隙结构、菌液和脲酶性质、胶凝液性质和固化方式等方面对碳酸钙特性影响的研究进展。研究结果表明：土体孔隙越小,越不利于微生物或脲酶入渗,固化均匀性越差;土颗粒接触点越多,可为碳酸钙提供的沉积点位越多,碳酸钙与土颗粒间的黏结和桥接作用越强,固化效果越好;一定菌液或脲酶浓度或脲酶活性范围内,碳酸钙的生成速率和生成总量随浓度及活性的增大而增大,但过高的浓度或活性易导致碳酸钙生成速率过快,从而在土体注入端发生堵塞;低浓度胶凝液得到的碳酸钙晶体更小,在土体中的分布更均匀;采用合适的注浆饱和度可提高具有黏结作用的碳酸钙的占比;采用多层交替注入或单相低pH值注入可提高碳酸钙在试样中分布的均匀性。基于碳酸钙沉淀特性的影响因素,提高固化土体的均匀性,验证其耐久性,室内试验结果在现场尺度的适应性和改进方案应该成为以后研究的重点。     

黄豆脲酶诱导碳酸钙沉淀多变量试验研究

植物源脲酶诱导碳酸钙沉淀（enzyme induced carbonate precipitation,简称EICP）可以显著改善砂土的工程力学特性,但在具体操作时,参数取值无对应规范,固化效果有待提升。基于黄豆脲酶,研究了温度、脲酶浓度、尿素浓度、钙浓度、pH值、钙源种类等变量对脲酶活性与碳酸钙沉淀的影响,并进行了沉淀物（碳酸钙晶体）的扫描式电子显微镜（scanning electron microscope,简称SEM）与X射线衍射（X-ray diffraction,简称XRD）测试,在此基础上开展了黄豆脲酶固化砂的无侧限抗压强度与固化效果试验研究。结果表明：脲酶活性随脲酶浓度的增加而线性增长,但存在温度阈值,温度超过阈值后,脲酶将完全失活,且阈值随脲酶浓度的增大而降低;尿素浓度与pH值共同影响脲酶活性,二者存在一个最优组合,当尿素浓度在0.1～1.0 mol/L时最优pH值为7,当尿素浓度在1.0～1.5 mol/L时最优pH值为8。脲酶是沉淀反应的催化剂,脲酶浓度越高,反应越完全,碳酸钙沉淀率越高;尿素与钙溶液则主要通过掺入量影响碳酸钙沉淀量,掺量比例宜为1:1,且二者浓度与pH值可通过影响脲酶活性来影响碳酸钙的沉淀情况;不同钙源对碳酸钙沉淀量的影响幅度不大。不同钙源沉淀碳酸钙晶体的成分与密度基本相同,但晶体结构差异较大,氯化钙沉淀碳酸钙晶体以块状为主,表面分布球状、类球状晶体,胶结面大,可作为EICP技术中较为理想的钙源。基于黄豆脲酶和氯化钙钙源固化砂的无侧限抗压强度约为掺粉煤灰砂样的6倍,通过SEM图像可发现,沉淀碳酸钙晶体包裹并黏结砂粒成为整体,固化效果非常理想。     

Interaction between dissolved silica and calcium carbonate: 1. Spontaneous precipitation of calcium carbonate in the presence of dissolved silica

The kinetics of spontaneous precipitation of CaCO₃ from aqueous solution in the presence of dissolved silica was investigated by recording pH as a function of time. The presence of dissolved silica, at concentrations below saturation with respect to the amorphous phase, decreases induction time for CaCO₃ nucleation, but does not affect CaCO₃ polymorphism. For a “pure” system without silica, the surface free energy, σ, determined from classical nucleation theory is 42 mJ m⁻². This agrees well with values reported in the literature for vaterite and indicates some degree of heterogeneous nucleation, which can occur because of the relatively low degree of supersaturation used for the experiments. In the presence of 1 and 2 mM silica, σ is 37 and 34 mJ m⁻², indicating an increasing degree of heterogeneous nucleation as the amount of polymeric silica increases. The ratio of Ca²⁺ to CO₃²⁻ activity was a governing parameter for determining which CaCO₃ polymorph precipitated. At high Ca²⁺ to CO₃²⁻ activity ratios, almost all initial solid was vaterite, whereas at low ratios, a mixture of vaterite and calcite was observed. In solutions with low Ca²⁺ to CO₃²⁻ activity ratios, the presence of silica at concentrations above saturation with respect to amorphous silica led to formation of only calcite and strongly influenced the crystalline structure and morphology of the precipitates. At high Ca²⁺ to CO₃²⁻ ratios, system behaviour did not differ from that without silica.     

Bio-geochemical reactive transport modeling of microbial induced calcite precipitation to predict the treatment of sand in one-dimensional flow

Microbial induced calcite precipitation (MICP) has been well studied to date in the laboratory as a viable alternative soil improvement technique that harnesses a natural bacterial process to induce cementation. Specifically, MICP utilizes the microbial process of hydrolysis of urea to induce pH increase leading to calcite precipitation. The study presented herein demonstrates the utility of a simple bio-geochemical reactive transport model to predict MICP in one-dimensional column experiments. The mathematical model was originally developed in the framework of the TOUGHREACT code to include kinetically controlled reaction rates for urea hydrolysis and calcite precipitation. Inverse modeling, via UCODE-2005, is utilized to calibrate and verify the model to experimental data including aqueous and mineral chemistry. Results indicate good agreement between data and simulated results for capturing the trends and magnitudes of a variety of MICP treatment schemes in half meter, one-dimensional flow columns. A design procedure is presented for predicting MICP in one-dimensional flow by sequentially coupling UCODE-2005 with TOUGHREACT.     

Effect of activated carbon on microbial-induced calcium carbonate precipitation of sand

Microbial-induced calcium carbonate precipitation (MICP) is a sustainable technique to transform or improve physical and mechanical properties of soils. This paper aims to study the effect of activated carbon (AC) on the property of bio-treated China Standard sand. Six sample groups were prepared considering various dosages of cementation solutions and bacterial suspensions. In each group, samples were prepared at six different AC ratios (0%, 0.2%, 0.5%, 1%, 2%, and 3% by weight of sand). Bacterial retention ability, calcium carbonate mass, unconfined compression strength (UCS), and microstructures of bio-treated samples were examined and evaluated in the presence of AC. It was found that the improved yield of calcium carbonate crystals and increased UCS were correlated to the enhanced bacterial retention ability attributed to AC. In addition, the test results showed that the amount of cementation solution played an important role in the MICP process, but volume variation of the bacterial suspension had a little effect on the bio-treated samples.     

Multicomponent reactive transport modeling of uranium bioremediation field experiments

A reaction network integrating abiotic and microbially mediated reactions has been developed to simulate biostimulation field experiments at a former Uranium Mill Tailings Remedial Action (UMTRA) site in Rifle, Colorado. The reaction network was calibrated using data from the 2002 field experiment, after which it was applied without additional calibration to field experiments performed in 2003 and 2007. The robustness of the model specification is significant in that (1) the 2003 biostimulation field experiment was performed with 3 times higher acetate concentrations than the previous biostimulation in the same field plot (i.e., the 2002 experiment), and (2) the 2007 field experiment was performed in a new unperturbed plot on the same site. The biogeochemical reactive transport simulations accounted for four terminal electron-accepting processes (TEAPs), two distinct functional microbial populations, two pools of bioavailable Fe(III) minerals (iron oxides and phyllosilicate iron), uranium aqueous and surface complexation, mineral precipitation and dissolution. The conceptual model for bioavailable iron reflects recent laboratory studies with sediments from the UMTRA site that demonstrated that the bulk (∼90%) of initial Fe(III) bioreduction is associated with phyllosilicate rather than oxide forms of iron. The uranium reaction network includes a U(VI) surface complexation model based on laboratory studies with Rifle site sediments and aqueous complexation reactions that include ternary complexes (e.g., calcium-uranyl-carbonate). The bioreduced U(IV), Fe(II), and sulfide components produced during the experiments are strongly associated with the solid phases and may play an important role in long-term uranium immobilization.     

The significance of Chara vegetation in the precipitation of lacustrine calcium carbonate

A significant portion of calcium carbonate is deposited in lake sediments as a result of biological processes related to the photosynthetic activity of phytoplankton in the pelagic realm and, in addition, macrophytes in the littoral zone. Lake Wigry, one of the largest lakes in Poland (north‐east Poland), is characterized by: (i) carbonate sediments with a CaCO₃ content exceeding 80% within the littoral zone; and (ii) large areas of submerged vegetation dominated by charophytes (macroscopic green algae, Characeae family). It is claimed that charophytes are highly effective in utilizing HCO₃^? and forming thick CaCO₃ encrustations. Thus, this study was aimed at evaluating the CaCO₃ production by dense Chara stands overgrowing the lake bottom reaching a depth of 4 m. In late July 2009, the fresh and dry mass of plants, the percentage contribution of calcium carbonate and the production of CaCO₃ per 1 m² were investigated along three transects at three depths (1 m, 2 m and 3 m, with each sample area equal to 0·0625 m²) per transect. The composition and structure of phytoplankton and the physico‐chemical properties of the water analysed in both the littoral and pelagic zones served as the environmental background and demonstrated moderately low fertility in the lake. The greatest dry plant mass exceeded 1000 g m^?2 and CaCO₃ encrustations constituted from 59% to over 76% of the charophyte dry weight. Thus, the maximum and average values of carbonates precipitated by charophytes were 685·5 and 438 g m^?2, respectively, which exceeded previously reported results. A correlation of carbonate production with the depth of Chara stands was detected, and intermediate depths offered the most favourable conditions for carbonate precipitation (589 g m^?2 on average). As precipitated carbonates are ultimately stored in bottom deposits, the results highlight the significance of charophytes in lacustrine CaCO₃ sedimentation.     

Bio-mediated calcium carbonate precipitation and its effect on the shear behaviour of calcareous sand

Calcareous sands have abundant intraparticle pores and are prone to particle breakage. This often leads to poor engineering properties, which poses a challenge to coastal infrastructure construction. A study using bio-cementation to improve the engineering properties of calcareous sand is presented in this paper. The macro- and microscopic properties of bio-cemented calcareous sand were characterized by drained triaxial tests and scanning electron microscopy observations. Experimental results show that the precipitated calcium carbonate can effectively fill the intra- and interparticle pores and bond adjacent particles, thus enhancing the shear strength of calcareous sand. The special structures (e.g. abundant intraparticle pores and rough surface) and mineral components (i.e. calcium carbonate) of calcareous sand are beneficial for improving bacterial retention in soil, which leads to a relatively uniform and dense calcium carbonate distribution on the sand particle surface, exhibiting a layer-by-layer growth pattern. This growth pattern and the abundant interparticle pores would result in less effective calcium carbonate. The strength enhancement of bio-cemented calcareous sand is significantly lower than that of bio-cemented silica sand at the same calcium carbonate content, which may be caused by the differences in the following: (a) soil skeleton strength; (b) the amount of effective calcium carbonate; and (c) interparticle pore-filling of calcium carbonate.

     

PHREEQC在地下水溶质反应-运移模拟中的应用

由于地下水污染的加剧,对地下水中污染物运移规律的研究日益受到重视。地下水中的溶质在运移过程中伴随着溶质组分间的化学反应,因此需要建立地下水溶质运移与化学反应的耦合模型。PHREEQC是近年来发展起来的描述局部平衡反应、动态生物化学反应的水文地球化学模拟软件。本文利用该模拟软件对一维地下水流动过程中溶质离子交换反应和动态氧化还原反应进行了模拟。结果表明,PHREEQC能够成功地进行溶质运移情况下复杂水化学反应模拟,但对于复杂地下水流和溶质运动的情况,有必要耦合其它的地下水流动和溶质运移软件来共同完成。     

微生物沉积碳酸钙固化珊瑚砂的试验研究

向珊瑚砂中注入巴斯德芽孢杆菌菌液、氯化钙和尿素的混合液,利用微生物沉积碳酸钙固化珊瑚砂;并对珊瑚砂固化体进行了渗透、强度及微观结构等试验。试验结果表明,巴斯德芽孢杆菌的活性随时间呈衰减趋势,但衰减速度缓慢,能较好地满足珊瑚砂固化的需要。随着菌液、氯化钙和尿素的混合液注入次数的增加,珊瑚砂柱渗透性逐步降低,最终渗透性降低了1～2个数量级。微生物固化后的珊瑚砂柱应力-应变曲线大致可分为3段,即应力随应变缓慢增加段、快速增加段以及突降段。试样发生压裂脆性破坏,无侧限抗压强度最高达到14 MPa左右。抗压强度随干密度增加而增大,随渗透性降低而增大。微生物固化后珊瑚砂颗粒被生成的碳酸钙完整的包裹,孔隙间极少见生成的碳酸钙,与普通硅砂微生物固化后的微观结构不同,较好地解释了渗透性降低不多的原因。     

碳酸钙纳米孔隙中凝聚水数学模型及实验研究

岩石纳米孔隙中的凝聚水与许多水文地质工程地质问题关系密切：干旱区凝聚水是维持当地生态平衡的重要水资源,石雕石刻文物保护中凝聚水问题是需要考虑的关键因素之一,页岩气工程中页岩纳米孔隙中的凝聚水对页岩气的聚集和流动有重要影响,全球碳循环问题中凝聚水会影响C02与碳酸盐岩的作用。本文给出了单位体积岩石形成的凝聚水的质量与温度、相对湿度、孔隙度、颗粒大小之间数学关系式。在这一关系式中,通过分离压理论计算吸附水,通过开尔文方程考虑了毛细作用。把解析计算结果与三个平行样四个不同湿度下的凝聚水量实验值对比,对所提出的数学表达式进行了验证。实验时选取直径500 nm的碳酸钙球形颗粒,采用夯实的办法加工成样,把样品置于恒温恒湿环境中令水汽在孔隙中凝聚,定期对样品称重计算凝聚水质量,直到凝聚过程达到平衡。     

Influence of lysozyme on the precipitation of calcium carbonate: a kinetic and morphologic study

Several mechanisms have been proposed to explain the interactions between proteins and mineral surfaces, among them a combination of electrostatic, stereochemical interactions and molecular recognition between the protein and the crystal surface. To identify the mechanisms of interaction in the lysozyme-calcium carbonate model system, the effect of this protein on the precipitation kinetics and morphology of calcite crystals was examined. The solution chemistry and morphology of the solid were monitored over time in a set of time-series free-drift experiments in which CaCO₃ was precipitated from solution in a closed system at 25°C and 1 atm total pressure, in the presence and absence of lysozyme. The precipitation of calcite was preceded by the precipitation of a metastable phase that later dissolved and gave rise to calcite as the sole phase. With increasing lysozyme concentration, the nucleation of both the metastable phase and calcite occurred at lower Ω_calcite, indicating that lysozyme favored the nucleation of both phases. Calcite growth rate was not affected by the presence of lysozyme, at least at protein concentrations ranging from 0 mg/mL to 10 mg/mL.Lysozyme modified the habit of calcite crystals. The degree of habit modification changed with protein concentration. At lower concentrations of lysozyme, the typical rhombohedral habit of calcite crystals was modified by the expression of {110} faces, which resulted from the preferential adsorption of protein on these faces. With increasing lysozyme concentration, the growth of {110}, {100}, and finally {001} faces was sequentially inhibited. This adsorption sequence may be explained by an electrostatic interaction between lysozyme and calcite, in which the inhibition of the growth of {110}, {100}, and {001} faces could be explained by a combined effect of the density of carbonate groups in the calcite face and the specific orientation (perpendicular) of these carbonate groups with respect to the calcite surface. Overgrowth of calcite in the presence of lysozyme demonstrated that the protein favored and controlled the nucleation on the calcite substrate. Overgrowth crystals nucleated epitaxially in lines which run diagonal to rhombohedral {104} faces.     

Multibody approach for reactive transport modeling in discontinuous-heterogeneous porous media

Computational Geosciences - In the context of long-term degradation of porous media, the coupling between fracture mechanics and reactive transport is investigated. A reactive transport model in a...     

酶诱导碳酸钙沉淀加固遗址土动力特性试验研究

中国西北地区地震频发,土遗址长期受到地震活动的不利影响。为了研究酶诱导碳酸钙沉淀技术（EICP）加固遗址土的动力特性,对1.55、1.65、1.75 g/cm³这3种初始干密度的遗址土进行EICP处理,并设置未经EICP处理的对照组。开展了不同围压、振动频率下的动三轴试验。结果表明：在相同动应力作用下,相比对照组,试验组的动应变更小,耗散的能量更少,阻尼比更小;在EICP加固后,随着干密度、围压、振动频率增大,可以降低动应变的产生,但这种效果依次减弱。动本构关系符合Hardin模型,干密度、围压、振动频率对模型参数a（动弹性模量）的影响程度逐渐减小;微观分析发现,EICP加固后,碳酸钙沉淀在土颗粒表面附着,填充孔隙,并与土颗粒相互胶结成致密结构,土体结构强度增强。     

微生物诱导碳酸盐岩沉淀过程及作用机理

微生物诱导碳酸钙沉淀(microbially induced calcium carbonate precipitation, MICP)是一种在自然界中广泛存在的生物矿化过程。由于MICP具有反应速度快、环境条件要求低、应用范围广、温室气体减排效应显著等特点,在地质、土木、水利、环境多个领域中广泛推广应用。文章在分析国内外相关研究成果的基础上,归纳整理出反硝化过程、硫酸盐还原作用、尿素分解作用等多种微生物诱导下碳酸钙矿化途径和作用机制。以尿素分解菌为代表,重点讨论微生物诱导碳酸盐沉淀过程中pH、温度、离子浓度等环境因素对生成矿物晶型晶貌等方面的影响,总结了MICP的环境应用机制,即环境中的重金属元素通过替换作用替换矿化矿物中的Ca²⁺或CO₃²⁻从而被固定。MICP作为一种简单高效的地质环境过程,在生态环境修复领域具有广阔的应用前景。     

The formation of iron hydroxide coatings in an Emscher Marl: inverse reactive transport modeling of reactive surface area

The possible effects of iron oxide coatings on the reactive surface area of calcite in column experiments have been studied and then modeled numerically. A column with six compartments separated by teflon filters was packed with Emscher Marl (essentially calcite). The marl was initially mixed with corundum as an internal standard. Hydrochloric acid with pH 3 was percolated through the column for a given period, after which the mineralogical changes were quantified by X-ray diffraction ex-situ. Then, the column compartments were re-filled and again percolated with HCl. This procedure was repeated five times. The losses and gains of calcite in the column compartments provided the data basis for modeling the entire experiment with the reactive transport code TOUGHREACT using a kinetic rate law. The experimental results showed that during the first period, loss of calcite in the first compartment is about 50 % less than that determined from the theoretical analysis. This showed the entrance of acid into the higher compartments through preferential flow paths (wormholes) which was observed at the boundary between sample and cell wall. This pattern could also be verified by the relatively high Peclet and low Damköhler numbers, showing a strongly advection-dominant system. Apart from calcite dissolution, structural Fe²⁺ released from calcite oxidized and formed iron hydroxide (FeOOH) coatings along preferential fluid pathways. Despite specific assumptions such as using pure calcite in the model, a comparison between modeling results and lab observations is instructive. The simulated calcite change patterns in the most compartments are consistent with the experiments. Some discrepancies are noted in the last compartment, which may bring the attention to a need for model improvements.