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1.
Highly supersaturated solutions of Ca2+ and CO2−3 ions rapidly precipitate amorphous calcium carbonate, ACC, the logarithmic thermodynamic solubility product of which is about −6.0 at 25°C. The ACC initially formed is transformed to a mixture of several crystalline calcium carbonate polymorphs within several minutes. The transformed polymorphs are vaterite and calcite at low temperature (14 to 30°C), and aragonite and calcite at high temperature (60 to 80°C). At intermediate temperatures (40 to 50°C) the formation of all three polymorphs was observed. Metastable polymorphs are gradually transformed to the stable form, calcite. It takes about 200 min at 25°C and 370 min at 30°C for the complete transformation of vaterite to calcite, and 1000–1300 min for that of aragonite to calcite at 60–80°C. At 50°C, vaterite is predominantly transformed at first to aragonite within 60 min, and then the aragonite is transformed to calcite in about 900 min. The results of the change in the ion activity product of the solution and the abundances of the polymorphs strongly suggest that the polymorphic transformation of vaterite and aragonite to calcite takes place through dissolution of the metastable phase and growth of the stable phase, calcite. The rate-determining step of the transformation is the growth of calcite. The relative abundance of vaterite becomes higher at 25°C with increasing concentrations of calcium and carbonate ions in the supersaturated solution. When the ion activity product of the initial supersaturated solution is lower than the solubility product of ACC at 25°C, only vaterite directly precipitates after some induction period. The vaterite crystals formed are free of calcite seeds and the vaterite saturated solutions are stable for several days.  相似文献   

2.
Xiao  Yang  He  Xiang  Wu  Wei  Stuedlein  Armin W.  Evans  T. Matthew  Chu  Jian  Liu  Hanlong  van Paassen  Leon A.  Wu  Huanran 《Acta Geotechnica》2021,16(10):3229-3237

A homogeneous microfluidic chip was used to investigate the pore-scale characteristics during the process of microbially induced calcium carbonate precipitation (MICP). An image-processing scheme was developed to measure the projecting areas of the precipitated calcium carbonate. Calcium carbonate first precipitated on the bacterium side before spreading to the rest of the chip. The distribution of calcium carbonate was more uniform along the length of the microchip than along the width. Raman back-scattering spectroscopy was used to examine the chemical composition of the precipitate, identifying calcite and vaterite as the main mineral phases. Bacterium traces were noted on crystal surfaces in SEM images, suggesting a higher adsorptive capacity for irregular precipitates than well-shaped crystals.

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3.
周根陶  郑永飞 《地质科学》2000,35(3):325-335
通过缓慢分解Ca2+-Mg2+-HCO3--Cl--H2O溶液和以菱锶矿(或碳钡矿、白铅矿)为晶种的附晶生长法,在0-90℃温度范围内定向合成了碳酸钙同质多象变体.矿物合成实验结果表明,随着温度升高,有利于亚稳态文石和不稳定六方方解石的生成;随着溶液中Mg2+离子浓度增大和Ca(HCO3)3溶液浓度减小,均有利于亚稳态文石的形成.以XRD和SEM技术为实验手段,详细研究了碳酸钙同质多象转变过程.结果显示:在流体参与的情况下,文石→方解石和六方方解石→方解石的同质多象转变速率很快,并且其转变的矿物学机理为溶解/再沉淀.  相似文献   

4.
产脲酶细菌普遍存在于自然界,其对碳酸钙的矿化作用被广泛用于工程地质和环境等各项工程领域;本研究旨在从北戴河新河河口海洋沉积物中分离产脲酶细菌,探讨其诱导形成碳酸钙的特征,为地质与工程领域的应用提供良好的材料.从海洋沉积物样品中共分离出33株细菌,经筛选,其中有10株细菌具有产脲酶活性,16S rRNA基因序列分析表明:...  相似文献   

5.
淡水珍珠中球文石的XRD谱   总被引:5,自引:1,他引:5  
马红艳  崔福斋 《矿物学报》2003,23(4):371-373
球文石是CaCO3的同质多象变体,在自然界中很少出现。对不同质量淡水珍珠进行XRD物相分析,结果表明不同颜色的优质淡水珍珠中几乎全部由文石组成,方解石不发育;劣质淡水珍珠中主要含有文石、球文石;在劣质的淡水无光珠发现有球文石,可能与这些珍珠混有较多的有机物有关,文中例举了含球文石与不含球文石的淡水珍珠XRD谱。  相似文献   

6.
浙江雷甸淡水无光珠中球文石的首次确认   总被引:1,自引:2,他引:1  
球文石(Vaterite)是CaCO3很不稳定的同质多象变体,在自然界里很少出现,通过光学显微镜在淡水无光珠中发现球文石尚属首次,本文研究了淡水无光珠内球文石的显微特征、X射线粉晶衍射特征及显微红外光谱特征,研究结果表明淡水无光珍珠内球文石粉晶衍射由强至弱五个强峰的d值为0.3266,0.2723,0.3553,0.1811,0.2057nm;其红外光谱特征波数为1489,1450,1420,1087,1050,876,830,762,743cm^-1。球文石的存在是影响淡水珍珠品质的主要内在因素之一。  相似文献   

7.
青海湖是我国唯一报道过的现代湖底沉积物中白云石、方解石和文石等多种碳酸盐矿物共存的高原内陆咸水湖泊.以青海湖水和除菌青海湖水作为载体,以CaCl2和MgCl2·6 H2O作为反应原料,在实验室常温条件下采取控制变量法制备出不同浓度Mg2+参与下的钙质沉淀物,探讨Mg2+浓度对沉淀物类型的影响.仅添加CaCl2时,青海湖...  相似文献   

8.
Bacterially mediated mineralization of vaterite   总被引:1,自引:0,他引:1  
Myxococcus xanthus, a common soil bacterium, plays an active role in the formation of spheroidal vaterite. Bacterial production of CO2 and NH3 and the transformation of the NH3 to and OH, thus increasing solution pH and carbonate alkalinity, set the physicochemical conditions (high supersaturation) leading to vaterite precipitation in the microenvironment around cells, and directly onto the surface of bacterial cells. In the latter case, fossilization of bacteria occurs. Vaterite crystals formed by aggregation of oriented nanocrystals with c-axis normal to the bacterial cell-wall, or to the core of the spherulite when bacteria were not encapsulated. While preferred orientation of vaterite c-axis appears to be determined by electrostatic affinity (ionotropic effect) between vaterite crystal (0001) planes and the negatively charged functional groups of organic molecules on the bacterium cell-wall or on extracellular polymeric substances (EPS), analysis of the changes in the culture medium chemistry as well as high resolution transmission electron microscopy (HRTEM) observations point to polymorph selection by physicochemical (kinetic) factors (high supersaturation) and stabilization by organics, both connected with bacterial activity. The latter is in agreement with inorganic precipitation of vaterite induced by NH3 and CO2 addition in the protein-rich sterile culture medium. Our results as well as recent studies on vaterite precipitation in the presence of different types of bacteria suggest that bacterially mediated vaterite precipitation is not strain-specific, and could be more common than previously thought.  相似文献   

9.
Vaterite, a rare hexagonal CaCO3 polymorph, was identified in precipitates forming at a supraglacial sulfur spring, in Borup Fiord Pass, northern Ellesmere Island, Canadian High Arctic. Vaterite occurs in a precipitate mound along with calcite, gypsum, and native sulfur. The unusual conditions of the site, including an extremely cold climate, supersaturated alkaline waters, and the presence of gypsum, mimics conditions used to grow vaterite in laboratory experiments. Stable isotope data suggest that vaterite may preferentially form during colder periods of the year. Vaterite found at the site is characterized by 2- to 10-μm rounded to spherical shaped particles (comprising smaller 0.5- to 2-μm spheres) as both individuals and in chainlike structures. The spherical habit of vaterite resembles carbonate structures that have been interpreted to be organic; however, δ13C values are indicative of an inorganic origin. The thick permafrost, and the extreme cold and dry environment make this site a good terrestrial analog for carbonate precipitates that might be expected at potential deposits associated with water discharge on other planetary bodies.  相似文献   

10.
文章通过对醇类物质参与下的碳酸钙成核过程进行研究,探讨生物流体中常见的羟基对矿物物相以及界面能的影响。研究结果表明多羟基醇有利于亚稳定球文石的形成,醇的加入会增加方解石和球文石的界面能,醇的羟基定向吸附造成的吸附位密度降低是提升矿物界面能最可能的机制,而溶剂氢键数量决定了碳酸根的自由度,有利于对称度低且CO32 - 不平行的球文石形成。水和乙醇—水体系氢键作用弱,界面能低的方解石物相成为热力学优势物相。研究结果凸显了生物成矿流体受羟基影响强烈,通过控制流体中羟基物质含量,生物体可以完全掌控碳酸钙物相的形成部位,加深了对生物成因碳酸钙形成过程的理解。  相似文献   

11.
崔猛  符晓  郑俊杰  吕苏颖  熊辉辉  曾晨  韩尚宇 《岩土力学》2022,43(11):3027-3035
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。  相似文献   

12.
The minerals and non-mineral inorganic constituents in Triassic and Tertiary low-rank coals from various coal deposits in South Australia were studied using selective chemical leaching and oxygen-plasma ashing techniques. Although gypsum may be present in some samples, most of the sodium, calcium and magnesium, as well as part of the sulphur, appears to occur as a combination of dissolved ions in pore water and exchangeable ions attached to carboxylate groups. Significant concentrations of iron and aluminium occur in acid-soluble form, probably as organometallic complexes within the hydrocarbon structure.Quartz is the dominant mineral in the Tertiary coal samples. It appears to be mainly detrital, but doubly terminated euhedral crystals suggest an authigenic origin in one of the deposits. Well crystallized kaolinite is common in the Triassic coals, while poorly crystallized kaolinite occurs in the Tertiary samples. Siderite, calcite and possibly collophane occur in the Triassic coals; sparse pyrite is present in both the Tertiary and the Triassic samples.The differences in minerals and other inorganic constituents between the Tertiary and Triassic deposits can be explained partly by variations in the composition of the pore waters permeating the strata, and partly by mobility of silica and alumina from different sources within the peat deposit. The relative mobility of the different inorganic constituents is also significant in beneficiation of the coal for use in combustion processes.  相似文献   

13.
煤中硫是多种有害微量元素的重要载体。基于形态硫分析、电感耦合等离子质谱及X射线衍射等方法分析沁水盆地晚古生代煤中硫和有害微量元素的分布规律,探讨了煤中硫对有害微量元素富集的影响,运用带能谱的扫描电镜和光学显微镜划分煤中硫化物的微观赋存特征。结果表明,沁水盆地煤中硫整体上以有机硫为主,平均占全硫的78%,只有在太原组个别高硫煤中以黄铁矿硫为占优势。显微镜和扫描电镜下可识别出煤中黄铁矿的微观赋存状态包括莓球状、薄膜状、晶粒状、结核状、团窝状黄铁矿和细粒黄铁矿集合体,白铁矿的微观赋存特征包括聚片状、板状和矛头状白铁矿,部分白铁矿与黄铁矿共生。沁水盆地煤中有害微量元素含量整体较低,黄铁矿是有害微量元素As、Se和Hg的重要载体,而有机硫决定了煤中U的富集。研究认为,成煤时期海水对泥炭沼泽的影响导致太原组煤中全硫和黄铁矿硫较高,太原组煤中硫的来源具有多样性,煤中黄铁矿具有多阶段演化的特点。  相似文献   

14.
近年来,珍珠中的六方球文石成为珍珠研究的一个热点。利用文石与六方球文石的特征拉曼光谱差异,对淡水无核珍珠样品的两种物象组成进行了测试研究。采用显微激光拉曼成像技术初步确定了淡水无核珍珠样品中六方球文石的位置、形状与大小。结果显示,其多分布于珍珠珠核部位,也可出现在珍珠表面。通过扫描电子显微镜进一步观察,珍珠表面上的六方球文石与文石的微形貌特征有较明显的区别。同时,还一并探讨了拉曼光谱在珍珠样品中出现的方向性效应以及有机色素产生的拉曼效应。  相似文献   

15.
煤中微量元素研究进展   总被引:30,自引:3,他引:30  
煤炭是我国的主要能源,在煤炭开采、运输、洗选、淋溶(滤)、燃烧等其它加工利用过程中,煤中的微量元素要发生迁移、析出,并入侵到大气、水、土壤和生态环境中,最终影响人类生存和生活环境。煤中微量元素十分重要,是因为它们与环境问题、动、植物及人类健康密切相关。在研究微量元素时必须考虑微量元素的性质及毒性,它们主要依靠其含量、种类、存在形式、pH值、氧化-还原条件及其它因素。在全面综合国内外研究文献的基础上,分析了煤中微量元素的发现、分布规律、赋存状态、成因机理及微量元素的应用等方面研究的历史、现状,并对今后研究的重点内容和发展方向进行了较为详细的论述和分析,并指出在进一步深入研究煤中微量元素地球化学的基础上,加强微量元素环境学方面的研究是今后煤中微量元素环境地球化学研究的重要内容。  相似文献   

16.
At burial depths of 800-1000 m, within the epicontinental Queensland Trough of north-east Australia (ODP Site 823), microcrystalline inter- and intraskeletal mosaics of anhedral (loaf-shaped, rounded) calcite have Sr2+ values ranging from below microprobe detection limits (<150 ppm) to 8100 ppm. Host rocks are well lithified, fine-grained mixed sediment to clayey wackestone and packstone of Middle and Late Miocene age. Petrography demonstrates that calcite precipitation has spanned shallow to deep burial, overlapping formation of framboidal pyrite in the upper 50 m; shallow-burial dolomitization (<300 m); and dedolomitization during sediment consolidation and incipient chemical compaction at greater (>400–500 m) depths. Petrographic observations illustrate that the calcite microfabric formed through coalescing crystal growth resulting from one or a combination of displacive growth in clay, porphyroid neomorphism of aragonite/vaterite, and clay replacement by calcite. Sr2+ mean concentrations in calcite between depths of 800 and 1000 m are similar to an expected equilibrium pore-water concentration, using a Dsr of 0.06, and may indicate active calcite precipitation. However, Sr2+ variation (2000–5000 ppm) within and among crystals, and concentrations that range well above predicted equilibrium values for a given depth, illustrate either variable Sr2+ retention during recrystallization of shelf-derived aragonite (and authigenic local vaterite) or relative uptake of Sr2+ during calcite precipitation with burial. Within the context of calcite formation during burial to 1 km, diagenetic attributes that affect the latter process include increased concentrations of pore-water Sr2+ with depth associated with aragonite recrystallization/dissolution; upward migration of Sr-rich pore water; and increased DSr related to local variation in precipitation/recrystallization rates, differential crystal sector growth rates and/or microvariation in aragonite distribution.  相似文献   

17.
Carbonate nodules have been encountered for many years in the southern Illinois Basin, in parts of southern Illinois, southern Indiana, and southwestern Kentucky. The nodules occur as oblate spheroids of calcium carbonate that are isolated in the shale immediate roof of coal mines. They are common in the Springfield coal seam, known as the No. 5 seam in Illinois, and as the No. 9 seam in western Kentucky. Several different mechanisms have been proposed for the formation of various semi-spherical objects in coal measure rocks. The distribution and association with rooted horizons suggest that carbonate nodules in black fossiliferous shale observed in the roof of a studied mine in the Springfield seam represent pedogenic carbonate paleosols, which formed in a caliche-favoring environment subsequent to Springfield mire deposition. This interpretation is supported by 87Sr/86Sr isotope ratios of 0.710893 ± 13 to 0.711035 ± 12, which indicate a freshwater rather than seawater source.Petrographic examination of rock textures and mineral grains indicates that nodules collected from two Illinois Basin coal mines are composed of subangular grains of fine-grained, crystalline microspar. Although the carbonate is not ferroan, iron hydroxide stains interstices between microspar grains. The rounded, commonly pinched boundaries of nodules truncate commonly imbricated microspar grains. In contrast, concentric growth patterns are not observed except as defined by secondary, subhedral to euhedral pyrite crystals that form a diffuse, concentric replacement zone around the nodule's outer rind. Polished slickensides, with well-developed radial slickenlines, are developed at highly compacted margins in black shale or mudstone that commonly encases the carbonate nodules.Of the 450 carbonate nodules documented at a study mine in the southern Illinois Basin, the long axes of 36% are preferentially aligned parallel to regional structures such as anticline axes and drag folds that are interpreted to have formed in response to compression during the Late Pennsylvanian-Permian Alleghanian orogeny. Mapping also suggests that clusters of carbonate nodules are spatially associated with the trends of low-angle drag folds in the immediate roof of the Springfield seam at the study mine. The preferential elongation and distribution with respect to tectonic structures suggest that regional compression influenced the shape and distribution of carbonate nodules, and that nodule lithification may have been approximately contemporaneous with regional deformation.  相似文献   

18.
The effect of mineral matter on the laboratory pyrolysis of sediments, kerogens and coals, and of coal macerals mixed with either alumina, bentonite, kaolinite, or calcium carbonate has been investigated. Some minerals are more active than others in effecting changes in the composition of the pyrolysate. The relative content of low molecular weight pyrolysis products is higher for kerogens pyrolyzed in a mineral matrix than for isolated kerogens. Our limited data suggests that this is due to both condensation and gasification of higher molecular weight constituents in the ‘primary’ pyrolysate. Differences in the content of aromatic versus aliphatic compounds have been noted when pyrograms from coal macerals are compared with pyrograms from coal maceral-mineral mixtures. We conclude that mineralogy is important in controlling the composition of kerogen pyrolysis products.  相似文献   

19.
This research studied the precipitation of calcium carbonate by populations of bacteria from domestic wastewater cultivated in both natural and artificial solid culture media. The only carbonate-forming bacteria detected appeared in an artificial medium added with calcium acetate. Precipitation occurred three days after inoculation, and the percentage was slightly higher than 65 %. Our results showed that nine major carbonate-forming colony types were the dominant heterotrophic platable bacteria growing aerobically in artificial media added with calcium acetate. According to their taxonomic affiliations (based on partial sequencing of the 16S-rRNA), the nine strains belonged to the following nine genera of Gram-negative and Gram-positive bacteria: Caulobacter, Blastomonas, Roseobacter, Staphylococcus, Bacillus, Gemmatimonas, Saccharopolyspora, Microthrix, and Sphingomonas. All of these strains formed calcium carbonate, precipitated as calcite and vaterite in different proportions and shapes (spheres, hemispheres, dumbbells, and pseudopolyhedral forms). The results of this study suggest that in real domestic wastewater, the precipitation of carbonates through bacterial action could not take place in situ because the concentrations of calcium did not create the optimal circumstances for biomineralization. However, in the artificial media, it was possible to induce this process by adding calcium ions.  相似文献   

20.
氟是煤中有害元素之一,燃煤型氟排放造成的污染已经对人类的健康安全构成威胁。研究煤中氟赋存状态及其沉积环境,对掌握高氟煤分布规律及控制燃煤造成的氟排放具有重要意义。通过对沁水煤田内6座煤矿15号煤样品的分析发现:煤中氟含量与灰分显著相关,与黄铁矿硫、有机硫无相关关系,表明煤中氟主要以无机物形式赋存,且与含硫矿物无关;与钾、镁、硅、铝等元素含量具有显著的相关关系,表明氟有可能的主要赋存形式为金云母、氟金云母等矿物,以及以吸附存在于高岭石、勃姆石、伊蒙混层等黏土矿物中;与钙、磷元素含量无显著相关性,表明氟不以氟磷灰石、含氟羟基磷灰石等矿物大量赋存。此外,通过对沁水煤田15号煤的沉积环境分析发现,弱还原环境、较低盐度、偏酸性、较强的水动力条件有利于该区域煤中氟的富集。  相似文献   

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