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1.
Tentative kinetic model for dolomite precipitation rate and its application to dolomite distribution
The ‘dolomite problem’ has a long history and remains one of the most intensely studied and debated topics in geology. Major amounts of dolomite are not directly forming today from seawater. This observation has led many investigators to develop geochemical/hydrologic models for dolomite formation in diagenetic environments. A fundamental limitation of the current models for the growth of sedimentary dolomite is the dearth of kinetic information for this phase, in contrast to that available for calcite and aragonite. We present a simple kinetic model describing dolomite growth as a function of supersaturation using data from published high temperature synthesis experiments and our own experimental results. This model is similar in form to empirical models used to describe precipitation and dissolution rates of other carbonate minerals. Despite the considerable uncertainties and assumptions implicit in this approach, the model satisfies a basic expectation of classical precipitation theory, i.e., that the distance from equilibrium is a basic driving force for reaction rate. The calculated reaction order is high (~ 3), and the combined effect of high order and large activation energy produces a very strong dependence of the rate on temperature and the degree of supersaturation of aqueous solutions with respect to this phase. Using the calculated parameters, we applied the model to well-documented case studies of sabkha dolomite at Abu Dhabi (Persian Gulf), and organogenic dolomite from the Gulf of California. Growth rates calculated from the model agree with independent estimates of the age of these dolomites to well within an order of magnitude. A comparison of precipitation rates in seawater also shows the rate of dolomite precipitation to converge strongly with that of calcite with increasing temperature. If correct, this result implies that dolomite may respond to relatively modest warming of surface environments by substantial increases in accumulation rate, and suggests that the distribution of sedimentary dolomite in the rock record may be to some extent a temperature signal. 相似文献
2.
Amlan Banerjee 《Journal of the Geological Society of India》2016,87(5):561-572
Reactive-transport models are developed here that produce dolomite via two scenarios: primary dolomite (no CaCO3 dissolution involved) versus secondary dolomite (dolomitization, involving CaCO3 dissolution). Using the available dolomite precipitation rate kinetics, calculations suggest that tens of meters of thick dolomite deposits cannot form at near room temperature (25-35°C) by inorganic precipitation mechanism, though this mechanism will provide dolomite aggregates that can act as the nuclei for dolomite crystallization during later dolomitization stage. Increase in supersaturation, Mg+2/Ca+2 ratio and CO3-2 on the formation of dolomite at near room temperature are subtle except for temperature.This study suggests that microbial mediation is needed for appreciable amount of primary dolomite formation. On the other hand, reactive-transport models depicting dolomitization (temperature range of 40 to 200°C) predicts the formation of two adjacent moving coupled reaction zones (calcite dissolution and dolomite precipitation) with sharp dolomitization front, and generation of >20% of secondary porosity. Due to elevated temperature of formation, dolomitization mechanism is efficient in converting existing calcite into dolomite at a much faster rate compared to primary dolomite formation. 相似文献
3.
《Sedimentology》2018,65(1):209-234
Dolomites of varied ages exhibit metre‐scale nested patterns of lateral periodic variation in permeability and porosity and, by inference, dolomite abundance as most examples are 100% dolomite. Two‐dimensional reaction–transport modelling simulations of bed‐scale dolomitization were used to assess whether those patterns in dolomite abundance could form during near‐surface replacement dolomitization. Simulations used a 2 m high and 18 m long model domain, a low‐Mg calcite grainstone precursor and an evaporated Mississippian seawater brine (430 parts per thousand salinity) as the dolomitizing fluid. The domain was initially populated with random variations in porosity and/or grain size. Results reveal that spatial patterns in dolomite abundance emerge when there is as little as 1% dolomite formed, with similarities between the modelled patterns and outcrop‐documented patterns. The nested patterns include a near‐random component that constitutes ≤40% of the total variance, short‐range correlation ranging from 1·5 to 3·3 m and a longer‐range periodic trend with a wavelength up to 6·5 m. The emergence of pattern in dolomite abundance is the result of an autogenic self‐organizing phenomenon. It is triggered by variation in initial calcite reactive surface area that occurs due to the random heterogeneities in initial porosity and/or grain sizes. The pattern develops due to a combination of kinetic disequilibrium reactions (dolomite precipitation and calcite dissolution) and positive feedbacks between dolomite growth, calcite dissolution and fluid flow. Flow is around loci of higher dolomite, lower porosity and higher reactive surface areas, but through loci of lower dolomite, higher porosity and lower reactive surface areas. The resulting less porous/more dolomite and more porous/less dolomite structures at the metre‐scale arise from those localized interactions. This self‐organizing mechanism for pattern formation constitutes a new model for geochemical self‐organization during dolomitization and is the only self‐organization model that is proven applicable to the formation of metre‐scale patterns during early, near‐surface dolomitization. 相似文献
4.
Yi-Pin Lin 《Geochimica et cosmochimica acta》2005,69(18):4495-4504
We studied the effects of seed material and solution composition on calcite crystal precipitation using a pH-stat system. The seed materials investigated included quartz, dolomite, two calcites with different particle size and specific surface area, and two dried precipitates from precipitative softening water treatment plants. Our results indicated that, of the seed materials examined, only calcite had the ability to initiate calcite precipitation in a solution with a degree of supersaturation of 5.3 over a period of two hours, and that the precipitation rate was proportional to the available surface area of the seed. For different solution compositions with the same degree of supersaturation, the calcite precipitation rate increased with increasing carbonate/calcium ratio, which contradicts the generally accepted empirical rate expression that the degree of supersaturation is the sole factor controlling precipitation kinetics. By applying a surface complexation model, the surface concentrations of two species, >CO3− and >CaCO3−, appear to be responsible for catalyzing calcite precipitation. 相似文献
5.
The possibility of recrystallization is a long‐standing barrier to deciphering the genetic origin of dolomites. There is often uncertainty regarding whether or not characteristics of ancient dolomites are primary or the consequence of later recrystallization unrelated to the original dolomitization event. Results from 65 new high‐temperature dolomite synthesis experiments (1 m , 1·0 Mg/Ca ratio solutions at 218°C) demonstrate dolomite recrystallization affecting stoichiometry, cation ordering and nanometre‐scale surface texture. The data support a model of dolomitization that proceeds by a series of four unique phases of replacement and recrystallization, which occur by various dissolution–precipitation reactions. During the first phase (induction period), no dolomite forms despite favourable conditions. The second phase (replacement period) occurs when Ca‐rich dolomite products, with a low degree of cation ordering, rapidly replace calcite reactants. During the replacement period, dolomite stoichiometry and the degree of cation ordering remain constant, and all dolomite crystal surfaces are covered by nanometre‐scale growth mounds. The third phase (primary recrystallization period), which occurs in the experiments between 97% and 100% dolomite, is characterized by a reduced replacement rate but concurrent increases in dolomite stoichiometry and cation ordering. The end of the primary recrystallization period is marked by dolomite crystal growth surfaces that are covered by flat, laterally extensive layers. The fourth phase of the reaction (secondary recrystallization period) occurs when all calcite is consumed and is characterized by stoichiometric dolomite with layers as well as a continued increase in the degree of cation ordering with time. Inferences of recrystallization, in natural dolomite, based on cation order or stoichiometry of dolomite, usually depend on assumptions about the precursor dolomite subjected to recrystallization. If it is assumed that the experimental evidence presented here is applicable to natural, low‐temperature dolomites, then the presence of mounds is direct evidence of a lack of recrystallization and the presence of layers is direct evidence of recrystallization. 相似文献
6.
Examination with scanning electron microscopy (SEM) and scanning force microscopy (SFM) revealed etch pits, layers and islands on dolomite crystal faces synthesized from calcite in Ca‐Mg‐Cl solutions at 200 °C and a wide variety of natural dolomites. Layers are broad, flat structures bounded by steps less than 100 nm high and greater than 1 μm wide. Islands are rounded topographic highs <20 nm high and <200 nm wide. The nanotopography of synthetic dolomite changed from islands throughout most of the reaction to layers at 100% dolomite. Island nanotopography formed on both Ca‐rich and near‐stoichiometric dolomite. Analyses of reaction products from dolomite synthesis indicates that there are no SFM‐detectable products formed in <10 h. SEM‐detectable products formed in 15 h. X‐ray diffraction (XRD)‐detectable products formed in ≈18 h, and the reaction went to completion in ≈40 h. Based on SFM analyses, the induction period for dolomitization in these experiments accounts for ≈20% of the total reaction time necessary to dolomitize CaCO3 completely under the experimental conditions used here. Island nano‐ topography is inferred to occur at higher degrees of supersaturation than layer nanotopography for three reasons. First, island nanotopography on synthetic calcite and gypsum forms at higher supersaturations than layer nanotopography. Secondly, island nanotopography formed in solutions with higher degrees of supersaturation with respect to dolomite. Thirdly, the greater surface roughness of a crystal face composed of islands compared with layers indicates that island surfaces have higher surface energy than layer surfaces. Therefore, the stability of island surfaces requires a higher degree of supersaturation. Because islands and layers form under a wide range of conditions, their presence provides broadly applicable criteria for evaluating relative degrees of supersaturation under which ancient dolomite formed. Comparison of synthetic dolomites with natural dolomites demonstrates (1) similar nanotopography on natural and synthetic dolomites and (2) both natural planar and non‐planar dolomite may have island nanotopography. 相似文献
7.
Geochemical controls on a calcite precipitating spring 总被引：2，自引：0，他引：2
A small spring fed stream was found to precipitate calcite by mainly inorganic processes and in a nonuniform manner. The spring water originated by rainwater falling in a 0.8 km2 basin, infiltrating, and dissolving calcite and dolomite followed by dissolution of gypsum or anhydrite. The Ca2+/Mg2+ indicates that calcite is probably precipitated in the subsurface from a supersaturated solution. This water emerges from the spring still about 5 times supersaturated with respect to calcite and continues calcite precipitation. When 10 times supersaturation is reached, due to CO2 degassing the precipitation is more rapid. The calcite accumulation from the stream with a flow of 5 l/s is calculated to be 12600 kg/yr with the highest rates in areas where CO2 degassing is the greatest. The non-equilibrium, as shown by the high calcite supersaturation, is also reflected in a variable partitioning pattern for Sr2+ between the water and calcite. 相似文献
8.
V. Helpa E. Rybacki R. Abart L. F. G. Morales D. Rhede P. Jeřábek G. Dresen 《Contributions to Mineralogy and Petrology》2014,167(4):1-14
Reaction rims of dolomite (CaMg[CO3]2) were produced by solid-state reactions at the contacts of oriented calcite (CaCO3) and magnesite (MgCO3) single crystals at 400 MPa pressure, 750–850 °C temperature, and 3–146 h annealing time to determine the reaction kinetics. The dolomite reaction rims show two different microstructural domains. Elongated palisades of dolomite grew perpendicular into the MgCO3 interface with length ranging from about 6 to 41 µm. At the same time, a 5–71 µm wide rim of equiaxed granular dolomite grew at the contact with CaCO3. Platinum markers showed that the original interface is located at the boundary between the granular and palisade-forming dolomite. In addition to dolomite, a 12–80 µm thick magnesio-calcite layer formed between the dolomite reaction rims and the calcite single crystals. All reaction products show at least an axiotactic crystallographic relationship with respect to calcite reactant, while full topotaxy to calcite prevails within the granular dolomite and magnesio-calcite. Dolomite grains frequently exhibit growth twins characterized by a rotation of 180° around one of the $[11\bar{2}0]$ equivalent axis. From mass balance considerations, it is inferred that the reaction rim of dolomite grew by counter diffusion of MgO and CaO. Assuming an Arrhenius-type temperature dependence, activation energies for diffusion of CaO and MgO are E a (CaO) = 192 ± 54 kJ/mol and E a (MgO) = 198 ± 44 kJ/mol, respectively. 相似文献
9.
Electron diffraction, analytical electron microscopy, and high voltage, high resolution electron microscopy have been used to investigate crystal defects in calcium-rich saddle dolomites having pronounced curvature of the faces. Results show that branching, ribbon-like defects in these so-called saddle dolomites are thin, coherent laths of calcitic material. The ribbons are profuse and explain the characteristic calcium excess found in most saddle dolomites. Because the lattice spacings of calcite are between 3.8% and 6.7% larger than the corresponding lattice spacings of dolomite, a calcitic ribbon causes local distortion of the host dolomite. The branching ribbons have a predominant {10¯14} orientation and are generally present in high density. They may represent the source of crystal distortion that ultimately manifests itself on the macroscopic scale. The calcitic ribbons form during growth from aqueous solution, although they have features in common with similar defects found in carbonatite carbonates. This fine-scale intergrowth microstructure may be a variant of even finer-scale modulated structures found in other sedimentary calcian dolomites. 相似文献
10.
"白云岩问题"一直是沉积地质学研究的热点和难点之一,白云岩在我国和世界范围内都是重要的油气储层。因此,深入认识白云岩成因对于碳酸岩油气勘探具有重要参考意义。白云岩成因有多种解释模式,如萨布哈蒸发模式、渗透回流模式、埋藏调节模式、混合水模式、潮汐泵模式等。近几十年来,随着低温白云石研究的不断深入,微生物白云石模式作为一种新的成因模式被提出并不断被完善。本文回顾了微生物成因白云石的研究进展,总结了低温白云石形成的3个动力学障碍(镁离子的高水合能、硫酸根的存在、碳酸根离子的低浓度和低活度),简要介绍了微生物成因白云石模式的建立、微生物成因白云石的生长过程及发育特征,系统分析了微生物在白云石形成过程中的调节作用,指出微生物(如硫酸盐还原菌、古甲烷菌)的存在可以改变溶液中的离子平衡,进而有利地克服白云石形成过程中的动力学障碍,并列举了低温微生物成因白云石的氧同位素指标在古温度恢复和过去气候变化研究中的应用,最后对微生物成因白云石相关研究方向(如多学科交叉、新技术应用等)加以展望。对微生物成因白云石模式的深入认识,将为正确解释"白云岩问题"提供新的途径,也将为石油学家关心的白云岩储层问题提供新的理论基础和研究思路。 相似文献
11.
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. 相似文献
12.
The composition of carbonate minerals formed in past and present oceans is assumed to be significantly controlled by temperature and seawater composition. To determine if and how temperature is kinetically responsible for the amount of Mg incorporated in calcite, we quantified the influence of temperature and specific dissolved components on the complex mechanism of calcite precipitation in seawater. A kinetic study was carried out in artificial seawater and NaCl-CaCl2 solutions, each having a total ionic strength of 0.7 M. The constant addition technique was used to maintain [Ca2+] at 10.5 mmol kg−1 while [] was varied to isolate the role of this variable on the precipitation rate of calcite.Our results show that the overall reaction of calcite precipitation in both seawater and NaCl-CaCl2 solutions is dominated by the following reaction:
13.
Professor Dr. Francis J. Turner 《Contributions to Mineralogy and Petrology》1965,11(4):393-397
Consideration of available thermodynamic data and the published results of direct experiments relating to (1) formation. of periclase from dolomite and (2) hydration of periclase to brucite, permits the following conclusions to be drawn: (1) At very low partial pressures of CO2 (perhaps of the order of 1 bar) and relatively high partial pressures of water (up to 2000 bars), dolomite can break down directly to brucite and calcite at temperatures above about 400° C, and below temperatures on the brucite dehydration curve. (2) The reaction dolomite calcite + periclase + CO2 in contact metamorphism near granitic bodies is likely to occur only at low partial pressures of CO2 (perhaps 10 or 20 bars); this can be achieved without direct formation of brucite, by maintaining a partial pressure of water of the order of 1000 bars or more. (3) At low CO2 pressures dolomite may re-form in the cooling stages of metamorphism by reaction between calcite, brucite, and CO2 at temperatures below about 400° C. 相似文献
14.
四川盆地西北部中二叠统栖霞组白云岩特征及成因探讨 总被引：1，自引：0，他引：1
白云岩特征及其形成机制的研究对白云岩化理论与白云岩储集层勘探具有重要意义。本文以四川盆地西北部中二叠统栖霞组白云岩为研究对象,通过野外剖面及岩心观察并采用铸体薄片、阴极发光、地球化学分析等方法对该段白云岩特征及成因进行研究。结果表明川西北地区栖霞组白云岩主要表现为块状晶粒白云岩、角砾状白云岩及斑状白云岩3种类型;碳同位素为正低值,氧同位素为负值,反映出其成岩过程中伴有早期淡水参与。结合工区构造沉积背景,对比以往经典白云岩化模式,发现四川盆地西北部中二叠统栖霞组白云岩化成因模式具有一定自身特点。通过对Folk “镁笼效应”理论进行延伸,认为栖霞组白云岩化模式在纵向上分为淡水渗流带、混合渗流带、混合潜流带及海水潜流带4个区带,其中混合渗流带和混合潜流带是白云岩发育的主要位置。在混合渗流带中,淡水与海水交替进入,未完全成岩的海洋沉积物质在成岩过程中受到淡水冲洗导致大量镁离子随淡水流入下部地层,而后又有海水携带镁离子进行补给,这为白云石形成提供了有利条件;混合潜流带内不断进入的混合流体携大量镁离子使得该带具有较高Mg/Ca值;而地幔上涌造成的地温升高克服了白云石形成的动力学屏障,有效促进了白云岩的形成。 相似文献
15.
Mineralogy,nucleation and growth of dolomite in the laboratory and sedimentary environment: A review 
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下载免费PDF全文 Dolomite [CaMg(CO3)2] forms in numerous geological settings, usually as a diagenetic replacement of limestone, and is an important component of petroleum reservoir rocks, rocks hosting base metal deposits and fresh water aquifers. Dolomite is a rhombohedral carbonate with a structure consisting of an ordered arrangement of alternating layers of Ca2+ and Mg2+ cations interspersed with anion layers normal to the c‐axis. Dolomite has symmetry, lower than the (CaCO3) symmetry of calcite primarily due to Ca–Mg ordering. High‐magnesium calcite also has symmetry and differs from dolomite in that Ca2+ and Mg2+ ions are not ordered. High‐magnesium calcite with near‐dolomite stoichiometry (≈50 mol% MgCO3) has been observed both in nature and in laboratory products and is referred to in the literature as protodolomite or very high‐magnesium calcite. Many dolomites display some degree of cation disorder (Ca2+ on Mg2+ sites and vice versa), which is detectable using transmission electron microscopy and X‐ray diffractometry. Laboratory syntheses at high temperature and pressure, as well as studies of natural dolomites show that factors affecting dolomite ordering, stoichiometry, nucleation and growth include temperature, alkalinity, pH, concentration of Mg and Ca, Mg to Ca ratio, fluid to rock ratio, mineralogy of the carbonate being replaced, and surface area available for nucleation. In spite of numerous attempts, dolomite has not been synthesized in the laboratory under near‐surface conditions. Examination of published X‐ray diffraction data demonstrates that assertions of dolomite synthesis in the laboratory under near‐ambient conditions by microbial mediation are unsubstantiated. These laboratory products show no evidence of cation ordering and appear to be very high‐magnesium calcite. Elevated‐temperature and elevated‐pressure experiments demonstrate that dolomite nucleation and growth always are preceded by very high‐magnesium calcite formation. It remains to be demonstrated whether microbial‐mediated growth of very high‐magnesium calcite in nature provides a precursor to dolomite nucleation and growth analogous to reaction paths in high‐temperature experiments. 相似文献
16.
近年来,随着对微生物白云石模式研究的不断深入,为解释“白云石问题”提供了新思路。前人对微生物白云石成因研究侧重于微生物对未固结沉积物的改造,即有机准同生白云石化作用,这与实验室中以微生物为媒介形成的“有机原生白云石”在成因机理上存在差异。笔者将微生物白云石机理引入湖相原生白云石成因解释中,认为在湖水—沉积物交界处也会发生微生物成因的原生白云石沉淀,即有机原生白云石。湖水与沉积物交界处的微环境存在明显区别,总体可分为有氧和缺氧2种亚环境,不同亚环境中生活有不同的微生物群落。根据湖泊亚环境特性和微生物种类及其在白云石形成过程中所发挥的作用,可以区分出细菌有氧氧化模式、硫酸盐还原模式和产甲烷模式3种微生物白云石模式。不同模式对应于不同的湖泊环境: 细菌有氧氧化模式主要发生于有氧、高Mg/Ca值的咸水/盐湖环境;硫酸盐还原模式主要发生于缺氧、高Mg/Ca值的咸水/盐湖环境;产甲烷模式主要发生于缺氧、低Mg/Ca值的淡水/咸水湖环境。另外,还探讨了pH值变化、SO 4 2 -
17.
羌塘盆地中央隆起带南侧隆额尼—昂达尔错布曲组古油藏白云岩特征及成因机制 总被引：2，自引：0，他引：2
以系统的剖面测制及室内综合研究为基础,系统总结了隆额尼—昂达而错古油藏白云岩的矿物学、晶体学、岩石组构、沉积相、碳和氧同位素及流体包裹体等特征,在该区白云岩中发现了完整的交代鲕粒结构。该区白云岩的典型组构为交代残余结构、雾心亮边结构、等厚环边胶结及世代生长结构,白云岩化集中在台地边缘浅滩、潮坪及台地边缘藻丘礁;白云石晶体有序度总体较高,白云岩δ13C和δ18O值较伴生灰岩偏高,白云岩形成时盐度低于正常海水盐度,温度t高于地表平均温度;白云岩中包裹体含量少而小,均一温度均从白云岩中后期充填方解石脉中获取,其均一温度的两个区间与该区两次大的构造运动及油气生成、运聚过程吻合,白云岩形成于油气注入之前。各种特征均反映出该区白云岩为混合水交代成因,研究丰富了对该古油藏白云岩特征及白云岩成因机制的认识。 相似文献
18.
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. 相似文献
19.
《Applied Geochemistry》1993,8(2):161-176
Heating of calcite-saturated groundwater induces no precipitation to thermodynamic equilibrium with respect to end-member Ca-carbonates. Column experiments, using native groundwater and aquifer sediment, were performed to study the controlling factors in the kinetics of carbonate precipitation for a natural system by injection of groundwater in a sediment core at 90°C. The temperature increase induced a fast precipitation of a CaFe-carbonate, containing Mn and phosphate, and a CaMgFe-carbonate, containing Mn, within at most 10 h. Both precipitates varied in composition and were partly amorphic, partly crystalline. Prolonged precipitation, after almost all Fe[II] had been removed, was extremely slow despite a twelve-fold supersaturation with respect to end-member calcite. The resulting supersaturation cannot be explained by either calcite precipitation kinetics, Mg-inhibition, Mg-calcite solubility control, or Ca-organic acid complexing, because these factors may explain a two-fold supersaturation at most. The maintenance of supersaturation is attributed to inhibition of precipitation by phosphate and/or organic acids. The influence of secondary reactions, as cation-exchange and silicate weathering, is of minor importance on the carbonate chemistry. Cation-exchange was observed in the initial stages of heated water injection. Potassium, NH4 and Fe become desorbed upon temperature increase. Related Ca-adsorption is insufficient to avoid Ca-carbonate precipitation. Weathering of silicates occurs continuously and leads to the release of Na, Ca and Mg. 相似文献
20.
Wilhelm Heinrich Paul Metz Werner Bayh 《Contributions to Mineralogy and Petrology》1986,93(2):215-221
Stoichiometric mixtures of tremolite and dolomite were heated to 50° C above equilibrium temperatures to form forsterite and calcite. The pressure of the CO2-H2O fluid was 5 Kb and \(X_{{\text{CO}}_{\text{2}} }\) varied from 0.1 to 0.6. The extent of the conversion was determined by the amount of CO2 produced. The resulting mixtures of unreacted tremolite and dolomite and of newly-formed forsterite and calcite were examined with a scanning electron microscope. All tremolite and dolomite grains showed obvious signs of dissolution. At fluid compositions with \(X_{{\text{CO}}_{\text{2}} }\) less than about 0.4, the forsterite and calcite crystals are randomly distributed throughout the charges, indicating that surfaces of the reactants are not a controlling factor with respect to the sites of nucleation of the products. A change is observed when \(X_{{\text{CO}}_{\text{2}} }\) is greater than about 0.4; the forsterite and calcite crystals now nucleate and grow at the surface of the dolomite grains, thus indicating a change in mechanism at medium CO2 concentrations. As the reaction progresses, the dolomite grains become more and more surrounded by forsterite and calcite, finally forming armoured relics of dolomite. Under experimental conditions this characteristic texture can only be formed if the CO2-concentration is greater than about 40 mole %. These findings make it possible to estimate the CO2-concentration from the texture of the dolomite+tremolite+forsterite+calcite assemblage. The results suggest a dissolution-precipitation mechanism for the reaction investigated. In a simplified form it consists of the following 4 steps:
- Dissolution of the reactants tremolite and dolomite.
- Diffusion of the dissolved constituents in the fluid.
- Heterogeneous nucleation of the product minerals.
- Growth of forsterite and calcite from the fluid.