黄土和沉积岩中分离方解石和白云石的方法实验

采用不同浓度的ＨＣｌ、ＨＡｃ、ＮＨ４Ａｃ及ＮＨ４Ａｃ－ＨＡｃ缓冲深液对典型黄土剖面的黄土样品进行了系统的浸取实验,结果表明,稀ＨＡｃ是分离方解石与白云石的最佳深剂,在浸取实验中对１４种不同元素含量进行测试,多数元素的含量有变化,用稀ＨＡｃ溶液浸取所得的浸取注中＾８７Ｓｒ／＾８６Ｓｒ的测定结果与使用稀ＨＣｌ浸取的浸取液中＾８７Ｓｒ／＾８６Ｓｒ测定值有一定的差别,方法可满足在古气候研究中对不同成因碳酸盐利用的要求。     

Beziehungen zwischen Calciumgehalt und Bildungsbedingungen der Dolomite

Zusammenfassung Nach einer kurzen Gegenüberstellung der Eigenschaften frühdiagenetischer und spätdiagenetischer Dolomite wird der Zusammenhang des Ordnungsgrades mit Ca-Überschuß und Kristallgröße des Dolomits empirisch dargestellt (Abb. 2 und 3). Untersuchungen im Alttertiär Libyens sowie im Malm und Zechstein Norddeutschlands ergaben, daß der Ca-Überschuß der Dolomite Rückschlüsse auf den Salinitätsgrad des Bildungsmilieus erlaubt (Abb. 4), daß jedoch vor allem in porösen Gesteinen ein allmählicher Gitterumbau zum stöchiometrischen Dolomit erfolgt (Abb. 7 und 8).

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As an introduction, penecontemporary dolomites are compared with epigenetical ones. The relationship between ordering degree and Ca-excess as well as crystal size are represented empirically (fig. 2 and 3). Investigations in the Lower Tertiary of Libya, and in the Upper Jurassic and Upper Permian of Northern Germany led to the conclusion, that the Ca-excess of dolomites may be indicative of the environment (fig. 4). The data however point to a gradual lattice adjustment towards an ideal 11 composition, especially in porous rocks (fig. 7 and 8).

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Résumé Après une rapide comparaison entre les caractéristiques des dolomies pénécontemporaines et epigénétiques, on donne des relations empiriques entre le degré d'ordre, l'excès de calcium et le diamètre des cristaux (fig. 2 et 3). Les recherches exécutées dans le Paléocène libyen, le Malm et le Zechstein de l'Allemagne du Nord ont montré que l'excès de calcium contenu dans les dolomies permet des conclusions sur le milieu (flg. 4), mais que toutefois un ajustement graduel des réseaux à une composition idéale 11 se produit tout particulièrement dans les roches poreuses (fig. 7 et 8).

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Für die Ermöglichung dieser Arbeiten und die Genehmigung ihrer Veröffentlichung danken wir der GewerkschaftElwerath, Erdölwerke Hannover und besonders Herrn Direktor Dr.Roll.     

连续测定方解石和白云石中碳,氧同位素的比值的方法及其意义

本文提出了利用方解石和白云石二者的不同活性，在不同的温度条件下，在同一份 碳酸盐岩样品中，连续侧定碳、氧同位素比值的新方法。测定结果精度高，能用于判定白云石的 成因，具有实用价值。     

连续测定方解石和白云石中碳、氧同位素比值的方法及其意义

本文提出了利用方解石和白云石二者的不同活性,在不同的温度条件下,在同一份碳酸盐岩样品中,连续测定碳、氧同位素比值的新方法。测定结果精度高,能用于判定白云石的成因,具有实用价值。     

Dissolution and Deformation Characteristics of Limestones Containing Different Calcite and Dolomite Content Induced by CO2-Water-Rock Interaction

To investigate the impacts of mineral composition on physical and mechanical properties of carbonate rocks, limestone specimens containing different contents in calcite and dolomite are selected to perform CO2-water-rock reaction experiments. The X-ray Diffraction (XRD) and Nuclear Magnetic Resonance (NMR) are carried out to examine the change characteristics of mineral dissolution and pore structure after reaction. The core flooding experiments with Fiber Bragg gratings are implemented to examine the stress sensitivity of carbonate rocks. The results show that the limestones containing pure calcite are more susceptible to acid dissolution compared to limestone containing impure dolomite. The calcite content in pure limestone decreases as the reaction undergoes. The dissolution of dolomite leads to the formation of calcite in impure limestone. Calcite dissolution leads to the formation of macropore and flow channels in pure limestone, while the effects of impure dolomite in impure limestone results in mesopore formation. When confining pressure is lower than 12 MPa, pure limestones demonstrate higher strain sensitivity coefficients compared to impure limestone containing dolomite after reaction. When confining pressure exceeds 12 MPa, the strain sensitivity coefficients of both pure and impure limestones become almost equal.     

Oxygen and Carbon Isotope Study of Calcite and Dolomite in the Disseminated Au-Ag Telluride Bulawan Deposit, Negros Island, Philippines

Abstract: The disseminated Au‐Ag telluride Bulawan deposit, Negros island, Philippines, is hosted by dacite porphyry breccia pipes which formed in a Middle Miocene dacite porphyry stock. Electrum and Au‐Ag tellurides occur mostly as grains intergrown with or filling voids between sphalerite, pyrite, chalcopyrite, galena and tennantite. Calcite, quartz and rare dolomite are the principal gangue minerals. Four types of alteration were recognized in the deposit, namely; propylitic, K‐feldspar‐sericitic, sericitic and carbonate alteration. Carbonate alteration is correlatable to the gold deposition stage and occurs mostly along fault zones. The δ¹⁸O and δ¹³C compositions of calcite and dolomite in propylite zone and ore‐stage dacite porphyry breccia were determined. The δ¹⁸O values of calcite in propylitized andesite range from +12.2 to +14.7%, and their δ¹³C values range from ‐6.1 to ‐1.0%. The δ¹⁸O values of calcite and dolomite in sericite‐ and carbonate‐altered, mineralized dacite porphyry breccia and dacite porphyry rocks range from +15.1 to +23.1%, and the δ¹³C values of calcite and dolomite range from ‐3.9 to +0.9%. The δ¹⁸O and δ¹³C values of the hydrothermal fluids were estimated from inferred temperatures of formation on the basis of fluid inclusion microthermometry. The δ¹⁸O values of hydrothermal fluid for the propylitic alteration were calculated to be +8.5 ‐ +9.5%, assuming 375°C. On the other hand, the δ¹⁸O values of ore solutions for base metal and Au mineralization were computed to be +13.6 ‐ +14.6%, assuming 270°C. The hydrothermal fluids that formed the Bulawan deposit are dilute and ¹⁸O‐enriched fluids which reacted with ¹⁸O‐ and ¹³C‐rich wallrocks such as limestone.     

Recrystallization of Magnesian Calcite Overgrowths on Calcite SeedsSuspended in Seawater

The formation and subsequent reactions of magnesiancalcite overgrowths on calcite were investigated bymeans of closed system seeded precipitationexperiments. These experiments demonstrated that(1) thin overgrowths of magnesian calcite are precipitatedon calcite seeds suspended in seawater;(2) the solubilities of the coatings increase outward from theseed crystals as a linear function of the log ofrelative coating thickness;(3) during the period ofthese experiments (up to 5.5 months), the magnesiancalcite coatings continued to increase in thickness,but became less soluble in composition. Thestabilization reaction, referred to asrecrystallization, can be described by the followingequation:Cax Mg(1-x) CO3 + [z + y(x + z)]Ca2++ 2yHCO3- ]= (1 + y)Ca(x + z)Mg(1 - x -z)CO3 + [z + y(x + z - 1)]Mg2++ y CO2 + yH20;]4) recrystallization rate is dependent on solutionsaturation state, with a reaction order of 3.2 forartificial seawater and 4.0 for natural seawater; and(5) by the cessation of the closed system experiments,overgrowth compositions approached that of the stablecalcite (a few mol % MgCO3).Armoring of suspended carbonate particles in thesurface oceans with magnesian calcite overgrowthswould provide an effective barrier to release of theoceanic supersaturation with respect to calcite. Thicknesses of such coatings would be limited by therecrystallization rate of the magnesian calcite. Estimates based on the recrystallization ratesdetermined in this work indicate coatings on the orderof 0.02 µm in thickness could form on particles asthey sink through the mixed layer. According to thesecalculations, the total amount of carbon precipitatedannually in magnesian calcite overgrowths iscomparable to the riverine flux of dissolved carbon tothe oceans. Field observations of severalinvestigators indicate the likely presence ofmagnesian calcite coatings on planktonic particles,and provide evidence for possible recrystallization ofbiogenic magnesian particles in the marineenvironment.     

Calcite Dissolution Kinetics

We compare the canonical treatment of calcite’s dissolution rate from the literature in a closed system, particle batch reactor, with the alternative approach suggested by Truesdale (Aquat Geochem, 2015). We show that the decay of rate over time can be understood in terms of the evolution and distribution of reactive sites on the surface of these particles. We also emphasize that interpretation of observed rates must not exclude the fundamental role of crystal defects, whose importance is already implicitly reflected in the common form of rate laws in geochemistry. The empirical behavior of overall rate in closed systems, such as those described by Truesdale, may thus reflect relationships between defect centers and the generation of steps over the calcite surface (previously documented for silicates), such that below a critical free energy limit, there is insufficient driving force to open hollow cores and thus a loss of reaction mechanism. Dissolution in this very-near-equilibrium regime will be dependent on the distribution of extant steps and the energetics of new kink site nucleation. However, these sensitivities are complicated in the case of particle systems by grain boundaries, edges, corners, and other terminations. Such discontinuities constitute a defect class whose overall kinetic importance will be strongly tied to particle diameter and which can act independently of the internal strain field imposed by screw and edge dislocations.     

“白云岩问题”与“前寒武纪之谜”研究进展

白云岩的成因是沉积学界倍受关注的研究主题;众多的白云岩化模式可以用来解释各种成岩白云岩的成因;然而原生白云岩的成因一直是困扰沉积学界的难题,被称为“白云岩问题”。究其原因主要在于：在近地表环境的常温、常压实验条件下不能生成完美有序的白云石矿物。近年来,野外观测和实验模拟研究发现某些微生物的生命活动可导致白云石于地表常温、常压条件下发生沉淀。如硫酸盐还原细菌和产烷菌的调节作用可以克服白云石晶核形成的动力学障碍,在这些厌氧菌的参与下,白云石晶核形成和沉淀并不需要高镁离子和过饱和状态的溶液环境。这种微生物学和沉积学的结合代表了一个新的研究方向,同时也为解决“白云岩问题”带来了新希望。泥晶白云岩化作用（mimetic dolomization）可以保留原矿物（文石或方解石）的晶形、原岩的微细组构,对解释地史时期保存原生构造的白云岩具重要的启示。“前寒武纪之谜”是指前寒武纪叠层石中缺乏钙化蓝细菌化石的现象。参与碳酸盐岩叠层石建造的微生物群组成可能随着地质历史的演化发生变化,蓝细菌在显生宙的叠层石建造过程中起主导作用,细胞体积更小的真细菌很可能是参与前寒武纪叠层石建造的主要微生物。     

The Dolomite Problem Revisited1

A reassessment of the abundance of dolomite in carbonate sediments has confirmed that carbonates deposited during the past 150 Ma contain, on average, less dolomite than Proterozoic and Paleozoic carbonates. The lower dolomite content of the more recent carbonate sediments results from the increase in the deposition of CaCO₃ in deep-sea sediments, and to the difficulty of dolomitizing deep-sea CaCO₃ by reaction with cold, unevaporated seawater. The decrease in the rate of dolomite formation during the past 150 Ma has led to an increase in the output of oceanic Mg+² by the reaction of seawater with clay minerals and with ocean-floor basalts. The increase in the output of marine Mg+² into these reservoirs has been brought about by an increase in the Mg+² concentration of seawater. During the past 40 Ma, the concentration of Mg+² in seawater has probably increased by ～18 mmol/kg, and probably has been accompanied by an equimolar increase in the concentration of SO₄?².     

Calcite dissolution kinetics in Na-Ca-Mg-Cl brines

Sedimentary basins can contain close to 20% by volume of pore fluids commonly classified as brines. These fluids can become undersaturated with respect to calcite as a result of migration, dispersive mixing, or anthropogenic injection of CO₂. This study measured calcite dissolution rates in geologically relevant Na-Ca-Mg-Cl synthetic brines (50-200 g L⁻¹ TDS). The dissolution rate dependency on brine composition, pCO₂ (0.1-1 bar), and temperature (25.0-82.5 °C) was modeled using the empirical rate equation

R=k(1-Ω)ⁿ     

Calcite dissolution kinetics in saline waters

The effect of ionic strength (I), pCO₂, and temperature on the dissolution rate of calcite was investigated in magnesium-free, phosphate-free, low calcium (m_Ca2+ ≈ 0.01 m) simple KCl and NaCl solutions over the undersaturation range of 0.4 ≤ Ω_calcite ≤ 0.8. First-order kinetics were found sufficient to describe the rate data where the rate constant (k) is dependent on the solution composition. Rates decreased with increasing I and were faster in KCl than NaCl solutions at the same I indicating that Na⁺ interacts more strongly with the calcite surface than K⁺ or that water is less available in NaCl solutions. Rates increased with increasing pCO₂ and temperature, and their influences diminished at high I. Arrhenius plots yielded a relatively high activation energy (E_a ≈ 20 ± 2 kJ mol^− 1) which indicated that dissolution was dominated by surface-controlled processes. The multiple regression model (MR) of Gledhill and Morse (2006a) was found to adequately describe the results at high I in NaCl solutions, but caution must be used when extrapolating to low I or pCO₂ values. These results are consistent with the hypothesis that the mole fraction of “free” solvent (X_{“free”H2O}) plays a significant role in the dissolution kinetics of calcite with a minimum value of  45–55% required for dissolution to proceed in undersaturated solutions at 25–55 °C and pCO₂ = 0.1–1 atm. This hypothesis has been incorporated into a modified version of the MR model of Gledhill and Morse (2006a) where X_{“free”H2O} has replaced I and the Ca²⁺ and Mg²⁺ terms have been dropped:

     

一株岩生真菌对方解石的风化作用

选用一株从碳酸盐岩表面分离的真菌,研究了实验条件下该真菌对方解石的风化作用.通过检测风化培养基与对照培养基的pH值、Ca2+浓度、挥发性代谢产物以及分析真菌一矿物相互作用过程中的矿物表面微观形态变化,研究该真菌对方解石的风化过程和作用机理.结果表明:在实验条件下该真菌对方解石具有较强的风化作用,风化培养基上清液中的Ca2+浓度分别是死菌对照的3.98倍和纯水对照的13.73倍;该真菌生长过程中会分泌有机酸和醇类等代谢产物,真菌和矿粉之间会形成菌体-矿物聚集体或复合体,促进方解石的风化.分析认为该真菌对方解石的风化作用包括机械破坏,代谢产物溶蚀、络合作用以及多种因素之间的协同作用.     

Dolomite effect on borosilicate glass alteration

Dolomite (CaMg(CO₃)₂) is one of the common rock-forming minerals in many geological media, in particular in clayey layers that are currently considered as potential host formations for a deep radioactive waste disposal facility. Magnesium in solution is one of the elements known to potentially enhance the alteration of nuclear glasses. The alteration of borosilicate glasses with dolomite as a Mg-bearing mineral source was investigated for 8 months in batch tests at 90 °C. Glass composition effects were investigated through two compositions (SiBNaAlCaZrO and SiBNaAlZrO) differing in their Ca content. The Ca-rich glass alteration is slightly enhanced in the presence of dolomite compared to the alteration observed in pure water. This greater alteration is explained by the precipitation of Mg silicate phases on the dolomite and glass surfaces. In contrast, the Ca-free glass alteration decreases in the presence of dolomite compared to the alteration observed in pure water. This behavior is explained by Ca incorporation in the amorphous layer (formed during glass alteration) coming from dolomite dissolution. Calcium acts as a layer reorganizer and limits glass alteration by reducing the diffusion of reactive species through the altered layer. Modeling was performed using the GRAAL model implemented within the CHESS/HYTEC geochemical code to discriminate and interpret the mechanisms involved in glass/dolomite interactions. Magnesium released by dolomite dissolution reacts with silica provided by glass alteration to form Mg silicates. This reaction leads to a pH decrease. The main mechanism controlling glass alteration is the ability of dolomite to dissolve. During the experiment the quantities of secondary phases formed were very small, but for longer time scales, this mechanism could supply sufficient Mg in solution to form large amounts of Mg silicates and sustain glass alteration. The ability of the GRAAL model to reproduce the concentrations of elements in solution and solid phases regardless of the amount of dolomite and the glass composition strongly supports the basic modeling hypothesis.     

微生物白云石模式评述

Vasconcelos等在实验室模拟巴西Lagoa Vermelha潟湖条件,成功地沉淀出白云石,由此提出了微生物白云石模式。该模式在南澳大利亚、阿拉伯海湾、西印度外陆棚边缘以及意大利南部等地区得到了不同研究者的肯定,我国鄂尔多斯盆地奥陶系马家沟组五段白云岩也可以解释为微生物成因。此模式对白云石形成机理的研究具有突破性的意义。当硫酸盐还原细菌利用SO42-时,也吸收了Mg2+,因为Mg2+与SO42-形成了很强的离子对。微生物由于其新陈代谢作用利用SO42-而克服了动力障碍,同时从离子对中释放出Mg2+。在白云石形成的化学反应中,微生物因素把硫酸根离子从反应的抑制剂变成了催化剂。白云石一旦成核,就会在埋藏过程中长大。尽管不是所有的白云石都可以用微生物白云石模式来解释,但野外研究和模拟实验都证明这一模式是有说服力和生命力的。     

Dolomite Controls on Phanerozoic Seawater Chemistry

We investigate the potential role of dolomite as a long-term buffer on Phanerozoic seawater composition. Using a comprehensive model of Phanerozoic geochemical cycling, we show how variations in the formation rate of sedimentary marine dolomite have buffered seawater saturation state. The total inventory of inorganic carbon reflects the sum of fluxes derived from continental weathering, basalt-seawater exchange, alumino-silicate diagenesis (reverse weathering), and global deposition of calcium carbonate. Although these fluxes are approximately balanced, model results indicate that seawater saturation state is sensitive to the marine dolomite depositional flux. This conclusion is consistent with and constrained by independent proxy data for seawater ion ratios, paleo-atmospheric CO₂ concentrations, and paleo-pH data, and dolomite mass-age distribution through Phanerozoic time. Abundant research indicates that dolomite’s occurrence in marine sediments is sensitive to many factors: temperature, seawater composition, paleogeographic setting, continental organization, etc. Although the complexity of the process of dolomite formation prevents a complete understanding of the relative role of these factors, our model results clearly underscore the importance of this mineral in the chemical history of Phanerozoic seawater.     

埋藏环境白云石结构类型

近年来我国在白云岩储层油气勘探方面取得了重大进展,这些白云岩储层绝大多数为埋藏阶段形成的白云岩,同时大量研究也证实地层中大部分白云岩形成于埋藏环境。国际学术界对埋藏环境白云石的成因结构分类比较细致,但在我国这方面的研究还不够深入,因此本文借助国际上对埋藏环境白云石成因结构的分类方法,并结合中国白云岩研究的实际情况尝试提出埋藏环境白云石结构分类方案。该方案首先以白云石在岩石中的产状分为基质白云石和胶结白云石两大类,再以晶粒大小、晶型、晶面特征、接触关系为分类依据,将埋藏环境白云石分为六种结构类型。     

Calcite dissolution in two deep eutrophic lakes

The calcium cycle, in particular carbonate dissolution, was analyzed in two deep eutrophic lakes, Lago di Lugano (288 m maximum depth) and Sempachersee (87 m) located in Switzerland. A box model approach was used to calculate calcite dissolution in the water column and at the sediment-water interface based on various lake monitoring data such as sediment traps, sediment cores, water and pore-water analysis. A model for stationary conditions allowing the calculation of calcite dissolution in the water column for a given particle size distribution was developed. The relative values of the simulated flux were consistent with sediment trap observations. The best fit of the dissolution rate constant of sinking calcite in Lago di Lugano was on the same order of magnitude (3 · 10⁻¹⁰ kg^1/3 s⁻¹) as published laboratory values for this surface controlled process.Both lakes show a similar specific calcite precipitation rate of 170 g Ca m⁻² a⁻¹. The diffusive flux across the sediment-water interface amounts to about 15 and 10% of total calcite precipitation in Sempachersee and Lago di Lugano, respectively. However, 61% of the precipitated calcite is dissolved in the water column of Lago di Lugano compared to only 13% in Sempachersee. These results point towards the importance of grain size distributions and settling times in stratified deep waters as the two most important factors determining calcite retention in sediments of hard water lakes.