微生物白云岩模式研究进展

白云石（岩）问题一直是沉积学领域长期关注的研究主题之一。近年来,在研究含有白云石的现代自然环境和促进原生白云石的沉淀实验中,都加入了微生物因素,并取得了令世人关注的效果,这无疑为白云石（岩）的成因研究提供了新思路与新途径。在前人研究基础上,总结现有的观察资料和实验结果,将微生物促进白云石沉淀的机理模式归纳为厌氧模式和需氧模式2种,并分别介绍这两种模式中硫酸盐还原细菌、产甲烷菌和嗜盐好氧细菌促进白云石沉淀的机理;与微生物相关的矿物形态学特征中,球形和哑铃形白云石及白云石最初的成核阶段所形成的纳米球粒状结构具有一定代表意义,尤其是纳米球粒状结构可以作为生物矿物学上微生物白云石的标志性结构。通过这些特殊的形态特征来寻找微生物作用的证据,或可为古代相似成因白云石（岩）的成因研究提供一种标志。     

四川汉源-峨边地区上震旦统灯影组藻白云岩特征及成因研究

"藻白云岩"术语的提出已有五十年历史,震旦系藻白云岩以其巨大的厚度,精美的原生结构、构造,以及丰富的微生物化石和矿产资源而闻名,但至今其成因仍存在争议。以四川汉源-峨边地区上震旦统灯影组藻白云岩为研究对象,对其宏观的剖面、岩石学、原生构造特征,微观的白云石和微生物化石形态、原生结构特征,以及相应的地球化学特征进行了详细研究。结果表明:研究区灯影组藻白云岩为一套在潮坪和潟湖环境下形成的微生物（碳酸盐）岩的岩石类型组合,以藻黏结型的叠层状、纹层状、葡萄状和均一状（藻）白云岩为主要的次级类型;藻白云岩中主要发育原生的隐晶状微生物白云石和次生的纤维状拟晶白云石,其形成与蓝细菌、硫酸盐还原细菌、中度嗜盐好氧细菌和红藻等微生物的矿化作用密切相关:沉积-同生阶段,主要由微生物诱导矿化作用形成大量纳米似立方体粒状和（亚）微米级片状微生物白云石,同时共（伴）生纤维状文石和高镁方解石;同生-准同生阶段,主要由微生物影响矿化作用形成纳米球粒状和微米级不规则状、球状和卵状微生物白云石,同时纤维状文石和高镁方解石因微生物催化矿化作用和拟晶白云石化作用形成纤维状拟晶白云石;随后微生物白云石与拟晶白云石一起组成具纹层状、叠层状、均一状等构造的藻白云岩。对藻白云岩特征及成因的研究有助于理解微生物-矿物交互作用和过程的复杂性、多样性,也为前寒武纪微生物矿化作用、微生物白云石和拟晶白云石研究提供了新的实例。     

白云石成因模式的研究进展及其适用性探讨

在分析大量国内外文献资料的基础上,将现有的20余种白云石的成因划分为原生白云石和次生白云石化两类模式,根据镁钙比等指标又将次生白云石化模式进一步细分为高镁钙比、低镁钙比、正常镁钙比白云石化及其它白云石化4种模式类型,并对其中几种经典的白云石化模式的真实性和适用性进行了探讨。认为蒸发泵白云石化模式和回流渗透白云石化模式受到了普遍认可;混合水白云石化模式遭受到持续挑战;海水白云石化模式和埋藏白云石化模式得到了广泛关注;热液白云石化模式和微生物白云石化模式逐渐成为新的主流模式。     

柴达木盆地西部SG-1钻孔中白云石成因探讨

由于无机环境下不能沉淀白云石,该矿物的成因一直是学术争论的焦点。柴达木盆地西部钻孔SG-1（长938 m）中出现了大量白云石和铁白云石,白云石主要分布在钻孔下部500 m,而铁白云石主要分布在下部418 m。结合湖泊从淡水湖、咸水湖、盐湖至干盐湖的演化过程,文章分析了白云石和铁白云石的成因。白云石是盐类矿物的一种、且无机环境下不能沉淀,蒸发作用和微生物介导是白云石矿物形成的两个重要影响因素。蒸发作用为白云石的形成提供了足够浓度的Mg2+,微生物的介导作用帮助Mg2+克服动力学障碍进入碳酸钙晶格形成白云石。白云石是湖泊演化早期析出的一种碳酸盐类矿物,主要在咸水湖环境中沉淀,盐湖环境中主要沉淀硫酸盐类和氯化物矿物,在盐湖这种高盐度环境下能够生存的微生物非常少,白云石含量明显降低。铁白云石是白云石矿物的一种,是Fe2+替代白云石中的Mg2+形成的次生矿物。Fe2+有两种来源：粘土矿物转换过程中的释放和深部热液来源。Fe2+进入白云石的过程主要是在无机、高温环境下完成的,但不排除微生物的介导作用。     

湖相原生白云石的微生物成因机理探讨*

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、SO42-的存在和硫化物对镁水合物脱水的影响以及微生物白云石沉淀的环境因子。对微生物成因的原生白云石模式的深入认识,将为湖相白云石成因研究提供新的理论基础和研究思路。     

白云岩成因的研究现状及相关发展趋势

白云岩占地壳沉积岩体积的20%,是碳酸盐岩地层中最主要的油气储渗体。白云岩成因是碳酸盐岩岩石学中最复杂、争论时间最久、最难解决的问题之一。根据机理的不同,当前各种主要的白云岩成因模式可划分为三大类:(1)原生白云石模式;(2)次生白云石化模式;(3)其他模式。虽然原生白云石的例子已被大量发现,但是,它们是否属真正的原生白云石仍将继续讨论下去。次生白云石化成因的实例远比原生白云石成因的多,这类模式可再细分为高盐度白云石化、低盐度白云石化、正常海水白云石化、热液白云石化等。其他模式主要有埋藏白云石化、生物白云石化、沉积—热液模式、玄武岩淋滤白云石化、出溶作用模式等。白云岩研究的热点问题及研究发展方向可以归纳为五个方面:全球气候变化与白云石化事件;大地构造环境和沉积作用对白云岩分布的控制;白云石化作用与层序地层学(相对海平面变化);新的研究手段的应用;“盖帽”白云岩。     

原生白云石与交代白云石晶体的微结构对比研究

应用高分辨的透射电镜（ＴＥＭ）对原生白云石与交代白云石晶体微结构进行了对比研究。原生白云石晶体中微结构以位错、调制结构为主，调制结构规则，调制波长稳定，属生长调制；交代白云石晶体中的调制结构很不规则，波长变化大，有方解石残留。能谱分析显示两种白云石晶体中调制区与非调制区Ｃａ、Ｍｇ相对含量相差很大。两者微结构差异反映了成因上的不同     

青藏高原风火山砂岩的磁性特征及其意义

风火山白垩系紫色砂岩样品的矿物学分析结果表明,大部分样品的磁性载体是铁白云石.根据退磁曲线估计其居里点为500℃左右.当退磁温度增加到600℃左右,铁白云石开始分解,形成磁铁矿,致使样品在此温度段退磁时,其磁性不但不减小反而骤然增加,甚至可达天然剩磁的十几倍,其原生成分受到破坏.因此,在低于居里点温度确定的本征剩磁及相应的古地磁数据将能反映特定的地质意义.由风火山白垩系古地磁数据可见,青藏高原巴颜喀拉地体白垩系以后仍然存在着较大规模的北向移动.     

松科1井嫩江组湖相含铁白云石的准确定名和矿物学特征

通过XRD衍射和电子探针分析,从矿物学命名的角度出发,提出松科1井嫩江组湖相白云岩的主要矿物是白云石和铁白云石之间的过渡类型——含铁白云石,而不是长期认为的铁白云石。矿物学特征表明:精测后的晶胞参数a、c、V值均大于标准白云石,更接近标准铁白云石,说明含铁白云石和铁白云石具有相同晶体结构,但在同一结构位置上,Fe2+和Mg2+的数量比存有差异,且结构中Fe2+对Mg2+的部分替代是导致晶胞轴长和体积增大的原因,从晶体结构的角度再次证实样品为含铁白云石。另外,通过计算,含铁白云石的有序度均值为0.40,CaCO3摩尔含量均值为55.48g/mol,表明较富钙的、低有序度的含铁白云石形成于结晶速度较快、不稳定的成岩环境中。     

新疆三塘湖盆地中二叠统芦草沟组湖相白云岩成因*

新疆三塘湖盆地中二叠统芦草沟组发育湖泊背景下的白云岩、灰岩、黑色泥岩、页岩及碎屑岩的互层沉积。白云岩主要有两类：一类为粉—泥晶白云岩,主要由含量约70％的泥晶白云石和含量约30％的粉晶白云石构成,白云石有序度为0.48,扫描电镜下主要有菱形、他形、球状和管状4种微形态,自形程度较好的菱形晶体多为含铁白云石;另一类为方沸钾长白云岩,主要由晶粒为0.08～0.35mm的细粒方沸石、泥晶钾长石（透长石）、泥晶白云石和铁白云石构成,个别为粗晶白云石,白云石有序度0.58。与粉—泥晶白云岩中的白云石相比,方沸钾长白云岩中的白云石以高的铁、锰含量为特征,扫描电镜下多为半自形的菱形晶体。两类白云岩中白云石的有序度均较低,且均为富Sr白云石,内部均缺乏次生交代证据。通过对两类白云岩成分、微量元素及稳定同位素的差异性分析,认为尽管两类白云岩都形成于浅—半深湖相强还原沉积环境,但是它们的形成机制有所不同,粉—泥晶白云岩具有原生沉淀白云石的特征,其中球状及管状的白云石可能与微生物吸附作用有关,而他形及菱形的白云石为直接沉淀的原生白云石;另一类方沸钾长白云岩中的白云石及铁白云石可能与湖底热泉的喷流沉积作用有关。     

Origin and diagenetic evolution of Ca–Mg–Fe carbonates in some coalfields of Japan

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.     

酒西盆地碎屑岩胶结物的形成问题

酒西盆地下白垩统陆相碎屑岩胶结物的形成关系到油气储集的重要问题,富铁的洪积扇沉积体系和非富铁的河流一湖泊沉积体系形成两种不同的胶结物组合类型,平面上可分为三带胶结物:混合胶结带、铁镁胶结带和浓聚成岩带。盆地边缘带是以铁、泥、钙为主的混合胶结物,中间为以碳酸铁镁矿物的白云石、铁白云石为主的胶结物,盆中带形成胶结物的浓聚成岩层,事实证明过渡的铁镁胶结带是最富于聚集油气的地带。本文还在纵向上探讨了泥质粘土矿物和碳酸盐胶结物的成岩变化。     

Microstructures in carbonates from the Alnø and Fen carbonatites

The nature of carbonates and related second phase minerals in carbonatite samples from the Alnø and Fen regions has been studied by optical and transmission electron microscopy, aided by X-ray diffraction and electron microprobe analysis.Calcite, dolomite and ankerite have been found to exhibit two phase microstructures. Coherent ribbons of calcitic material occur in dolomite and ankerite, while the calcite grains commonly contain a fine dispersion of plate-like and sometimes rod-like precipitates. Calcite and dolomite frequently occur in contact with the same crystallographic lattice orientation, the small lattice mismatch being indicated by moiré patterns at the grain boundaries and occasional misfit dislocations.The two-phase structure of calcite in dolomite reported for the first time in this paper is thought to be a high temperature analogue of the modulated microstructures reported recently in calcian sedimentary dolomites (Wenk et al. 1983).     

Double carbonate breakdown reactions at high pressures: an experimental study in the system CaO–MgO–FeO–MnO–CO2

The pressure–temperature conditions of the reactions of the double carbonates CaM(CO₃)₂, where M = Mg (dolomite), Fe (ankerite) and Mn (kutnohorite), to MCO₃ plus CaCO₃ (aragonite) have been investigated at 5–8 GPa, 600–1,100°C, using multi-anvil apparatus. The reaction dolomite = magnesite + aragonite is in good agreement with the results of Sato and Katsura (Earth Planet Sci 184:529–534, 2001), but in poor agreement with the results of Luth (Contrib Mineral Petrol 141:222–232, 2001). The dolomite is partially disordered at 620°C, and fully disordered at 1,100°C. All ankerite and kutnohorite samples, including the synthetic starting materials, are disordered. The P–T slopes of the three reactions increase in the order M = Mg, Fe, Mn. The shallower slope for the reaction involving magnesite is due partly to its having a higher compressibility than expected from unit-cell volume considerations. At low pressures there is a preference for partitioning into the double carbonate of Mg > Fe > Mn. At high pressures the partitioning preference is reversed. Using the measured reaction positions, the P–T conditions at which dolomite solid solutions will break down on increasing P and T in subduction zones can be estimated.     

Refinement and comparison of the crystal structures of a dolomite and of an Fe-rich ankerite

Summary The crystal structures of a dolomite and of an iron rich ankerite were refined from three-dimensional X-ray data by least squares methods toR0.03. The angle of rotation of the CO₃ group is 6.35(5)^o in dolomite but only 5.28(5)^o in ankerite, a consequence of the different sizes of the (Mg, Fe)O₆ octahedra. The carbonate group deviates very slightly from planarity in both minerals. The Ca–O distances are somewhat larger in both minerals than in calcite; the Mg–O distance in dolomite, on the contrary, is somewhat smaller than in magnesite.

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Verfeinerung und Vergleich der Kristallstrukturen eines Dolomits und eines Fe-reichen Ankerits

Zusammenfassung Die Kristallstrukturen eines Dolomits und eines eisenreichen Ankerits wurden aus dreidimensionalen Röntgendaten mittels der Methode der kleinsten Quadrate aufR0,03 verfeinert. Der Verdrehungswinkel der CO₃-Gruppe ist im Dolomit 6,35(5)^o, im Ankerit nur 5,28(5)^o; das ist eine Folge der unterschiedlichen Größen der (Mg, Fe)O₆-Oktaeder. Die Gestalt der Karbonatgruppe weicht in beiden Mineralen ganz leicht von planar ab. Die Ca–O-Abstände sind in beiden Mineralen etwas größer als im Calcit, der Mg–O-Abstand ist hingegen im Dolomit etwas kleiner als im Magnesit.

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Dolomite–silica stromatolites in Miocene lacustrine deposits from the Duero Basin, Spain: the role of organotemplates in the precipitation of dolomite

This research provides an ancient analogue for biologically mediated dolomite precipitation in microbial mats and biofilms, and describes the involvement of highly structured extracellular polymeric secretion (EPS) templates in dolomite nucleation. The structure of EPS is shown to match the hexagonal–trigonal lattice geometry of dolomite, which favoured the epitaxial crystallization of dolomite on the organic substrate. This structure of EPS also matches the arrangement of silica nanospheres in opal, which further accounts for the organically‐templated formation of opal enabling the non‐replacive co‐existence of dolomite and silica. The study is focused on a 50 m thick dolomite succession that is exposed in central areas of the Tertiary Duero Basin and was deposited in a mudflat‐saline lake sedimentary complex during the Middle to Late Miocene (9 to 15 Ma). In the intermediate intervals of the succession, poorly indurated dolomite beds pass gradually into silica beds. On the basis of sedimentological, compositional, geochemical and petrographic data, silica and dolomite beds have been interpreted as mineralized microbial mats. The silica beds formed in marginal areas of the lake in response to intense evaporative concentrations; this resulted in the rapid and early precipitation of opal. Silicification accounted for the exceptional preservation of the microbial mat structure, including biofilms, filamentous and coccoid microbes, and EPS. Extracellular polymeric secretions have a layered structure, each layer being composed of fibres which are arranged in accordance with a reticular pattern, with frequent intersection angles at 120° and 60°. Therefore, the structure of EPS matches the lattice geometry of dolomite and the arrangement of silica nanospheres in opal. Additionally, EPS binds different elements, with preference to Si and Mg. The concurrence of suitable composition and surface lattice morphologies in the EPS favoured the crystallization of dolomite on the substrate. In some cases, dolomite nucleation took place epicellularly on coccoid micro‐organisms, which gave way to spheroid crystals. Organic surfaces enable the inorganic mineral precipitation by lowering the free energy barrier to nucleation. Most of the microbial mats probably developed on the lake floor, under sub‐aqueous conditions, where the decomposition of organic matter took place. The subsequent formation of openly packed dolomite crystals, with inter‐related Si‐enriched fibrils throughout, is evidence for the pre‐existence of fibrillar structures in the mats. Miocene dolomite crystals are poorly ordered and non‐stoichiometric, with a slight Ca‐excess (up to 5%), which is indicative of the low diagenetic potential the microbial dolomite has towards a more ordered and stoichiometric structure; this confirms that microbial imprints can be preserved in the geological record, and validates their use as biosignatures.     

Estimation of dolomite formation: Dolomite precipitation and dolomitization

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.     

Superstructures in ankerite and calcite

Two rhombohedral carbonates, ferroan dolomite (ankerite) and magnesian calcite from lower Jurassic ammonites, have been studied by transmission electron microscopy. The samples show small domains with the morphology of platelets parallel to (11 \(\bar 2\) 0) which have exceptionally well ordered superstructures and characteristic c-reflections. Diffraction patterns and contrast analysis of atomic resolution images indicate that the domains observed in ankerite are rich in Ca [Ca_0.75(Mg, Fe)_0.25CO₃] and those in calcite rich in Mg, and there is strong evidence that cation ordering is the cause for the observed superstructures which are proposed mainly on diffraction evidence. Rhombohedral carbonates have a close similarity to NaCl, with CO₃-groups substituting for Cl. Cation ordering patterns can therefore be discussed in analogy to f.c.c. alloys. We make use of ordering waves to describe superstructures and to qualitatively interpret kinetic conditions for their formation.