鲕粒原生矿物识别及对海水化学成分变化的指示意义

鲕粒是碳酸盐沉积过程中一类非常特殊的颗粒类型, 为研究当时的沉积背景、水动力条件、气候环境, 甚至储层特征提供了重要线索。然而, 鲕粒的矿物组成及控制因素问题, 长期受到忽视。组成鲕粒的原生矿物类型在地质历史时期呈周期性变化, 在显生宙表现为三个以文石和高镁方解石占主导的时期以及两个以低镁方解石占主导的时期, 这也被称作“文石海”和“方解石海”时期。原生矿物的组成, 制约着鲕粒的纹层结构、保存程度以及成岩特征, 还蕴含着海水化学成分变化的线索。鲕粒原生矿物识别主要依据:①原生纹层结构;②保存程度;③微量元素浓度, 尤其是Sr-Mg的浓度。文石质鲕粒受文石不稳定性的影响, 原生结构保存程度较差;一般保存有典型的文石残余纹层结构(例如砖砌结构、溶解变形结构以及偏心结构等);在封闭成岩环境下原生矿物为文石质的鲕粒Sr浓度往往大于2 000 ppm;纹层结构主要为切线状(占主导)和放射状。方解石质鲕粒包括低镁方解石和高镁方解石两种类型:低镁方解石为稳定矿物, 原生结构一般保存良好。尽管高镁方解石也为亚稳定矿物, 但成岩转换后的保存程度好于文石。两者Sr含量一般均低于1 000 ppm, Mg含量一般在0~20 mol % MgCO₃(两者以4 mol % MgCO₃为界)。高镁方解石受成岩作用影响, 在纹层中往往保留有微粒白云石包裹体;海相地层中保存的方解石质鲕粒为放射状或同心-放射状结构。另外还存在一类由两种矿物共同构成的双矿物鲕粒, 可以通过分析两类纹层在结构和保存特征上的差异进行区分。鲕粒原生矿物成分随时间的波动变化受到海水化学条件, 尤其是Mg/Ca比值, 大气二氧化碳分压以及碳酸盐饱和度的控制。Mg/Ca比值的波动决定着鲕粒原生矿物类型的长期变化规律。一些突发性事件可能会扰动(区域)短时间尺度下鲕粒原生矿物的组成, 造成鲕粒原生矿物的转换。通过研究碳酸盐鲕粒原生矿物特征以及控制因素进而了解海水的化学特征, 是独立于古生物学和地球化学分析之外的一种较为可靠的沉积学方法。     

New interpretations of Great Salt Lake ooids and of ancient non-skeletal carbonate mineralogy

Earlier interpretations of textural alteration affecting Great Salt Lake ooids have greatly influenced concepts of ooid diagenesis. Scanning electron microscope study shows, however, that the coarse radial aragonite rays are depositional, that no recrystallization of pellet cores has occurred, and that Great Salt Lake ooids have not suffered noticeable diagenesis. As suggested by Kahle (1974), radial texture in ancient calcitic ooids is probably mainly original, not diagenetic. Retention of such fine textures has been attributed to organic matter (since found to be equivalent in modern skeletal and non-skeletal grains) or to paramorphic replacement (proposed for non-skeletal grains whose original aragonite mineralogy was only inferred from modern analogs). Pleistocene ooids known to have been aragonite alter like aragonite shells to coarse neomorphic calcite, often with aragonite relics. The striking uniformity of that coarse texture in neomorphic calcite replacing known skeletal aragonites throughout the geologic record has been noted for over 100 years. In contrast, Mississippian ooids retain fine texture as do calcite layers of coexisting gastropods, but unlike the strongly altered aragonite layers of these same gastropods. Therefore, inferences of original aragonitic mineralogy of ancient non-skeletal carbonate grains (including muds) which are now calcite but retain fine texture appear unwarranted, as do assumptions of differential diagenetic behaviour of ancient aragonitic skeletal and non-skeletal grains. Accordingly, modern depositional environments of marine ooids and carbonate muds must be rejected as chemically unrepresentative of comparable ancient environments. It is inferred that ancient non-skeletal carbonates were originally predominantly or exclusively calcite because of an earlier lower oceanic Mg/Ca ratio (<2/1) which altered progressively to values favouring aragonite (modern Mg/Ca value = 5/1). Major influencing factors are: selective removal of calcium by planktonic foraminifers and coccolithophorids since Jurassic-Cretaceous time and by abundant younger, Mg-poor aragonite skeletons and an erratic trend toward decreasing dolomite formation (decreasing removal of oceanic Mg). The change to aragonite dominance over calcite for non-skeletal carbonates was probably during early to middle Cenozoic time.     

Ooids in Purbeck limestones (lowermost Cretaceous) of the Swiss and French Jura

ABSTRACT Ooids occurring in the shallow-water Purbeckian carbonate sediments of the Jura mountains can be grouped into six types. Gradations from one type to another and coexistence of the various types are common. Type 1 ooids are small and well rounded. They display fine concentric micritic laminae. In many cases their cortices are dissolved and replaced by void-filling spar. Microsparitic neomorphic replacement occurs locally. Type 2 ooids are large and have irregular shapes. They show fine micritic laminae and occasional layers of fine-radial crystals. They commonly evolve into oncoids. Ooids of type 3 display many fine-radial cortical laminae and are patchily micritized. They are medium in size and mostly well rounded. This type of ooid may pass into large, irregularly shaped coated grains. Type 4 ooids have 1 to 4 cortical laminae with a fine-radial structure and patchy micritization. They are medium in size and well rounded. Type 5 ooids have only one lamina with a coarse-radial structure. They are small and well rounded. Associated are spherical grains containing bundles of elongate crystals. Ooids of type 6 show superpositions of two or more different, radial and or fine micritic laminae. The cortical structure may also change laterally in the same lamina. The preferential dissolution of type 1 ooid cortices to form oomoulds indicates a primary composition of unstable carbonate. Sedimentological features and comparison with modern ooid occurrences point to formation on high-energy sandbars in normal-marine waters. Type 2 ooids grew in marine-lagoonal environments with quiet water and abundant cyanobacteria. The radially structured ooid cortices of types 3, 4 and 5 show no dissolution features. This implies that they were originally composed of stable carbonates, or that an unstable carbonate phase was transformed into a stable one at an early stage of diagenesis. Type 3 ooids occur together with marine faunas and indicate high water energy. Ooids of type 4 and type 5 originated probably from relatively quiet water of variable salinity. Coexistence of different ooid types and mixed forms of type 6 implies gradual or rapid changes in hydrodynamic, geochemical and microbiological conditions which were a feature of the Purbeckian depositional environments.     

Cathodoluminescent bimineralic ooids from the Pleistocene of the Florida continental shelf

A bored and encrusted late Pleistocene ooid grainstone was recovered from the seafloor at a depth of approximately 40 m on the outer continental shelf of eastern Florida. Ooid cortices are dominantly bimineralic, generally consisting of inner layers of radial magnesian calcite and outer layers of tangential aragonite. Ooid nuclei are dominantly rounded cryptocrystalline grains, although quartz grains and a variety of skeletal grains also occur as nuclei. Ooids are partially cemented by blocky calcite, and interparticle porosity is partially filled by micrite. Radial cortex layers are composed of brightly cathodoluminescent magnesian calcite having a composition of approximately 12 mol% MgCO₃ and 1000 ppm strontium. The iron and manganese concentrations in radial cortex layers are generally in the range of 500–1000 ppm and 100–250 ppm, respectively. Tangential cortex layers are composed of noncathodoluminescent aragonite containing approximately 11 500 ppm strontium and less than 0.5 mol% MgCO₃. Iron concentrations in tangential cortex layers are generally in the range of 150–400 ppm, and manganese concentrations are generally below the detection limit of 100 ppm. Echinoderm skeletal fragments, which are present as accessory grains, are composed of brightly cathodoluminescent magnesian calcite. Some ooid nuclei and the thin outer edges of some blocky calcite cement are cathodoluminescent; micrite matrix and the bulk of blocky calcite cement are noncathodoluminescent. Ooids do not exhibit textural evidence of recrystallization. The ooid grainstone underwent an episode of meteoric diagenesis. but ooid cortices were not affected by the event. We propose a previously unrecognized process by which the magnesian calcite cortex layers underwent diagenetic alteration in oxygen-depleted seawater. During this diagenesis, magnesium was lost and manganese was incorporated without apparent textural alteration and without mineralogical stabilization. Thus, we Suggest that cathodoluminescence may result from diagenetic alteration on the sea-floor.     

美国得克萨斯古生界和中生界鲕粒的微孔隙度

本文所述的由1-5μm自形菱形方解石组成的微晶化鲕粒采自得克萨斯奥陶系-侏罗系的鲕粒灰岩和泥粒灰岩,其中:露头样品4个,岩心样品3个,岩屑样品7个。微晶化鲕粒的孔隙度可大于15%,渗透率为1毫达西.鲕粒的微晶化不是由淋滤作用所引起,而是在矿物稳定化过程中由文石转化而成方解石。     

Brick-like texture and radial rays in Triassic pisolites of Lombardy,Italy: A clue to distinguish ancient aragonitic pisolites

Triassic pisolites from the Calcare Rosso, Lombardy, Italy, were formed in a hypersaline vadose environment and now show alternating dolomite and calcite laminae. The calcite consists either of microsparite laminae with a brick-like fabric, or of a mass of mosaic crystals with the external form of square-ended rays.These features suggest that the original laminae and rays were aragonitic, like those of the Holocene supratidal pisolites of the Persian Gulf, which consist of alternating laminae of unoriented nannomicrite with Mg-rich mucilaginous material, and aragonitic fibers with radial orientation separated by mucilaginous films. It is suggested that the transformation to brick-like and ray textures passed through the following diagenetic path: (1) original formation of fibrous aragonite laminae; (2) local aggrading recrystallization of aragonite fibers to large square-ended rays during hypersaline phases; (3) dolomitization of Mg-rich mucilaginous nannomicrite laminae during hyposaline phases; (4) inversion of the aragonite fibers and rays to calcite on a piece-by piece basis that preserved the original textural details, when the pH or Mg/Ca ratio dropped.The brick-like and ray fabrics have not been found in laminae of continental freshwater pisolites because these were deposited as equant and stable crystals of low-Mg calcite. These textures consequently make it possible to establish the chemistry of the depositional and early diagenetic milieu for some ancient pisolitic rocks.     

Organic matter, putative nannobacteria and the formation of ooids and hardgrounds

Modern ooids from Joulters Cay, when baked at 500 °C, turn various shades of black depending upon the organic content. Mucus-rich laminae occur at quasi-regular intervals of a few micrometres within the cortex. When mucus is still present, it turns black; when it is absent, there is a gap. The cortex consists of two types of aragonite: (1) 'batons' of circular cross-section capped by a single 0·1-μm (100-nm) ball, which can be interpreted as a single nannobacteria cell that precipitated the baton; (2) elongate crystals made of multiple rows of minute balls of about 0·03 μm (30 nm), which may or may not have been small organisms in the size range of viruses. There are also some crystals that show no evidence of organic precipitation. Hardground cementation begins with the formation of a terminal mucus-rich ring on the ooid that bakes black and is crowded with 0·1-μm (100-nm) balls. Some ooids are then joined by a meniscus also made of mucus with aragonite crystals. The final, most abundant hardground cement forms a fur of inorganic aragonite crystals often shaped like plywood sheets, although some 'organic', elongate crystals composed of ≈0·03 μm (≈30 nm) balls are also found in the later cement. For a century, ooids have been known to be closely associated with organic matter; this paper goes further and proposes that the bulk of the ooid may be precipitated by nannobacterial processes. Hardground formation, in the beginning, may also be a microbiological process, but most cementation is accomplished inorganically.     

The early diagenetic origin of Lower Carboniferous mottled limestones (pseudobreccias)

Dark mottles are a prominent and widespread feature of the regressive, cyclic, shallow marine limestones which form the late Asbian succession in many parts of Britain. The colour difference which defines mottles in outcrop is caused by distinct but often subtle petrographic differences in the limestone fabric. Specifically, mottles contain a light brown coloured opaque inclusion-rich calcite spar with characteristic dull brown luminescence; ‘mottle spar’. Outside mottle margins this calcite spar is absent, with clear inequant blocky cements forming the pore filling phase. ‘Mottle spar’ comprises a fabric of irregular crystals predominantly 5–40 μm in diameter, with more regular crystals up to 100 μm diameter often occurring in intraparticle and large interparticle pores. Under cathodoluminescence, ‘mottle spar’ displays crystal morphologies and growth patterns which indicate that both localized neomorphism and patchy cementation contributed to mottle formation. Cathodoluminescence cement stratigraphy shows that ‘mottle spar’ pre-dates all other major pore filling cements in the local Asbian succession, but post-dates marine micritization. ‘Mottle spar’ sharply defines the moulds of former aragonitic allochems which are now filled by the later clear, inequant spar cements. This shows that aragonite dissolution occurred after the formation of ‘mottle spar’. Mottles in calcretes contain unaltered allochems which have been protected from the effects of subaerial micritization by ‘mottle spar’, although mottles are often affected by subaerial brecciation. This evidence shows that mottles formed during early diagenesis; after marine micritization, but before dissolution of aragonite, subaerial exposure and meteoritic phreatic cementation. Mottles represented lithified patches of very low porosity which are interpreted to have formed in the marine/freshwater mixing zone, during the repeated phases of regression and emergence in the late Asbian.     

Relationships between lithology and diagenesis in a limeston—marl facies transition: an electron microprobe study

A 3 km long lateral facies transition from Oligo-Miocene skeletal grainstones into packstones and mudstones displays systematic variation in carbonate skeletal fragment alteration and secondary carbonate mineral composition. Within the skeletal grainstone end-member all aragonitic grains have dissolved, all Mg-calcite skeletal fragments have altered to calcite, and calcite has been precipitated as both void-filling spar and as syntaxial overgrowths on echinoid fragments. Within the transitional grainstone-packstone lithologies some skeletal fragments show preservation of their original mineralogy, while calcite, ferroan calcite spar and dolomite have precipitated in void spaces. Within the packstone-mudstone end-member of the transition, aragonitic grains have been preserved and Mg-calcite skeletal fragments have retained most of their magnesium. Thin, originally porous grainstone layers within the pack-stone-mudstones contain sideroplesite and ferroan calcite spar in void spaces, and iron has been incorporated in skeletal fragments which were originally Mg-calcite. In these grains iron has been incorporated at the expense of magnesium until the grains approach the composition of the surrounding ferroan calcite cement. The lateral variation in diagenetic alteration across this facies transition is a function of differing groundwater movement and composition, controlled ultimately by the composition, porosity and permeability of the host lithologies.     

光合作用生物膜诱发的放射鲕粒:以江苏徐州贾旺剖面寒武系苗岭统张夏组为例*

几年来针对巴哈马现代文石鲕粒的持续性研究表明,微生物和细胞外聚合物质(EPS)在鲕粒的形成和发育中起着关键而重要的作用,从而产生了一个重要的认识,即: 鲕粒可以看作是“纹层状的有机沉积构造”并遵循着微生物岩体系的一些形成特征。但是,鲕粒30亿年的发育历史、多样化的产出环境、特征性的矿物构成和各种各样的沉积组构,确实赋予了鲕粒生长和形成机理的复杂性和神秘性,因为鲕粒在何处而且如何形成、以及鲕粒究竟记录着何种生物与非生物过程的许多问题还存在剧烈争论。来自于江苏徐州贾旺剖面苗岭统张夏组上部鲕粒滩相灰岩,由较为典型的方解石放射鲕粒所组成,表现出放射状、放射—同心状和泥晶质的沉积组构,而且在鲕粒核心、鲕粒皮层以及在鲕粒间的不规则团块或凝块的暗色泥晶质构成中高密度地保存着精美的葛万菌(Girvanella)化石,进一步表明了这些暗色泥晶构成代表着较为特征的光合作用生物膜,从而提供了一个苗岭世方解石海中放射鲕粒形成较为直接的微生物证据,以及与光合作用生物膜之间复杂的成因联系,因为葛万菌是相对较为肯定地类比于近代钙化织线菌(Plectonema)的丝状蓝细菌化石,尽管还可类比于现代的伪枝菌(Scytonema)。虽然形成放射状鲕粒皮层的放射纤维状方解石的沉淀作用确实不能解释为直接的微生物沉淀作用的结果,但是,这些放射鲕粒确实表现出光合作用生物膜诱发、滋养并促进了放射纤维状方解石皮层增生作用的重要证据,为拓宽“鲕粒谜”的阐释提供了一个较为重要的典型实例,而且还成为寒武纪苗岭世方解石海与后生动物辐射相耦合的蓝细菌繁荣的重要证据。     

Aragonite relic preservation in Jurassic calcite-replaced bivalves

Shells of the aragonite bivalve Neomiodon (Great Estuarine Group, Jurassic, Scotland) replaced by coarse neomorphic calcite contain oriented relics of the original aragonite ultrastructure. The presence of these relics in such old altered shells, as well as the high Sr content of the replacement calcite, indicate that the process of calcite replacement of aragonite is not a cumulative slow process involving repeated alteration events, but rather a rapid, one-step process. Aragonite relics, once encased in neomorphic spar, will survive as unequivocal evidence of original aragonite mineralogy, barring total remobilization of the enclosing stable calcite, a generally unlikely event. The retention of this residual aragonite and high-Sr calcite supports recent isotopic studies which suggest that the multiple phases of alteration (‘recrystallization’) invoked in earlier literature are unlikely events in the diagenesis of most undolomitized limestones. Retention of aragonite relics appears to be independent of whether alteration occurs in shallow meteoric or, as in the case of our Neomiodon material, deeper burial environments. Pseudopleochroism of the replaced Neomiodon shells appears to be due to organic, largely graphitic, relics, not to the aragonite relics.     

寒武纪丝状蓝细菌生物膜主导和诱发的巨型鲕粒:以河南新安县石井剖面苗岭统徐庄组为例*

多样化的产出环境和30×10⁸年的分布历史表明,鲕粒成因一直是一个谜一样的沉积学难题,争论的关键问题是其究竟是有机(微生物)成因还是无机成因。来自于华北地台寒武系苗岭统徐庄组鲕粒滩相灰岩顶部的方解石巨鲕表现出同心状、放射—同心状和泥晶质的沉积组构,在鲕粒核心和鲕粒皮层中保存着精美的葛万菌(Girvanella)化石所主导的光合作用生物膜的钙化作用残余物,这为研究鲕粒形成与光合作用生物膜之间复杂的成因联系提供了一个较为直接的微生物证据,因为葛万菌可相对较为肯定地类比于近代的钙化织线菌(Plectonema)丝状蓝细菌化石。所以说,在伴随着后生动物辐射的寒武纪蓝细菌繁盛的方解石海中,尽管形成放射状鲕粒皮层的放射纤维状方解石的沉淀作用机理还没有得到完全彻底的了解,但是这些巨鲕确实表现出光合作用生物膜诱发、滋养并促进了鲕粒形成的直接证据,进一步支持了“鲕粒沉积可以作为一种不同的微生物岩体系新类型”的重要科学理念。     

Fabrics,facies control and diagenesis of lacustrine ooids and associated grains from the Upper Triassic,southwest England

Petrographic analysis of ooids from the Upper Triassic (Mercia Mudstone Group) of southwest England provides an opportunity to assess in detail the origins, transport pathways and diagenesis of an ancient oolite. The Clevedon Oolite is dolomitized and contains a variety of dissolved ooids (oomoulds) and associated grains. The oomoulds occur in well‐sorted, planar and cross‐stratified grainstones, packstones, sandstones and conglomerates associated with shoreface, intershoal, foreshore, beachrock and littoral strandplain deposits. The ooids grew in suspension in the shoreface zone and developed a radial aragonite microstructure. The ooids grew to 0.80 mm in diameter, after which they fractured or ceased growing. Broken grains deposited on or near mobile shoals were rapidly recoated, while other grains, deposited in less agitated, intershoal and lower foreshore areas, were micritized or microbially bound into grapestone aggregates. Locally peloids, intraclasts, quartz grains and micritized grains from intershoal areas supplied nuclei for ooids on nearby shoals. Grains deposited in foreshore areas were rapidly cemented into beachrock and reworked into conglomerates. Soon after deposition, the ooids were subjected to widespread aragonite dissolution followed by dolomitization. The lack of pre‐dolomitization calcite, together with the abundance of early (pre‐compaction) dolospar cements and fabric‐selective dolomitization of micritic fabrics, suggest aragonite dissolution by dolomitizing fluids. Copyright © 2002 John Wiley & Sons, Ltd.     

寒武纪丝状蓝细菌生物膜主导和诱发的巨型鲕粒:以河南新安县石井剖面苗岭统徐庄组为例

多样化的产出环境和30×108年的分布历史表明,鲕粒成因一直是一个谜一样的沉积学难题,争论的关键问题是其究竟是有机(微生物)成因还是无机成因.来自于华北地台寒武系苗岭统徐庄组鲕粒滩相灰岩顶部的方解石巨鲕表现出同心状、放射—同心状和泥晶质的沉积组构,在鲕粒核心和鲕粒皮层中保存着精美的葛万菌(Girvanella)化石所主...     

Pellets, ooids, sepiolite and silica in three calcretes of the southwestern United States

Pellets and ooids are widespread and locally abundant in mature calcrete profiles in the Argus Range, California; near Wickieup, Arizona; and in Kyle Canyon, Nevada. Most concentrations of pellets and ooids either overlie laminar calcrete at various levels in the calcrete profile or fill subhorizontal fractures in the petrocalcic horizon. In all three profiles the petrocalcic horizon has been thickened by the pelletal, chemically deposited fracture fillings. Pellets range from 0.02 to 8.0 mm in diameter and consist principally of micritic calcite and sepiolite. Ooid coatings are chiefly calcite and opal or calcite and sepiolite. The pellets represent small concretions, some of which grew by accretion, either in void space or by displacing adjacent sediment, and the others of which were formed by cementation of pellet-shaped bodies of porous micrite. Ooid coatings with opal or sepiolite may have been deposited as a gel with sufficient strength for surface tension to thin the coatings over angular corners of nuclei so as to increase the roundness and sphericity of the particles. Major problems in calcrete genesis are (1) the cause of subhorizontal fractures and the mechanism for widening a fracture as sediment accumulates in it and (2) what determines the deposition of calcite, sepiolite, and opal as pellets and ooid coatings or as laminar layers.     

Petrology of recent caliche pisolites, spherulites, and speleothem deposits from central Texas

Recent caliche, including nodules, pisolites, crusts, internal sediment, speleothem deposits, and spherulites, has formed within the dolomitic Cretaceous Edwards Formation of central Texas. As weathering altered the host strata, rhombic crystals of calcite were precipitated concomitantly with dissolution of the dolomite, thereby forming nodules. The highly altered dolomite (i.e. pulverulite) was then removed and spar, internal sediment, and travertine accumulated in the internodular voids. Nodular masses of calcite and dolomite are the most prominent constituent of the caliche. Some of the nodules have a well developed concentric structure as well as other characteristics similar to hypersaline pisolites. Features which appear to be useful in distinguishing caliche from hypersaline pisolites are: regional geological setting, association with other caliche and palaeosoil deposits, types of fossils present, and the presence of rhombic calcite and/or bladed sparry calcite with triangular shaped cross-section. A brick-like calcite texture and relict aragonite rays characterize hypersaline pisolites. Incipient neomorphism of the nodules and pisolites has resulted in the development of a radial pattern of spar within these structures. Geopetal deposits of internal sediment, including terra rossa soil, inhibited spar growth in the upward direction; consequently, spar is much better developed on the undersides of pisolites. Crusts and travertine flowstone (speleothem) deposits are intimately associated with the nodular masses and internal sediment. The brecciated thin crusts and travertine flowstone are end products of the same processes. The crusts formed during times of periodic desiccation of the growing surface while the flowstone formed when water was relatively abundant. Spherulitic bodies within the caliche, commonly 1–2 mm in diameter, display a radial texture and yet are composed of single crystals of calcite. The structures are the product of neomorphosed Microcodium or Microcodium-like globular bodies.     

鲕粒成因研究的新进展

鲕粒的成因一直是一个谜一样的沉积学难题。Brehm等在2006年的实验室研究的结果表明,将鲕粒的形成可以与叠层石进行类比,是一个特殊的球状微生物席的产物,从而将鲕粒归为微生物成因。最近,来自于巴哈马现代鲕粒的研究,Duguid等在2010年认为,鲕粒形成与微生物活动不存在一个直接的关系,重新强调了鲕粒形成的化学过程,即...     

Aragonite laminae in hot water travertine crusts, Rapolano Terme, Italy

Small (5–30 μm) aggregates of aragonite needles occur in calcite crystal crusts of present day hot water slope travertines at Rapolano Terme in Tuscany, Italy. The aggregates are mainly concentrated in irregular, wispy and dark laminae which cross-cut calcite crystal feathers to create a pervasive millimetre scale banded appearance in the deposit; they also occur less commonly scattered irregularly through the calcite layers. The aragonite needle aggregates are in the form of crosses, fascicles (sheaf shaped bundles, or dumbbell shaped), rosettes and spherulites. Locally, irregular masses of needles also occur. The fascicles, rosettes and spherulites have hollow centres which resemble microbial components (?fungal spores, bacterial colonies and pollen), suggesting that the aragonite crystals are biotically nucleated. The lamination is interpreted to reflect diurnal control. Stimulation of microbial activity during daylight concentrates cells in laminae and promotes aragonite calcification. Calcite feather crystals, although traversed by the aragonite aggregate laminae, have a clear appearance under the light microscope. They form more or less continuously through the diurnal cycle by abiotic precipitation. The constant association of aragonite with organic nuclei, irrespective of whether the latter are in laminae or scattered through the calcite layers, supports a biotic control on aragonite formation. Lamination in Pleistocene travertines is superficially similar to that in the present day deposits, but is diagenetically altered. In the Pleistocene deposits, the calcite feathers appear dark under the light microscope and the aragonite aggregates, where they are not altered to dark calcite, are dissolved, together with parts of the adjacent spar calcite, and therefore appear light coloured.     

Diagenetic alterations in temperate shelf carbonates from southeastern Australia

Temperate shelf carbonates form in cool marine waters and have skeletal and mineralogical compositions which are different from their tropical counterparts. They commonly lack non-skeletal grains and are often composed of low- and high-magnesium calcite with subordinate aragonite. Many of the aragonitic components found in tropical carbonates, such as corals, ooids, blue-green algae and lime mud, are absent.

Temperate shelf carbonates undergo diagenesis in marine waters with lower carbonate saturation than do tropical carbonates, and are exposed to cool climates with moderate to low rainfall. Marine cementation is rare because of low carbonate saturations in the surrounding waters. However, aragonite and high-magnesium calcite cements have been reported forming under specialized conditions associated with biogenic precipitation, submarine methane and sulphate-reducing bacteria, and more commonly in the intertidal environment where evaporation has increased carbonate concentrations.

In Pleistocene and Tertiary temperate shelf carbonates from southeastern Australia, evidence of marine diagenesis is rare to absent. Diagenetic stabilization of aragonite and high-magnesium calcite has taken from 80,000 y to 1 My, or longer, during subaerial exposure. This is slower than rates reported from tropical climates. A general lack of aragonite in some facies within these temperate carbonates leads to a lack of secondary porosity and only sparse low-magnesium calcite cement, even after prolonged fresh-water diagenesis. However, with lengthy exposure and under the right climatic conditions, karstic solution and calcrete precipitation can occur.

In sequences containing siliciclastic clays, pyrite and glauconite, abundant iron is present in interstitial waters leading to the precipitation of ferroan calcite cements in the phreatic and shallow burial environments, and to the substitution of iron for magnesium in stabilizing high-magnesium calcite skeletal material.

A unique void-filling, micritic internal sediment occurs in discrete layers in many of the Tertiary temperate shelf carbonate sequences in southeastern Australia. This internal sediment is localized as a pore-filling material above permeability barriers such as fine-grained sediments or volcanics, and above paleo-water tables which formed during periods of subaerial exposure. It is a feature of the vadose zone and lithifies to form a dense micritic low-magnesium calcite cement with characteristic pink/brown coloration, often associated with erosion surfaces and nodule beds.

Dolomite is uncommon in the southeastern Australian temperate shelf carbonates. It forms associated with preferential fluid pathways or mixing zones. Ferroan dolomite forms in siliciclastic clay-rich carbonates in the shallow burial environment. The ubiquitous fine, evaporite-related dolomite so common in tropical carbonates is absent.     

Pyritized ooids,stringed ooids and reticulate tubular structures from within the black shale at Amjhor,Bihar, India

Carbonate ooids, notionally incompatible with an euxinic environment, and some curious reticulate tubular structures with fibrous carbonate walls are described from intraclasts occurring in Proterozoic black shales containing the pyrite deposit at Amjhor. While some of the tubes are visibly due to coalescence of ooids, others are interpreted as worm burrows on the basis of their strata-transgressive orientation, branching nature and larger diameter than those of the ooids.All stages of pyritization of ooids and tube-cores, displaying truncation of the growth-fabric of calcite grains by growing pyrite crystals, point to a late- or post-diagenetic age of pyritization. The clasts containing ooids and tubes are believed to have been transported from a shallow-bank and/or a nearshore environment into a lagoonal, euxinic basin. An environmental model, consistent with the observed data, is proposed to account for the ooid—black shale association.