佛罗里达大陆架更新世双矿物鲕粒的阴极发光性

在东佛罗里达外大陆架大约40m的海底，发现一种被钻孔和包壳的晚更新世鲕粒灰岩。鲕粒的包壳主要由两种矿物组成，通常情况下，内是放射状排殊镁方解石，而外层则是同心环状排列的文石。多数鲕粒的核心是磨圆的隐晶质颗粒，但也有一部分英颗粒和各种骨粒组成。鲕粒由块状方解石胶结物不完全胶结，部分粒间孔由微晶充填。放射壳层由具亮的阴极发光性的镁方解石组成，含大约12mol％的MбCO3和1000ppm的锶。在放射壳层中，铁和锰含量的一般变化范围分别为500－1000ppm和100－250ppm。同习环状壳层由不具阴极发光的文石组成，含大约11500ppm的锶和小于0．5mol％的MбCO3.心环状壳层中铁的含量范围一般为150－400ppm，而锰通常小于100ppm的检测限。作为次要伴生颗粒的棘皮动物碎片山镁方解石组成，具亮的阴极发光性。一些鲕粒的核心和块状方解石胶结物的薄外缘具阴极发光。微晶基质和大片的块状方解石胶结物不具阴极发兴。在鲕粒中，未见显示重结晶作用的结构迹象。这些鲕粒灰岩经历了大气淡水成岩作用阶段，但鲕粒壳层却未受其影响。我们认为，镁方解石层普在缺氧的海水中遭受成岩蚀变，这是一个尚未被人们认识的过程。在该过程中，镁推动而锰加入，但没有明显的结构蚀变，也没有发生矿物的稳定化作用，因此，我们认为其阴极发光性可能是海底的成岩蚀变造成的。     

关于生物矿物的某些问题

生物矿物的形成阶段可分非晶质、过渡、成熟和石化4个阶段。生物矿物在门类由低到高,时代由新到老的分布上存在着一种演化趋向,硫化物→硫酸盐→铁锰氧化物→非晶硅→钙白云石→碳磷灰石→镁方解石→文石→方解石这种演化趋向也重演于个体发育阶段,反映在示序接触关系中。古代原始镁方解石可以根据现实主义原则、铁方解石交代作用、微量元素和同位素成分加以识别。     

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。     

中国南方发现大型文石笋

中国南方大量石笋剖面研究表明,石笋矿物组成有方解石、文石、方解石-文石三种类型。石笋沉积纹(微)层结构构造特征大同小异,但是文石石笋的放射状纹(微)层构造更显著。文石石笋沉积生长的气候环境是滴水多而稳定,水温低、气温略高的冷、湿的洞穴气候条件。文石转变为方解石常保留文石的针状、柱状晶形,并存在于石笋沉积生长的始终。文石结构构造转化在常温或低温、常压或低压下自调整作用的成晶成岩环境进行,其强度取决于所在洞穴气候环境、滴水在石笋的渗流和石笋的含水度。转化作用不影响同位素分馏,石笋同时全面记录古气候环境信息。研究文石石笋对重建古气候环境、成岩成矿作用都有重要理论和实践意义。     

碳酸盐岩层系中非碳酸盐矿物分析及地质应用——以塔中地区奥陶系为例

<正>Knoblauch(1963)及Bausch(1980)的研究证明,所有泥岩、粉砂岩及砂岩中能出现的矿物可以在碳酸盐岩中出现。碳酸盐岩层系中除了包括常见的碳酸盐矿物(方解石(或低镁方解石)、镁方解石(高镁方解石)、文石、白云石、菱铁矿、菱镁矿、菱锰矿等),还包括少量(一般1%)的自生非碳酸盐矿物(硅质、黄铁矿、石膏和硬石膏等),以及陆源碎屑矿物(石英、长石、黏土矿物和重矿物等)。在以碳酸     

西沙群岛晚第四纪碳酸盐岩淡水成岩作用

基于西沙永兴岛上最新钻孔（SSZK1）取得的55.92 m岩芯的 U?Th定年、矿物、薄片、主微量元素及碳氧稳定同位素等资料,开展了西沙群岛晚第四纪碳酸盐岩沉积相和淡水成岩作用的研究。根据不同的矿物组成特征,可将SSZK1钻孔岩芯分为上、中、下三段: 下 段（33.89~55.92 m,主要为低镁方解石）、中 段（18.39~33.89 m,主要为文石和低镁方解石）、上段（0~18.39 m,主要为文石、高镁方解石和低镁方解石）。由于下段碳酸盐岩几乎全为稳定的低镁方解石组成,碳氧同位素值的严重负偏和小幅度变化,可推断其经历了程度较大的淡水成岩作用。中段和上段还存在不稳定的文石和高镁方解石,碳氧同位素值相对下段正偏和高幅高频变化,推测其淡水成岩作用的程度比下段要小。中段碳氧同位素值高幅高频变化同时也说明该段的矿物纵向变化较复杂。这种矿物组成的复杂变化可能是由于晚第四纪海平面频繁变化,该段被大气水渗流带和潜流带交替占据引起的。主微量元素的变化同时受到淡水成岩作用和沉积环境的影响。在中段、下段中可识别出sq1、sq2、sq3、sq4四个完整的相旋回。Na₂O,S,Sr 和碳氧同位素受到的淡水成岩作用而被消耗和负偏,且由于老一期的旋回经历了更长时间的淡水成岩作用,新、老旋回间的 Na₂O,S,Sr含量值和碳氧同位素值有明显差异。利用新、老时期形成的旋回间淡水成岩作用剩余Na₂O,S,Sr含量和碳氧同位素值的差别可以将新、老两个旋回区分开来。     

西沙更新世礁炭岩大气淡水成岩的地球化学证据

重点探讨了西琛一井更新世礁灰岩的氧炭同位素和微量元素化学特征及其与大气淡成岩的关系。西琛一井全新统,基本上未成岩,矿物组分石和高镁方解石为主“晚更新统出现明显方解石化,矿物组合以低镁方解石为主,少量石;     

相山铀矿岩芯HySpex成像高光谱数据蚀变矿物提取及其地质意义

成像高光谱遥感具有图谱合一的优势,能够根据光谱特征直接识别地物,是遥感领域的前沿方向。本文使用江西省相山铀矿田岩芯HySpex成像高光谱数据,采用基于专家知识的MTMF和波段运算方法开展了蚀变矿物填图,提取了赤铁矿、伊利石、绿泥石和方解石4种蚀变矿物,制作了铀矿岩芯高光谱蚀变矿物分布图。通过分析高光谱蚀变矿物类型、组合和分布规律,在岩芯中划分出中心蚀变带、近矿蚀变带和矿旁蚀变带,中心蚀变带蚀变矿物为赤铁矿+伊利石+绿泥石+方解石,近矿蚀变带为伊利石+方解石,矿旁蚀变带为零星分布的伊利石+方解石。其中,岩芯高光谱遥感提取出的绿泥石第二吸收峰位于2270 nm,光谱特征分析显示属于富铁绿泥石,与前人得出的与铀矿化密切相关的绿泥石主要为富铁绿泥石的结论一致。铀矿岩芯HySpex岩芯成像高光谱数据应用实践表明该数据在地质领域具有较好的应用效果和广泛前景。     

论洞穴石笋结构构造转变

大量大型石笋纵剖面研究表明,石笋矿物组成有方解石、文石、文石(方解石)-方解石(文石)三种类型,三类的结构、纹(微)层和放射状构造、结构构造转变等特征类同,并存在于碳酸盐沉积石笋生长的全过程,但文石笋的细微粒针(柱)状(微粒)结构、放射状、纹(微)层构造更显著.石笋结构构造转变的主要表现是:文石转变成方解石;文石、方解石次生增大,呈现不断晶化的成晶过程.文石转变为方解石,常保留文石的针状、针柱状结构和柱状聚晶体,呈文石假象,文石次生加大仍保存其结构构造和聚晶;方解石次生增大,常保存其粒状、菱面体、偏三角面体、聚片双晶和柱状、板状聚晶.石笋结构构造转变及其晶化强度,受控于洞穴温度、湿度、滴水和凝结水对石笋的渗透、淋漓,主要受石笋含水度大的制约.组成石笋的碳酸盐沉积、组合、结晶、晶化次生增大等,结构构造的形成及其弱、中、强转变,都在常(低)温常(低)压的洞穴气候环境中进行,是自调整作用的沉积、成晶、成岩晶化过程,没有外来物质加入,因而不影响同位素分馏和古气候环境记录.石笋结构构造转变研究,对古气候环境重建与生态修复、成晶成矿理论和实践、同位素测年校正和运用都有重要意义.     

日本远野砂岩型铀矿床的稳定同位素地球化学和成岩矿化

日本本州岛中部的远野砂岩型铀矿区地层由中新统下部的湖相沉积岩（１８￣２２Ｍａ）和上部的海相（１５￣１６Ｍａ）沉积岩组成。方解石和黄铁矿是该地层中的主要成岩蚀变产物。湖相和海相的方解石和黄铁矿的特征差别很大。湖相沉积物中方解石的δ＾１３Ｃ值低（－１９‰￣－６‰ＰＤＢ），而海相地层中的δ＾１３Ｃ值高（－１１‰￣＋３‰）。这意味着海相碳酸盐在上部海相沉积岩上所起的作用较大，下部湖相地层中方解石的碳既来源     

Diagenetic controls on the isotopic composition of carbonate‐associated sulphate in the Permian Capitan Reef Complex,West Texas

Late Palaeozoic‐age strata from the Capitan Reef in west Texas show facies‐dependent heterogeneity in the sulphur isotopic composition of carbonate‐associated sulphate, which is trace sulphate incorporated into carbonate minerals that is often used to reconstruct the sulphur isotopic composition of ancient seawater. However, diagenetic pore fluid processes may influence the sulphur isotopic composition of carbonate‐associated sulphate. These processes variously modify the sulphur isotopic composition of incorporated sulphate from syndepositional seawater in shelf crest, outer shelf, shelf margin and slope depositional settings. This study used a new multicollector inductively‐coupled plasma mass spectrometry technique to determine the sulphur isotopic composition of samples of individual depositional and diagenetic textures. Carbonate rocks representing peritidal facies in the Yates and Tansill formations preserve the sulphur isotopic composition of Guadalupian seawater sulphate despite alteration of the carbon and oxygen isotopic compositions by meteoric and dolomitizing diagenetic processes. However, sulphur isotopic data indicate that limestones deposited in reef and slope facies in the Capitan and Bell Canyon formations largely incorporate sulphate from anoxic marine‐phreatic pore fluids isotopically modified from seawater by microbial sulphate reduction, despite generally preserving the carbon and oxygen isotopic compositions of Permian seawater. Some early and all late meteoric calcite cements have carbonate‐associated sulphate with a sulphur isotopic composition distinct from that of Permian seawater. Detailed petrographic and sedimentary context for carbonate‐associated sulphate analyses will allow for improved reconstructions of ancient seawater composition and diagenetic conditions in ancient carbonate platforms. The results of this study indicate that carbonate rocks that diagenetically stabilize in high‐energy environments without pore fluid sulphate gradients can provide a robust archive of ancient seawater's sulphur isotopic composition.     

The application of cathodoluminescence to interpreting the diagenesis of an ancient calcrete profile

A laterally extensive calcrete profile has been identified in the Late Asbian (Lower Carboniferous) shallow marine shelf limestones of the Llangollen area, North Wales. The upper surface of the profile is defined by a laterally discontinuous palaeokarstic surface and by laminated calcareous crusts which developed within the underlying limestone. The profile contains a unique series of early pore-filling vadose cements which only occur down to 1 m below the palaeokarstic surface. Cathodoluminescence reveals that these cements pre-date the late pore-filling meteoric phreatic cements which occur throughout local Asbian lithologies. A spar cement stratigraphy has been established for the calcrete profile. Subaerial vadose cements comprise two generations of non-luminescent cement, followed by a brightly luminescent generation which occasionally shows an acicular habit. This needle-fibre calcite represents the final stage of vadose cementation. Precipitation of vadose cements was contemporary with subaerial alteration and micritization of the limestone. Textures, visible only with cathodoluminescence, provide evidence of recurrent periods of fabric dissolution. The most extensive phase of dissolution occurred immediately after the precipitation of the non-luminescent subaerial vadose cements. Several different textures have been recorded, each reflecting the morphology of a partially dissolved substrate. Dissolution textures are generally confined to the walls of the larger pores and to early brecciation fractures. These probably acted as fluid pathways in the calcrete during early subaerial diagenesis. Much of the non-marine micrite in the calcrete profile appears as needle-fibre calcite under cathodoluminescence. This acicular calcite was probably formed in response to localized supersaturation of meteoric pore fluids caused by periods of near-surface evaporation. Since needle-fibre luminescence is strongly variable, these ambient conditions are not believed to have directly controlled the activator ion concentrations of cementing pore waters. Needle-fibre calcite is considered to be a cement precipitate which has almost completely recrystallized to micrite, probably during the late stages of subaerial diagenesis. Two generations of subaerial micrite which define a ‘micrite stratigraphy’, have been distinguished under cathodoluminescence. Reconstructing the diagenetic history of this ancient calcrete profile has revealed that subaerial alteration was multistaged, with many diagenetic processes acting simultaneously during a single phase of emergence.     

鄂尔多斯盆地下古生界石灰岩岩相及碳、氧稳定同位素特征

鄂尔多斯盆地下古生界石灰岩的岩相及碳、氧稳定同位素组成变化大,具有多种成因类型。通过薄片鉴定、岩石及矿物微区碳、氧稳定同位素测试以及包裹体测温资料研究,发现正常海水成因的泥晶灰岩及颗粒灰岩具有较高的δ18O、δ13C;受淡水淋滤、溶蚀的颗粒灰岩、角砾泥晶灰岩、豹斑含云灰岩或灰云岩的δ13C随淡水淋滤及溶蚀程度升高而明显降低,但其δ18O变化较小;去膏化成因的巨晶次生灰岩在阴极发光下具环带结构,并具有较低的δ18O、δ13C,去云化成因的中-细晶次生灰岩多呈麦粒或蚕蛹结构,其δ18O、δ13C相对较高;早期及表生淡水方解石胶结物的δ18O、δ13C均为低值,Mn离子含量低,阴极发光暗淡;晚期热液方解石胶结物具异常低的δ18O、δ13C,包裹体均一温度介于100~150℃,富含Mn离子,阴极发光明亮。研究结果表明,岩相特征、碳、氧稳定同位素组成以及包裹体测温数据是确定石灰岩沉积、成岩环境以及成因类型的重要指标。     

Petrography and geochemistry of Paleocene–Eocene limestones in the Ching-dar syncline, eastern Iran

The Ching-dar syncline is located to the west of the city of Birjand, in the east of han. The ca. 500 m thick studied section at the eastern flank of the syncline contains a sequence of almost continuous shallow- marine limestones that exhibit no major sedimentary breaks or evidence for volcanic activity. Skeletal grains consist of large benthic foraminifera and green algae whereas non-skeletal grains are mostly peloids and intraclasts. They were deposited on a shallow-marine carbonate ramp. The limestones have undergone extensive diagenetic processes with varying intensities, the most important of which are micritization, cementation, compaction （chemical and mechanical）, internal filling and stylolitization. Chemical analysis of the limestone samples revealed high calcium and low magnesium content. Major and minor element values were used to determine the original carbonate mineralogy of these lime- stones. Petrographic evidence and elemental values indicate that calcite was the original carbonate mineral in the limestones of the Ching-dar syncline. The elemental composition of the Ching-dar car- bonates also demonstrates that they have stabilized in a meteoric phreatic environment. Variation of Sr/ Ca vs. Mn values suggests that diagenetic alteration occurred in an open geochemical system.     

The diagenesis of the late Dinantian Derbyshire-East Midland carbonate shelf, central England

Carbonate cements in late Dinantian (Asbian and Brigantian) limestones of the Derbyshire carbonate platform record a diagenetic history starting with early vadose meteoric cementation and finishing with burial and localized mineral and oil emplacement. The sequence is documented using cement petrography, cathodoluminescence, trace element geochemistry and C and O isotopes. The earliest cements (Pre-Zone 1) are locally developed non-luminescent brown sparry calcite below intrastratal palaeokarsts and calcretes. They contain negligible Fe, Mn and Sr but up to 1000 ppm Mg. Their isotopic compositions centre around δ¹⁸O =?8.5‰, δ¹³C=?5.0‰. Calcretes contain less ¹³C. Subsequent cements are widespread as inclusion-free, low-Mg, low-Fe crinoid overgrowths and are described as having a‘dead-bright-dull’cathodoluminescence. The‘dead’cements (Zone 1) are mostly non-luminescent but contain dissolution hiatuses overlain by finely detailed bright subzones that correlate over several kilometres. Across‘dead'/bright subzones there is a clear trend in Mg (500–900 ppm), Mn (100–450 ppm) and Fe (80-230 ppm). Zone 1 cements have isotopic compositions centred around δ¹⁸O =?8.0‰ and δ¹³C=?2.5‰. Zone 2 cement is bright, thin and complexly subzoned. It is geochemically similar to bright subzones of Zone 1 cements. Dull Zone 3 cement pre-dates pressure dissolution and fills 70% or more of the pore space. It generally contains little Mn, Fe and Sr but can have more than 1000 ppm Mg, increasing stratigraphically upwards. The δ¹⁸O compositions range from ?5.5 to ?15‰ and the δ¹³C range is ?1 to + 3.2^0/00. Zone 4 fills veins and stylolite seams in addition to pores. It is synchronous with Pb, Ba, F ore mineralization and oil migration. Zone 4 is ferroan with around 500 ppm Fe, up to 2500 ppm Mg and up to 1500 ppm Mn. Isotopic compositions range widely; δ¹⁵O =?2.7 to ?9‰ and δ¹³C=?3.8 to+2.50‰. Unaltered marine brachiopods suggest a Dinantian seawater composition around δ¹⁵O = 0‰ (SMOW), but vital isotopic effects probably mask the original δ¹³C (PDB) value. Pre-Zone 1 calcites are meteoric vadose cements with light soil-derived δ¹³C and light meteoric δ¹⁸O. An unusually fractionated‘pluvial’δ¹⁵O(SMOW) value of around — 6‰ is indicated for local Dinantian meteoric water. Calcrete δ¹⁸O values are heavier through evaporation. Zone 1 textures and geochemistry indicate a meteoric phreatic environment. Fe and Mn trends in the bright subzones indicate stagnation, and precipitation occurred in increments from widespread cyclically developed shallow meteoric water bodies. Meteoric alteration of the rock body was pervasive by the end of Zone 1 with a general resetting of isotopic values. Zone 3 is volumetrically important and external sources of water and carbonate are required. Emplacement was during the Namurian-early Westphalian by meteoric water sourced at a karst landscape on the uplifted eastern edge of the Derbyshire-East Midland shelf. The light δ¹⁸O values mainly reflect burial temperatures and an unusually high local heat flow, but an input of highly fractionated hinterland-derived meteoric water at the unconformity is also likely. Relatively heavy δ¹³C values reflect the less-altered state of the source carbonate and aquifer. Zone 4 is partly vein fed and spans burial down to 2000 m and the onset of tectonism. Light organic-matter-derived δ¹³C and heavy δ¹⁸O values suggest basin-derived formation water. Combined with textural evidence of geopressures, this relates to local high-temperature ore mineralization and oil migration. Low water-to-rock ratios with host-rock buffering probably affected the final isotopic compositions of Zone 4, masking extremes both of temperature and organic-matter-derived CO₂.     

Calcite cementation during bacterial manganese, iron and sulphate reduction in Jurassic shallow marine carbonates

Faunally restricted argillaceous wackestones from the Middle Jurassic of eastern England contain evidence of early diagenetic skeletal aragonite dissolution and stabilization of the carbonate matrix, closely followed by precipitation of zoned calcite cements, and precipitation of pyrite. Distinctive cathodoluminescence and trace element trends through the authigenic calcites, their negative δ¹³C compositions and the location of pyrite in the paragenetic sequence indicate that calcite precipitation took place during sequential bacterial Mn, Fe and sulphate reduction. Calcite δ¹⁸O values are compatible with cementation from essentially marine pore fluids, although compositions vary owing to minor contamination with ¹⁸O-depleted ‘late’cements. Mg and Sr concentrations in the calcites are lower than those in recent marine calcite cements. This may be a result of kinetic factors associated with the shallow burial cementation microenvironments. Bicarbonate for sustained precipitation of the authigenic calcites was derived largely from aragonite remobilization, augmented by that produced through anaerobic organic matter oxidation in the metal and sulphate reduction environments. Aragonite dissolution is thought to have been induced by acidity generated during aerobic bacterial oxidation of organic matter. Distinction of post-oxic metal reduction and anoxic sulphate reduction diagenetic environments in modern carbonate sediments is uncommon outside pelagic settings, and early bacterially mediated diagenesis in modern platform carbonates is associated with extensive carbonate dissolution. High detrital Fe contents of the Jurassic sediments, and their restricted depositional environment, were probably the critical factors promoting early cementation. These precipitates constitute a unique example of calcite authigenesis in shallow water limestones during bacterial Mn and Fe reduction.     

Rare earth element geochemistry of scleractinian coral skeleton during meteoric diagenesis: a sequence through neomorphism of aragonite to calcite

Rare earth element geochemistry in carbonate rocks is utilized increasingly for studying both modern oceans and palaeoceanography, with additional applications for investigating water–rock interactions in groundwater and carbonate diagenesis. However, the study of rare earth element geochemistry in ancient rocks requires the preservation of their distribution patterns through subsequent diagenesis. The subjects of this study, Pleistocene scleractinian coral skeletons from Windley Key, Florida, have undergone partial to complete neomorphism from aragonite to calcite in a meteoric setting; they allow direct comparison of rare earth element distributions in original coral skeleton and in neomorphic calcite. Neomorphism occurred in a vadose setting along a thin film, with degradation of organic matter playing an initial role in controlling the morphology of the diagenetic front. As expected, minor element concentrations vary significantly between skeletal aragonite and neomorphic calcite, with Sr, Ba and U decreasing in concentration and Mn increasing in concentration in the calcite, suggesting that neomorphism took place in an open system. However, rare earth elements were largely retained during neomorphism, with precipitating cements taking up excess rare earth elements released from dissolved carbonates from higher in the karst system. Preserved rare earth element patterns in the stabilized calcite closely reflect the original rare earth element patterns of the corals and associated reef carbonates. However, minor increases in light rare earth element depletion and negative Ce anomalies may reflect shallow oxidized groundwater processes, whereas decreasing light rare earth element depletion may reflect mixing of rare earth elements from associated microbialites or contamination from insoluble residues. Regardless of these minor disturbances, the results indicate that rare earth elements, unlike many minor elements, behave very conservatively during meteoric diagenesis. As the meteoric transformation of aragonite to calcite is a near worst case scenario for survival of original marine trace element distributions, this study suggests that original rare earth element patterns may commonly be preserved in ancient limestones, thus providing support for the use of ancient marine limestones as proxies for marine rare earth element geochemistry.     

碳酸盐岩中方解石胶结物的阴极发光环带与微量元素构成的关系——以塔河油田奥陶系碳酸盐岩为例

对塔河油田奥陶系碳酸盐岩中方解石胶结物的阴极发光性和微量元素构成研究发现,一些与大气水成岩环境有关的方解石胶结物显示出亮、暗相间阴极发光环带,微量元素含量与阴极发光环带之间具有良好的对应关系,亮带具有较高的Mn、Fe含量,暗带则具有较高的Sr、Na含量,显示方解石胶结过程中大气水作用强度的变化。这些碳酸盐矿物的阴极发光环带受元素构成变化控制,并反映成岩流体中元素含量的变化和/或结晶速率的变化,这在一定程度上与大气水环境相对开放的成岩条件有关。相对晚期的环带发光较亮,并具有较高的Mn和较低的Sr、Na含量,显示与加里东—海西期构造运动有关的古岩溶过程中大气水作用逐渐加强的总体成岩趋势。     

Genesis and diagenesis of hiatus- and breccia-concretions from the mid-Cretaceous of Texas and northern Mexico

A study of septarian concretions from late Cretaceous shale sequences of Texas and northern Mexico reveals complex burial-exhumation histories. First generation concretions and pre-fossilized moulds formed in silty clays before significant compaction occurred. Syneresis cracks developed and were filled by length slow fibrous calcite with a decrease in iron content toward the centre of each vein; in some cases this was succeeded by growth of equant or bladed calcite. Subsequent erosion of enclosing sediment caused collapse and break up of concretions, leaving fragments and some unbroken concretions exposed to encrustation and boring on the sea floor. These were subsequently buried and enclosed in a second generation of concretions, which also developed syneresis cracks. The calcite that filled these latter cracks was generally bladed (sometimes followed by equant calcite) and contains more iron toward the centre of the vein. Differences between the calcite filling first and second generation septarian veins indicates changing diagenetic regimes during burial in the marine environment, without a major shift in diagenetic conditions, such as the introduction of meteoric waters. These conclusions have significant implications to cementation in ancient limestones, which show textural and chemical sequences similar to those present in the septarian concretions described.     

Geochemical,and stable and radiogenic isotope records in Devonian and Early Carboniferous carbonates from Valle de Tena,central Pyrenees (Spain): evidence for their diagenetic environments

Mineralogical, textural and geochemical investigations were made to determine the post-depositional evolution of Devonian and Early Carboniferous carbonates from Valle de Tena. The carbonate association is made up of low-Mg calcite, which occurs as micrite, spar cements, neomorphic patches and spar filling veinlets. Non-stoichiometric dolomite and ankerite occur as cements (dolomite also as replacements) in the Middle Devonian, post-dating calcite types. All these phases pre-date tectonic stylolites, indicating compaction after stabilization of the carbonate minerals. Strontium concentrations indicate that Early Devonian and Early Carboniferous micrites initially precipitated as aragonite; Middle and Late Devonian micrites precipitated as high-Mg calcites. Both precursors were diagenetically stabilized to low-Mg calcites through interaction with meteoric waters in phreatic environments. Trace elements in dolomite and ankerite indicate precipitation from Sr-enriched meteoric water. All studied carbonates, except Middle Devonian limestones, precipitated in reducing environments, which favoured incorporation of Fe and Mn. Late calcite generations precipitated from more saline waters than micrites. Light ¹⁸O values in micrites suggest alteration mainly in meteoric-phreatic environments. The dolomites and ankerites precipitated from more ¹⁸O-depleted fluids than the calcites, suggesting a greater contribution from meteoric waters. Variations in ¹³C of micrites represent primary secular trends, according to published ¹³C variations. The ¹³C oscillations within each succession probably relate to sea-level oscillations. Strontium isotopes also point to a meteoric origin of diagenetic fluids. Model calculations suggest that O and Sr isotopes equilibrated between calcites and fluid at relatively low water/rock ratios, whereas C isotopic signatures are inherited from limestones.