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。     

塔里木盆地柯坪-巴楚地区早古生代白云岩类型及微量元素地球化学特征

通过对柯平-巴楚早古生代碳酸盐岩露头样品的染色薄片鉴定、阴极发光研究和微量元素测定及分析,根据其结构成因特征把研究区白云岩分为8种类型:(1)微-粉晶白云石;(2)具原生灰岩残余结构白云石;(3)细晶直面自形-半自形漂浮基质白云石;(4)细晶直面半自形-自形白云石;(5)中-粗晶曲面他形白云石;(6)中晶直面自形-半自形白云石胶结物;(7)粗晶曲面鞍形白云石基质,和(8)粗晶曲面鞍形白云石胶结物。样品微量元素地球化学的总体特征是轻稀土富集,重稀土亏损,不同样品的特征变化元素不同。鞍形白云石Eu正异常最高说明受到热液作用的影响。方解石的Ce/Ce*的值大于1,说明受到后期陆源碎屑影响比较大,而白云岩的Ce/Ce*的值都小于1,说明是幔源成因的。(La/Ce)N和(La/Yb)N比值亦进一步证明上述结论。鞍形白云石的Sr含量较低,Ba元素含量高,说明在成岩流体作用过程中Sr丢失,Ba富集说明是热液成因的鞍形白云岩。样品Sr/Ba比值均大于1,说明受到不同程度热液作用影响。U/Th比值也证明受到不同程度的热液改造。     

白云石成因研究新方法--白云石晶体结构分析

传统的白云石研究方法对于白云石成因分析具有多解性,对于已有白云石成因模式的套用或重新建立新的白云石成因模式将白云石的形成机理过于简单化、模式化。白云石的晶体结构保存了晶体的形成环境、结晶速度、晶体生长与变化特征、流体特征的证据,白云石晶体结构分析是进行白云石成因分析的有效手段,之前很少有研究者从晶体结构角度进行白云石成因分析。在岩石学和地球化学研究的基础上,本文对四川盆地灯影组-寒武系鞍状白云石、纤状白云石、残余颗粒细晶白云石、孔洞充填粗晶白云石和泥晶白云石五种白云石进行了微组构取样,并利用X衍射仪、透射电镜等晶体结构研究手段,从晶体结构角度对五种白云石组构的有序度、晶胞参数、晶格条纹、晶面间距、晶格缺陷等晶体结构参数进行了差异性研究,分析了它们不同的形成环境和成岩演化特征,初步建立了不同类型白云石晶体结构判识标志。     

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、SO_4~(2-)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。     

塔里木盆地中央隆起中部中下奥陶统白云石类型及形成机理

根据岩心及薄片观察,按照矿物晶体的大小、形状以及自形程度的差异,将塔里木盆地中央隆起中部中下奥陶统碳酸盐岩地层中的白云石分为6种类型,包括泥微晶白云石、粉—细晶自形—半自形漂浮状白云石、粉—细晶半自行—他形白云石、粉—细晶自形(环带)白云石、细—粗晶他形白云石、粗晶鞍形白云石。综合不同类型白云石的结构特征、碳氧锶同位素值、阴极发光等特征,认为中下奥陶统白云石主要由三种成岩作用形成:泥微晶白云石主要是在准同生期由回流白云石化形成;大部分粉—粗晶白云石是在埋藏期由埋藏白云石化形成,其中浅埋藏期是大规模白云石化的阶段;粗晶鞍形白云石主要由与高温热液活动相关的热液白云石化形成。     

沉积型滑石的测定方法

本文用沸腾的氯化铵水溶液处理样品,使滑石与方解石,白云石分离,然后进行滑石含量的测定。 1.氯化铵对若干矿物的溶解情况: 取一定量单矿物于250毫升烧杯中,加入100毫升不同浓度的氯化铵水溶液,煮沸一定时间。冷后,定容至100毫升,干过滤。分取溶液测定钙、镁,计算矿物的浸取率。 从上述分离试验看出,5％的沸腾氯化铵水溶液,能有效地溶解方解石和白云石,而不溶解滑石。     

川北元坝地区长兴组白云石化作用机制及其对储层形成的影响

通过岩心观察和薄片鉴定,在岩石学和矿物学特征分析基础上,结合白云石有序度测定,碳、氧同位素、锶同位素和稀土元素组成及配分模式分析,详细研究了川北元坝地区长兴组白云石化作用的特征、机制及模式,结果表明长兴组发育微晶白云石(岩)、粉-中晶他形白云石、粉-中晶自形白云石和异形白云石等四种类型,它们的有序度由低变高;白云石的碳、氧同位素、锶同位素和稀土元素组成及配分模式特征表明,长兴组微晶白云石(岩)、粉-中晶他形白云石、粉-中晶自形白云石主要形成于浓缩海水环境、正常海水环境、或者与正常海水相似的地层水环境中,并遭受过热液地质作用的改造,从微晶白云石(岩)→粉-中晶他形白云石→粉-中晶自形白云石是一个沉积埋藏过程中多阶段白云石化作用的产物,异形白云石则由热液作用形成;根据长兴组白云石的矿物学和地球化学特征及白云石化作用与层序和沉积相之间的关系,分别可以用准同生期蒸发泵白云石化作用模式、准同生期渗透回流白云石化作用模式、成岩早期浅埋藏状态下地层水白云石化作用模式和成岩晚期热液白云石化作用模式来解释微晶白云石(岩),粉-中晶他形白云石、粉-中晶自形白云石和异形白云石的形成。白云石化作用是有利于长兴组储层形成的建设性成岩作用。     

白云石的晶体结构特征和X-射线研究

本文讨论了白云石的晶体结构特征和有序-无序问题.发现了面网间距d_(116)与白云石中CaCO_3含量之间有良好的相关关系。面网间距可以用X-射线粉晶衍射方法测定,于是可以用d_(116)值换算出白云石的成分。其结果表明,X-射线粉晶衍射方法可以广泛用来研究天然产出的白云石。     

豫西北奥陶系马家沟组三段豹斑灰岩的生物潜穴成因及成岩演化

通过野外露头实地观测和室内薄片分析,对豫西北奥陶系马家沟组三段豹斑灰岩的发育特征及成因进行了研究。结果表明：研究区马家沟组三段豹斑灰岩中“豹斑”形态多样,形似生物潜穴,结合遗迹学特征分析,可将“豹斑”按其形态划分为Psilonichnus、Chnodrites、Thalassinoides、Helminthopsis及Planolites等5种生物潜穴类型,不同类型生物潜穴的出现主要受到沉积环境的制约;生物潜穴充填物按照其不同白云石化程度可被划分为泥晶白云石充填物及粉-细晶白云石充填物两种类型,其中泥晶白云石主要存在于Psilonichnus及Chnodrites两种潜穴中,而粉-细晶白云石则主要存在于Thalassinoides、Helminthopsis及Planolites之中;潜穴充填物的白云石化过程可被分为白云石化前的准备阶段、白云石的形成阶段及白云石的后期调整等三个阶段,不同潜穴的白云石化状态差异就是在此过程中形成的。     

我国部分地区白云岩岩石矿物学研究及其意义

本文对不同地区不同层位不同类型的白云石进行较系统的矿物学测试.用数据对比的方式说明白云石的主要元素配比和晶格结构的完善程度,受形成时间和成岩环境的控制。一般说,第三纪以后形成的白云石,主要化学成分Ca比Mg多,Ca约占55％,Mg约占45％,单位晶胞比理想白云石大得多,有序度低(<0.50)。第三纪以前形成的白云石,总的看,其主要化学成分,单位晶胞大小均较接近于理想白云石,有序度高,但和形成时代并不成线性关系,而和岩石类型及成因有关。细晶到粗晶白云石优于泥—粉晶白云石;就成因而言,成岩及后生回流渗透交代白     

辽河盆地西部凹陷沙河街组砂岩碳酸盐胶结物特征

碳酸盐胶结物中氧碳同位素组成研究是分析成岩过程中流体-岩石相互作用的重要技术方法.综合运用岩石学、矿物学和地球化学方法，对辽河盆地西部凹陷沙河街组砂岩中碳酸盐胶结物的化学组成和碳酸盐胶结物及成岩流体同位素组成特征进行系统分析.研究表明，研究区碳酸盐岩主要为方解石和白云石，胶结物主要类型为嵌晶式胶结、孔隙式胶结、斑块状胶结和星点状胶结.碳、氧稳定同位素组成能有效地反映成岩-成矿流体及其他物质的来源，碳酸盐胶结物与现今浅层地下水氧同位素组成差异巨大而与变质水同位素组成具有相似性，反映了盆地演化过程中活动热流体对成岩作用的影响.包裹体的氢、氧同位素组成可表征成矿溶液的演化特征，砂岩碳酸盐胶结物包裹体更富集氢的轻同位素和氧的重同位素，表明发生了明显的“氧-18漂移”.碳酸盐胶结的成矿溶液表现出“受热雨水”的同位素组成特征，反映了深源活动热流体对成岩作用的影响.      

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.     

Analysis of carbon and oxygen stable isotopes in carbonate rocks by the laser micro-sampling technique

The analysis of stable isotopes of carbon and oxygen in different carbonate rocks by the phosphoric acid method is not easier than that by the laser sampling method developed in recent years, which optically focuses laser beams with sufficient energy on a micro area of a thin section in a vacuum sample box via microscope. CO 2 produced by heating decomposition of carbonate was purified by the vacuum system, and the stable isotopic values of carbon and oxygen were calculated and analyzed on a mass spectrometer. This paper adopted the laser micro-sampling technique to analyze the stable isotopes of carbon and oxygen in dolomite, carbonate cement, stromatolite and different forms of dawsonite (donbassite). Results indicated that the laser micro-sampling method is effective in analyzing carbonate composition and could be a convincing proof for justification on carbonate composition analysis.     

祁连山木里三露天天然气水合物层段碳酸盐矿物学地球化学特征

祁连山木里三露天天然气水合物与碳酸盐相伴产出是一种常见现象。为探讨这些碳酸盐的形成环境,对碳酸盐进行了矿物X射线衍射分析、主微量元素 测试以及碳氧同位素测试。X射线衍射结果表明,样品中碳酸盐矿物主要由方解石、白云石以及少量菱铁矿组成。微量元素和稀土元素特征显示碳酸盐形成于干旱氧化环境。δ¹³C_VPDB为-2.3 ‰~3.77‰,平均为2.43‰;δ18OVPDB为-17.90‰~-10.69‰,变化范围不大,碳氧同位素显示碳酸盐矿物中的碳可能为天然气水合物分解、白云石沉淀和湖水混染等联合作用所致,氧的 来源可能受大气降水影响。     

Geochemical constraints on the genesis of the Bayan Obo Fe-Nb-REE deposit in Inner Mongolia, China

Trace element and isotopic compositions of carbonate from ore bodies, country rock which hosts the ore bodies (H8 dolomite), a carbonatite dyke exposed in Dulahala near Bayan Obo, and rare earth element (REE)-rich dolomite in Bayan Obo have been determined to understand the genesis of the Bayan Obo Fe-Nb-REE ore deposit, the world’s largest resource of REE. The REE and trace element distribution patterns of samples from the REE-rich carbonatite dykes are identical to those of mineralized carbonate rocks, indicating a genetic linkage between the REE-rich carbonatite and mineralization in this region. By contrast, carbon and oxygen isotopes in the mineralized carbonate varied significantly, δ¹³C = −7.98‰ to −1.12‰, δ¹⁸O = 8.60-25.69‰, which are distinctively different from those in mantle-derived carbonatite. Abnormal isotopic fractionations between dolomite and calcite suggest that these two minerals are in disequilibrium in the carbonatite dyke, ore bodies, and H8 marble from Bayan Obo. This isotopic characteristic is also found in mineralized sedimentary marine micrite from Heinaobao, ∼25 km southeast of the Bayan Obo Fe-Nb-REE ore deposit. These facts imply that the carbonate minerals in the Bayan Obo deposit have resulted from sedimentary carbonate rocks being metasomatised by mantle-derived fluids, likely derived from a REE-enriched carbonatitic magma. The initial Nd isotope values of ore bodies and carbonatite dykes are identical, indicating that ore bodies, carbonatite dykes and veins may have a similar REE source.     

X射线粉晶衍射仪在大理岩鉴定与分类中的应用

大理岩主要有方解石大理岩、白云石大理岩和菱镁矿大理岩三种。以往大理岩是依据偏光显微镜下观察岩石结构构造及矿物成分进行分类定名,由于方解石、白云石、菱镁矿都属于三方晶系,具有闪突起、高级白干涉色、一轴晶负光性和菱形解理等相同晶体光学特征,偏光显微镜下区分十分困难。为了准确鉴定大理岩中碳酸盐矿物种类及其相对含量,本文利用岩石薄片偏光显微镜和X射线粉晶衍射技术对32件大理岩岩石样品进行分析测试。岩石薄片鉴定结果表明:大理岩造岩矿物主要有方解石、白云石、菱镁矿、石英、斜长石、白云母、黑云母、绿泥石、黏土和金属矿物。根据岩石结构构造及矿物组分特征,可把32件大理岩样品划分为方解石大理岩、长英质方解石大理岩、石英绿泥白云石大理岩、白云石大理岩、云英质白云石大理岩和菱镁矿大理岩等15个类型。X射线粉晶衍射分析表明:大理岩造岩矿物主要有方解石、白云石、菱镁矿、石英、斜长石、钾长石、云母、绿泥石、滑石和蒙脱石。综合分析认为:岩石薄片偏光显微镜鉴定技术很难区分方解石、白云石和菱镁矿等碳酸盐矿物,以及细小的石英、钾长石和斜长石、滑石和白云母等鳞片状硅酸盐矿物;X射线粉晶衍射分析技术不仅能准确检测出大理岩中方解石、白云石和菱镁矿等碳酸盐矿物种类及相对含量(方解石、白云石和菱镁矿的X射线衍射主峰有明显差异,d值分别为0.303 nm、0.288 nm和0.274 nm),而且能够有效鉴别岩石中粉砂级斜长石、钾长石与石英(三种矿物的X射线衍射主峰d值分别为0.319 nm、0.324 nm、0.334 nm);且能区分蒙脱石、绿泥石、云母和滑石等层状硅酸盐矿物(四种硅酸盐矿物的X射线衍射主峰d值分别为1.400 nm、0.705 nm、0.989 nm、0.938 nm)。综合岩石薄片偏光显微镜鉴定和X射线粉晶衍射分析结果,最终确定32件大理岩样品划分为22个岩石类型。研究认为:仅根据岩石薄片偏光显微镜鉴定或X射线粉晶衍射技术其中一种方法不能准确鉴定大理岩岩石,应将大理岩岩石野外观察、岩石薄片鉴定和X射线粉晶衍射技术结合起来,才能准确确定大理岩岩石类型。     

南海台西南区碳酸盐岩矿物学和稳定同位素组成特征——天然气水合物存在的主要证据之一

南海台西南区是中国南海中天然气水合物赋存的最有利场所。研究表明,该区的碳酸盐岩主要以结壳、烟囱的形式出现,结壳的裂隙或孔洞中常常充填有淡黄-白色的文石晶体。碳酸盐岩中自生碳酸盐矿物主要为文石、高镁方解石,少量白云石、铁白云石和菱铁矿。扫描电子显微镜(SEM)分析表明,文石主要呈针状、长柱状、放射束状,高镁方解石呈颗粒状。碳酸盐岩的碳同位素δ13C值主要在-56·878‰~-32·829‰PDB之间,大多数小于-40‰PDB,显示了生物甲烷成因碳源的特征;氧同位素δ18O值在2·1875‰~5·045‰PDB之间,主要在4‰PDB以上,这种较重的氧同位素比值表明,天然气水合物分解产生的富18O水体可能是碳酸盐岩沉淀的流体源。矿物学和碳氧稳定同位素研究表明,南海台西南区的碳酸盐岩为细菌性甲烷成因碳酸盐岩,可能与天然气水合物有关,显示了该区水合物存在的可能性很大。     

Stable isotope (O and C) geochemistry of non-sulfide Zn–Pb deposits; case study: Chah-Talkh non-sulfide Zn–Pb deposit (Sirjan,south of Iran)

The study of oxygen and carbon isotopic ratios has gained importance to determine the origin of ore-bearing fluids, carbon origin, and also to determine the formation temperature of non-sulfide Pb and Zn minerals. In order to determine the origin of fluids and carbon existing in Zn carbonate minerals in Chah-Talkh deposit, initially the amounts of δ¹⁸O_SMOW and δ¹³C_PDB changes in various zinc minerals in important deposits in Iran and the world were studied, and then by comparing these values in Chah-Talkh deposit with those of other deposits, the origin of fluids responsible for ore forming, carbon, and formation temperature of Chah-Talkh deposit was determined. The range of δ¹⁸O_SMOW changes in smithsonite mineral in non-sulfide lead and zinc deposits varies from 18.3 to 31.6 ‰, and δ¹⁸O_SMOW in hydrozincite mineral varies from 7.8 to 27 ‰. Due to the impossibility of smithsonite sampling from Chah-Talkh deposit (due to it being fine-grained and dispersed), hydrozincite minerals which have high isotopic similarities with smithsonite are used for the isotopic analysis of carbon and oxygen. The range of δ¹⁸O_SMOW changes in hydrozincite mineral of Chah-Talkh deposit varies from 7.8 to 15.15 ‰, which places in the domain of metamorphic water. The extensiveness of δ¹⁸O_SMOW changes in Chah-Talkh indicates the role of at least two fluids in the formation of non-sulfide minerals. The obtained formation temperature of non-sulfide minerals (hydrozincite) in Chah-Talkh deposit is 70 to 100 °C, which indicates the role of metamorphic fluids in the formation of deposit. Complete weathering of sulfide minerals to a depth of 134 m confirms the role of rising metamorphic fluids in the formation of non-sulfide minerals. The δ¹³C_PDB values of Chah-Talkh deposit are set in the range of atmospheric CO₂ and carbonate rocks, in which the existence of atmospheric CO₂ indicates the role of atmospheric fluids, and the existence of carbonate carbon rock indicates of the role of metamorphic fluids in the precipitation of non-sulfide Zn minerals.     

Mineralogical and geochemical (stable C and O isotopes) variability of marbles from the Moldanubian Zone (Bohemian Massif,Czech Republic): implications for provenance studies

Metacarbonates of the Moldanubian Zone (Bohemian Massif, Czech Republic) were studied to obtain qualitative and quantitative mineralogical-petrographic as well as stable isotopic data for the purpose of stone provenance studies, potentially applicable in material research studies of cultural heritage artefacts. Twenty-six samples from twelve different historical quarries, as well as two samples from historical artefacts, were analysed by both mineralogical-petrographic and geochemical methods including: polarizing microscopy, cathodoluminescence, scanning electron microscopy with microanalysis, petrographic image analysis, powder X-ray diffraction, and isotope ratio mass spectrometry. The petrographic characteristics allowed for the discrimination of groups of (1) calcitic marbles, (2) dolomitic marbles, and (3) carbonate–silicate rocks. These groups exhibit characteristic features such as (1) the presence/abundance of major rock-forming minerals, (2) grain geometric characteristics (specifically, mean carbonate grain size and index of grain size homogeneity), and (3) the presence of specific accessory phases. The content of non-carbonate minerals, some rock fabric parameters, as well as the carbon and oxygen isotope data exhibited significant variability, even within a single quarry in the case of some impure marbles and carbonate–silicate rocks. Although the carbon and oxygen isotopic ranges displayed overlaps among the quarries studied, the isotopic signatures throughout the Moldanubian Zone allowed for discrimination of a group of white calcitic marbles with high carbon and oxygen depletion, as well as white dolomite–calcitic marble with higher carbon isotope values when compared with other marble resources of the Bohemian Massif. A combination of the isotopic signature with detailed mineralogical-petrographic characteristics seems to provide sufficient information for discrimination of the Moldanubian marbles from one another. The provenance of the Vrchotovy Janovice artefact is very probably from the Rabí quarry, among the Moldanubian marbles. The provenance of the artefact from the Prague Klementinum was not definitively assigned; however, the Nehodiv quarry was considered its probable source locality.