岩溶缝洞充填物碳氧同位素特征及环境意义——以塔河油田奥陶系鹰山组为例

塔河油田奥陶系鹰山组岩溶缝洞是该地区主要的碳酸盐岩储层,弄清岩溶缝洞充填物特征有利于寻找最优储集体,对该区石油地质研究具有重要意义。通过对塔河油田31口钻井岩心观察、描述和充填物类型统计,选取7口典型钻井奥陶系鹰山组岩溶缝洞充填物取样,并对充填物样品δ¹³C和δ¹⁸O进行测试分析。结果表明：(1)充填物碳氧同位素变化范围较大,δ¹³C为0.75‰～-10.14‰,δ¹⁸O为-5.94‰～-14.14‰。(2)奥陶系鹰山组岩溶缝洞充填物存在4中不同类型的形成环境：同生期或早期成岩岩溶环境、风化壳岩溶环境、埋藏岩溶环境、较晚期岩溶环境。该研究成果对古岩溶型油气储层研究及油气勘探具有重要意义。     

蓟县早寒武-新元古不整合界面处风化壳碳酸盐碳、氧同位素组成特征

由于土壤中有机质降解产生的CO₂ 和淡水成岩作用的影响,在蓟县早寒武世和晚元古代景儿峪组不整合界面处古风化壳中碳酸盐的δ¹³C值和δ¹⁸O 值明显偏负,从风化壳向下往原岩的方向,δ¹³C和δ¹⁸O 数值逐渐增加;此外,与风化壳上、下碳酸盐岩地层的δ¹³C和δ¹⁸O 数值具有明显的差别。上述同位素组成特征可以用于其它古风化壳剖面及地层不整合界面的判识。     

鄂尔多斯奥陶系碳酸盐岩碳氧同位素特征及其意义*

鄂尔多斯古生代海相地层沉积厚度巨大。鄂尔多斯奥陶系碳酸盐岩的碳氧同位素组成受后期成岩作用影响较小,基本保留了原始海洋的同位素组成： δ¹³C值分布于-7.30‰～2.26‰之间,均值-0.30‰;δ¹⁸O值分布于-13.14‰～-1.94‰之间,均值-6.38‰,碳氧同位素组成与全球基本一致。区域上,鄂尔多斯西缘具有相对较高的δ¹³C值,南缘次之,而东缘最低。纵向上,碳同位素组成逐渐增重,并在中晚奥陶世发生明显的正向偏移,δ¹³C均值由马家沟组的-0.36‰增加到平凉组的0.15‰,至背锅山组增加至0.68‰。碳同位素的区域分布差异表明鄂尔多斯西缘水体相对较深,南缘次之,东缘相对较浅,由早奥陶世至晚奥陶世水体逐渐加深,碳同位素组成反映的海平面变化趋势与沉积相演化一致。鄂尔多斯西南缘中晚奥陶世碳同位素组成的正向偏移,标志着较高的生产力和有机碳埋藏率,具有重要的石油地质学意义,西南缘的平凉组/乌拉力克组和背锅山组是下古生界最重要和有效的烃源岩层。     

重庆南川三汇场寒武系碳酸盐岩中不同期次大气淡水作用的证据

多期构造叠加及多种成岩环境下的早古生代碳酸盐岩储集层形成机理十分复杂。重庆南川三汇场剖面寒武系碳酸盐岩出露完整,是研究沉积与成岩史的理想解剖点之一。研究表明,三汇场剖面寒武系白云岩分别经历了早期海水胶结、大气淡水淋滤、准同生白云岩化、中浅层埋藏、中期构造大气水作用、中晚期埋藏及热液作用和构造晚期表生大气水成岩作用,不同期次的大气淡水作用特征不同。在早成岩期,沿向上变浅的高频层序界面附近发育了鲕模孔、窗格溶孔等组构性溶孔,胶结物和充填物的δ¹⁸O、δ¹³C值均比同期海水负偏,⁸⁷Sr/⁸⁶Sr值与同期海水相近,不发光(CL),含有较小的液相包裹体;加里东晚期—海西期,发育了非组构扩溶孔洞缝,伴有氧化沥青,不发光充填物的δ¹⁸O、δ¹³C负偏、⁸⁷Sr/⁸⁶Sr值正偏,发育含烃的低温不混溶包裹体,并叠加后期的深埋藏及热液成岩作用;燕山期和喜马拉雅期, 发育孤立的非组构溶蚀孔洞、缝洞,多被巨晶方解石或黏土充填,方解石中δ¹⁸O、δ¹³C强烈负偏($\delta^{13}C_{PDB}$=-4.6‰~-23.4‰,$\delta^{18}C_{PDB}$=-8.6‰~-17.8‰)、含有低温不混溶包裹体(<28.5℃),是有机质或生物甲烷(细)菌参于下的表生大气水成岩作用产物。     

中国南方灯影峡期海洋碳酸盐岩原始δ13C和δ18O组成及海水温度

中国南方灯影峡期(晚前寒武纪)是白云岩广泛发育的海洋碳酸盐沉积时期,在灯影组中部发育从海水直接沉积沉淀的原生白云岩,目前仍保留其原始组构特征。从40个原生白云石(岩)中测得:泥晶白云石的δ¹³C值为3.64‰,δ¹⁸O值为-1.17‰(n=6);白云岩的13C值为3.52‰,δ¹⁸O值为-1.86‰(n=15);海水纤状白云石胶结物δ¹³C值为2.90‰,δ¹⁸O值2.65‰(n=8);海水刃状白云石胶结物的δ¹³C值为2.96‰,δ¹⁸O值为-2.41‰(n=8);晶纹层和海水纤状白云石胶结物的δ¹³C值为2.79‰,δ¹⁸O值为-3.13‰。40个岩样的δ¹³C平均值为3.25‰±0.44‰,δ¹⁸O平均值为-2.12‰±0.98‰(均以PDB标准)。对于灯影峡期海相云岩的原始δ¹³C和δ¹⁸O值,不采用所有样品的平均值,而是采用原生白云石沉积物与海水白云石结物δ¹³C值和δ¹⁸O值两个图示分布区重叠部分的最重同位素值,即：δ¹C值为4.43‰(PDB标准),δ¹⁸O值为-0.62‰(PDB标准),将其作为灯影峡期海洋碳酸盐岩的原始同位素组成。对海水原生白云石胶结物包裹体盐度进行了测定,海水δ¹⁸O计算值为2.90(SMOW标准),用原始δ¹⁸O值计算的原生白云石形成时的海水温度为40.8 ℃。这说明中国南方灯影峡的海洋为炎热的较高的海水温度环境。     

衢州市上方镇方解石矿床碳、氧同位素地球化学特征

为研究浙江省衢州市上方镇方解石矿床的成岩成矿环境,采集了上方镇方解石矿床中的大理岩样品,用MAT-253型气体同位素质谱仪对其进行了碳、氧同位素分析测试。结果表明,样品的δ¹³C_PDB和δ¹⁸O_SMOW均值分别为-1.32‰和18.25‰,计算的盐度指数Z值为97.42～130.08,均值为118.50,在δ¹⁸O_SMOW-δ¹³C_PDB图解上大多数样品点落于海相碳酸盐与碳酸盐溶解作用范围内,上方镇方解石矿床大理岩的原岩应为沉积成因,可能形成于宽阔的海洋环境。     

湘西奥陶系红色碳酸盐岩碳、氧同位素组成特征及古环境意义

红色碳酸盐岩是华南奥陶系的一种具有紫红—砖红色调的代表性沉积岩,其中可能蕴含特殊的古环境信息。湖南湘西三百洞地区具有一条出露良好、厚层为主的红色碳酸盐岩剖面,主要发育于大湾组和牯牛潭组内,文章对该段地层采集了355件碳、氧同位素和Mn、Sr元素分析样品,以及10件牙形刺化石样品进行研究。根据牙形刺样品约束,大湾组底界可能大致相当于弗洛阶顶界,大湾组和牯牛潭组界线在达瑞威尔阶中下部,牯牛潭组顶界大致相当于达瑞威尔阶顶界。据显微薄片鉴定、δ¹³C-δ¹⁸O相关性分析和Mn-Sr元素评估,推断样品受到成岩作用影响不大。355件同位素测试样品显示三百洞剖面的δ¹³C和δ¹⁸O均为低幅高频振荡,δ¹³C在-0.38‰～1.67‰之间,δ¹⁸O在-9.34‰～-7.21‰之间,其中可与全球对比的同位素事件有大坪阶底部碳同位素负漂事件(BDNICE)和达瑞威尔阶中部碳同位素漂移事件(MDICE),可以间接对比的有达瑞威尔阶下部碳同位素负漂事件(LDNICE),此外还有2...     

鄂尔多斯盆地南部奥陶系碳酸盐储层的胶结作用

鄂尔多斯盆地南部奥陶系马家沟组主要由原始沉积的碳酸盐岩和岩溶角砾岩组成.储集空间以次生孔隙为主.中奥陶世沉积作用之后不久,即发生了溶解作用、白云石沉淀、干化脱水作用、机械压实作用、岩溶作用和胶结作用.胶结作用很普遍,主要发生在中石炭世之后的埋藏条件下,是对储层重要的破坏作用.充填于硬石膏结核溶模孔和非组构选择性溶蚀孔、洞、缝的方解石和白云石是最常见的胶结物.这些方解石和白云石胶结物具泥晶、嵌晶状或粒状晶粒结构.泥晶白云石基质的δ18O值-10.98‰～-0.8‰,平均-5.54‰;δ13C值-4.76‰～5.77‰,平均1.51‰.充填于溶蚀孔、缝中的白云石的δ18O值-12.54‰ ～-2.67‰,平均-7.34‰; δ13C值-5.56‰～3.48‰,平均0.28‰.充填于溶蚀孔、缝方解石的δ18O值-15.42‰ ～-6.02‰,平均-9.51‰;δ13C值-12.44‰～1.33‰,平均-3.20‰.总的来说,白云石和方解石胶结物的δ18O和δ13C值低于泥晶白云石基质的,原因是形成晚,受淡水淋滤、埋藏作用和有机质影响较大.泥晶白云石基质的Na含量0～ 350 μg/g,平均59μg/g; Sr含量0～380 μg/g,平均10 μg/g;Fe含量0～ 14 570 μg/g,平均1 040 μg/g; Mn含量0～4 670 μg/g,平均183 μg/g.充填于次生孔隙中的胶结物的Na、Sr、Mn含量与泥晶白云石基质的差别不大,因这些元素含量均低.充填于次生孔隙的碳酸盐胶结物较泥晶白云石基质有明显高的Fe含量.胶结物包裹体的均一温度在90℃ ～ 140C范围内.胶结物沉淀于埋藏较深,温度较高的还原条件下.流体包裹体的气相成分以CH4最为普遍,液相成分以H2O占绝大多数.早期胶结物形成于天然气形成前,晚期胶结物形成于天然气形成之后.岩溶洼地是胶结作用最发育的地带.     

鄂尔多斯盆地奥陶系马家沟组马五段白云岩的同位素地球化学特征

鄂尔多斯盆地中央气田奥陶系马家沟组马五段白云岩是重要的油气储集层,多年来,马家沟组白云岩的成因问题一直是地质研究者讨论的热点话题.对马五段白云岩的C、O、Sr同位素地球化学资料的分析表明,孔洞充填的白云石(含鞍状白云石)和白云岩的δ13C、δ18O值极其近似,且白云岩的δ18OPDB值比奥陶纪海水值要偏负1.752‰～4.395‰(平均2.911‰);成岩流体(水)的占δ18OSMOW平均值为+8‰,比当时海水值偏正;87Sr/86Sr比值比奥陶纪海水87Sr/86Sr比值要高.从C、O同位素数据上看,形成白云岩和沉淀于孔洞中的白云石(含鞍状白云石)的流体为同源流体;造成白云岩的δ18O值偏负的原因主要是埋藏条件的"温度效应";87Sr/86Sr比值偏高可能是交代流体来自或流经了富含放射成因Sr的铝硅酸盐基底或硅质碎屑岩.这些特征表明马五段白云岩很可能形成于埋藏环境.     

四川灯影组白云石化流体多样化特征及白云岩差异性成因

灯影组白云岩是四川盆地超深层油气勘探的重点领域,但目前人们对该套白云岩成因争议仍较大,且缺乏系统研究.通过对四川盆地灯影组白云岩C-O-Sr同位素和稀土元素数据的系统分析来研究白云石化流体的化学性质和成因,进而约束白云岩的差异性成因机制.研究表明：(1)灯影组白云岩碳同位素值较均一,δ¹³C值基本分布在0‰～+5.0‰之间,而氧同位素值变化较大.近地表环境基质白云岩和早期白云石胶结物δ¹⁸O均大于-8.0‰,埋藏环境白云石胶结物δ18O均小于-8.0‰,而热液白云石化胶结物δ¹⁸O均小于-10.0‰.(2)基质白云岩和早期白云石胶结物具有与同期海水相似的⁸⁷Sr/⁸⁶Sr值(0.708～0.709),指示其继承于海水流体;而埋藏环境白云石胶结物⁸⁷Sr/⁸⁶Sr比值明显大于同期海水,指示其为地层流体和深部热液流体来源.(3)灯影组白云岩稀土元素均亏损轻稀土元素、富集重稀土元素.基质白云岩和早期白云石胶结物可见Ce负异常、未见Eu明显异...     

美国怀俄明州拉那依段岩相及碳氧同位素地球化学特征

1980年6月,本文作者之一的K. Kelts曾去美国参加由经济古生物学者和矿物学者协会组织的地质旅行。该行主要是观察和研究怀俄明州西南始新统绿河组的沉积环境。对此次旅行中带回瑞士苏黎世联邦理工学院地质研究所的样品,曾作了切片、X-射线衍射和碳氧同位素分析。     

Diagenetic overprinting of the sphaerosiderite palaeoclimate proxy: are records of pedogenic groundwater δ18O values preserved?

Meteoric sphaerosiderite lines (MSLs), defined by invariant δ¹⁸O and variable δ¹³C values, are obtained from ancient wetland palaeosol sphaerosiderites (millimetre‐scale FeCO₃ nodules), and are a stable isotope proxy record of terrestrial meteoric isotopic compositions. The palaeoclimatic utility of sphaerosiderite has been well tested; however, diagenetically altered horizons that do not yield simple MSLs have been encountered. Well‐preserved sphaerosiderites typically exhibit smooth exteriors, spherulitic crystalline microstructures and relatively pure (> 95 mol% FeCO₃) compositions. Diagenetically altered sphaerosiderites typically exhibit corroded margins, replacement textures and increased crystal lattice substitution of Ca²⁺, Mg²⁺ and Mn²⁺ for Fe²⁺. Examples of diagenetically altered Cretaceous sphaerosiderite‐bearing palaeosols from the Dakota Formation (Kansas), the Swan River Formation (Saskatchewan) and the Success S2 Formation (Saskatchewan) were examined in this study to determine the extent to which original, early diagenetic δ¹⁸O and δ¹³C values are preserved. All three units contain poikilotopic calcite cements with significantly different δ¹⁸O and δ¹³C values from the co‐occurring sphaerosiderites. The complete isolation of all carbonate phases is necessary to ensure that inadvertent physical mixing does not affect the isotopic analyses. The Dakota and Swan River samples ultimately yield distinct MSLs for the sphaerosiderites, and MCLs (meteoric calcite lines) for the calcite cements. The Success S2 sample yields a covariant δ¹⁸O vs. δ¹³C trend resulting from precipitation in pore fluids that were mixtures between meteoric and modified marine phreatic waters. The calcite cements in the Success S2 Formation yield meteoric δ¹⁸O and δ¹³C values. A stable isotope mass balance model was used to produce hyperbolic fluid mixing trends between meteoric and modified marine end‐member compositions. Modelled hyperbolic fluid mixing curves for the Success S2 Formation suggest precipitation from fluids that were < 25% sea water.     

麦盖提斜坡奥陶系碳酸盐岩碳氧同位素特征及其意义

依据实测的塔里木盆地麦盖提斜坡玉北地区41个碳酸盐岩碳氧同位素数据,结合岩石学方法,研究了碳氧同位素的组成、演化及其地质意义。数据显示,δ~(13) C值主要分布在-2.6‰~0.7‰,均值为-1.0‰;δ~(18) O值分布在-9.4‰~-3.5‰,均值为-6.9‰。玉北地区古盐度为118.39~126.34,平均为121.94。奥陶系碳酸盐岩淡水改造作用明显。碳氧同位素的组成和演化不但可以指示沉积环境,而且还与生物生产率以及古海平面变化呈正相关性:δ~(13) C的低值对应于局限台地台内滩亚相沉积环境;δ~(13) C的高值对应于开阔台地滩间海、台内滩亚相沉积环境。碳氧同位素组成还对成岩环境有明显响应:鹰山组δ~(13) C与δ~(18) O均向高负值偏移,表明经历过强烈的表生岩溶作用;蓬莱坝组δ~(13) C低—中负值,δ~(18) O表现为高负值,在白云岩储层中可见鞍状白云石及燧石,主要为深埋藏成岩环境;良里塔格组同位素特征为δ~(18) O高负值,δ~(13) C低正值,并且在进入埋藏岩溶阶段之前还经历过风化壳岩溶作用。     

Ordovician low- to intermediate-Mg calcite marine cements from Sweden: marine alteration and implications for oxygen isotopes in Ordovician seawater

Petrography demonstrates the presence of three types of fibrous calcite cement in buildup deposits of the Kullsberg Limestone (middle Caradoc), central Sweden. Translucent fibrous calcite has intrinsic blue luminescence (CL) indicative of pure calcite. This cement has 2–5 mol% MgCO₃, low Mn and Fe (≤ 100 p.p.m.), and is considered to be slightly altered to unaltered, primary low- to intermediate-Mg calcite. Grey turbid fibrous calcite has variable but generally low MgCO₃ content (most analyses <2 mol%) and variable CL response, with Mn and Fe concentrations up to 1200 and 500 p.p.m., respectively. The heterogeneous characteristics of this variety of fibrous calcite are caused by diagenetic alteration of a translucent fibrous calcite precursor. Light-brown turbid fibrous calcite has low MgCO₃ (near 1 mol%) and variable Mn (up to 800 p.p.m.) and Fe (up to 500 p.p.m.) concentrations, with an abundance of bright luminescent patches, which formed during alteration caused by reducing diagenetic fluids. The δ¹³C and δ¹⁸O values of all fibrous calcite form a tight field (δ¹³C=1·7 to 3·1‰ PDB, δ¹⁸O= ? 2·6 to ? 4·1‰ PDB) compared with fibrous calcite isotope values from other units. Fibrous calcite δ¹⁸O values are larger than adjacent meteoric or burial cements, which have δ¹⁸O δ ? 8‰ PDB. Consequently, most diagenetic alteration of Kullsberg fibrous calcite is interpreted to have occurred in the marine diagenetic realm. First-generation equant and bladed calcite cements, which pre-date fibrous calcite, are interpreted as unaltered, low-Mg calcite marine cements based on δ¹³C and δ¹⁸O data (δ¹³C = 2·3 to 2·7‰ PDB, δ¹⁸O= ? 2·8 to ? 3·5‰ PDB). Unlike fibrous cement, which reflects global sea water chemistry, first-generation equant and bladed calcite are indicators of localized modification of seawater chemistry in restricted settings. Kullsberg abiotic marine cements have larger δ¹⁸O values than most Caradoc marine precipitates from equatorial Laurentia. Positive Kullsberg δ¹⁸O values are attributed to lower seawater temperatures and/or slightly elevated salinity on the Baltic platform relative to seawater from which other marine precipitates formed.     

Diagenesis and geochemistry of porites corals from Papua New Guinea: Implications for paleoclimate reconstruction

Coral proxy records of sea surface temperature (SST) and hydrological balance have become important tools in the field of tropical paleoclimatology. However, coral aragonite is subject to post-depositional diagenetic alteration in both the marine and vadose environments. To understand the impact of diagenesis on coral climate proxies, two mid-Holocene Porites corals from raised reefs on Muschu Island, Papua New Guinea, were analysed for Sr/Ca, δ¹⁸O, and δ¹³C along transects from 100% aragonite to 100% calcite. Thin-section analysis showed a characteristic vadose zone diagenetic sequence, beginning with leaching of primary aragonite and fine calcite overgrowths, transitional to calcite void filling and neomorphic, fabric selective replacement of the coral skeleton. Average calcite Sr/Ca and δ¹⁸O values were lower than those for coral aragonite, decreasing from 0.0088 to 0.0021 and −5.2 to −8.1‰, respectively. The relatively low Sr/Ca of the secondary calcite reflects the Sr/Ca of dissolving phases and the large difference between aragonite and calcite Sr/Ca partition coefficients. The decrease in δ¹⁸O of calcite relative to coral aragonite is a function of the δ¹⁸O of precipitation. Carbon-isotope ratios in secondary calcite are variable, though generally lower relative to aragonite, ranging from −2.5 to −10.4%. The variability of δ¹³C in secondary calcite reflects the amount of soil CO₂ contributing ¹³C-depleted carbon to the precipitating fluids. Diagenesis has a greater impact on Sr/Ca than on δ¹⁸O; the calcite compositions reported here convert to SST anomalies of 115°C and 14°C, respectively. Based on calcite Sr/Ca compositions in this study and in the literature, the sensitivity of coral Sr/Ca-SST to vadose-zone calcite diagenesis is 1.1 to 1.5°C per percent calcite. In contrast, the rate of change in coral δ¹⁸O-SST is relatively small (−0.2 to 0.2°C per percent calcite). We show that large shifts in δ¹⁸O, reported for mid-Holocene and Last Interglacial corals with warmer than present Sr/Ca-SSTs, cannot be caused by calcite diagenesis. Low-level calcite diagenesis can be detected through X-ray diffraction techniques, thin section analysis, and high spatial resolution sampling of the coral skeleton and thus should not impede the production of accurate coral paleoclimate reconstructions.     

Fibrous calcite from the Ordovician of Tennessee: preservation of marine oxygen isotopic composition and its implications

Three categories of fibrous calcite from early to middle Caradoc platform-marginal buildups in east Tennessee can be delineated using cathodoluminescent microscopy, minor element chemistry and stable C-O isotopic composition. Bright luminescent fibrous cement has elevated Mn (>1000 p.p.m.), negative δ¹³C and intermediate δ¹⁸O values relative to other types of fibrous calcite. This cement reflects fibrous calcite that interacted with reducing Mn-rich fluids. Dully luminescent fibrous cement has elevated Fe (>400 p.p.m.), positive δ¹³C and negative δ¹⁸O values relative to other fibrous cements. This cement was stabilized by burial fluids. Nonluminescent fibrous cement has low Mn and Fe (generally below 400 p.p.m.) and positive δ¹³C and δ¹⁸O values relative to other types of fibrous calcite. The latter cement is interpreted to be the best material for determining the isotopic composition of calcite precipitated in equilibrium with early to middle Caradoc seawater, which is δ¹³C=1% PDB and δ¹⁸O=?4 to ?5‰ PDB. Results from this study and Ashgillian brachiopods indicate that the average δ¹⁸O composition of the Ordovician ocean, during nonglacial periods, was probably never more negative than ?3‰ SMOW. Assuming an Ordovician seawater δ¹⁸O value of ?1‰ SMOW, Holston Formation fibrous cements would have precipitated at temperatures between 27 and 36 °C, which is near the upper temperature limit for metazoans. A seawater δ¹⁸O value of ?2‰ SMOW yields temperatures ranging from 23 to 31 °C, while a ?3‰ SMOW value yields temperatures of 18–26 °C.     

Environmental setting, (micro)morphologies and stable C–O isotope composition of cold climate carbonate precipitates—a review and evaluation of their potential as paleoclimatic proxies

Given the growing interest in carbonate deposits from polar regions as paleoclimatic proxies, this review paper first provides a classification of the various types of cold-climate carbonate precipitates followed by a summary of the ¹³C and ¹⁸O composition of the carbonate deposits and parent water from which the carbonates precipitated. The cold-climate carbonate precipitates were classified into three broad categories: powders, crusts and speleothem. The carbonate powders include those that precipitated in relation to aufeis aggradation (cryogenic aufeis calcite) and in relation to the growth of various annual/perennial ice formations in freezing caves (cryptocrystalline calcite and calcite pearls). The carbonate crusts can be further subdivided based on their lithic environment; those that precipitated on the upper surface of bedrock/clasts (i.e. subglacially precipitated calcite and evaporative calcite crusts); those that are located on the underside of clasts (i.e. pedogenic carbonates); and those that precipitated in rock outcrop fissures (i.e. endostromatolites). The cold-climate carbonate precipitates have a highly variable isotopic composition with δ¹⁸O values ranging between −6.5‰ and 28‰ VSMOW and δ¹³C values in the −10–20‰ VPDB range. However, each type of carbonate precipitates has a specific δ¹³C and δ¹⁸O range, suggesting that their environmental setting and the mechanism by which they formed controls their ¹³C and ¹⁸O signature. It was found that carbonate deposits that precipitated under equilibrium physico-chemical conditions had a δ¹³C value that is in equilibrium with that of the parent water, while its δ¹⁸O composition was more variable, as it is in part controlled by the temperature of reaction and by the δ¹⁸O and calcite saturation state of the parent water. By contrast, the δ¹⁸O composition of biologically precipitated carbonate deposits (endostromatolites) reflect that of the parent water, while its δ¹³C composition was enriched over that of the parent water due to bacterial methanogenesis. In the case of kinetically precipitated carbonate deposits, the δ¹⁸O and δ¹³C values are out-of-equilibrium relative to that of the parent water due to the faster rate of reaction.     

Stable isotope evidence for the origin of diagenetic carbonate minerals from the Lower Jurassic Inmar Formation, southern Israel

The oxygen isotope compositions of diagenetic carbonate minerals from the Lower Jurassic Inmar Formation, southern Israel, have been used to identify porewater types during diagenesis. Changes in porewater composition can be related to major geological events within southern Israel. In particular, saline brines played an important role in late (Pliocene-Pleistocene) dolomitization of these rocks. Diagenetic carbonates included early siderite (δ¹⁸O_SMOW=+24.4 to +26.5‰δ¹³C_PDB=?1.1 to +0.8‰), late dolomite, ferroan dolomite and ankerite (δ¹⁸O_SMOW=+18.4 to +25.8‰; δ¹³C_PDB=?2.1 to +0.2‰), and calcite (δ¹⁸O_SMOW=+21.3 to +32.6‰; δ¹³C_PDB=?4.2 to + 3.2‰). The petrographic and isotopic results suggest that siderite formed early in the diagenetic history at shallow depths. The dolomitic phases formed at greater depths late in diagenesis. Crystallization of secondary calcite spans early to late diagenesis, consistent with its large range in isotopic values. A strong negative correlation exists between burial depth (temperature) and the oxygen isotopic compositions of the dolomitic cements. In addition, the δ¹⁸O values of the dolomitic phases in the northern Negev and Judea Mountains are in isotopic equilibrium with present formation waters. This behaviour suggests that formation of secondary dolomite post-dates the tectonic activity responsible for the present relief of southern Israel (Upper Miocene to Pliocene) and that the dolomite crystallized from present formation waters. Such is not the case in the Central Negev. In that locality, present formation waters have much lower salinities and δ¹⁸O values, indicating invasion of freshwater, and are out of isotopic equilibrium with secondary dolomite. Recharge of the Inmar Formation by meteoric water in the Central Negev occurred in the Pleistocene, and halted formation of dolomite.     

Speleothem preservation and diagenesis in South African hominin sites implications for paleoenvironments and geochronology

Plio‐Pleistocene speleothems from australopithecine‐bearing caves of South Africa have the potential to yield paleoenvironmental and geochronological information using isotope geochemistry. Prior to such studies it is important to assess the preservation of geochemical signals within the calcitic and aragonitic speleothems, given the tendency of aragonitic speleothems to recrystallize to calcite. This study documents the geochemical suitability of speleothems from the principal hominin‐bearing deposits of South Africa. We use petrography, together with stable isotope and trace element analysis, to identify the occurrence of primary aragonite, primary calcite, and secondary calcite. This study highlights the presence of diagenetic alteration at many of the sites, often observed as interbedded primary and secondary fabrics. Trace element and stable isotopic values distinguish primary calcite from secondary calcite and offer insights into geochemical aspects of the past cave environment. δ¹³C values of the primary and secondary calcites range from +6 to −9‰ and δ¹⁸O values range from −4 to −6‰. The data are thus typical of meteoric calcites with highly variable δ¹³C and relatively invariant δ¹⁸O. High carbon isotope values in these deposits are associated with the effects of recrystallization and rapid outgassing of CO₂ during precipitation. Mg/Ca and Sr/Ca ratios differ between primary and secondary calcite speleothems, aiding their identification. Carbon and oxygen isotope values in primary calcite reflect the proportion of C₃ and C₄ vegetation in the local environment and the oxygen isotope composition of rainfall. Primary calcite speleothems preserve the pristine geochemical signals vital for ongoing paleoenvironmental and geochronological research. © 2009 Wiley Periodicals, Inc.     

Isotopic constraints on growth conditions of multiphase calcite–pyrite–barite concretions in Carboniferous mudstones

Carbonate concretions in the Lower Carboniferous Caton Shale Formation contain diagenetic pyrite, calcite and barite in the concretion matrix or in different generations of septarian fissures. Pyrite was formed by sulphate reduction throughout the sediment before concretionary growth, then continued to form mainly in the concretion centres. The septarian calcites show a continuous isotopic trend from δ¹³C=?28·7‰ PDB and δ¹⁸O=?1·6‰ PDB through to δ¹³C=?6·9‰ PDB and δ¹⁸O=?14·6‰ PDB. This trend arises from (1) a carbonate source initially from sulphate reduction, to which was added increasing contributions of methanogenic carbonate; and (2) burial/temperature effects or the addition of isotopically light oxygen from meteoric water. The concretionary matrix carbonates must have at least partially predated the earliest septarian cements, and thus used the same carbonate sources. Consequently, their isotopic composition (δ¹³C=?12·0 to ?10·1‰ PDB and δ¹⁸O=?5·7 to ?5·6‰ PDB) can only result from mixing a carbonate cement derived from sulphate reduction with cements containing increasing proportions of carbonate from methanogenesis and, directly or indirectly, also from skeletal carbonate. Concretionary growth was therefore pervasive, with cements being added progressively throughout the concretion body during growth. The concretions contain barite in the concretion matrix and in septarian fissures. Barite in the earlier matrix phase has an isotopic composition (δ³⁴S=+24·8‰ CDT and δ¹⁸O=+16·4‰ SMOW), indicating formation from near‐surface, sulphate‐depleted porewaters. Barites in the later septarian phase have unusual isotopic compositions (δ³⁴S=+6 to +11‰ CDT and δ¹⁸O=+8 to +11‰ SMOW), which require the late addition of isotopically light sulphate to the porewaters, either from anoxic sulphide oxidation (using ferric iron) or from sulphate dissolved in meteoric water. Carbon isotope and biomarker data indicate that oil trapped within septarian fissures was derived from the maturation of kerogen in the enclosing sediments.