Paleoclimate of some Permo-Triassic carbonates of Malaysia

Four hundred thin-sections of Permian (Chuping and Summalayang Limestones) and Triassic (Kodiang Limestone) carbonates of Malaysia were studied, mainly to interpret probable climatic zones during their formation.

Chuping Limestone is rich in skeletal grains and intraclasts formed in shallow, high-energy environments. Original mineralogy of skeletal grains and early diagenetic cements were chiefly calcites with some aragonite. The faunal assemblage is similar to that of subpolar carbonates. The brachiopods are characterized by heavy δ¹³C and light δ¹⁸O and these values lie in the same field as an Early Permian fauna from eastern Australia. The δ¹⁸O values of fauna show unrealistic temperatures because the fauna has equilibrated with melt waters. However, calculated original δ¹⁸O values of the fauna from δ¹³C indicate temperatures ranging from 2 to 13°C with δ_w of +1.2. These features reflect cool-temperate (to ?subpolar) conditions.

Summalayang Limestone is rich in fusulinids and was deposited in bar to shelf environments. Fusulinids are often filled with fine, equigranular sparry calcite. Early diagenetic origin of these cements is indicated by erosion of cements during transportation and also by the cross-cutting relationship of veins with cements. These cements were originally Mg calcites. The foramol faunal assemblage, and predominantly Mg calcite mineralogy of both fauna and cements, reflect temperate climate.

Kodiang Limestone was deposited in peritidal environments. This limestone formation has all the characteristic features of modern, warm, tropical carbonates such as chlorozoan assemblage, diverse non-skeletal grains, abundant early diagenetic dolomites and predominance of aragonitic fauna, non-skeletal grains and cements.

The formation of temperate carbonates during the Permian suggests that Malaysia was probably part of Gondwanaland.     

中国湖相碳酸盐岩时空分布与碳氧同位素特征*

湖相碳酸盐岩产状多样,多以夹层形式分布在碎屑岩剖面中,也见以结核或钙质微体化石等薄层赋存于泥岩、页岩等碎屑岩中,具有层数多、单层薄、呈韵律性变化等特点。受构造背景、物源输入和古环境等因素控制,中国湖相碳酸盐沉积最早出现于二叠纪,主要发育时段为古近纪,具有沉积时间跨度大、分布面积广的特征。湖相碳酸盐岩按成因可分为原生沉积型、成岩改造型和热液喷流型3类。中国湖相碳酸盐岩的碳氧同位素特征可揭示原生和成岩过程中水介质环境的差异性: (1)δ¹³C和 δ¹⁸O 密切相关,且δ¹³C多正偏,指示封闭型咸水、半咸水湖泊环境;(2)δ¹³C和 δ¹⁸O 无相关性,且δ¹³C多负偏,指示开放型湖泊环境;(3)δ¹³C严重正偏,指示成岩作用时发酵带的环境受到古细菌参与的甲烷生成作用的影响。     

A study of the chemistry of pore fluids and authigenic carbonates in methane seep environments: Kodiak Trench, Hydrate Ridge, Monterey Bay, and Eel River Basin

Analyses of the chemical and isotopic composition of carbonates rocks recovered from methane seepage areas of the Kodiak Trench, Hydrate Ridge, Monterey Bay Clam Flats, and the Eel River Basin, coupled with the studies of the chemistry of the pore fluids, have shown that these carbonates have grown within the sediment column. Geochemical profiles of pore fluids show that, in deep water seeps (Kodiak Trench—4450 m; Monterey Bay—1000 m; Hydrate Ridge—650 m), δ¹³C (DIC) values are low (isotopically light), whereas in the Eel River area ( 350–500 m), δ¹³C (DIC) values are much higher (isotopically heavier). In all cases, the δ¹³C values indicate that processes of methane oxidation, associated with sulfate reduction, are dominant in the shallow sediments. Data on the isotopic composition of authigenic carbonates found at sites in Kodiak Trench, Eel River Basin South, and Eel River Basin North indicate a variable composition and origin in different geochemical environments. Some of the authigenic carbonates from the study sites show a trend in their δ¹³C values similar to those of the pore fluids obtained in their vicinity, suggesting formation at relatively shallow depths, but others indicate formation at greater sediment depths. The latter usually consist of high magnesium calcite or dolomite, which, from their high values of δ¹³C (up to 23‰;) and δ¹⁸O (up to 7.5‰), suggest formation in the deeper horizons of the sediments, in the zone of methanogenesis. These observations are in agreement with observations by other workers at Hydrate Ridge, in Monterey Bay, and in the Eel River Basin.     

A stable isotope record from freshwater lake shells of the eastern Tibetan Plateau, China, during the past two centuries

Lake Xingcuo is a small, closed, hardwater lake situated in the eastern Tibetan Plateau. Stable isotope data (δ¹⁸O and δ¹³C) from the freshwater snail Gyraulus sibirica (Dunker) in a 34-cm-long, radioactive isotope-dated sediment core represent the past 200 years of Lake Xingcuo environmental history. Carbon and oxygen isotope ratios in the shells of the snail yield information on the isotopic composition of the water in which the shell was formed, which in turn relates to climatic conditions prevailing during the snail's life-span. Living and fossil shells from Lake Xingcuo were collected. δ¹⁸O values in the living shells from Lake Xingcuo are in equilibrium with ambient waters, while δ¹³C values may trace snail dietary carbon. On comparing δ¹⁸O and δ¹³C in the shell of Gyraulus sibirica with monitored data for the period 1954-1995, we found that the δ¹⁸O composition in the shell is an efficient proxy revealing air temperature during the warmer months from April to September. There is a positive correlation between the δ¹⁸O in the shells of Gyraulus sibirica and the running average temperature of the warmer months. Climatic variability in the eastern Tibetan Plateau for the past two centuries has been inferred from the δ¹⁸O record from the freshwater snails in the sediments of Lake Xingcuo. As such, the last 200 years' palaeoclimatic record for this region can be separated into three periods representing oscillations between warm and cool conditions consistent with the Guliya ice record in the Tibetan Plateau.     

Two types of gneisses associated with eclogite at Shuanghe in the Dabie terrane: carbon isotope, zircon U–Pb dating and oxygen isotope

There are two types of gneisses, biotite paragneiss and granitic orthogneiss, to be closely associated with UHP eclogite at Shuanghe in the Dabie terrane. Both concentration and isotope composition of bulk carbon in apatite and host gneisses were determined by the EA-MS online technique. Structural carbonate within the apatite was detected by the XRD and FTIR techniques. Significant ¹³C-depletion was observed in the apatite with δ¹³C values of −28.6‰ to −22.3‰ and the carbon concentrations of 0.70–4.98 wt.% CO₂ despite a large variation in δ¹⁸O from −4.3‰ to +10.6‰ for these gneisses. There is significant heterogeneity in both δ¹³C and δ¹⁸O within the gneisses on the scale of several tens meters, pointing to the presence of secondary processes after the UHP metamorphism. Considerable amounts of carbonate carbon occur in some of the gneisses that were also depleted in ¹³C primarily, but subjected to overprint of ¹³C-rich CO₂-bearing fluid after the UHP metamorphism. The ¹³C-depleted carbon in the gneisses is interpreted to be inherited from their precursors that suffered meteoric–hydrothermal alteration before plate subduction. Both low δ¹³C values and structural carbonate in the apatite suggest the presence of ¹³C-poor CO₂ in the UHP metamorphic fluid. The ¹³C-poor CO₂ is undoubtedly derived from oxidation of organic matter in the subsurface fluid during the prograde UHP metamorphism.

Zircons from two samples of the granitic orthogneiss exhibit low δ¹⁸O values of −4.1‰ to −1.1‰, demonstrating that its protolith was significantly depleted in ¹⁸O prior to magma crystallization. U–Pb discordia datings for the ¹⁸O-depleted zircons yield Neoproterozoic ages of 724–768 Ma for the protolith of the granitic orthogneiss, consistent with protolith ages of most eclogites and orthogneisses from the other regions in the Dabie–Sulu orogen. Therefore, the meteoric–hydrothermal alteration is directly dated to occur at mid-Neoproterozoic, and may be correlated with the Rodinia supercontinental breakup and the snowball Earth event. It is thus deduced that the igneous protolith of the granitic orthogneiss and some eclogites would intrude into the older sequences composing the sedimentary protoliths of the biotite paragneiss and some eclogites along the northern margin of the Yangtze plate at mid-Neoproterozoic, and drove local meteoric–hydrothermal circulation systems in which both ¹³C- and ¹⁸O-depleted fluid interacted with the protoliths of these UHP rocks now exposed in the Dabie terrane.     

塔里木盆地中央隆起区上寒武统—下奥陶统白云岩地球化学特征及白云石化流体演化规律*

以详细的岩石学研究为基础,综合利用碳、氧、锶同位素等地球化学资料,深入分析了塔里木盆地中央隆起区上寒武统—下奥陶统白云石化流体演化规律以及白云岩成因机制。结果表明,上寒武统白云岩主要由泥晶—粉晶白云岩、微生物白云岩和(残余)颗粒白云岩等原始结构保留较好的白云岩构成,其C、Sr同位素与同期海水相近,O同位素值偏正,属于同生/准同生期与轻微蒸发海水有关的白云石化的产物;下奥陶统白云岩以细晶自形—半自形白云石为主,原始结构保留差,其C、Sr同位素与同期海水近似,但O同位素值略微偏负,主要为浅埋藏期白云石化的产物。部分早期白云岩在中—深埋藏过程中受埋藏重结晶和构造—热液白云石化的影响,形成细晶—粗晶他形白云岩和缝洞鞍形白云石充填物,该阶段白云石化流体主要来自于地层内封存的海源流体、深部热液以及蒸发岩层间热卤水,多期多源流体的共同作用导致该类白云岩具有较宽的Sr同位素组成和明显负偏的O同位素值。总体上,研究区白云岩具有早期形成(近地表到浅埋藏期大规模交代)、中期加强(中—深埋藏期部分重结晶)、晚期改造(热液局部调整)的整体演化趋势。     

Oxygen isotope ratios of phenocrysts from alkali basalts of the Pannonian basin: Evidence for an O-isotopically homogeneous upper mantle beneath a subduction-influenced area

Oxygen isotope compositions of olivine and pyroxene phenocrysts and pyroxene and amphibole megacrysts from Neogene alkali basalts of the Pannonian basin (0.5–11 Ma) have been determined by laser fluorination. Measured δ¹⁸O values in olivine and clinopyroxene phenocrysts show rather restricted variations from 5.00 to 5.20‰ and from 5.07 to 5.34%., respectively, with cpx-ol fractionations Δ¹⁸O(cpx-ol) ranging from + 0.04 to + 0.29‰. These δ¹⁸O values are significantly lower than those of the corresponding whole rocks, suggesting that low temperature alteration has increased the ¹⁸O/¹⁶O ratios of the groundmass of host rocks, even in fresh looking samples, whereas their phenocrysts have retained original oxygen isotope compositions. The uniform oxygen isotope ratio in the phenocrysts suggests that the mantle source of the alkali basalts was also homogeneous with respect to its oxygen isotope composition, which is in contrast to the relatively wide variation of Sr, Nd and Pb isotope ratios in the source. Variations in radiogenic isotope compositions in the basalts have been explained by the interaction of subduction-related fluids with the mantle source of the basalts. If this is the case, then the fluids which caused significant changes in the Sr and Pb isotope ratios of the mantle source clearly did not noticeably modify its oxygen isotope composition. These data support the opinion that the upper mantle is more homogeneous with respect to its oxygen isotope composition than it was previously considered.     

Oxygen and carbon isotope composition of cold-water Berriedale Limestone (Lower Permian), Tasmania, Australia

The Berriedale Limestone formed at about 80°S paleolatitude and contains many glacial dropstones. It formed during a period of major Gondwana deglaciation.

The Berriedale Limestone contains mostly bryozoans, brachiopods and bivalves, with some intraclasts and rare pellets. The faunal diversity is low and the fauna are similar to the modern cold-water foramol faunal assemblage. Micrite, microspar and spar occur as equant to well developed rhombs of calcite. The coarse spar cements are bored and are ruptured by dropstones, indicating submarine origin of low-Mg calcite at water-temperatures of around 3°C. The mixing zone cementation was preceded by erosion of early formed crystals. The eroded crystals occur as inclusions in mixing zone cements.

The fauna are characterized by heavy δ¹³C and light δ¹⁸O. The whole-rock field of δ¹⁸O-δ¹³C falls at the edge of “Normal Marine Limestone” and deviates to lighter δ¹⁸O values (down to −16.7‰ PDB). Lightest δ¹⁸O values ( −22‰ PDB) of fresh-water sparry calcite cement are similar to those in the Early Permian continental tillites, suggesting that the Permian sea was diluted by isotopically light melt waters. Micrite δ¹⁸O values (−9.2 to −12.6‰ PDB) are within the range of whole-rock values. The δ¹⁸O values of calcite in shales are lighter than limestone values.

The δ¹⁸O values of the fauna give an unrealistic range of sea-water temperatures because the fauna have equilibrated with variable amounts of melt waters. However, calculated original δ¹⁸O values of the fauna indicate temperatures < 4°C. The heaviest δ¹⁸O of fauna gives cold temperatures of 9°C (with δ_w −2.8‰) and −3°C (with δ_w −6‰). The lightest values of sparry calcite cements (−22‰ PDB) indicate that the limestone reacted with cold melt waters.

The δ¹⁸O of Permian sea is estimated to be about +1.2‰ and was diluted by melt waters as light as −27‰ SMOW.     

Burial-dominated cementation in non-tropical carbonates of the Oligocene Te Kuiti Group, New Zealand

Cementation of bryozoan-echinoid-benthic foraminiferal temperate shelf carbonates of the Oligocene Te Kuiti Group, North Island, New Zealand, occurred mainly during subsurface burial. The calcite cements in the limestones are dominated by equant and syntaxial rim spar which typically becomes ferroan (given an iron supply) and, compared to the skeletal material with normal marine δ¹⁸O values from +2 to −1‰, more depleted in ¹⁸O with depth of burial, the δ¹⁸O composition of bulk cement samples ranging from −1 to −7‰. These trends reflect the establishment in pore waters during sediment burial of reducing conditions and gradually increasing temperatures (20–50°C), respectively. The δ¹³C values (0 to +3‰) of the cements remain the same as the host marine shells, suggesting the source of carbon in the cements was simply redistributed marine carbonate derived from shell dissolution.

Two gradational burial diagenetic environments influenced by marine-derived porewaters are arbitrarily distinguished: shallow burial phase and moderate burial phase. During the shallow burial phase, down to 500–600 m sub-bottom depth, the carbonates lost at least 25% of their original porosity by mechanical compaction and were selectively cemented by non-ferroan or usually ferroan, variably luminescent, slightly ¹⁸O-depleted sparry calcite cement (δ¹⁸O −2 to −4‰), mainly as syntaxial rims about echinoid grains. These shallow-burial cements form less than about 10% of total cement in the majority of the limestones and their source was probably mainly mild intergranular dissolution of calcitic skeletal fragments accompanying the onset of chemical compaction. During the moderate burial phase, between about 600 and 1100 m sub-bottom depth, porosity loss continued (typically to about 70% of its original value) as a result of pressure-solution of calcitic bioclasts associated with more advanced stages of chemical compaction. This involved development of a wide variety of non-sutured and microstylolitic solution seams, including both single and composite, wispy or continuous, bedding-parallel types and non-parallel reticulate forms. The released carbonate was precipitated as ferroan (or non-ferroan where iron supply was negligible), dull luminescent, strongly ¹⁸O-depleted (δ¹⁸O −4 to −7‰), mainly equant calcite spar cement, occluding available pore space in the limestones.     

四川盆地东部地区寒武系洗象池群碳酸盐岩碳、氧同位素特征及其意义*

四川盆地东部地区寒武系洗象池群碳酸盐岩的碳、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,笔者根据采集的111个碳、氧同位素数据,研究、讨论了盆地东部地区中上寒武统碳酸盐岩碳、氧同位素组成、演化及地质意义。研究表明,δ¹³C值变化介于-3.36‰~2.65‰之间,均值为-1.027‰,绝大多数的样品都分布在-2‰~2‰的区间,δ¹⁸O值分布于-11.1‰~-6.01‰之间,均值为-7.991‰,在-10‰~-6‰的范围内波动。通过对碳、氧同位素数据分析研究,认为四川盆地东部地区洗象池群主要发育在盐度较高、温暖—炎热的近岸海相沉积环境;洗象池群沉积早期和中期经历了短暂而快速的海侵后进入缓慢的海退,在晚期缓慢海侵后的快速海退,碳同位素组成反映的海平面变化趋势与沉积相演化一致。洗象池群沉积中期显著的碳同位素正向漂移,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。     

准噶尔盆地玛湖凹陷下二叠统风城组含碱层段韵律特征及成因*

准噶尔盆地玛湖凹陷早二叠世风城组沉积时期为典型的碳酸盐型咸化湖盆,湖盆咸化过程中析出大量的碱矿(钠碳酸盐类矿物)。通过含碱层段主量元素、碳氧同位素分析,结合岩心宏观及微观矿物岩石特征,探讨了含碱层段韵律特征及形成机理。研究层段碱矿与沉凝灰岩互层,形成明暗相间的咸化韵律。浅色碱矿层质地较纯,主要为苏打和小苏打,主量元素表现为 Na₂O含量高,CaO、MgO、SiO₂和Al₂O₃含量低;暗色层段主要为含斑点状碳钠钙石的沉凝灰岩,主量元素表现为Na₂O含量低,CaO、MgO、SiO₂和Al₂O₃含量高。浅色碱矿层和暗色沉凝灰岩段碳氧同位素值均为正,表明其沉积水体具高盐度特征。浅色含碱层段具有更高的 δ¹⁸O 值,反映了碱矿层沉积时期强烈蒸发的气候条件。根据δ¹⁸O/δ¹³C值的波动将研究层段划分为炎热干旱和相对湿润的气候条件,并据此解释不同韵律层盐类矿物形成机理。暗色的沉凝灰岩沉积代表地表流水注入量大于蒸发量,沉凝灰岩中盐类矿物含量少或者呈斑点状从颗粒间的卤水中析出;随着蒸发量的增高以及古气候由温暖潮湿转变为干旱炎热,地表流水注入量急剧减少,强烈蒸发控制了碱矿的沉积,形成浅色质地较纯的碱矿层。气候的频繁交替形成了风二段碱矿与沉凝灰岩频繁互层的特征。     

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。     

重庆东部地区寒武系龙王庙组碳、氧同位素特征及其意义

在野外露头和镜下薄片观察分析的基础上,对重庆东部地区下寒武统龙王庙组83个碳酸盐岩样品的碳、氧同位素进行测试,并分析了其所保留的海水原始信息的有效性。结果表明,扣除无效数据后,重庆地区龙王庙组δ¹³C值分布在-4.300‰~2.694‰之间,平均值为-0.031‰;δ¹⁸O值分布在-9.880‰~-0.100‰之间,平均值为-7.396‰;纵向上,碳同位素值整体呈现先降低后升高的趋势,底部、中上部及顶部为正值且变化幅度小;中下部整体为负值且波动幅度大,正、负漂移事件频发。古环境恢复结果显示,龙王庙期重庆东部地区整体处于海相沉积环境,海水盐度在龙王庙组早期较低,晚期较高;海水温度主要介于20~30,℃之间,属温暖或炎热的亚热带气候;龙王庙期共经历3期海退—海侵作用,海平面上升、海洋生产力增加、有机碳快速埋藏使得海洋中¹³C含量升高,反之则使其降低。龙王庙组沉积中期与末期,δ¹³C值负偏,水体较浅,盐度较高,是白云岩发育的最有利阶段。     

台西南深海底栖有孔虫及其5万年来冷泉微生境变迁记录

为探讨冷泉区底栖有孔虫组合特征、受控因素及其冷泉微生境随时间的变迁,本文对台西南海盆取自九龙甲烷礁和海洋四号区冷泉区的973-4和973-5两根岩心展开了底栖有孔虫及其壳体氧碳同位素研究。测年结果揭示两根岩心为晚更新世约5万年来海洋氧同位素期(MIS)MIS 3至MIS 1早期的沉积序列。两个站位共识别了底栖有孔虫79属233种,优势类别在973-4组合中为Uvigerina(23.3%)、Bulimina(10.71%)和Cibicidoides(9.87%),在973-5组合中是Bulimina(20.6%),两站位的组合优势和常见属种均以内生类别为主。有孔虫分异度显然同时受到正常深海环境因子TOC和沉积物粒度的影响。总体上,优势和常见类群与TOC相关性较弱,但与δ¹⁸O_{Uvigerina spp.}有不同程度的相关性,说明有孔虫还受冷泉特殊营养物质和流体因子影响。5万年来,973-4和973-5站位底栖有孔虫组合生活的冷泉微生境,经历了由双壳-自生碳酸盐岩(MIS 3至MIS 2早期)向双壳-菌席(MIS 2晚期至MIS 1早期)的变迁。底栖有孔虫的优势类群也随微生境的变迁而演替,如973-4站位MIS 3-MIS 1的优势类群依次为U.peregrina、Cibicidoides-Bulimina、U.vadescens和Cibicides,973-5站位为Chilostomella+ Globobulimina、Cibicidoides、Bulimina。有孔虫壳体氧碳同位素特征也随时间改变,从MIS 3到MIS 2早期,在自生碳酸盐岩水岩交换背景下,具有富δ¹⁸O和亏损δ¹³C特点(3.5‰~4.49‰,-2‰~-0.2‰); MIS 2晚期—MIS 1早期因双壳和菌席的生物地球化学作用影响,具有略富集δ¹⁸O和略微亏损δ¹³C的特征(2.5‰~3.5‰,-1‰~-0.1‰)。自5万年来两个区甲烷渗漏逐渐减弱,其间发生了几次增强事件。973-4站位记录了1次持续时间约10 ka的增强事件(35~25 ka);973-5站位记录3次(45 ka,35 ka,14~12 ka)。其中,45 ka时海底上涌的甲烷通量可能最大,在海底表面形成水合物。35 ka时的甲烷喷溢增强事件可能为区域性事件。     

Oxygen and carbon isotopic constraints on the development of eclogites, Holsnøy, Norway

Eclogite formation on the island of Holsnøy required the addition of water to anhydrous granulite-facies protoliths. In order to assess this process, oxygen and carbon isotope ratios of whole rock powders and mineral separates from eclogites and granulites have been measured. Whole rock oxygen isotope ratios range from 7.3 to 6.0%. SMOW in granulites (average = 6.38%.) and 7.2 to 6.1%. in eclogites (average = 6.55%.). Field relations permit identification of the granulite protolith of eclogites. Oxygen isotope measurements show shifts of up to 0.5%. between some eclogites compared to their corresponding granulite protoliths, indicating open system and locally heterogeneous fluid behavior. Mineral pair fractionations in the eclogites show disequilibrium, are incompatible with slow cooling and diffusive exchange between phases, and suggest that open system fluid movement continued after eclogite-facies metamorphism. Carbonate is also present in some of the eclogites as a primary mineral (dolomite) and as part of a retrograde assemblage (calcite). Textural evidence suggests that carbonate formation occurred during and after eclogite formation, however all measured carbonate is out of isotopic equilibrium with eclogite facies minerals, due to the influx of retrograde fluids. Massive calcite marble pods, containing amphibolite facies cale-silicate minerals, have average δ¹⁸O of 9.5 ± 0.6%., while calcite in retrograded eclogites has δ¹⁸O 17.7 ± 2.7%., The δ¹³C (≈ −4 ± 0.8%.) is indistinguishable between these two groups.

Both whole rock and carbonate stable isotope data are interpreted as indicating a continued history of fluid infiltration during and after peak eclogite facies metamorphism. The most probable source of fluids are from dewatered sediments tectonically juxtaposed during the Caledonian orogeny.     

Oxygen, carbon, and strontium isotope geochemistry of diamond-bearing carbonate rocks from Kumdy-Kol, Kokchetav Massif, Kazakhstan

Diamond-bearing carbonate rocks from Kumdy-Kol, Kokchetav massif, Kazakhstan, were strongly altered by fluids flowing through fractures and infiltrating along grain boundaries during exhumation. Alteration includes retrogradation of high-grade silicate assemblages by hydrous minerals, replacement of diamond by graphite and of dolomite by calcite. Diamond-bearing carbonate rocks are among the most intensely altered isotopically with δ¹⁸O_VSMOW values as low as +9‰, δ¹³C_VPDB=−9‰, and ⁸⁷Sr/⁸⁶Sr as high as 0.8050. Evidence of isotopic equilibration between coexisting dolomite and high-Mg calcite during ultrahigh-pressure metamorphism (UHPM) is preserved only rarely in samples isolated from infiltrating fluids by distance from fractures. Isotopic heterogeneity and isotopic disequilibrium are widespread on a hand-specimen scale. Because of this lack of homogeneity, bulk analyses cannot provide definitive measurements of ¹³C/¹²C fractionation between coexisting diamond and carbonate. Our study adequately documents alteration on a scale commensurate with observed vein structures. But, testing the hypothesis of metamorphic origin of microdiamonds has not fully succeeded because our analytical spatial resolution, limited to 0.5 mm, is not small enough to measure individual dolomite inclusions or individual diamond crystals.     

豫西下二叠统太原组遗迹化石与古氧相的响应特征*

基于对豫西禹州和焦作地区下二叠统太原组中的遗迹化石组成与产状特征的研究,以及对不同颜色Zoophycos潜穴充填物中碳氧同位素和微量元素含量的测试分析,取得成果如下: (1)灰白色充填物中δ¹³C值较低,主要介于-2‰~-4‰之间;灰色充填物中δ¹³C值大多在-0.8‰~-2‰之间。二者的V/(V+Ni)值均小于0.46,Ce/La值均小于1.5。反映其为富氧相,即氧化环境。(2)红褐色充填物中δ¹³C值一般在-0.2‰~-0.9‰之间,V/(V+Ni)值大于0.46,反映其为贫氧相,即弱还原环境。(3)黑色充填物中δ¹³C值最高,多数在0.2‰~1.6‰之间,Ce/La值大于1.8,反映其为厌氧相,即还原环境。综合分析上述特征,提出了3种古氧相(富氧相、贫氧相和厌氧相)的遗迹化石响应关系及其形成的沉积背景模式。这一研究成果可为精细分析豫西下二叠统太原组碳酸盐岩的沉积环境演变规律提供直观的生物遗迹识别标志。     

C, O, S and Sr isotope studies on the genesis of Fe-carbonate and barite mineralizations in the Attepe iron district (Adana, Southern Turkey)

The Attepe district consists of Precambrian, Lower–Middle Cambrian, Upper Cambrian–Lower Ordovician and Mesozoic formations. It contains several iron deposits and occurrences. Three types of iron-mineralizations can be distinguished in the area; (i) Sedimentary Fe-sulfide in Precambrian bituminous metapelitic rocks, and Fe-oxides in Precambrian metasandstones (SISO), (ii) vein-type Fe-carbonate and oxides composed of mainly siderite, ankerite and hematite including barite in Lower–Middle Cambrian metacarbonates of the Çaltepe Formation (HICO), (iii) karstic Fe-oxides and hydroxides essentially in the Lower–Middle Cambrian metacarbonates and the unweathered Fe-carbonates (KIO). The latter type is more widespread and located at the upper parts of the most important mineable iron deposits like Attepe deposit.

Oxygen-, carbon-, sulfur- and strontium-isotope studies have been performed on siderites and barites in the vein-type ores, and on calcites in the recrystallized Çaltepe Limestones to investigate the sources and formation mechanism of primary ore-forming constituents. The δ¹³C values of siderites and calcites in limestones of the Çaltepe Formation range from −10.10‰ to −8.20‰, and from −0.8‰ to 2.30‰. Both carbonate minerals show δ¹⁸O values between 17.50–18.30‰ and 16.20–23.00‰, respectively. The δ¹³C and δ¹⁸O isotopic variations do not indicate any direct or linear relations between siderites and limestones. However, it is possible that the carbon and oxygen isotopic compositions of carbonate minerals could be changed to some extent, when limestones were subjected to hydrothermal processes or thermal alterations during metamorphism.

The isotopic values of barites display 32.40–38.30‰ for δ³⁴S and 12.20–14.70‰ for δ¹⁸O. The strontium isotope ratios (0.717169–0.718601) of barites and the sulfur isotope compositions of barites and pyrites suggest that there are no direct linkages of ore-forming compounds neither with a magmatic source nor with sedimentary pyrite formations in the Precambrian bituminous shales of the Attepe formation.

According to the field observations and the stable isotope data, siderites and ankerites should be formed by interaction between iron-rich hydrothermal fluids and Çaltepe limestones, whereas isotope ratios of barites indicate that they were formed by mixing of sulfur-rich meteoric waters and deeply circulated hydrothermal solutions.     

Neo-Proterozoic rift-related syenites (Northern Damara Belt, Namibia): Geochemical and Nd–Sr–Pb–O isotope constraints for mantle sources and petrogenesis

Major element, trace element and Nd–Sr–Pb–O isotope data for a suite of Neo-Proterozic, pre-orogenic, rift-related syenites from the Northern Damara orogen (Namibia) constrain their sources and petrogenesis. New U–Pb ages obtained on euhdreal titanite of inferred magmatic origin constrain the age of intrusion of the Lofdal and Oas syenites to ca. 750 Ma compatible with previous high-precision zircon analyses from the Oas complex. Major rock types from Lofdal and Oas are mildly sodic nepheline-normative and quartz-normative syenites and were primarily generated by fractional crystallization from a mantle-derived alkaline magma. Primitive samples from Lofdal and Oas show depletion of Rb, K and Th relative to Ba and Nb together with variable negative anomalies of P and Ti on a primitive mantle-normalized diagram. Evolved samples from Oas develop significant negative Ba, Sr, P and Ti anomalies and positive U and Th anomalies mainly as a function of crystal fractionation processes. The lack of a pronounced negative Nb anomaly in samples from Lofdal suggests that involvement of a crustal component is negligible. For the nepheline-normative samples from Lofdal, the unradiogenic Sr and radiogenic Nd isotope composition and low δ¹⁸O values suggest derivation of these samples from a moderately depleted lithospheric upper mantle with crustal-like U/Pb ratios (⁸⁷Sr/⁸⁶Sr: 0.7031–0.7035, ε Nd: ca. + 1, δ¹⁸O: 7‰, ²⁰⁶Pb/²⁰⁴Pb: ca.18.00, ²⁰⁷Pb/²⁰⁴Pb: 15.58–15.60). Primitive samples of the Oas quartz-normative syenites have identical isotope characteristics (⁸⁷Sr/⁸⁶Sr: 0.7034, ε Nd: ca. + 1, δ¹⁸O: 6.5‰, ²⁰⁶Pb/²⁰⁴Pb: ca.18.00, ²⁰⁷Pb/²⁰⁴Pb: 15.59) whereas more differentiated samples have higher ⁸⁷Sr/⁸⁶Sr ratios (0.709–0.714), slightly higher δ¹⁸O values (7.0–7.1‰), less radiogenic ε Nd values (− 1.1 to − 1.4) and more radiogenic ²⁰⁶Pb/²⁰⁴Pb ratios up to 18.27. These features together with model calculations using Sr–Nd–Pb isotopes suggest modification of a primary syenite magma by combined AFC processes involving ancient continental crust. In this case, high Nb abundances of the parental syenite liquid prevent the development of significant negative Nb anomalies that may be expected due to interaction with continental crust.     

Stable isotope geochemistry of marbles from the coesite UHP terrains of Dabieshan and Sulu, China

Marbles from Dabieshan and Sulu, China, suffered ultra high pressure (UHP) metamorphism in the coesite–eclogite facies at approximately 700°C and 30 kbars during Triassic continental collision and subduction. The marbles range in isotopic composition from +7 to +25 δ¹⁸O_VSMOW and from 0 to +6 δ¹³C_VPDB. High δ¹³C values are representative of unmodified protoliths and are similar to those of ¹³C-enriched Sinian carbonate rocks from the Yangtze craton. High oxygen isotope ratios reflect pristine protoliths but the low values may have been caused by infiltration of low ¹⁸O meteoric water during diagenesis and dolomitization, by fracture-controlled infiltration of water during subduction, by metamorphic mineral reactions, or by a combination of these processes. No evidence of regional isotopic transport during UHP metamorphism has been found. Sampling on scales of 1 to 100 m shows marbles to be inhomogeneous in both carbon and oxygen isotopes. Only samples separated by less than 10 cm have equilibrated oxygen and carbon isotope compositions. Limited isotopic equilibration between adjacent rocks is consistent with the preservation of unaltered UHP minerals and indicates that the metamorphic fluid–rock system was rock-dominated during and following peak metamorphism. A freely flowing, pervasive fluid phase was not present during UHP metamorphism. There is no evidence of isotopic exchange between marble and the upper mantle into which it was subducted. Correlation of geochemical similarities of UHP marbles with Sinian limestones implies that the subducted edge of the Yangtze craton extends at least as far north as the coesite–eclogite facies rocks of Dabieshan. Deposition of protolith carbonates may have taken place in a cold climate either preceding or following but not coincident with Neoproterozoic glaciation.