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1.
微量元素是岩溶洞穴沉积中非常重要的一类古气候环境替代指标,为近20年来国内外的一个研究热点。总结前人的研究,主要取得了以下一些重要认识:（1）洞穴上覆土壤 和围岩是洞穴次生碳酸盐沉积Mg、Sr的主要来源;（2）Mg/Ca与Sr/Ca能够指示气候环境变化,但需结合其它指标综合考虑。（3）洞穴次生碳酸盐沉积Mg/Ca与Sr/Ca受多种气候环境因素（包括土壤和围岩的组成和性质、水-岩相互作用、先期碳酸盐沉积、分配系数等）影响,其古气候环境指示意义具有多解性;（4）矿物结晶作用对Mg/Ca与Sr/Ca有一定的影响,特别是文石在向方解石转变的过程中容易丢失Mg、Sr,此外,杂质的混入也将抑制Mg、Sr进入方解石,从而引起洞穴次生碳酸盐沉积Mg/Ca与Sr/Ca比值的变化。今后应进一步加强对石笋中这些微量元素的影响机制研究,尤其是对一些影响因素与微量元素含量变化之间的定量关系进行探讨。   相似文献   

2.
前人对Site 4B站位海底浅表层沉积物的研究显示该站位历史上可能存在甲烷渗漏事件。为研究该站位的甲烷渗漏历史,分析了Site 4B站位柱状沉积物的元素地球化学特征,及沉积物中Mg/Ca和Sr/Ca比随深度的变化规律以及自生碳酸盐矿物的分布特征。元素相关性分析表明:研究区Ca、Sr等碳酸盐相关的元素极有可能来自于与甲烷渗漏有关的自生碳酸盐。结合沉积物的粒度特征,认为Site 4B站位在15.78 ka B.P.之前泥火山活动造成甲烷渗漏,且甲烷渗漏速率具有增大—减小的周期性变化特点。研究站位在24.15 ka B.P.、27.47 ka B.P.、31.05 ka B.P.具有相对较高的甲烷渗漏速率,且在31.05 ka B.P.达到最大值。研究结果对探明南海北部的甲烷渗漏历史具有重要的意义。  相似文献   

3.
石笋矿物类型、成因及其对气候和环境的指示   总被引：5，自引：2，他引：3  
洞穴石笋的矿物组成分为方解石、文石和文石-方解石三种类型。本文总结了国内外已有的研究成果,并结合野外观测现象和数据,讨论了影响石笋矿物形成和转变的因素,分析了利用石笋矿物类型特征研究古气候和古环境变化的可行性。洞内滴水饱和度和滴水中Mg/Ca比值是影响石笋矿物类型的主要因素:当滴水Mg/Ca 比值较低（Mg/Ca＜1或<<1）时,滴水饱和度较低易形成方解石,而文石沉积则需要更高的滴水饱和度;当滴水Mg/Ca 比值较高（Mg/Ca≥1）时,方解石相对文石沉积需要更高的滴水饱和度。洞穴围岩镁含量高且滴水多而稳定的洞内环境是我国南方大量文石笋发育的主要原因。长期处于滴水淋滤环境的文石笋容易向方解石转变,但若滴水中Mg2+浓度较大,此转变过程会受到抑制。在围岩镁含量较低的洞穴中,干旱时期渗流水滞留时间长、滴水速率变慢,会造成滴水中Mg/Ca比值升高并引起文石沉积。因此,石笋矿物类型及矿物相转变可指示气候和环境的变化。   相似文献   

4.
A 4-year study in a central Texas cave quantifies multiple mechanisms that control dripwater composition and how these mechanisms vary at different drip sites. We monitored cave-air compositions, in situ calcite growth, dripwater composition and drip rate every 4-6 weeks. Three groups of drip sites are delineated (Groups 1-3) based on geochemical variations in dripwater composition. Quantitative modeling of mineral-solution reactions within the host carbonate rock and cave environments is used to identify mechanisms that can account for variations in dripwater compositions. The covariation of Mg/Ca (and Sr/Ca) and Sr isotopes is key in delineating whether Mg/Ca and Sr/Ca variations are dictated by water-rock interaction (i.e., calcite or dolomite recrystallization) or prior calcite precipitation (PCP). Group 1 dripwater compositions reflects a narrow range of the extent of water-rock interaction followed by varying amounts of prior calcite precipitation (PCP). Group 2 dripwater compositions are controlled by varying amounts of water-rock interaction with little to no PCP influence. Group 3 dripwater compositions are dictated by variable extents of both water-rock interaction and PCP. Group 1 drip sites show seasonal variations in dripwater Mg/Ca and Sr/Ca, whereas the other drip sites do not. In contrast to the findings of most previous dripwater Mg/Ca-Sr/Ca studies, these seasonal variations (at Group 1 drip sites) are independent of changes in water flux (i.e., rainfall and/or drip rate), and instead significantly correlate with changes in cave-air CO2 concentrations. These results are consistent with lower cave-air CO2, related to cool season ventilation of the cave atmosphere, enhancing calcite precipitation and leading to dripwater geochemical evolution via PCP. Group 1 dripwater Mg/Ca and Sr/Ca seasonality and evidence for PCP as a mechanism that can account for that seasonality, have two implications for many other regions where seasonal ventilation of caves is likely: (1) speleothem trace-element records may provide seasonal signals, and (2) such records may be biased toward recording climate conditions during the season when calcite is depositing. Additionally, we use our results to construct a forward model that illustrates the types of speleothem Mg/Ca and Sr/Ca variations that would result from varying controls on dripwater compositions. The model provides a basis for interpreting paleo-dripwater controls from high frequency Mg/Ca and Sr/Ca variations for speleothems from caves at which long term monitoring studies are not feasible.  相似文献   

5.
Magnesium/calcium, Sr/Ca, and Na/Ca atom ratios were determined in the calcite and aragonite regions of Mytilus edulis shells which were grown in semi-artificial ‘seawater’ solutions having varying Mg/Ca, Sr/Ca, and Na/Ca ratios. These ratios were measured by instrumental neutron activation, atomic absorption, and electron microprobe analytical techniques. Strontium/calcium ratios in both calcite and aragonite were linearly proportional to solution Sr/Ca ratios. Magnesium/calcium ratios in calcite increased exponentially when solution Mg/Ca ratios were raised above the normal seawater ratio; whereas in aragonite, Mg/Ca ratios increased linearly with increases in solution Mg/Ca ratios. Sodium/calcium and sulfur/calcium ratios in calcite covaried with Mg/Ga solution ratios. Conversely, in aragonite, Na/Ca ratios varied linearly with solution Na/Ca ratios.Magnesium is known to inhibit calcite precipitation at its normal seawater concentration. We infer from the results of the work reported here that Mytilus edulis controls the Mg activity of the outer extrapallial fluid, thus facilitating the precipitation of calcitic shell. Increases in sulfur content suggest that changes in shell organic matrix content occur as a result of environmental stress. Certain increases in Mg content may also be correlated to stress. Sodium/calcium variations, and their absolute amounts in calcite and aragonite, are best explained by assuming that a substantial amount of Na is adsorbed on the calcium carbonate crystal surface. Strontium/calcium ratios show more promise than either Mg/Ca or Na/Ca ratios as seawater paleochemistry indicators, because the Sr/Ca distribution coefficients for both aragonite and calcite are independent of seawater Ca and Sr concentrations.  相似文献   

6.
We investigated the geochemical characteristics of major, trace and rare earth elements and Sr–Nd isotope patterns of bed sediments from the headwaters and upper reaches of the six large rivers draining the Tibetan Plateau (the Jinsha River—Yangtze, Lancang River—Mekong, Nujiang River—Salween, Huang He—Yellow, Indus, and Yarlung Tsangpo—Brahmaputra). By using Ca/Al versus Mg/Al, La/Sc versus Co/Th, and 87Sr/86Sr versus εNd (0) binary differentiation diagrams of provenance, some typical contributors to the different catchment sediments can be identified. In the Three-River (the Jinsha, Lancang, and Nujiang Rivers) tectonomagmatic belt, acidic–intermediate-acidic volcanic rocks are very important provenance of sediments. Carbonate rocks and Permian Emeishan basalts are dominant in the Jinsha River. The Yellow River sediments have similar geochemical characteristics with loess in catchments. The Indus and Yarlung Tsangpo Rivers sediments are mainly from ultra-K volcanic rocks and Cenozoic granitoids widely distributed in the Indus–Yarlung suture. The intensity of chemical weathering in these river catchments is evaluated by calculating the chemical indices of alteration (CIA) of sediments and comparing them with bedrocks. The CIA values of the six river sediments are from 46.5 to 69.6, closing to those of bedrocks in the corresponding catchment, which indicates relatively weak chemical weathering intensity. Lithology, climate, and topography affect the chemical weathering intensity in these river catchments.  相似文献   

7.
Trace element ratios in the Bt2 stalagmite from Botuverá cave, Southern Brazil, are explored as a proxy for changes in the local rainfall recharge during the last 116 ky. BP Mg/Ca and Sr/Ca ratios, measured with an electron microprobe, are significantly positively correlated with one another throughout the entire record, and vary in a way that is very consistent with variations of δ18O in the same speleothem during the last glacial period. We suggest that prior calcite precipitation in the vadose zone of the cave system is the main factor affecting the incorporation of Mg and Sr into calcite of the stalagmite. This interpretation is supported by trace element correlation patterns and by results from a hydrochemistry study performed in a cave located in the same region and in a similar environmental setting. Therefore, we conclude that higher (lower) Mg/Ca and Sr/Ca values are associated with lower (higher) levels of recharge into the karstic aquifer, as such conditions lead to an increase (decrease) in the volume of calcite precipitated in the unsaturated zone above the cave during dry (wet) climate periods.Trace element variations point to generally dryer (wetter) conditions during lower (high) phases of summer insolation in the southern hemisphere. These periods coincide with decreased (increased) activity of the South American summer monsoon, as revealed by δ18O stalagmite records. In addition trace element variations show that rather wet conditions persisted throughout most of the last glacial period from approximately 70 to 17 ky BP. We suggest that during this period the glacial boundary conditions, especially ice volume buildup in the northern hemisphere, played an important role for monsoon rainfall intensification in the region.  相似文献   

8.
Among several lithostratigraphic subdivisions of the Gaj Formation of Miocene age, the Jhill limestone is entirely different with respect to its colour, texture and structures. This limestone unit has been evaluated to elaborate its geochemical and sedimentological characteristics. The distribution of various elements in the acid-soluble fraction has been studied in order to determine their mineralogy, sedimentary environment, facies and diagenesis. Mineralogy, recrystallization and other diagenetic changes are the main factors affecting the distribution of trace elements and their mutual relationships in the limestones. Samples of the Jhill limestone show depletion in large-sized ions (Sr, Pb & K) and also in the ions that are not compatible with calcite space group. Elements (Fe, Mn, Zn, Cu & Co) having distribution coefficient (D) above unity for natural calcites, are more enriched. Microscopic and X-ray studies revealed nearly complete conversion of aragonite into stable low-Mg calcite. An attempt has also been made to verify the reefal conditions for these limestones on the basis of geochemical studies. The plots of Sr and other facies-indicator elements show that the majority of the beds belong to forereef flank facies with some algal banks. Low Mg/Ca and Sr/Ca ratios suggest that a phreatic diagenetic environment prevailed after the deposition. High concentrations of Cr, Ni, and Co in the Jhill limestone show a positive correlation with a higher amount of insoluble residue, which reflects a relatively high rate of influx of terrigenous material.  相似文献   

9.
The Mg/Ca ratio of seawater has varied significantly throughout the Phanerozoic Eon, primarily as a function of the rate of ocean crust production. Specimens of the crustose coralline alga Neogoniolithon sp. were grown in artificial seawaters encompassing the range of Mg/Ca ratios shown to have existed throughout the Phanerozoic. Significantly, the coralline algae’s skeletal Mg/Ca ratio varied in lockstep with the Mg/Ca ratio of the artificial seawater. Specimens grown in seawater treatments formulated with identical Mg/Ca ratios but differing absolute concentrations of Mg and Ca exhibited no significant differences in skeletal Mg/Ca ratios, thereby emphasizing the importance of the ambient Mg/Ca ratio, and not the absolute concentration of Mg, in determining the Mg/Ca ratio of coralline algal calcite. Specimens grown in seawater of the lowest molar Mg/Ca ratio (mMg/Ca = 1.0) actually changed their skeletal mineralogy from high-Mg (skeletal mMg/Ca > 0.04) to low-Mg calcite (skeletal mMg/Ca < 0.04), suggesting that ancient calcitic red algae, which exhibit morphologies and modes of calcification comparable to Neogoniolithon sp., would have produced low-Mg calcite from the middle Cambrian to middle Mississippian and during the middle to Late Cretaceous, when oceanic mMg/Ca approached unity. By influencing the original Mg content of carbonate facies in which these algae have been ubiquitous, this condition has significant implications for the geochemistry and diagenesis of algal limestones throughout most of the Phanerozoic. The crustose coralline algae’s precipitation of high-Mg calcite from seawater that favors the abiotic precipitation of aragonite indicates that these algae dictate the precipitation of the calcitic polymorph of CaCO3. However, the algae’s nearly abiotic pattern of Mg fractionation in their skeletal calcite suggests that their biomineralogical control is limited to polymorph specification and is generally ineffectual in the regulation of skeletal Mg incorporation. Therefore, the Mg/Ca ratio of well-preserved fossils of crustose coralline algae, when corrected for the effect of seawater temperature, may be an archive of oceanic Mg/Ca throughout the Phanerozoic. Magnesium fractionation algorithms that model algal skeletal Mg/Ca as a function of seawater Mg/Ca and temperature are presented herein. The results of this study support the empirical fossil evidence that secular variation of oceanic Mg/Ca has caused the mineralogy and skeletal chemistry of many calcifying marine organisms to change significantly over geologic time.  相似文献   

10.
溧水盆地位于长江中下游成矿带东部,与庐枞、宁芜等火山岩盆地相似,发育中生代火山岩。为了探讨溧水盆地不同旋回火山岩形成时代、岩浆源区及岩浆活动的大地构造背景及其与铁铜成矿关系等问题,本次研究选取溧水盆地广泛出露且与成矿关系密切的中生代龙王山旋回和大王山旋回火山岩进行了锆石精确定年和Hf同位素分析以及全岩主微量元素分析。研究表明溧水盆地岩浆活动起始时间为~135 Ma,峰期时间为135~124 Ma。龙王山、大王山旋回火山岩Hf同位素特征相似,εHf(t)值范围大多在-6~-11之间,暗示其源区可能相似。岩石地球化学特征显示龙王山—大王山旋回岩浆由中基性向中酸性过渡,并向高钾富碱方向演化,空间上从北西-南东方向演变,与盆地内铁铜金锶矿的形成有关。龙王山旋回火山岩明显Sr正异常,推测龙王山旋回可能是Sr矿的矿源层。结合岩石地球化学和同位素特征,认为岩浆源区为可能为富集地幔,在喷发早期受到了少量陆壳物质的混染。溧水盆地与长江中下游其它火山岩盆地形成时代相似,可能受同一构造背景控制。结合前人研究成果分析认为在~135 Ma为太平洋板块俯冲的转折点,即俯冲作用减弱,俯冲板块发生后撤,形成区域性拉张环境,从而形成的一系列火山岩盆地。  相似文献   

11.
The relationship between potential elemental proxies (Mg/Ca, Sr/Ca and Mn/Ca ratios) and environmental factors was investigated for the bivalve Pecten maximus in a detailed field study undertaken in the Menai Strait, Wales, U.K. An age model constructed for each shell by comparison of measured and predicted oxygen-isotope ratios allowed comparison on a calendar time scale of shell elemental data with environmental variables, as well as estimation of shell growth rates. The seasonal variation of shell Mn/Ca ratios followed a similar pattern to one previously described for dissolved Mn2+ in the Menai Strait, although further calibration work is needed to validate such a relationship. Shell Sr/Ca ratios unexpectedly were found to co-vary most significantly with calcification temperature, whilst shell Mg/Ca ratios were the next most significant control. The temporal variation in the factors that control shell Sr/Ca ratios strongly suggest the former observation most likely to be the result of a secondary influence on shell Sr/Ca ratios by kinetic effects, the latter driven by seasonal variation in shell growth rate that is in turn influenced in part by seawater temperature. P. maximus shell Mg/Ca ratio to calcification temperature relationships exhibit an inverse correlation during autumn to early spring (October to March-April) and a positive correlation from late spring through summer (May-June to September). No clear explanation is evident for the former trend, but the similarity of the records from the three shells analysed indicate that it is a real signal and not a spurious observation. These observations confirm that application of the Mg/Ca proxy in P. maximus shells remains problematic, even for seasonal or absolute temperature reconstructions. For the range of calcification temperatures of 5-19 °C, our shell Mg/Ca ratios in P. maximus are approximately one-fourth those in inorganic calcite, half those in the bivalve Pinna nobilis, twice those in the bivalve Mytilus trossulus, and four to five times higher than Mg/Ca ratios in planktonic and benthonic foraminifera. Our findings further support observations that Mg/Ca ratios in bivalve shell calcite are an unreliable temperature proxy, as well as substantial taxon- and species-specific variation in Mg incorporation into bivalves and other calcifying organisms, with profound implications for the application of this geochemical proxy to the bivalve fossil record.  相似文献   

12.
The middle part of the volcanosedimentary Zaonega Formation of the Ludikovian Suprahorizon (approximately 2.0 Ga) includes large carbonates concretions and lenses in shungite layers. Carbonate lenses and concretions are primarily elongated and flattened, and their thickness varies from tens of centimeters to a few meters. Some lenses retain relicts of lamination. Concretions are composed of calcite or dolomite. They contain abundant organic matter, as well as mica, talc, chlorite, quartz, and pyrite crystals. The calcite concretions contain some dolomite admixture (Mg/Ca = 0.011?0.045) and differ from sedimentary limestones by a low Fe/Mn value (0.3–2.1). The Sr content is as much as 385–505 μg/g in most samples and is low (86 μg/g) only in one sample. The Rb-Sr systematics of carbonate concretions was studied with the stepwise dissolution procedure, which included processing with the ammonium acetate solution (AMA fraction) to partially remove the secondary carbonate material, with dissolution of the residue in acetic acid (ACA fraction). In individual calcite samples, discrepancy between the measured 87Sr/86Sr values in the AMA and ACA calcite fractions shows a variation range of 0.0008–0.0033. The initial 87Sr/86Sr ratio in the ACA fractions of the studied samples varies from 0.7053 to 0.7162. The ratio shows a positive correlation with Mg/Ca and the proportion of siliciclastic admixture and negative correlation with the Mn content. The concretions were formed when the sediments subsided, probably, during the transition from a zone with “mild” reductive conditions to zones with active sulfate reduction and methanogenesis. In the sulfate reduction zone, where most pyrite-bearing concretions were formed, the sediment was not geochemically exchaged with the bottom water and was evolved into a closed or semiclosed system. Processes of diagenesis in this zone promoted the release of the radiogenic 87Sr from the associated siliciclastic minerals, resulting in growth of the initial 87Sr/86Sr in concretions up to 0.7108–0.7162. Some calcite concretions, which lacked pyrite (or contained its minimal amount) were likely formed in a thin surficial sediment layer located above the sulfate reduction zone. Therefore, they precipitated Sr in isotope equilibrium with Sr of the bottom water. However, large concretions and carbonate lenses with an insignificant siliciclastic admixture could retain the signature of early diagenesis or even sedimentation. The initial 87Sr/86Sr ratio in one of such samples with the siliciclastic admixture of 6.2% makes it possible to estimate the maximal value of this ratio (0.7053) in the Ludikovian paleobasin.  相似文献   

13.
Combined stable isotope (δ18O and δ13C) and trace element (Mg, Sr) geochemistry from bulk tufa calcite and ostracod shell calcite from an early Holocene British tufa reveal clear records of Holocene palaeoclimatic change. Variation in δ18O is caused principally by change in the isotopic composition of Holocene rainfall (recharge), itself caused mainly by change in air temperature. The δ13C variability through much of the deposit reflects increasing influence of soil‐zone CO2, owing to progressive woodland soil development. Bulk tufa Mg/Ca and Sr/Ca are controlled by their concentrations in the spring water. Importantly, Mg/Ca ratios are not related to δ18O values and thus show no temperature dependence. First‐order sympathetic relationships between δ13C values and Mg/Ca and Sr/Ca are controlled by aquifer processes (residence times, CO2 degassing and calcite dissolution/reprecipitation) and probably record intensity of palaeorainfall (recharge) effects. Stable isotope records from ostracod shells show evidence of vital effects relative to bulk tufa data. The ostracod isotopic records are markedly ‘spiky’ because the ostracods record ‘snapshots’ of relatively short duration (years), whereas the bulk tufa samples record averages of longer time periods, probably decades. The δ18O record appears to show early Holocene warming, a thermal maximum at ca. 8900 cal. yr BP and the global 8200 yr BP cold event. Combined δ13C, Mg/Ca and Sr/Ca data suggest that early Holocene warming was accompanied by decreasing rainfall intensity. The Mg/Ca data suggest that the 8200 yr BP cold event was also dry. Warmer and wetter conditions were re‐established after the 8200 yr BP cold event until the top of the preserved tufa sequence at ca. 7100 cal. yr BP. Copyright © 2004 John Wiley & Sons, Ltd.  相似文献   

14.
Euhedral quartz and albite crystals are common in Devonian (Givetian-Frasnian) shallow-marine shelf carbonates from the Belgian Ardennes. Several features such as morphology, the presence of carbonate inclusions, inversion temperatures and occurrence in the insoluble residues of stylolitic surfaces indicate that these crystals have developed authigenically. Oxygen isotope ratios point to an intermediate deep burial realm of origin at temperatures of 60–90°C. The predominance of illite and the almost total absence of smectite clay minerals is interpreted as an indication that illitization produced the silica needed for authigenesis. The mineral composition of inclusions indicates that the carbonate host rock must have consisted of low-Mg calcite already at the time of authigenesis. These inclusions represent an earlier diagenetic stage than the present carbonate rock, since they were protected from further diagenetic alteration by the surrounding quartz. The calcite inclusions display a higher Sr/Ca and Mg/Ca ratio than the carbonate host-rock. Because neomorphic diagenesis of the carbonate continued after silicate authigenesis, the contents of Mg and Sr in the calcite of the host carbonate are even lower. The authigenic feldspar mineralogy seems to be determined by the composition of the host-sediment.  相似文献   

15.
Geological and geochemical data indicate that the formation of the granulite-like rocks in the contact aureole of the Yurchik gabbronorite intrusion of the Ganal Range, Kamchatka, was caused by the contact metamorphism, metasomatism, and local melting of the initial volcanosedimentary rocks of the Vakhtalka Sequence of the Ganal Group. The temperature in the inner part of the aureole reached 700–800°C and caused the transformation of the basic volcanic rocks of the sequence into two pyroxene-plagioclase, clinopyroxene-amphibole-plagioclase, and amphibole-plagioclase hornfelses, while sedimentary rocks were converted into garnet-biotite ± cordierite hornfelses. The hornfelsed basic volcanic rocks were locally subjected to metasomatic alteration and magmatic replacement with formation of biotite-orthopyroxene-plagioclase metasomatic bodies containing biotite-orthopyroxene-plagioclase ± garnet veinlets and aggregates. During these processes, sedimentary interlayers were converted into garnet enderbites at 700–800°C and 3.2–4.8 kbar. The comparison of the chemical composition of basic volcanic rocks of the Vakhtalka Sequence and their transformation products indicates that the metasomatic alteration and magmatic replacement correspond to siliceous-alkaline metasomatism (granitization) and cause subsequent and uneven influx of SiO2, Al2O3, Na2O, K2O, Rb, Ba, Zr, Nb, and Cl and removal of Fe, Mg, Mn, Ca, Cr, Co, Ti, Y, and S. REE data on basic metavolcanic rocks, hornfelses, and metasomatites suggest that the processes of hornfelsation, metasomatism, and magmatic replacement of the initial volcanic rocks were accompanied by significant increase in LREE and slight decrease in HREE. The Sr and Nd isotope study of the rocks in the aureole showed that the initial basic volcanic rocks of the Vakhtalka Sequence are isotopically close to both mature island arc tholeiites and mid-ocean ridge basalts. The metasomatic alteration and magmatic replacement of volcanic rocks in the aureole lead to the decrease of 143Nd/144Nd and increase of 87Sr/86Sr approximately parallel to mantle array. Pb isotopic ratios in the studied rocks become more radiogenic from initial metavolcanic rocks to metasomatites. It is suggested that the processes of metamorphism, metasomatism, and magmatic replacement were caused by highly mineralized mantle fluids, which percolated along magmatic channels serving as pathways for gabbroid magma.  相似文献   

16.
Marine sedimentary section across the Paleocene/Eocene (P/E) boundary interval is preserved in the Dungan Formation (Lower Indus Basin), Pakistan. Four dinoflagellate zones in the P/E interval of the Rakhi Nala section (Lower Indus Basin) are identified and correlated. The quantitative analysis of the dinoflagellate cyst assemblages together with geochemical data are used to reconstruct the palaeoenvironment across the P/E interval. The dinocyst assemblages allow the local correlation of the Dungan Formation (part) of the Sulaiman Range with the Patala Formation (part) of the Upper Indus Basin and global correlation of the Zone Pak-DV with the Apectodinium acme Zone of the Northern and Southern hemispheres. The onset of the carbon isotopic excursion (CIE) associated with Paleocene Eocene Thermal Maximum (PETM) is used globally to identify the P/E boundary. The CIE for the total organic carbon (fine fraction) δ13CFF is of a magnitude of ?1.7‰ is recorded for the first time in the Indus Basin. The Apectodinium acme precedes and straddles the onset of the CIE in the Indus Basin. This Apectodinium acme is also accompanied by a planktonic and benthonic foraminifera “barren zone.” The CIE in the Indus Basin, coupled with the changes in the dinocyst distribution and the benthonic and planktonic foraminifera assemblages, provides evidence of the changes associated with the PETM in this little-known part of the world. The benthonic foraminiferal assemblage indicates bathyal environment of deposition at the time of P/E boundary interval; the presence of dominantly open marine dinoflagellates and high planktonic foraminiferal ratio suggest that the water column at this site was well connected with the rest of the Tethys.  相似文献   

17.
A crystal-growth model is proposed, which allows ions of a trace element to enter the Ca and Mg sites of dolomite in proportion to the size of the ions relative to that of Ca and Mg ions, and which assigns equal portions of the trace element to the Ca site of dolomite and the Ca site of associated calcite. The model produces calcite/dolomite distribution coefficients of 0.79 for Mn and 0.43 for Fe, which may be compared with 0.85 and 0.28 as observed in marble, and a distribution coefficient of 2.0 for Sr and Ba, which may be compared with observed values of 2.3 for Sr and 1.8 for Ba.  相似文献   

18.
Each of two calcitic stalagmites from Grotte de Clamouse, Herault, southern France, displays a discrete aragonite layer dated at around 1100 yr BP. The layer of fanning aragonite ray crystals is immediately preceded by calcite with Mg and Sr compositions that are uniquely high for the past 3 kyr. Trace element compositions close to the boundary between original aragonite and calcite are consistent with quasi‐equilibrium partitioning of trace elements between the phases. Study of modern dripwaters demonstrates that pronounced covariation of Mg/Ca and Sr/Ca ratios in dripwater occurs owing to large amounts of calcite precipitation upflow of the drips that fed the stalagmites. Trace element to Ca ratios are enhanced during seasonally dry periods. Ion microprobe data demonstrate a pronounced covariation of trace elements, including Mg and Sr in calcite, and Sr, U and Ba in aragonite. The mean peak spacing is close to the long‐term mean of annual growth rates determined by differences in U‐series ages and so the trace element peaks are interpreted as annual. The trace element chemistry of the stalagmites on annual to inter‐annual scales thus directly reflects the amounts of prior calcite precipitation, interpreted as an index of aridity. The longer‐term context is a multi‐decadal period of aridity (1200–1100 yr BP) possibly correlated with an analogous episode in Central America. The arid period culminated in the nucleation of aragonite, but within a decade was followed by a return to precursor conditions. Copyright © 2005 John Wiley & Sons, Ltd.  相似文献   

19.
Calcite is frequently cited as a source of excess Ca, Sr and alkalinity in solutes discharging from silicate terrains yet, no previous effort has been made to assess systematically the overall abundance, composition and petrogenesis of accessory calcite in granitoid rocks. This study addresses this issue by analyzing a worldwide distribution of more than 100 granitoid rocks. Calcite is found to be universally present in a concentration range between 0.028 to 18.8 g kg−1 (mean = 2.52 g kg−1). Calcite occurrences include small to large isolated anhedral grains, fracture and cavity infillings, and sericitized cores of plagioclase. No correlation exists between the amount of calcite present and major rock oxide compositions, including CaO. Ion microprobe analyses of in situ calcite grains indicate relatively low Sr (120 to 660 ppm), negligible Rb and 87Sr/86Sr ratios equal to or higher than those of coexisting plagioclase. Solutes, including Ca and alkalinity produced by batch leaching of the granitoid rocks (5% CO2 in DI water for 75 d at 25°C), are dominated by the dissolution of calcite relative to silicate minerals. The correlation of these parameters with higher calcite concentrations decreases as leachates approach thermodynamic saturation. In longer term column experiments (1.5 yr), reactive calcite becomes exhausted, solute Ca and Sr become controlled by feldspar dissolution and 87Sr/86Sr by biotite oxidation. Some accessory calcite in granitoid rocks is related to intrusion into carbonate wall rock or produced by later hydrothermal alteration. However, the ubiquitous occurrence of calcite also suggests formation during late stage (subsolidus) magmatic processes. This conclusion is supported by petrographic observations and 87Sr/86Sr analyses. A review of thermodynamic data indicates that at moderate pressures and reasonable CO2 fugacities, calcite is a stable phase at temperatures of 400 to 700°C.  相似文献   

20.
Marble occurs abundantly in a 31,000 km2 segment of the southernGrenville Province of the Canadian Precambrian Shield, whereit is associated with quartzite, biotite-garnet gneiss, andamphibolite to form the Grenville Group. An 1800 km2 area onthe western margin of this segment, north of the Ottawa river,displays a great variety of carbonate rocks, which may be dividedinto two groups: (I) major marble, with calcite, dolomite, graphite, phlogopite,Ca amphibole, Ca pyroxene, forsterite, humite group minerals, (II) minor marble, with pink calcite, phlogopite, Ca amphibole,Ca pyroxene, K feldspar, scapolite, sphene. Rocks of the first group are associated with plagioclase gneissand amphibolite, and are metamorphosed limestone, little affectedby metasomatism; rocks of the second group, which are less common,are associated with potassium feldspar gneiss and heterogeneousgranitic and syenitic rocks, and are inferred to be metasomaticrocks. Numerous mineral reactions have taken place in the carbonaterocks during metamorphism. The calcite-dolomite reaction, whichgoverns the Mg content of calcite, indicates a metamorphic temperatureof about 650 °C. Forsterite was possibly produced from low-Alamphibole, and forsterite + spinel from high-Al amphibole. Thecrystallization of some silicate minerals in the minor marbleunits, and the enrichment in the contained calcite in Fe andSr are attributed to metasomatic reactions. Metamorphic ion-exchangereactions involving carbonates produced the following distributioncoefficients: Sr in calcite/Sr in dolomite = 2.5 Mn in calcite/Mn in dolomite = 0.89 Fe in calcite/Fe in dolomite = 0.29 from which inferences may be drawn concerning the distributionof these elements between the Ca and Mg sites within dolomiteduring metamorphic crystallization. Ion-exchange reactions involvingsilicates produced the following distribution of Mn: humite group Ca pyroxene.Ca amphibole phlogopite where the numbers are distribution coefficients. An equilibriumdistribution of Fe between silicates and calcite in the minormarble was evidently not attained during metasomatic crystallization.Numerous retrograde reactions have taken place, including thealteration of pyroxene to amphibole, forsterite to serpentine,and the exsolution of dolomite from calcite. Forsterite in marble, and orthopyroxene in the associated gneissesand amphibolites crystallized sporadically in the Laurentianhighlands, but not in the lowlands of the Ottawa rift valley,where peak metamorphic temperatures may have been slightly lower.In the highlands, reactions to produce forsterite and orthopyroxenewere initiated in response to a local increase in temperature,local peculiarities in the chemical composition of amphibole,which produced these minerals, or a local decrease in the activityof CO2 and H2O in the grain-boundary phase.  相似文献   

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