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1.
《Quaternary Science Reviews》2007,26(11-12):1670-1689
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.  相似文献   

2.
Stable isotopes were measured in the carbonate and organic matter of palaeosols in the Somma–Vesuvius area, southern Italy in order to test whether they are suitable proxy records for climatic and ecological changes in this area during the past 18000 yr. The ages of the soils span from ca. 18 to ca. 3 kyr BP. Surprisingly, the Last Glacial to Holocene climate transition was not accompanied by significant change in δ18O of pedogenic carbonate. This could be explained by changes in evaporation rate and in isotope fractionation between water and precipitated carbonate with temperature, which counterbalanced the expected change in isotope composition of meteoric water. Because of the rise in temperature and humidity and the progressive increase in tree cover during the Holocene, the Holocene soil carbonates closely reflect the isotopic composition of meteoric water. A cooling of about 2°C after the Avellino eruption (3.8 ka) accounts for a sudden decrease of about 1‰ in δ18O of pedogenic carbonate recorded after this eruption. The δ13C values of organic matter and pedogenic carbonate covary, indicating an effective isotope equilibrium between the organic matter, as the source of CO2, and the pedogenic carbonate. Carbon isotopes suggest prevailing C3 vegetation and negligible mixing with volcanogenic or atmospheric CO2. Copyright © 2000 John Wiley & Sons, Ltd.  相似文献   

3.
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.  相似文献   

4.
Caliche is a fairly widespread pedogenic carbonate that commonly has been used to reconstruct palaeoclimatological conditions. Stable isotopic analyses of three types of caliche nodules from Mission Bay, Texas, provide insights into the values and limitations in palaeoenvironmental interpretations. Soft incipient nodules (type I) and partially lithified chalky nodules (type II), composed of low Mg‐calcite, are in situ pedogenic products in the late Quaternary soils; they represent young to intermediate caliche nodules with no obvious diagenesis and, with constraints, can be used to investigate palaeoenvironmental conditions. The well‐lithified hard nodules (type III) dispersed on the beach and shallow bay exhibit complex shapes, fabrics, mineralogy and geochemical compositions. They are mature nodules that have undergone substantial diagenesis and, therefore, are believed to have lost their initial environmental signatures. The incipient nodules in the presently active grey soil and the older subjacent brown soil display significantly different δ13C values, ?8·4 and ?4·4‰, respectively, which indicates a change in palaeovegetation from C3/C4 mixed to C3‐dominated flora. The δ13C values probably reflect a marked climate shift from warm and dry to cool and wet conditions in the middle Holocene. However, in the same grey soil, there is a sub‐set of incipient caliche nodules with δ13C values around 0·1‰, which is probably due to the input of localized carbon sources in the soil (e.g. shell fragments). The occurrence of essentially identical nodules appearing from the same modern soil horizon with significantly different δ13C values questions the universal reliability of this type of data for palaeoenvironmental interpretation. This study demonstrates that, whereas the stable isotopic compositions of caliche nodules can be used for palaeoenvironmental reconstruction, diagenesis and the influence of localized carbonate sources in the soils could lead to erroneous interpretations.  相似文献   

5.
Carbonate cements in late Dinantian (Asbian and Brigantian) limestones of the Derbyshire carbonate platform record a diagenetic history starting with early vadose meteoric cementation and finishing with burial and localized mineral and oil emplacement. The sequence is documented using cement petrography, cathodoluminescence, trace element geochemistry and C and O isotopes. The earliest cements (Pre-Zone 1) are locally developed non-luminescent brown sparry calcite below intrastratal palaeokarsts and calcretes. They contain negligible Fe, Mn and Sr but up to 1000 ppm Mg. Their isotopic compositions centre around δ18O =?8.5‰, δ13C=?5.0‰. Calcretes contain less 13C. Subsequent cements are widespread as inclusion-free, low-Mg, low-Fe crinoid overgrowths and are described as having a‘dead-bright-dull’cathodoluminescence. The‘dead’cements (Zone 1) are mostly non-luminescent but contain dissolution hiatuses overlain by finely detailed bright subzones that correlate over several kilometres. Across‘dead'/bright subzones there is a clear trend in Mg (500–900 ppm), Mn (100–450 ppm) and Fe (80-230 ppm). Zone 1 cements have isotopic compositions centred around δ18O =?8.0‰ and δ13C=?2.5‰. Zone 2 cement is bright, thin and complexly subzoned. It is geochemically similar to bright subzones of Zone 1 cements. Dull Zone 3 cement pre-dates pressure dissolution and fills 70% or more of the pore space. It generally contains little Mn, Fe and Sr but can have more than 1000 ppm Mg, increasing stratigraphically upwards. The δ18O compositions range from ?5.5 to ?15‰ and the δ13C range is ?1 to + 3.20/00. Zone 4 fills veins and stylolite seams in addition to pores. It is synchronous with Pb, Ba, F ore mineralization and oil migration. Zone 4 is ferroan with around 500 ppm Fe, up to 2500 ppm Mg and up to 1500 ppm Mn. Isotopic compositions range widely; δ15O =?2.7 to ?9‰ and δ13C=?3.8 to+2.50‰. Unaltered marine brachiopods suggest a Dinantian seawater composition around δ15O = 0‰ (SMOW), but vital isotopic effects probably mask the original δ13C (PDB) value. Pre-Zone 1 calcites are meteoric vadose cements with light soil-derived δ13C and light meteoric δ18O. An unusually fractionated‘pluvial’δ15O(SMOW) value of around — 6‰ is indicated for local Dinantian meteoric water. Calcrete δ18O values are heavier through evaporation. Zone 1 textures and geochemistry indicate a meteoric phreatic environment. Fe and Mn trends in the bright subzones indicate stagnation, and precipitation occurred in increments from widespread cyclically developed shallow meteoric water bodies. Meteoric alteration of the rock body was pervasive by the end of Zone 1 with a general resetting of isotopic values. Zone 3 is volumetrically important and external sources of water and carbonate are required. Emplacement was during the Namurian-early Westphalian by meteoric water sourced at a karst landscape on the uplifted eastern edge of the Derbyshire-East Midland shelf. The light δ18O values mainly reflect burial temperatures and an unusually high local heat flow, but an input of highly fractionated hinterland-derived meteoric water at the unconformity is also likely. Relatively heavy δ13C values reflect the less-altered state of the source carbonate and aquifer. Zone 4 is partly vein fed and spans burial down to 2000 m and the onset of tectonism. Light organic-matter-derived δ13C and heavy δ18O values suggest basin-derived formation water. Combined with textural evidence of geopressures, this relates to local high-temperature ore mineralization and oil migration. Low water-to-rock ratios with host-rock buffering probably affected the final isotopic compositions of Zone 4, masking extremes both of temperature and organic-matter-derived CO2.  相似文献   

6.
Although carbonate-associated sulfate (CAS) is used widely as a proxy for the sulfur isotope composition of ancient seawater, little is known about the effects of diagenesis on retention of primary δ34S signals. Our case study of the Key Largo Limestone, Pleistocene, Florida, is the first systematic assessment of the impact of meteoric diagenesis on CAS properties. Geochemical and petrographic data show that meteoric diagenesis has affected the exposed coralline facies to varying degrees, yielding differences now expressed as sharp reaction fronts between primary and secondary carbonate minerals within individual coral heads. Specifically, analyses across high-resolution transects in the Key Largo Limestone show that concentrations of strontium and sodium decrease across the recrystallization front from original aragonite to meteoric low-magnesium calcite by factors of roughly 5 and 10, respectively. Predictably, δ18O values decrease across these same fronts. The δ13C relationships are more complex, with the most depleted values observed in the latest-formed calcite. Such trends likely reflect carbon isotope buffering capacity that decreased as reaction progressed, as well as protracted development of soil profiles and the associated terrestrial biomass and thus depleted δ13C during sea-level lowstand. Conversely, δ34S values of CAS vary within a narrow ‘buffered’ range from 20.6 to 22.6‰ (compared to 20.8-22.0‰ of coeval Pleistocene seawater) across the same mineralogical transition, despite sulfate concentrations that drop in the diagenetic calcite by an average factor of 12. Collectively, these data point to robust preservation of primary δ34S for carbonates that have experienced intense meteoric diagenesis, which is encouraging news for those using the isotopic composition of CAS as a paleoceanographic proxy. At the same time, the vulnerability of CAS concentrations to diagenetic resetting is clear.  相似文献   

7.
The Middle Muschelkalk (Middle Triassic) of the Catalan Coastal Range (north-east Spain) comprises sandstone, mudstone, anhydrite and minor carbonate layers. Interbedded sandstones and mudstones which are dominant in the north-eastern parts of the basin are terminal alluvial fan deposits. South-westward in the basin, the rocks become dominated by interbedded evaporites and mudstones deposited in sabkha/mudflat environments. The diagenetic and pore water evolution patterns of the Middle Muschelkalk suggest a strong facies control. During eodiagenesis, formation of microdolomite, anhydrite, baryte, magnesite, K-feldspar and mixed-layer chlorite/smectite was favoured within and adjacent to the sabkha/mudflat facies, whereas calcite, haematite, mixed-layer illite/smectite and quartz formed mainly in the alluvial facies. Low δ18OSMOW values for microdolomite (+23.7 to +28.4%) and K-feldspar overgrowths (+17.3 to +17.7%) suggest either low-temperature, isotopic disequilibrium or precipitation from low-18O porewaters. Low-18O waters might have developed, at least in part, during low-temperature alteration of volcanic rock fragments. During mesodiagenesis, precipitation of quartz overgrowths and coarse dolomite occurred in the alluvial sandstones, whereas recrystallization of microdolomite was dominant in the sabkha/mudflat facies. The isotopic compositions of these mesogenetic phases reflect increasing temperature during burial. Upon uplift and erosion, telogenetic calcite and trace haematite precipitated in fractures and replaced dolomite. The isotopic composition of the calcite (δ18OSMOW=+21.5 to +25.6%o; δ13C= 7.7 to - 5.6%o) and presence of haematite indicate infiltration of meteoric waters.  相似文献   

8.
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.  相似文献   

9.
张云峰  王清晨 《地质科学》2007,42(3):570-578
对济阳坳陷奥陶系碳酸盐原岩及孔洞缝中充填方解石进行了C、O同位素测定,结果表明孔洞缝充填方解石的δ13C和δ18O值比原岩偏负。奥陶系三山子组和马家沟组孔缝中充填的方解石C、O同位素演化有很大区别,前者的δ13C和δ18O值均为负值,δ13C向较高负值偏移,δ18O值向较低负值偏移;马家沟组八陡段孔缝充填方解石的δ13C和δ18O值也多为负值,δ13C向较正值方向偏移,δ18O值向较高负值偏移。奥陶系碳酸盐岩孔缝充填方解石形成于大气淡水环境和埋藏成岩环境,次生孔洞可能主要形成于早期表生阶段,裂缝形成于中-新生代的构造运动,方解石主要充填于埋藏环境中。次生孔缝的主要形成时期早于油气大量运移期,对古潜山油藏的形成有利。  相似文献   

10.
Abstract Positive shifts in global seawater δ13CDIC are related to changes in the ratio of organic relative to inorganic carbon burial in oceanic basins, whereas factors such as climatic cooling and the accumulation of polar ice are known to cause positive shifts in δ18O. Here, an alternative model is proposed for the formation of local positive isotope shifts in shallow-marine settings. The model involves geochemically altered platform-top water masses and the effects of early meteoric diagenesis on carbonate isotopic composition. Both mechanisms are active on modern (sub)tropical carbonate platforms and result in low carbonate δ13C and δ18O relative to typical oceanic values. During high-amplitude transgressive events, the impact of isotopically light meteoric fluids on the carbonate geochemistry is much reduced, and 13C-depleted platform-top water mixes with open oceanic water masses having higher isotope values. Both factors are recorded as a transient increase in carbonate 13C and 18O relative to low background values. These processes must be taken into consideration when interpreting the geochemical record of ancient epeiric seas.  相似文献   

11.
碳酸盐矿物是火山岩储层内重要的矿物成分,长岭断陷火山岩储层内的自生碳酸盐矿物主要是方解石.本文通过对营城组储层内方解石矿物的碳氧同位素特征分析,探讨储层内碳酸盐矿物成因.研究表明,长岭断陷火山岩储层内方解石δ13 CV-PDB值范围为-12.7‰～0.4‰,δ18OV-SMOw值范围为3.8‰～12‰,具有高δ18O值.与方解石平衡的CO2碳同位素计算值范围较宽,为-16.0‰～2.2‰,表明其形成物质的多源性.在δ18 O-δ13C图解中显示,形成碳酸盐矿物的CO2来源于幔源-岩浆无机成因的CO2和有机质演化过程中产生的CO2,以无机成因CO2源为主.这些无机成因CO2、有机成因CO2和沉积有机质热演化产生的有机酸溶于流体,形成酸性流体.火山岩储层中碳酸盐矿物的形成实质就是这种酸性流体与储层围岩反应的结果.  相似文献   

12.
Soils overlying two porphyry Cu deposits (Spence, Gaby Sur) and the Pampa del Tamarugal, Atacama Desert, Northern Chile were collected in order to investigate the extent to which saline groundwaters influence “soil” chemistry in regions with thick Miocene and younger sediment cover. Soil carbonate (calcite) was analyzed for C and O isotopes and pedogenic gypsum for S isotopes. Soil calcite is present in all soils at the Spence deposit, but increases volumetrically above two fracture zones that cut the Miocene gravels, including gravels that overlie the deposit. The C isotope composition of carbonate from the soils overlying fracture zones is indistinguishable from pedogenic carbonate elsewhere at the Spence deposit; all δ13CVPDB values fall within a narrow range (1.40–4.23‰), consistent with the carbonate having formed in equilibrium with atmospheric CO2. However, δ18OVPDB for carbonate over both fracture zones is statistically different from carbonate elsewhere (average δ18OVPDB = 0.82‰ vs. −2.23‰, respectively), suggesting involvement of groundwater in their formation. The composition of soils at the Tamarugal anomaly has been most strongly affected by earthquake-related surface flooding and evaporation of groundwater; δ13CVPDB values (−4.28‰ to −2.04‰) are interpreted to be a mixture of dissolved inorganic C (DIC) from groundwater and atmospheric CO2. At the Spence deposit, soils only rarely contain sufficient SO4 for S isotope analysis; the SO4-bearing soils occur only above the fracture zones in the gravel. Results are uniform (3.7–4.9‰ δ34SCDT), which is near the middle of the range for SO4 in groundwater (0.9–7.3‰). Sulfur in soils at the Gaby Sur deposit (3.8–6.1‰ δ34SCDT) is dominated by gypsum, which primarily occurs on the flanks and tops of hills, suggesting deposition from SO4-rich fogs. Sulfate in Gaby Sur deposit gypsum is possibly derived by condensation of airborne SO4 from volcanic SO2 from the nearby Andes. At the Gaby Sur deposit and Tamarugal anomaly, pedogenic stable isotopes cannot distinguish between S from porphyry or redeposited SO4 from interior salars.The three sites studied have had different histories of salt accumulation and display variable influence of groundwater, which is interpreted to have been forced to the surface during earthquakes. The clear accumulation of salts associated with fractures at the Spence deposit, and shifts in the isotopic composition of carbonate and sulfate in the fractures despite clear evidence of relatively recent removal of salts indicates that transfer from groundwater is an ongoing process. The interpretation that groundwaters can influence the isotopic composition of pedogenic calcrete and gypsum has important implications for previous studies that have not considered this mechanism.  相似文献   

13.
The differentiated Mesozoic alkali dolerite Prospect Intrusion contains a wide range of secondary minerals, including carbonates (primarily calcite), laumontite, prehnite and heulandite, whose stability relationships imply a formation temperature of <200°C. The δ18O data for carbonates define a higher temperature (160 – 195°C) suite, and a lower temperature (51 – 73°C) suite. The δ13C, δ18O and 87Sr/86Sr isotope systematics for these carbonates suggest derivation of the higher temperature group from magmatic fluids, whereas the other group had a major meteoric component that probably originated from porewater in the country rock. Source fluids for prehnite were meteoric rather than magmatic in origin based on their δD and δ18O ratios. Early in the intrusion's emplacement, CO2-rich hydrothermal fluids formed a carbonate rind sealing the upper part of the hydrothermal system and produced the higher temperature carbonates (calcite) and laumontite. Later, cooler fluids with a meteoric component infiltrated vesicles and fractures, depositing the lower temperature carbonates (calcite, aragonite), heulandite and prehnite.  相似文献   

14.
Loess‐paleosol sequences are important terrestrial archives of palaeoenvironmental change. Such sequences are rich in pedogenic carbonate, the oxygen and carbon isotopic values of which can provide important palaeoenvironmental information. Although some studies have pioneered the use of O and C isotopes in loess‐paleosol sequences, they are not routinely used as palaeoclimate proxies. In this study we analysed the sedimentology, micromorphology, geochronology and isotopic geochemistry of a Middle Pleistocene loess‐paleosol section, located at Kärlich, Germany. The section studied correlates with the Elsterian glacial (MIS 12) and Holsteinian interglacial (MIS 11). Embedded tephra layers yielded 40Ar/39Ar ages of 466±3 ka, 447±1 ka and 361±3 ka. The sedimentology and micromorphology of the sequence record a shift from accretionary loess accumulation (MIS 12) to prolonged pedogenesis at a stable land surface (MIS 11). Soil carbonate δ18O values record an enrichment of ～3‰ during the accumulation of the loess, reaching peak values comparable with those found in the MIS 11 soil. The δ18O signal is interpreted as reflecting temperature, highlighting the potential of δ18O analysis of European loess soil carbonates as a means of reconstructing palaeotemperature history.  相似文献   

15.
The calcite fossils of the Derbyhaven Beds, Isle of Man, have δ13C values (+ 1·8 PDB) similar to modern, shallow-water marine skeletons, but the δ18O values (?6·1 PDB) are much lighter than modern skeletons. The light oxygen values indicate either re-equilibration with isotopically light water before cementation started, or Carboniferous sea water with δ18O of ?6‰. Aragonite dissolution was followed by precipitation of zoned calcite cement. In this cement, up to six intracrystalline zones, recognized in stained thin sections, show isotopic variation. Carbon varies from + 3-8 to + 1-2‰. and oxygen from ? 2-6 to ? 12-4‰. with decreasing age of the cement. This trend is attributed to increasing temperature and to isotopic evolution of the pore waters during burial. The zoned calcite is sequentially followed by dolomite and kaolinite cements which continue the trend towards light isotopic values. This trend is continued with younger, fault-controlled dolomite, and is terminated by vein-filling calcite and dolomite. The younger calcite, interpreted as a near-surface precipitate from meteoric waters, is unrelated to the older sequence of carbonates and has distinctly different carbon isotope ratios: δ13C ? 6-8‰.  相似文献   

16.
A. Sáez  L. Cabrera 《Sedimentology》2002,49(5):1073-1094
ABSTRACT A small, closed, lacustrine system developed during the restraining overstep stages of the Oligocene As Pontes strike‐slip basin (Spain). The increase in basin accommodation and the headward spread of the drainage, which increased the water input, triggered a change from shallow, holomictic to deeper, meromictic conditions. The lower, shallow, lacustrine assemblage consists of mudstone–carbonate cycles recording lacustrine–palustrine ramp deposition in a saline lake. High Sr content in some early diagenetic calcites suggests that aragonite and calcite made up the primary carbonate muds. Early dolomitization took place together with widespread pedogenic activity. The upper, deep, freshwater, lacustrine assemblage includes bundles of carbonate–clay rhythmites and fine‐grained turbidite beds. Primary calcite and diagenetic siderite make up the carbonate laminae. The Mg content of the primary carbonates records variations in Mg/Ca ratios in lacustrine waters. δ18O and δ13C covariance trends in calcite reinforce closed drainage conditions. δ18O data indicate that the lake system changed rapidly from short‐lived isotopically light periods (i.e. from seasonal to pluriannual) to longer steady‐state periods of heavier δ18O (i.e. from pluriannual to millennial). The small δ13C changes in the covariant trends were caused by dilute inflow, changing the contributions of dissolved organic carbon in the system and/or internal variations in lacustrine organic productivity and recycling. In both shallow and deep carbonate facies, sulphate reduction and methanogenesis may account, respectively, for the larger negative and positive δ13C shifts recorded in the early diagenetic carbonates (calcite, dolomite and siderite). The lacustrine system was very susceptible to high‐frequency, climatically forced water balance variations. These climatic oscillations interfered with the low‐frequency tectonic and morphological changes in the basin catchment. This resulted in the superposition of high‐order depositional, mineralogical and geochemical cycles and rhythms on the lower order lacustrine infill sequence.  相似文献   

17.
Modern terrestrial speleothem-like calcareous deposits in streams draining a disused lime quarry on Black Mountain, South Wales have anomalously negative δ18O and δ13C compositions compared with other similar European deposits. Black Mountain water chemistry is unusual only in its locally very high pH (> 11.5) and carbonate ion concentrations. The high pH is caused by dissolution of lime spoil, resulting in high OH– concentrations. This high alkalinity causes uptake of atmospheric CO2 and strong fractionation of both carbon and oxygen stable isotopes, resulting in calcite precipitates with unusually negative isotopic compositions. Since shifts in δ18O of < 1° are highly significant for Holocene palaeoclimate reconstructions, depletions caused by hyperalkaline waters must be avoided. While extreme lime spoil contamination should be obvious, less heavily affected sites will record smaller fractionation effects and might escape detection. Even small depletions from low-level contamination will have large effects on palaeotemperatures based on carbonate crust δ18O values.  相似文献   

18.
Zoned calcites were found in the phragmacone chambers of three Sonniniid ammonites from marine Middle Jurassic sandstones (Isle of Skye, U.K.). Each ammonite has a unique sequence of up to nine zones of calcite which fill or partially fill the chambers. Zones are defined by changes in the density of minute opaque inclusions and variation in trace-element composition. Proximal (early) calcites have undulose extinction and some exhibit the specific fabrics of fascicular-optic and radiaxial fibrous calcites. Microdolomite inclusions are found in one specimen. Early calcites, interpreted as replacements after a single isopachous fringe of acicular carbonate (probably high magnesium calcite), are succeeded by blocky ferroan calcite cement. In one specimen there are two distinct generations of calcite, in the others there is a continuous mosaic incorporating both early calcites and late cement. Isotopic composition of the early calcite zones demonstrates the initial importance of organic derived carbon (δ13C =— 26‰, δ18O ‰ O). Further cementation and mineralogical stabilization took place at increased temperatures and probably after modification of the pore water isotopic composition (calcites with δ13C =— O‰, δ18O～— 10‰). The distinctive fabrics and zonal patterns probably developed during the replacement of the precursor cement and are not primary growth features. Reversals in isotopic and trace element trends are believed to be related to the rate of neomorphic crystal growth and hence to the degree of exchange with external pore waters. Further increase in temperature, probably during Tertiary igneous activity, gave rise to the extremely light δ18O values of the late cements in the ammonite which had previously had least contact with external waters (cements with δ13C ～ O, δ18O ～— 20‰).  相似文献   

19.
Surface lake sediments,28 from Hoh Xil,24 from northeastern China,99 from Lake Bosten,31 from Ulungur and 26 from Heihai were collected to determine δ13C and δ18O values.Considering the impact factors,conductivity,alkalinity,pH,TOC,C/N and carbonate-content in the sediments,Cl,P,S,and metal element ratios of Mg/Ca,Sr/Ca,Fe/Mn of bulk sediments as environmental variables enable evaluation of their influences on δ13C and δ18O using principal component analysis(PCA) method.The closure and residence time of lakes can influence the correlation between δ13C and δ18O.Lake water will change from fresh to brackish with increasing reduction and eutrophication effects.Mg/Ca in the bulk sediment indicates the characteristic of residence time,Sr/Ca and Fe/Mn infer the salinity of lakes.Carbonate formation processes and types can influence the δ13C–δ18O correlation.δ18O will be heavier from Mg-calcite and aragonite formed in a high-salinity water body than calcite formed in freshwater conditions.When carbonate content is less than 30%,there is no relationship with either δ13C or δ18O,and also none between δ13C and δ18O.More than 30%,carbonate content,however,co-varies highly to δ13C and δ18O,and there is also a high correlation between δ13C and δ18O.Vegetation conditions and primary productivity of lakes can influence the characteristics of δ13C and δ18O,and their co-variance.Total organic matter content(TOC) in the sediments is higher with more terrestrial and submerged plants infilling.In northeastern and northwestern China,when organic matter in the lake sediments comes from endogenous floating organisms and algae,the δ13C value is high.δ13C is in the range of 4‰ to 0‰ when organic matter comes mainly from floating organisms(C/N<6);in the range of 4‰ to 8‰ when organic matter comes from diatoms(C/N=6 to 8);and 8‰ to 4‰ when organic matter comes from aquatic and terrestrial plants(C/N>8).  相似文献   

20.
The relationship between molluscan shell growth rate and skeletal δ18O and δ13C was investigated in a detailed field study for the scallop, Pecten maximus. Seasonal variation in shell growth rate was found to be a governing factor influencing shell δ18O and δ13C. At low shell growth rates, shell δ18O were more positive (of the order +0.4‰) and δ13C more negative (up to −2‰) as compared with predicted values for precipitation of inorganic calcite in isotopic equilibrium with seawater. The deviations in δ18O were hypothesized as reflecting possible differences in solution carbonate chemistry at the site of mineralization in the extrapallial fluid as compared with that of the external seawater medium. The deviations in shell δ13C were consistent with incorporation of isotopically depleted respiratory 13C (i.e., a metabolic effect). A trend toward more depleted shell δ18O and δ13C values occurred at higher shell growth rates, with negative δ18O values as compared with predicted equilibrium at shell growth rates above 0.13 mm per day. These simultaneous negative deviations in skeletal δ18O and δ13C were interpreted as resulting from a kinetic effect. The implications for environmental reconstruction from molluscan isotopic records are discussed in light of a model of isotopic behavior based on the findings of the study.  相似文献   

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