Climatic change recorded by stable isotopes and trace elements in a British Holocene tufa

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.     

Climatic variations in MIS 11 recorded by stable isotopes and trace elements in a French tufa (La Celle,Seine Valley)

Marine Isotope Stage (MIS) 11 palaeoclimate has so far been documented in marine and ice sheet isotopic records. However, excepting some lacustrine pollen records, very little is known about palaeoclimatic conditions in continental areas. This study uses geochemical records in calcareous tufa deposits from rivers as a basis for reconstructing temperate palaeoclimatic conditions. Tufa deposits are now proven to record high‐quality palaeoclimatic information in recent to Holocene deposits. Work on older interglacial tufas is just starting and in this paper we present the first comprehensive results from a MIS 11 tufa. The tufa comes from the Seine Valley (La Celle, northern France). Geochemical data in the tufa calcite are interpreted to record primarily air temperature (δ¹⁸O) and humidity (δ¹³C and Mg/Ca and Sr/Ca). The combined data identify a warm and wet climatic optimum followed by two temperature decreases associated with oscillations in humidity. These marked climatic variations recorded through the La Celle profile are strongly coherent with the palaeoenvironmental reconstructions from malacological data. The abrupt climatic and environmental events recorded could be related to short‐term degradation of vegetation cover in Europe, which is itself controlled by global palaeoclimatic events. Copyright © 2012 John Wiley & Sons, Ltd.     

相山铀矿田黄铁矿微量元素、硫同位素特征及其地质意义

相山铀矿田位于江西省境内的相山火山盆地中,是中国目前最大的火山岩型铀矿田。文章利用电子探针(EPMA)和激光剥蚀多接收电感耦合等离子质谱仪(LA-MC-ICP-MS)技术对矿田内几个典型铀矿床(居隆庵、河元背和沙洲矿床)中矿前期热液蚀变阶段形成的黄铁矿分别进行了微量元素及S同位素组成特征研究。研究结果表明,矿田内铀矿床中黄铁矿的Co/Ni比值主要介于2.00～6.00,支持其为热液成因。黄铁矿的δ34S值总体变化于+0.1‰～+16.2‰,但西部与北部铀矿床之间黄铁矿δ34S值存在显著差异:西部铀矿床(居隆庵、河元背)中黄铁矿δ34S值为+0.1‰～+8.4‰,介于矿田内新元古代基底变质沉积岩δ34S值(+7.9‰～+9.4‰)与壳源岩浆δ34S值(-5.0‰～+5.0‰)之间,暗示S可能来自基底变质沉积岩硫与围岩(流纹英安岩和碎斑熔岩)中硫化物的硫的混合;北部沙洲铀矿床中黄铁矿的δ34S值为+7.5‰～+16.2‰,与蒸发硫酸盐δ34S值相接近,表明硫的来源可能主要与矿田西北侧红盆内硫酸盐的热化学还原(TSR)相关,围岩(花岗斑岩)中的Fe2+在还原过程中发挥了重要作用。同时,热化学还原产生的H2S与围岩中的Fe2+进一步结合形成黄铁矿。铀成矿期含铀热液中的六价U(Ⅵ)与铀成矿前期形成的上述黄铁矿发生氧化还原反应,导致铀沉淀成矿。     

Continuous 60-year stable isotopic and earth-alkali element records in a modern laminated tufa (Jaruga,river Krka,Croatia): Implications for climate reconstruction

A continuous 60-year record (1938–1998) of stable isotope compositions of carbon and oxygen, as well as trace metal (Mg, Sr, Ba) concentrations in a laminated calcite crust precipitated in a short artificial tunnel on a non-equilibrium groundwater-fed karstic river is presented. Chemical and isotopic records have been compared to hydrometeorological data, available for the last 48 years. An attempt is made to relate isotopic and geochemical variations in the crust to environmental parameters, such as temperature, precipitation and changes in vegetation cover, as well as to postdepositional recrystallisation of the older crust material. Isotopic composition of the crust is largely influenced by non-equilibrium precipitation, which favours the incorporation of isotopically depleted C and O into the carbonate. Furthermore, because of the complicated hydrological situation, there is no observable correlation between the stable oxygen isotope composition of water and temperature. The result is that the ¹⁸O isotopic thermometers overestimate the measured precipitation temperatures. Temperatures calculated from Mg/Ca ratios of water and the carbonate match the δ¹⁸O palaeotemperatures within ± 2.4 °C in the older part of the crust, precipitated before the onset of industrial pollution of the river. It was demonstrated that the application of Mg palaeothermometry in natural systems, where the Mg/Ca ratio of water is influenced not only by temperature, but also by other environmental parameters such as precipitation, surface runoff, groundwater retention time and anthropogenic influences, is subject to a large uncertainty, up to 10 °C.     

Special and seasonal variations of trace metals in PM10 in Chongqing

Nineteen trace metals in PM10 were measured by X-ray fluorescence spectroscopy （XRF） at three sites in Chongqing. The special and seasonal variations of trace metals in PM10 samples collected in the downtown were different from those in the background area of Jinyunshan. The source identification indicated that particulate materials were contributed mainly by two sources.     

川西新元古代花岗质杂岩体的锆石SHRIMP U-Pb年龄、元素和Nd-Sr同位素地球化学研究:岩石成因与构造意义

扬子块体西缘新元古代岩浆活动十分强烈,其成因对于研究Rodinia超大陆的演化有重要意义.目前对这些岩浆的成因和形成的构造背景存在地幔柱和岛弧两种不同的观点.本文对川西康滇裂谷中四川西昌一带出露的摩挲营花岗岩体和性质相似的周边花岗质小岩体,以及岩体中出露的基性岩墙进行了SHRIMP锆石U-Pb年龄、元素和Sr-Nd同位素的研究表明这些酸性、基性岩体形成于842～790Ma,基本为同时代的侵入岩;花岗岩基中普遍发育中性包体,为岩浆混合作用的表现;花岗岩起源于古老的下地壳,基性岩起源于亏损的软流圈地幔.本文的研究结果支持华南位于澳大利亚和Laurentia大陆之间的Rodinia超大陆重建模式.     

Pb-Sr-He isotope and trace element geochemistry of the Cape Verde Archipelago

New lead, strontium and helium isotopic data, together with trace element concentrations, have been determined for basalts from the Cape Verde archipelago (Central Atlantic). Isotopic and chemical variations are observed at the scale of the archipelago and lead to the definition of two distinct groupings, in keeping with earlier studies. The Northern Islands (Santo Antão, São Vicente, São Nicolau and Sal) present Pb isotopic compositions below the Northern Hemisphere Reference Line (NHRL) (cf. Hart, 1984), unradiogenic Sr and relatively primitive ⁴He/³He ratios. In contrast, the Southern Islands (Fogo and Santiago) display Pb isotopes above the NHRL, moderately radiogenic Sr and MORB-like helium signatures. We propose that the dichotomy between the Northern and Southern Islands results from the presence of three isotopically distinct components in the source of the Cape Verde basalts: (1) recycled ∼1.6-Ga oceanic crust (high ²⁰⁶Pb/²⁰⁴Pb, low ⁸⁷Sr/⁸⁶Sr and high ⁴He/³He); (2) lower mantle material (high ³He); and (3) subcontinental lithosphere (low ²⁰⁶Pb/²⁰⁴Pb, high ⁸⁷Sr/⁸⁶Sr and moderately radiogenic ⁴He/³He ratios). The signature of the Northern Islands reflects mixing between recycled oceanic crust and lower mantle, to which small proportions of entrained depleted material from the local upper mantle are added. Basalts from the Southern Islands, however, require the addition of an enriched component thought to be subcontinental lithospheric material instead of depleted mantle. The subcontinental lithosphere may stem from delamination and subsequent incorporation into the Cape Verde plume, or may be remnant from delamination just before the opening of the Central Atlantic. Basalts from São Nicolau reflect the interaction with an additional component, which is identified as oceanic crustal material.     

Special and seasonal variations of trace metals in PM_(10) in Chongqing

1Introduction Tracemetalsarereleasedtotheatmosphereduring combustionoffossilfuelsandwood,aswellasemis sionsfromavarietyofprocessesactingoncrustalmin erals,includingvolcanism,erosionandsurfaceweath ering.Onaglobalscale,resuspendedsurfacedusts havemadeagreatcontributiontothetotalnaturale missionoftracemetalstotheatmosphere,withCr,Mn andVaccountingfor>50%andCu,Mo,Ni,Pb,Sb andZnaccountingfor>20%,whilevolcanicactivity probablygeneratedasmuchas20%atmosphericCd,Hg,As,Cr,Cu,Ni,PbandSb(Pacyna,19…     

Petrographic and trace element analysis of uranium-rich tufa calcite, middle Miocene Barstow Formation, California, USA

An integrated petrographic and spectroscopic (X‐ray diffraction, phosphor imaging and synchrotron X‐ray absorption spectroscopy) study of tufas from the Miocene Barstow Formation, California, relates sample morphology, mineralogy and geochemical composition. The tufas, composed mainly of calcite that formed at the interface between an ancient alkaline lake and ground or spring waters, have textures similar to those of microbially mediated terrestrial stromatolites and travertines. The tufas have elevated concentrations of a number of trace elements including Mn, Fe, Sr and U. Synchrotron X‐ray fluorescence analyses show that U concentrations can exceed 500 p.p.m. X‐ray absorption spectroscopy indicates that the U in these samples is incorporated as U(IV). It is suggested here that alkaline lake waters had a high U/Ca ratio and tufa calcite formed where groundwater or (possibly epithermal) springs brought in Ca and trace elements such as Sr. The rapid, and possibly microbially mediated, precipitation of calcite allowed for incorporation of high concentrations of trace metals as either structural substitutes or extremely fine‐scale inclusions.     

A laser fluorination method for oxygen isotope analysis of biogenic silica and a new oxygen isotope calibration of modern diatoms in freshwater environments

An empirical calibration for the oxygen isotope fractionation between biogenic silica and water was determined for diatom frustules sampled from living diatom communities in the Jemez Mountains of northern New Mexico, USA. Over a temperature range from 5.1 to 37.8 °C, the silica-water fractionation is defined by the equation 1000 ln α_{(silica-water)} = 2.39(±0.13) × 10⁶T⁻² + 4.23(±1.49). This relationship is in close agreement with other published silica-water fractionation factors for laboratory cultured diatom samples; however, it is as much as 8‰ lower than equilibrium quartz-water fractionations and 3-4‰ lower than observed silica-water fractionations in diatomaceous silica collected from sediment traps and sediment cores. There are three possible explanations for the disparate silica-water fractionation factors observed in diatom silica: (1) silica does not precipitate in equilibrium with ambient water, (2) silica does precipitate in equilibrium with ambient water, but the silica-water fractionation factor for diatom silica is considerably less than the equilibrium fractionation factor for quartz-water, or (3) silica precipitation is influenced by a ‘vital’ effect, where the δ¹⁸O value of the water inside the diatom cell walls is lower than the δ¹⁸O values of ambient water.Post-mortem loss of organic material results in an alteration or ‘maturation’ of diatom silica in which silica reequilibrates with a silica-water fractionation closer to the equilibrium quartz-water fractionation. Alteration is likely to occur rapidly after the diatom frustule loses its organic coating, either as it settles through the water column or at the sediment-water interface; δ¹⁸O values recorded by paleo-diatom silica therefore do not record growing conditions but more likely record conditions at the sediment-water interface. In the case of lacustrine environments, where the bottom water remains at a nearly constant 4 °C, the reequilibration of diatom silica with bottom conditions could reduce or remove the conflating effects of temperature on δ¹⁸O values recorded by paleo-diatom silica and provide direct information on the δ¹⁸O value of the lake water.     

Climatic Signals in the Last 200 Years from Stable Isotope Record in the Shells of Freshwater Snails in Lake Xingcuo,Eastern Tibet Plateau,China

Lake Xingcuo is a small closed,hard-water lake ,situated on eastern Tibet Plateau.Stable isotope data(δ^18O and δ^13C) from the freshwater snail Gyraulus sibirica(Dunker)in a34 cm long,radioactive isotope-dated sediment core represent the last 200 years of Lake Xingcuo environmental history.Carbon and oxygen isotope ratios in the shells of the freshwater snail bear information on the isotopic composition of the water in which the shells were formed ,which in turn characterizes the climatic conditions prevailing during the snail‘s life span.Whole-shell and incremental growth data were collected from modern and fossil shells from Lake Xingcuo.The δ18^O values of modern shells from Lake Xingcuo are in equilibrium with high δ^13CTDIC.By calibrating δ^18O and δ^13C in the shell Gyraulus sibirica(Dunker)with in-strument-measured data for the period 1954-1992,we found that the δ^18O of the snail shells is an efficient indicator to reveal air temperature in the warmer half year instead of that around the whole year,and that there is a certain positive correlation between index δ^18O and the run-ning average temperature in the warmer half-yiar period.Climatic variability on eastern Tibet Plateau,for the last two centuries,has been successfully inferred from the δ^18O record in freshwater snails in the sediments of Lake Xingcuo.As such,the last 200 years of palaeocli-matic record for this region can be separated into three periods representing oscillations between warming and cooling,which are confirmed by the Guliya ice record on the Tibet Plateau.     

江西永平Cu-W矿床成矿岩体的锆石U-Pb年龄、Hf同位素、微量元素特征及其意义

江西永平矿床位于钦杭成矿带东段,是该成矿带内矽卡岩型Cu-W共生成矿的典型代表.为查明永平似斑状黑云母花岗岩的源区特征及其与Cu-W矿化的关系,文章对该花岗岩进行了岩石学、锆石U-Pb年代学、微量元素地球化学及Hf同位素研究.结果表明,似斑状黑云母花岗岩的锆石LA-ICP-MS U-Pb年龄为160 Ma,与空间上密切相关的矽卡岩Cu-W矿床(辉钼矿Re-Os年龄为156 Ma)具有密切的时间联系,表明永平Cu-W矿床成岩成矿作用均发生于中晚侏罗世.锆石的Ce4+/Ce3+平均值为283,表明其具有高的氧逸度,指示出很好的Cu成矿潜力.锆石的εHf(t)值为-9.60～-2.27,并且有高w(MgO)(0.84％～1.33％)和Mg#(44～49)值,表明该区花岗质岩浆来源于古老地壳物质的部分熔融,并有地幔物质的加入.通过与区内同期Cu矿化和W-Sn矿化花岗岩对比,成Cu和成Cu-W矿花岗岩的氧逸度高于成W-Sn花岗岩,成Cu-W花岗岩εHf(t)值介于成Cu和成W-Sn花岗岩之间.因此,岩浆高氧逸度和一定比例的壳幔混合可能是形成Cu-W矿的重要条件.     

C and O stable isotope variability in recent freshwater carbonates (River Krka, Croatia)

Three types of recent carbonate precipitates from the River Krka, Croatia, were analysed: (1) bulk tufa from four main cascades in a 34 km long section of the river flow through the Krka National Park; (2) a laminar stromatolite‐like incrustation formed in the tunnel of a hydroelectric power plant close to the lowest cascade; and (3) recent precipitates collected on artificial substrates during winter, spring and summer periods. Stable isotope compositions of carbon (δ¹³C) and oxygen (δ¹⁸O) in the carbonate and organic carbon (δ¹³C_org) were determined and compared with δ¹⁸O of water and δ¹³C of dissolved inorganic carbon (DIC). The source of DIC, which provides C for tufa precipitation, was determined from the slope of the line ([DIC]/[DIC₀]?1) vs. (δ¹³C‐DIC × ([DIC]/[DIC₀])) ( Sayles & Curry, 1988 ). The δ¹³C value of added DIC was ?13·6‰, corresponding to the dissolution of CO₂ with δ¹³C between ?19·5 and ?23·0‰ Vienna Pee Dee Belemnite (VPDB). The observed difference between the measured and calculated equilibrium temperature of precipitation of bulk tufa barriers indicates that the higher the water temperature, the larger the error in the estimated temperature of precipitation. This implies that the climatic signals may be valid only in tufas precipitated at lower and relatively stable temperatures. The laminar crust comprising a continuous record of the last 40 years of precipitation shows a consistent trend of increasing δ¹³C and decreasing δ¹⁸O. The lack of covariation between δ¹³C and δ¹⁸O indicates that precipitation of calcite was not kinetically controlled for either of the elements. δ¹³C and δ¹⁸O of precipitates collected on different artificial substrates show that surface characteristics both of substrates and colonizing biota play an important role in C and O isotope fractionation during carbonate precipitation.     

Environmental change and seasonal behavior of mastodons in the Great Lakes region inferred from stable isotope analysis

We investigate seasonal variations in the diet and drinking water of four Great Lakes mastodon (Mammut americanum) specimens using stable isotope analysis of serially sampled inner-enamel bioapatite structural carbonate (δ¹³C_sc, δ¹⁸O_sc), and previously published bulk analyses. Isotopic analyses and thin section measurements showed that mastodon tooth enamel extension rates (~ 12–4 mm/yr, decreasing toward the cervix) were lower than those of mammoths or modern elephants. Mastodons had distinct and highly regular seasonal variations in δ¹³C_sc and δ¹⁸O_sc, which we interpret in the context of local glacial history and vegetation changes. Seasonal variations in δ¹⁸O were large but variations in δ¹³C were small, and may have been obscured if coarser sampling methods than our inner-enamel sampling approach were used. Thus, our approach may be particularly useful for understanding relatively small seasonal changes in δ¹³C within C₃ environments. The seasonal patterns, though not entirely conclusive, suggest that the Ontario mastodons did not migrate over very long distances. Rather, the climate and seasonal dietary patterns of mastodons within the region changed over time, from ~ 12,400 to 10,400 ¹⁴C yr BP (~ 15,000 – 12,000 cal yr BP). Insights gained using these methods can contribute to a better understanding of megafaunal extinctions and Paleoamerican lifeways.     

Origin of facies zonation in microbial carbonate platform slopes: Clues from trace element and stable isotope geochemistry (Middle Triassic,Dolomites, Italy)

Limestones containing radiaxial fibrous cements were sampled along the southern slope of the late Anisian (Middle Triassic) Latemar carbonate platform in the Dolomites, northern Italy. The Latemar upper slopes comprise massive microbial boundstone, whereas lower slopes are made of clinostratified grainstone, rudstone and breccia. Samples are representative of a seawater column from near sea‐level to an aphotic zone at about 500 m water depth. Radiaxial fibrous cements were analyzed for carbon (δ¹³C) and oxygen (δ¹⁸O) stable isotopic composition, as well as major and trace element content, to shed light on the origin of the slope facies zonation. The δ¹³C vary between 1·7‰ and 2·3‰ (Vienna Pee‐Dee Belemnite), with lowest values at palaeo‐water depths between 70 m and 300 m. Radiaxial fibrous cements yielded seawater‐like rare earth element patterns with light rare earth element depletion (Nd_SN/Yb_SN ≈ 0·4), superchondritic yttrium/holmium ratios (≈55) and negative cerium anomalies. Cadmium reaches maximum values of ca 0·5 to 0·7 μg/g at palaeo‐water depths between 70 m and 300 m; barium contents (0·8 to 1·8 μg/g) increase linearly with depth. The downslope patterns of δ¹³C and cadmium suggest increased nutrient and organic matter contents at depths between ca 70 m and 300 m and point to an active biological pump. The peak in cadmium and the minimum of δ¹³C mark a zone of maximum organic matter respiration and high nutrient and organic matter availability. The base of this zone at ca 300 m depth corresponds with the transition from massive microbial boundstone to clinostratified grainstone, rudstone and breccia. The microbial boundstone facies apparently formed only in seawater enriched in organic matter, possibly because this organic matter sustained benthic microbial communities at Latemar. The base of slope microbialites on high‐relief microbial carbonate platforms may be a proxy for the depth to maximum respiration zones of Palaeozoic and Mesozoic periplatform basins.     

Application of the trace element and isotope geochemistry of strontium to studies of carbonate diagenesis

Carbonate rocks and natural waters exhibit a wide range in the concentration and isotopic composition of strontium. This wide range and the quantifiable covariation of these parameters can provide diagnostic tools for understanding processes of fluid-rock interaction. Careful consideration of the uncertainties associated with trace element partitioning, sample heterogeneity and fluid-rock interaction mechanisms is required to advance the application of the trace element and isotope geochemistry of strontium to studies of diagenesis, goundwater evolution, ancient seawater chemistry and isotope stratigraphy. A principal uncertainty involved in the application of Sr concentration variations to carbonate systems is the large range of experimental and empirical results for trace element partitioning of Sr between mineral and solution. This variation may be a function of precipitation rate, mineral stoichiometry, crystal growth mechanism, fluid composition and temperature. Calcite and dolomite in ancient limestones commonly have significantly lower Sr concentrations (20–70 p.p.m.) than would be expected from published trace element distribution coefficient values and Sr/Ca ratios of most modern sedimentary pore waters. This discrepancy probably reflects the uncertainties associated with determining distribution coefficient values. As techniques improve for the analytical measurement and theoretical modelling of Sr concentration and isotopic variations, the petrological analysis of carbonate samples becomes increasingly important. The presence of even small percentages of non-carbonate phases with high Rb concentrations and high ⁸⁷ Sr⁸⁶ Sr values, such as clay minerals, can have significant effects on the measured ⁸⁷ Sr/⁸⁶ Sr values of carbonate rocks, due to the decay of ⁸⁷Rb to ⁸⁷ Sr. For example, a Permian marine limestone with 50 p.p.m. Sr and 1 p.p.m. Rb will have a present-day ⁸⁷ Sr/⁸⁶ Sr value that is >2 × 10^?4 higher than its original value. This difference is an order of magnitude greater than the analytical uncertainty, and illustrates the importance of assessing the need for and accuracy of such corrections. A quantitative evaluation of the effects of water-rock interaction on Sr concentrations and isotope compositions in carbonates strengthens the application of these geochemical tracers. Geochemical modelling that combines the use of trace elements and isotopes can be used to distinguish between different mechanisms of water-rock interaction, including diffusive and advective transport of diagenetic constituents in meteoric pore fluids during the recrystallization of carbonate minerals. Quantitative modelling may also be used to construct diagnostic fluid-rock interaction trends that are independent of distribution coefficient values, and to distinguish between mixing of mineral end-members and fluid-rock interaction.     

江苏盘石山玄武岩中橄榄岩包体的氧同位素和微量元素地球化学

本文研究了8个来自江苏盘石山新生代碱性玄武岩中的橄榄岩包体，利用ICP—MS技术测定了橄榄岩中单斜辉石的微量元素组成；利用激光氟化技术系统地分析了橄榄石、单斜辉石和斜方辉石的氧同位素比值。结果显示，盘石山橄榄岩包体矿物的氧同位素比值落在“正常”地幔矿物的氧同位素变化范围之内，而且矿物之间达到了氧同位素平衡。部分单斜辉石不相容元素富集的特征表明，有些样品经历了隐性地幔交代作用（cryptical metasomatism），配合氧同位素的数据来看，影响盘石山上地幔的交代介质为来自地幔内部的熔体，不合有地壳组分。从盘石山和安徽女山（盘石山以北约100km）的对比看来，影响女山上地幔的洋壳流体可能来自于华南一华北陆陆碰撞之前的海洋板块俯冲，因此华南一华北的深部缝合带可能就在女山和盘石山之间。     

Boron isotope variations in nature: a synthesis

The large relative mass difference between the two stable isotopes of boron, ¹⁰B and ¹¹B, and the high geochemical reactivity of boron lead to significant isotope fractionation by natural processes. Published ¹¹B values (relative to the NBS SRM-951 standard) span a wide range of 90. The lowest ¹¹B values around — 30 are reported for non-marine evaporite minerals and certain tourmalines. The most ¹¹B-enriched reservoir known to date are brines from Australian salt lakes and the Dead Sea of Israel with ¹¹B values up to +59. Dissolved boron in present-day seawater has a constant world-wide ¹¹B value of + 39.5. In this paper, available ¹¹B data of a variety of natural fluid and solid samples from different geological environments are compiled and some of the most relevant aspects, including possible tracer applications of boron-isotope geochemistry, are summarized.

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Résumé La grande différence relative de masse entre les isotopes stables du bore, ¹⁰B et ¹¹B, et la grande réactivité geochimique du bore ont pour conséquence un fractionnement isotopique naturel important. Les valeurs de ¹¹B publiées (par rapport au standard NBS SRM-951) varient de 90. Les valeurs de ¹¹B les plus basses (–30) correspondent aux evaporites non-marines et à certaines tourmalines. Le réservoir le plus enrichi en ¹¹B est représenté par les saumures des lacs salés d' Australie et par la Mer Morte en Israël, qui ont des valuers de ¹¹B allent jusqu'à + 59. L'eau de mer a une valeur de ¹¹B mondialement constante de + 39.5. Des valeurs de ¹¹B des solutions naturelles ainsi que des roches et minéraux de différentes origines, publiées jusqu'à présent, sont présentées ici. En outre quelques aspects importants concernant la géochimie des isotopes du bore y compris quelques applications sont exposés.

     

Climatic dependence of stable carbon and oxygen isotope signals recorded in speleothems: From soil water to speleothem calcite

Understanding the relationship between stable isotope signals recorded in speleothems (δ¹³C and δ¹⁸O) and the isotopic composition of the carbonate species in the soil water is of great importance for their interpretation in terms of past climate variability. Here the evolution of the carbon isotope composition of soil water on its way down to the cave during dissolution of limestone is studied for both closed and open-closed conditions with respect to CO₂.The water entering the cave flows as a thin film towards the drip site. CO₂ degasses from this film within approx. 10 s by molecular diffusion. Subsequently, chemical and isotopic equilibrium is established on a time scale of several 10-100 s. The δ¹³C value of the drip water is mainly determined by the isotopic composition of soil CO₂. The evolution of the δ¹⁸O value of the carbonate species is determined by the long exchange time T_ex, between oxygen in carbonate and water of several 10,000 s. Even if the oxygen of the CO₂ in soil water is in isotopic equilibrium with that of the water, dissolution of limestone delivers oxygen with a different isotopic composition changing the δ¹⁸O value of the carbonate species. Consequently, the δ¹⁸O value of the rainwater will only be reflected in the drip water if it has stayed in the rock for a sufficiently long time.After the water has entered the cave, the carbon and oxygen isotope composition of the drip water may be altered by CO₂-exchange with the cave air. Exchange times, , of about 3000 s are derived. Thus, only drip water, which drips in less than 3000 s onto the stalagmite surface, is suitable to imprint climatic signals into speleothem calcite deposited from it.Precipitation of calcite proceeds with time constants, τ_p, of several 100 s. Different rate constants and equilibrium concentrations for the heavy and light isotopes, respectively, result in isotope fractionation during calcite precipitation. Since T_ex ? τ_p, exchange with the oxygen in the water can be neglected, and the isotopic evolution of carbon and oxygen proceed analogously. For drip intervals T_d < 0.1τ_p the isotopic compositions of both carbon and oxygen in the solution evolve linearly in time. The calcite precipitated at the apex of the stalagmite reflects the isotopic signal of the drip water.For long drip intervals, when calcite is deposited from a stagnant water film, long drip intervals may have a significant effect on the isotopic composition of the DIC. In this case, the isotopic composition of the calcite deposited at the apex must be determined by averaging over the drip interval. Such processes must be considered when speleothems are used as proxies of past climate variability.