矿物氧同位素模式温度计算

根据对现遥氧扩散模型的解析分析,通过模拟矿物之间的氧同位素交换轨迹进行模式温度计算,改进了常规矿物对氧同位素地质温度计方法。将模式温度计算与矿物氧－扩散封闭次上结合,建立了一个系统独立的同位素温度计算方法,因此所得到的同位素温度能够更好地反映矿物在高温岩石冷却过程中,的氧同位素交换行为;模式温度计算有如下优点：（１）考虑到了矿物之间扩散引起的同位素交换;（２）遵循质量守恒原理,更严格地适用于有限封     

腕足化石古温度研究

温度变化研究是理解地球气候系统变化的关键环节之一.通过对海水温度变化的了解,可以系统地了解全球气候演化规律及其驱动机制.由于腕足化石具有保存完好以及分布年限长等优势,提取腕足化石中氧同位素信息进行古生代海水温度变化研究,已成为常用手段,但利用其Mg/Ca比值进行古温度变化的探讨却很少报道.通过对四川龙门山泥盆纪腕足化石中氧同位素以及Fe、Mn、Sr、Mg、Ca等微量元素的提取,结合微体结构观察、阴极发光等实验,在判定腕足化石保存良好的前提下,发现根据腕足化石中Mg/Ca(mmol/mol,下同)比值计算的温度相比氧同位素推算的温度,同生物学、古地理学证据显示的温度更为接近.此结果可能是由于利用氧同位素计算温度时古海水氧同位素未知及其不稳定性造成的.尽管腕足化石Mg/Ca比值温度计同样受海水的盐度以及pH等因素的影响,但计算结果显示,其反演的古温度比较接近真实的温度变化.      

白云母、高岭石矿物中羟基的o同位素分析方法研究

羟基矿物内部存在两种位于不同结构位置上的氧原子硅氧四面体氧和羟基氧,二者之间的Ｏ同位素分馏可能比任何共生矿物对都大,是一种潜在的单矿物同位素地质温度计。单矿物同位素地质温度计较矿物对同位素地质温度计有很多优点。准确测量矿物中羟基的Ｏ同位素组成是建立单矿物同位素地质温度计的关键。本文介绍了一种精确测量白云母、高岭石矿物中羟基的Ｏ同位素组成的新方法火焰加热真空脱水氟化法。δ１８ＯＯＨ的分析精度达到０３‰,羟基氧的提取率达到９９％～１００％。实验证明羟基矿物在高温真空脱水过程中不存在Ｏ同位素动力学分馏,羟基水     

团簇同位素的基本原理与地质应用*

团簇同位素指的是含有2个及2个以上的重同位素结合在一起形成的同位素体。团簇同位素的数值定义为同位素体的相对丰度偏离随机分布状态的程度。测量该相对丰度较低的同位素体需要高精度的质谱仪,难点在于利用同位素组成已知的参考气体和不同同位素组成的加热气体,以获得绝对参考体系下的数值。团簇同位素体的相对丰度非常低,但是具有非常独特的物理和化学性质。比如碳酸盐矿物中¹³C¹⁸O¹⁶O的丰度对温度具有敏感性,而与矿物的全岩同位素以及矿物形成时期的流体性质无关,因此可以利用测量的碳酸盐团簇同位素来获得矿物的生长温度,再利用矿物的氧同位素(δ¹⁸O),根据传统的氧同位素温度计原理,可以进一步获得矿物的生长流体(水)的氧同位素。目前,团簇同位素温度计已经在古气候(温度)重建、古高度恢复、碳酸盐岩的成岩作用以及甲烷的成因分析等方面得到了广泛应用。评估深埋高温过程引起的C-O化学键重置对碳酸盐团簇同位素的影响、测试仪器产生对团簇同位素的非线性误差校正、以及其他丰度更低的团簇同位素体或大分子的团簇同位素的测量,是下一步的研究方向。     

团簇同位素的基本原理与地质应用

团簇同位素指的是含有2个及2个以上的重同位素结合在一起形成的同位素体。团簇同位素的数值定义为同位素体的相对丰度偏离随机分布状态的程度。测量该相对丰度较低的同位素体需要高精度的质谱仪,难点在于利用同位素组成已知的参考气体和不同同位素组成的加热气体,以获得绝对参考体系下的数值。团簇同位素体的相对丰度非常低,但是具有非常独特的物理和化学性质。比如碳酸盐矿物中~(13)C~(18)O~(16)O的丰度对温度具有敏感性,而与矿物的全岩同位素以及矿物形成时期的流体性质无关,因此可以利用测量的碳酸盐团簇同位素来获得矿物的生长温度,再利用矿物的氧同位素(δ~(18)O),根据传统的氧同位素温度计原理,可以进一步获得矿物的生长流体(水)的氧同位素。目前,团簇同位素温度计已经在古气候(温度)重建、古高度恢复、碳酸盐岩的成岩作用以及甲烷的成因分析等方面得到了广泛应用。评估深埋高温过程引起的C-O化学键重置对碳酸盐团簇同位素的影响、测试仪器产生对团簇同位素的非线性误差校正、以及其他丰度更低的团簇同位素体或大分子的团簇同位素的测量,是下一步的研究方向。     

桂林洞穴沉积物的氧、碳同位素特征

<正>在现代稳定同位素研究中,往往利用达到同位素平衡的一对共生矿物或矿物——水之间的同位素组成来作为地质温度计,以了解其形成时的温度。对于岩溶洞穴环境来说,主要是利用方解石——水之间的同位素平衡反应。C.H.Hendy（1971）)详细研究了洞穴堆积过程中可能出现的各种地球化学作用及其对同位素分布的影响,认为当CO2从水中迅速逸失或进行水的蒸发作用时,产生同位素动力分馏,沉积物中相对富集的O18,不能作为古温度标志,而只有当CO2从水中缓慢逸出时,方解石和水之间氧同位素的平衡反应方可作为地质温度计。其平衡常数（K）主要取决于形成的温度。     

陆生蜗牛壳体碳氧同位素在古环境中的应用综述

陆生蜗牛壳体碳、氧稳定同位素组成分别受蜗牛生长时期植被中碳同位素组成和大气水中氧同位素组成的控制,已成为古气候和古环境重建的重要代用指标.本文详细介绍了蜗牛壳体碳酸盐碳、氧同位素古气候重建的指示机理、样品预处理方法及其在14C测年、古气候和古植被研究中的应用现状.在此基础上讨论了蜗牛壳体碳酸盐碳、氧同位素古气候解释中存在的问题,介绍了该领域未来的研究方向与趋势.     

重庆南川三泉奥陶系宝塔组碳同位素特征及地层对比

对重庆市南川区三泉镇宝塔组进行连续而高密度的碳、氧同位素和牙形刺采样与分析。分析结果显示,碳同位素值及曲线形态与晚奥陶世凯迪期碳同位素正漂移事件Gutternberg Inorganic Carbon Excursion (GICE)一致,并显示出的三个次级峰值。宝塔组自下而上发育牙形刺:Protopangerodus insculptus带和Hamarodus brevirameus带。通过与四川盆地及周缘地区其他剖面宝塔组碳同位素曲线的对比,发现GICE事件在不同剖面发育程度不完全一致,南部发育较北部更全,宝塔组起始沉积时间有差异。通过与湖北、安徽、塔里木盆地、北美和瑞典地区的对比,认为中扬子地区宝塔组可能发育不完全;塔里木盆地其浪组与四川盆地宝塔组可对比;再次证实GICE事件具有全球性属性,其多次波动的特征可能与地球古海洋环境变化和奥陶纪生物大辐射有密切关系。     

同位素温度计中极大值、极小值的意义

同位素地质温度计是应用同位素分馏系数和温度的对应关系研究和恢复古温度的一种有效方法.一般情况下,同位素分馏系数值和温度是一一对应的,但是偶尔也出现同一分馏系数值和多个温度对应的现象,存在极大值和极小值.     

利用湖泊自生碳酸盐岩氧碳同位素特征分析古湖泊类型的方法——实际应用中的要点及分析程式

以文献资料为素材,讨论了湖泊自生碳酸盐岩样品构成中岩性成分、采样点分布及数据量对样品氧碳同位素相关性及其能否反映古湖泊氧碳同位素相关性影响,指出根据相关性分析古湖泊类型时,必须充分考察样品岩性成分一致性、地质层位同一性、地质及地理分布合理性,着重考察样品数据量的充足性.综述了利用湖泊自生碳酸盐岩氧碳同位素特征分析古湖泊类型的方法,提出"一氧、二碳、三相关、四综合"的基本分析程式.     

二次离子质谱微区原位牙形石氧同位素分析及其在古海表水温记录中的应用

利用生物成因磷灰石的氧同位素信息能够重建古海水温度,尤其是牙形石,结合其在生物地层学上的研究,它的数据解释具有明确的古环境意义。牙形石微小的个体一直是其精确地球化学分析的限制因素。作为对牙形石微区原位氧同位素测试方法的探索研究,本文利用Cameca IMS--1280 型二次离子质谱仪对牙形石进行了微区原位氧同位素组成测试,通过分析得到可靠的古表层海水温度 ( SST) 记录,表明从晚二叠世到早三叠世SST 存在明显的上升过程。相比常规Ag3PO4 实验方法,牙形石微区原位氧同位素分析方法更加快速,而且能够有效避免牙形石易受到污染的部位,获得更为可靠的牙形石氧同位素组成的测定结果。     

川东地区华蓥山海相三叠系不同类型岩石对海水信息的保存性评估

通过对川东地区华蓥山海相三叠系不同岩石类型样品的微观组构、阴极发光和微量元素等分析表明:川东地区华蓥山海相三叠系不同的岩石类型样品具有不同的抵抗成岩蚀变能力,其对海水信息的保存程度也不一致;钙质泥岩所记录的有关信息已基本不能代表海水,多数微晶灰岩所记录的有关信息可以较好地代表海水,而粉晶白云岩只有部分样品可以代表海水的...     

Carbon and oxygen isotope compositions of the carbonate facies in the Vindhyan Supergroup, central India

The Vindhyan sedimentary succession in central India spans a wide time bracket from the Paleoproterozoic to the Neoproterozoic period. Chronostratigraphic significance of stable carbon and oxygen isotope ratios of the carbonate phase in Vindhyan sediments has been discussed in some recent studies. However, the subtle controls of facies variation, depositional setting and post-depositional diagenesis on stable isotope compositions are not yet clearly understood. The Vindhyan Supergroup hosts four carbonate units, exhibiting a wide variability in depositional processes and paleogeography. A detailed facies-specific carbon and oxygen isotope study of the carbonate units was undertaken by us to investigate the effect of these processes and to identify the least altered isotope values. It is seen that both carbon and oxygen isotope compositions have been affected by early meteoric water diagenesis. The effect of diagenetic alteration is, however, more pronounced in case of oxygen isotopes than carbon isotopes. Stable isotope compositions remained insensitive to facies only when sediments accumulated in a shallow shelf setting without being exposed. Major alteration of original isotope ratios was observed in case of shallow marine carbonates, which became exposed to meteoric fluids during early diagenetic stage. Duration of exposure possibly determined the magnitude of alteration and shift from the original values. Moreover, dolomitization is found to be accompanied by appreciable alteration of isotope compositions in some of the carbonates. The present study suggests that variations in sediment depositional settings, in particular the possibility of subaerial exposure, need to be considered while extracting chronostratigraphic significance from δ¹³C data.     

Testing Sr/Sr as a paleosalinity indicator on mixed marine, brackish-water and terrestrial vertebrate skeletal apatite in late Paleocene-early Eocene near-coastal sediments, Mississippi

Mixed marine, brackish-water and terrestrial vertebrate skeletal apatite is found in the late Paleocene-early Eocene Tuscahoma and Bashi Formations of Mississippi. The co-Occurrence in these near-coastal marine deposits of skeletal apatite with different provenances offers a unique opportunity for unraveling the effects of diagenesis on apatite ⁸⁷Sr/⁸⁶Sr composition, with bearings on the use of this isotope pair as paleosalinity indicator. The results show that the Sr isotopes of all originally poorly ordered phases of skeletal apatite have extensively re-equilibrated with pore water with significantly lower ⁸⁷Sr/⁸⁶Sr ratios than late Paleocene-early Eocene seawater. For example, marine shark and ray teeth from the Bashi Formation all have clearly nonmarine ⁸⁷Sr/⁸⁶Sr ratios, 0.7073-0.7075, compared with a coeval seawater ratio in the range 0.7077-0.7078. However, separated shark tooth enamel, with a high original crystallinity, appears to have retained all or most of its in vivo Sr isotopic signature until the present. Here we also show that ⁸⁷Sr/⁸⁶Sr results on recent vertebrate skeletal material from different environments are in good agreement with expected values for respective habitat.

Earlier analyses of calcite material from the Bashi Formation indicated the existence of a shift in seawater ⁸⁷Sr/⁸⁶Sr to a lower value at the Paleocene-Eocene boundary. The strong influence of pore water with low, nonmarine ⁸⁷Sr/⁸⁶Sr on the apatite in the Bashi Formation suggests that the proposed isotopic shift may be an artifact related to diagenetic processes.     

Oxygen isotope evolution of biogenic calcite and apatite during the Middle and Late Devonian

Oxygen isotope ratios of well-preserved brachiopod calcite and conodont apatite were used to reconstruct the palaeotemperature history of the Middle and Late Devonian. By assuming an oxygen isotopic composition of –1 V-SMOW for Devonian seawater, the oxygen isotope values of Eifelian and early Givetian brachiopods and conodonts give average palaeotemperatures ranging from 22 to 25 °C. Late Givetian and Frasnian palaeotemperatures calculated from ¹⁸O values of conodont apatite are close to 25 °C in the early Frasnian and increase to 32 °C in the latest Frasnian and early Famennian. Oxygen isotope ratios of late Givetian and Frasnian brachiopods are significantly lower than equilibrium values calculated from conodont apatite ¹⁸O values and give unrealistically warm temperatures ranging from 30 to 40 °C. Diagenetic recrystallization of shell calcite, different habitats of conodonts and brachiopods, as well as non-equilibrium fractionation processes during the precipitation of brachiopod calcite cannot explain the ¹⁸O depletion of brachiopod calcite. Moreover, the ¹⁸O depletion of brachiopod calcite with respect to equilibrium ¹⁸O values calculated from conodont apatite is too large to be explained by a change in seawater pH that might have influenced the oxygen isotopic composition of brachiopod calcite. The realistic palaeotemperatures derived from ¹⁸O _apatite may suggest that biogenic apatite records the oxygen isotopic composition and palaeotemperature of Palaeozoic oceans more faithfully than brachiopod calcite, and do not support the hypothesis that the ¹⁸O/¹⁶O ratio of Devonian seawater was significantly different from that of the modern ocean.     

重晶石沉积类型及成因评述--兼论扬子地区下寒武统重晶石的富集机制

重晶石沉积类型丰富,具有多种成因过程。通常,沉积型重晶石可分为生物、热液、成岩和冷泉重晶石四种类型。富钡与富硫酸盐的流体（海水、早成岩孔隙水或热液流体）及其相互作用过程（水柱、热液系统、沉积柱、沉积物-水界面附近）决定了重晶石的沉积环境、宏微观产出方式、同位素组成及相应的地质意义。另外,根据扬子地区下寒武统富重晶石沉积的地质特征,简述了其各种富集机制的适用性及争论。据此建议,结合埃迪卡拉纪-寒武纪转折时期的古海洋背景,对其进行详细的沉积学及地球化学分析,有助于深化成因认识,弥合分歧。     

Reconstruction of palaeosalinity using carbon isotopes and benthic associations: a comparison

Carbon and oxygen isotopes were determined on 40 recrystallized shells of Late Jurassic bivalves from the Lusitanian Basin of Portugal. In contrast with the oxygen isotopes, which exhibited considerable diagenetic distortion, the carbon isotopes are thought to preserve a record of the salinity of the Jurassic marginal marine seas in which these bivalves lived. The reconstructed palaeosalinities range from 35%o (euhaline) to 5% (oligohaline). Comparing these values with the palaeosalinity reconstructed from a palaeoecological analysis of 17 stratigraphic levels within the basin, the independently derived values agree in most cases. Strongly differing values are explained as being due to biotic factors and to diagenetic distortion of the isotopic signal; they are less likely to be due to smallscale time-averaging or insufficient microstratigraphic sampling. On the whole, the carbon isotope analyses are thought to produce reasonable palaeosalinity values, although data from infaunal, originally aragonitic bivalves appear to be less reliable than those from epifaunal bivalves with a predominantly or exclusively calcitic shell. As diagenetic alteration of the carbon isotope signal is, however, unpredictable and biotic effects on the isotopic composition are insufficiently known, palaeosalinity reconstructions based on stable isotope data should be supported by palaeoecological data.     

四川盆地东北部晚二叠世-早三叠世白云岩与同期海水锶同位素组成的对比研究

在四川盆地东北部14条野外剖面和地下钻井的二叠系长兴组、三叠系飞仙关组和嘉陵江组石灰岩和白云岩岩石学研究的基础上,对其中189个不同类型的碳酸盐样品(包括代表海水的石灰岩样品和在不同成岩阶段形成的各种白云岩样品)进行了锶同位素组成和相应的MgO、CaO和Mn、Sr元素分析,获得了系统的晚二叠-早三叠世海水的锶同位素组成数据并建立了相应演化曲线.在此基础上,对不同地层组/段和不同类型白云岩的锶同位素组成与同期海水锶同位素组成进行了对照研究,取得了如下主要认识:(1)川东北晚二叠-早三叠世白云岩的锶同位素组成与同期海水具有类似的演化趋势,结合白云岩的低锰、高锶特征,说明白云化流体与海水存在显著的亲缘关系,与铝硅酸盐地层无关;(2)白云岩的锶同位素组成与同期海水存在差别,各地层组/段白云岩的87Sr/86Sr比值都不同程度地高于同期海水,但从下往上,即从长兴组、飞2+3段、嘉2段到嘉4段,这种差值逐渐缩小,嘉4段白云岩的锶同位素组成已和同期海水基本一致;(3)川东北长兴组、飞2+3段白云岩形成的时间显著晚于同层石灰岩,白云化流体为时间上更晚的海源流体,但嘉2、嘉4段白云岩的形成时间仅略晚于同层石灰岩,白云化流体来源于非常近同期的蒸发浓缩的高Mg/Ca比值海水,一些嘉4段的白云岩的白云化流体就是同期海水,因而这些白云岩是同生或准同生的;(4)如果把白云化的时间看作白云岩的形成时间,则违背地层叠置原理是川东北长兴组和飞仙关组结晶白云岩的主要特征之一,其形成机制可用非同期海源流体的隐伏回流-对流模式来解释,嘉陵江组白云岩形成机制可用活跃回流-萨布哈模式来解释.白云岩和代表同期海水的石灰岩锶同位素组成的对比为解决白云化流体与海水之间的时间关系提供一种新的研究途径.     

川东北普光气田下三叠统飞仙关组白云岩成因——来自岩石结构与Sr同位素和Sr含量的证据

研究了川东北普光气田下三叠统飞仙关组白云岩储层的岩石结构Sr的含量和Sr同位素组成,讨论了它的成因,飞仙关组优质储层为成岩期埋藏交代白云化作用的产物,来自岩石结构和Sr同位素和Sr含量的证据包括如下几个方面:(1)与准同生白云岩比较,埋藏白云岩的岩石结构和Sr同位素和Sr含量地球化学特征与前者有显著差别;(2)飞仙关组所有各类碳酸盐岩(或矿物)具有早三叠世海水Sr同位素组成特征,~(87)Sr/~(86)Sr比值变化范围为0.706588～0.708187,覆盖了全球早三叠世海水Sr同位素的变化范围(0.7076～0.7078),平均值0.707656与全球早三叠世平均值(0.707743)基本一致;(3)埋藏白云岩~(87)Sr/86Sr比值变化范围为0.707122～0.707419,平均值0.707421,都略低于全球早三叠世海水Sr同位素变化范围和平均值,但与已报道的川东北早三叠世飞仙关期海水Sr同位素变化范围(0.707330～0.707383)和平均值(0.707350)都非常接近,说明白云石化流体具有强烈的川东北地区早三叠世飞仙关期海水Sr同位素组成特征;(4)综合岩石结构、Sr同位素和Sr含量地球化学特征,证明飞仙关组白云岩储层为成岩期埋藏交代作用产物,白云石化流体来自地层中高Sr和高盐度的海源地层水.     

云南鹤庆锰矿碳氧同位素特征分析

云南鹤庆锰矿位于扬子地台西南缘,对其岩石样品的碳氧同位素分析表明,上三叠统松桂组经历了一次海进和一次漫长的海退期。生物(藻类)代谢与海水发生同位素交换、古气候环境的变化和古海水深度的变化都使反演的古温度偏高;古盐度分析显示正常海相沉积特征,略低的盐度与碳同位素偏低有关。钻孔样品的氧同位素主要由盐度变化而产生一个高值范围,且对应碳同位素低值区,由于海平面下降,有机质埋藏率低导致碳同位素向负值漂移。根据以上分析认为,沉积时期的环境至少是一个半局限的浅海近陆源盆地,伴随扬子地台不断抬升,气候由潮湿、炎热转变为干燥的大陆性气候,锰矿的形成也是伴随海退海水变浅而沉积成矿。