Lead in archaeological samples: an isotopic study by ICP-MS

Inductively coupled plasma mass spectrometry (ICP-MS) has been used to measure the concentration and isotopic composition of Pb in archaeological human and animal skeletal remains, soil from a village site of the Omaha tribe (U.S.A.) and cosmetic pigments.Lead concentrations in human bones from the Omaha tribe vary between 4.8 and 2570 μg/g, with younger people having the highest concentrations. Lead concentrations in animal bones from an Omaha village vary between 0.6 and 3.7 μg/g, and those of three soil samples range between 18 and 21 μg/g. Lead concentrations found in human bones from Anasazi (Utah, U.S.A.) and Alta (Peru) populations vary between 0.7 and 3.2 μg/g.Isotope ratios of a reagent grade Pb(NO₃)₂ solutions were measured by thermal ionization mass spectrometry (TIMS), as well as by ICP-MS to provide laboratory reference materials. The accuracy of the ICP-MS measurements relative to TIMS for the standard solution were found to be within 0.02–0.31% for²⁰⁶Pb/²⁰⁴Pb, 0.02–0.55% for²⁰⁷Pb/²⁰⁴Pb, and 0.16–0.56% for²⁰⁸Pb/²⁰⁴Pb. The precision of measurements on artifacts was 0.42–0.65% for²⁰⁶Pb/²⁰⁴Pb and 0.41–0.62% for²⁰⁷Pb/²⁰⁴Pb, whereas the precision for the same ratios for the bones was 0.85–1.8 and 0.82–1.67%, respectively. For the cosmetic lead-bearing pigments, a precision of 0.07–0.15% was found for both²⁰⁶Pb/²⁰⁴Pb and²⁰⁷Pb/²⁰⁴Pb ratios. Lead isotope ratios of artifacts give a radiogenic Pb signature, of which are close to signatures from PbZn mines of the central U.S. region. Lead isotope ratios of the pigments give non-radiogenic Pb signatures. Lead isotope ratios of the bones differ from those of the artifacts, and although similar in isotopic ratio to the pigments, they are more scattered, suggesting potential mixing of Pb from different regions.     

W同位素高精度负离子热电离质谱(NTIMS)测定方法

W同位素的高精度测定对于研究地球、月球和太阳系其他行星的起源和早期演化、核幔相互作用等领域具有重要意义。本文开展了负离子热电离质谱(NTIMS)高精度W同位素测定方法研究(测定WO_3~-)。采用多接收动态跳扫方式对W同位素进行测定,实时在线测定~(18)O/~(16)O,并利用实验室实时在线氧校正NTIMS Os同位素分析时获得的~(17)O/~(16)O-~(18)O/~(16)O同位素分馏趋势线计算~(17)O/~(16)O,进行氧校正计算。对多接收动态和多接收静态数据处理方式及不同的同位素分馏校正方法进行了详细对比研究。在上述工作基础上,最终建立了以~(186)W/~(184)W=0.92767进行标准化,采用多接收动态方法进行数据处理的在线氧校正W同位素NTIMS测定方法。~(182)W/~(184)W测定结果的外部精度(2RSD)可达3×10~(-6)～6×10~(-6),基本满足地球、月球和行星早期演化等W同位素研究工作的需要。     

The stable isotopic composition of coral skeletons: control by environmental variables

The reef corals Pocillopora damicornis and Montipora verrucosa were cultured under various controlled temperature and light conditions. The corals were analyzed for growth rate, tissue pigment content and skeletal ¹³C and ¹⁸O. Coral skeletal δ¹³C values varied with light dose and correlated with changes in zooxanthellar pigment. The δ¹³C values of skeletal aragonite seem to be modified by oxidation of photosynthetically produced organic matter.Functionally significant relationships between coral skeletal δ¹⁸O values and temperature have been determined. The temperature coefficients of the δ¹⁸O values [?4.4°C (%.)^?1] are similar to the first order coefficient in the equilibrium paleotemperature equation, but the δ¹⁸O values have taxonomically consistent offsets from equilibrium. The offsets may be attributed to the coral metabolism with slight but statistically significant differences between the two genera. Environmental and metabolic variables other than temperature have little or no effect on skeletal δ¹⁸O.     

Natural variations of Se isotopic composition determined by hydride generation multiple collector inductively coupled plasma mass spectrometry

Multiple-collector inductively coupled plasma mass spectrometry has been used for the precise measurement of the isotopic composition of Se in geological samples. Se is chemically purified before analysis by using cotton impregnated with thioglycollic acid. This preconcentration step is required for the removal of matrix-interfering elements for hydride generation, such as transitional metals, and also for the quantitative separation of other hydride-forming elements, such as Ge, Sb, and As. The analyte is introduced in the plasma torch with a continuous-flow hydride generation system. Instrumental mass fractionation is corrected with a “standard-sample bracketing” approach. By use of this new technique, the minimum Se required per analysis is lowered to 10 ng, which is one order of magnitude less than the amount needed for the N-TIMS technique. The estimated external precision calculated for the ⁸²Se/⁷⁶Se isotope ratio is 0.25‰ (2σ), and the data are reported as delta notation (‰) relative to our internal standard (MERCK elemental standard solution). Measurements of Se isotopes are presented for samples of standard solutions and geological reference materials, such as silicate rocks, soils, and sediments. The Se isotopic composition of selected terrestrial and extraterrestrial materials are also presented. An overall Se isotope variation of 8‰ has been observed, suggesting that Se isotopes fractionate readily and are extremely useful tracers of natural processes.     

Lead and uranium isotopic behavior in diagenetic and epigenetic manganese nodules, Timna Basin, Israel, determined by MC-ICP-MS

Isotope ratios of U and Pb were measured in two types of Mn nodules from the Cambrian Timna Formation, Israel. Type A nodules are mainly composed of pyrolusite and hollandite, with Mn, Ba, Pb and U concentrations of 30–60%, 0.2–2.5%, 0.2–1.0% and 500–3500 ppm, respectively, whereas type B nodules were formed by alteration of the former, and contain mainly coronadite, with Mn, Ba, Pb and U concentrations of 7–48%, 0.2–7%, 0.6–5% and 10–160 ppm, respectively. The isotopic composition of U and Pb was measured by MC-ICP-MS on Mn-rich solutions (up to 100 mg/L) without and with chromatographic separation. The values for the 207/206 and 208/206 ratios have been determined with precisions of up to 50 ppm and those of 206/204, 207/204 and 208/204 – up to 200 ppm. The values for the 234/238 ratios have been determined with precisions of 0.4–1%. The results of the separated and unseparated solutions were shown to be equal within the error. Thus there is no significant matrix effect while measuring U and Pb in Mn rich solution using the MC-ICP-MS.The isotopic composition of Pb and U support the distinction between the two types of Mn nodules. Type A nodules have a wide range of ²⁰⁶Pb/²⁰⁴Pb ratios (18.278–19.776), and an almost constant ratio of ²⁰⁸Pb/²⁰⁴Pb. In contrast, type B nodules have almost constant ²⁰⁶Pb/²⁰⁴Pb ratios and a wide range of ²⁰⁸Pb/²⁰⁴Pb ratios (37.986–38.079). Type A nodules form a linear array on a ²⁰⁷Pb/²⁰⁴Pb vs ²⁰⁶Pb/²⁰⁴Pb diagram, while type B nodules form a tight group characterized by lower Pb isotope ratios that slightly deviate from the type A array. The ²³⁴U/²³⁸U ratio differs between the two types of nodules; type A nodules exhibit a uniform and close to equilibrium ²³⁴U/²³⁸U ratio while type B nodules show a wide range of ²³⁴U/²³⁸U ratios above and below the equilibrium value. The isotopic composition of Pb in type A nodules might reflect Pb contributions from plutonic rock weathering, exposed at the time of deposition or later, to the Cambrian sea. These nodules have remained unaffected by processes that occurred since the Cambrian. The higher ²⁰⁸Pb/²⁰⁴Pb values of type B indicate that these nodules were formed from a Th-enriched solution probably during epigenetic processes which occurred also during the last 1 Ma.Thus the two isotopic systems of U and Pb can record formation, leaching and redeposition of Mn ores.     

激光探针等离子体质谱法（LAM—ICPMS）用于年龄锆石U—Pb定年

利用激光探针等离子体普（ＬＡＭ－ＩＣＰＭＳ）技术对中生代锆石进行了详细的２０６Ｐｂ／＾２３８定年研究。采用线扫描（Ｌｉｎｅ ｓｃａｎ）进样法减小了传统的剥深（Ｄｅｐｔｈ ｐｒｏｆｉｌｅ）进样法所引起的激光熔蚀分异效应;优化仪器参数可三ＩＣＰ－ＭＳ对Ｐｂ和Ｕ的质量歧视效应。测得了精确的＾２０６Ｐｂ／＾２３８Ｕ比值及年龄。研究结果表明,均匀颗粒锆石的＾２０６Ｐｂ／＾２３８Ｕ比值测量精度为２％～１０％,     

Jurassic kimberlites from Picton and Varty Lake,Ontario: Geochemical and stable isotopic characteristics

Micaceous ultramafic dikes of Jurassic age from Picton and Varty Lake, Ontario, consist mineralogically of olivine — phlogopite — serpentine — calcite-spinel. The rocks are characterized by abundant Ba-rich phlogopite (up to 6.5 wt.% BaO) and spinels with a diagnostic kimberlite trend-1. Compositionally the dikes are characterized by extreme silica-undersaturation (21–30 wt.% SiO₂), primitive Mg/(Mg + Fe^T) ratios (0.75–0.83), large enrichments of volatile components (CO₂ and H₂O), and relatively high abundances of both incompatible and compatible trace elements. The dikes exhibit pronounced enrichments of light rare earth elements (LREE) (La_N=320–1330) combined with strongly fractionated patterns (La_N/Yb_N=45–108). Calcite in the dikes is a primary magmatic phase, from textural relations and C-isotopic compositions ( ¹³C= –4.0 to –8.3). A calcite-rich aphanitic phase of the Picton dike is interpreted to be a late stage magmatic differentiate, which possibly involved olivine fractionation. Although the dikes lack most of the macrocrysts generally considered to be important diagnostic minerals of kimberlite magmatism, the geochemical, mineralogical and C- and O-isotopic characteristics collectively indicate that the dikes are evolved varieties of hypabyssal facies kimerlite.     

不同模式模拟的降水稳定同位素效应的比较和评估

利用引入水稳定同位素循环的ECHAM4、GISS E、HadCM3、MUGCM以及iAWBM的模拟数据,分析了全球降水中稳定同位素效应的空间分布特征,对不同模式的模拟结果之间以及模拟结果与GNIP（Global Network of Isotopes in Precipitation）的实际监测结果之间进行了比较,旨在对稳定同位素大气环流模式的模拟有效性进行评价,改善对水循环中水稳定同位素效应的理解和认识。结果显示,5个模式均很好地再现了全球降水中平均δ18O和平均δ18O季节差的空间分布特征,降水中稳定同位素的温度效应、降水量效应的分布特点以及全球大气水线GMWL（Global Meteoric Water Line）均被很好地模拟出。比较而言,ECHAM4模拟的降水中的平均δ18O以及δ18O平均季节差的空间分布与GNIP的实际分布最接近,拟合水平也最高;ECHAM4、GISS E、MUGCM和iAWBM再现全球温度效应空间分布的能力较强,拟合水平大致相当;由iAWBM模拟的降水量效应空间分布与实际分布之间的相关性最强,5个模式模拟的与实测的δ18O/P相关系数符号相同的站点数大致位于同一水平;GISS E和iAWBM模拟的全球大气水线与实测的GMWL最接近。     

Experimental study of evaporation and isotopic mass fractionation of potassium in silicate melts

The behavior of Na and K during evaporation from chondrule composition melts was studied using a vacuum furnace. Though Na is the less volatile of the two as an element, it is lost more rapidly than K from silicate melts. Mass fractionation of K isotopes was measured by ion microprobe and Rayleigh fractionation is observed for vacuum evaporation (10⁻⁵ atm). With higher pressures of air, the K loss rate decreases but with increasing hydrogen pressure, K is lost more rapidly. δ⁴¹K decreases with higher pressures, because of back reaction between melt and K in the gas. With long heating duration, the release of light K condensed within the furnace leads to interaction with the K-depleted melt and a further reduction of δ⁴¹K. Natural chondrules differ in some ways from our experimental residues. Some (especially type IIA) have superchondritic Na and K, despite their assumed formation in nebular hydrogen, which enhances volatile loss, and chondrules do not show K isotopic fractionation. Type I chondrules in Semarkona (LL3.0) either plot on our evaporation trend, or are depleted in K but slightly enriched in Na, relative to K. In Bishunpur (LL3.1), type I chondrules are mostly K-depleted but moderately to strongly enriched in Na. In petrologic type 3.2 to 3.4 chondrites they are enriched in both K and Na, like type II chondrules. The alkali contents suggest type I chondrules experienced evaporation and subsequent metasomatism. Their normal δ⁴¹K values suggest closed-system evaporation of a chondritic precursor in a gas with relatively high K pressures due to vaporization of dust accompanying chondrule precursor aggregates. Type II chondrules are volatile-rich, as well as unfractionated in K isotopes. They probably formed in a gas with higher pK than in the case of type I chondrules, due to heating of a more dust-rich parcel of gas.     

Dissolution of uranophane: An AFM, XPS, SEM and ICP study

Dissolution experiments on single crystals of uranophane and uranophane-β, Ca(H₂O)₅[(UO₂)(SiO₃(OH)]₂, from the Shinkolobwe mine of the Democratic Republic of Congo, were done in an aqueous HCl solution of pH 3.5 for 3 h, in HCl solutions of pH 2 for 5, 10 and 30 min, and in Pb²⁺-, Ba-, Sr-, Ca- and Mg-HCl solutions of pH 2 for 30 min. The basal surfaces of the treated uranophane crystals were examined using atomic-force microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). Solutions after dissolution experiments on single crystals and synthetic powders were analysed with inductively coupled plasma-optical emission spectroscopy (ICP-OES) and mass spectroscopy (ICP-MS). The morphology of the observed etch pits (measured by AFM) were compared to the morphology, predicted on the basis of the bond-valence deficiency of polyhedron chains along the edges of the basal surface. Etch pits form in HCl solutions of pH 2. Their decrease in depth with the duration of the dissolution experiment is explained with the stepwave dissolution model, which describes the lowering of the surrounding area of an etch pit with continuous waves of steps emanated from the etch pit into the rest of the crystal surface. Hillocks form in an HCl solution of pH 3.5, and the chemical composition of the surface (as indicated by XPS) shows that these hillocks are the result of the precipitation of a uranyl-hydroxy-hydrate phase. Well-orientated hillocks form on the surface of uranophane in a SrCl₂-HCl solution of pH 2. They are part of an aged silica coating of composition Si₂O₂(OH)₄(H₂O)_n. An amorphous layer forms on the surface of uranophane in a MgCl₂-HCl solution of pH 2, which has a composition and structure similar to silicic acid. Small crystallites of uranyl-hydroxy-hydrate phases form on the surface of uranophane after treatment in Pb(NO₃)₂-HCl and BaCl₂-HCl solutions of pH 2. Dissolution experiments on synthetic uranophane powders show that in the early stage of the experiments, the dissolution rate of uranophane increase in the sequence Pb(NO₃)₂-HCl < BaCl₂-HCl < CaCl₂-HCl < HCl < SrCl₂-HCl < MgCl₂-HCl, indicating that the dissolution of uranophane is more enhanced in solutions containing divalent cations of small ionic radii and high Lewis acidity (Mg, MgCl⁺).     

Hydrothermal venting activities in the Early Cambrian,South China: Petrological,geochronological and stable isotopic constraints

Multi-episodic (three episodes at least) hydrothermal silica chimneys are identified in the black chert successions (up to ～ 100 m thick locally), overlain by thick black shales (up to a few 100 m thick), in the Ediacaran–Cambrian boundary successions along the southern marginal zone of the Yangtze Platform, South China. Their occurrences are constrained within the lowermost Cambrian by the SHRIMP U–Pb zircon dating and stable isotopic chemostratigaphic data, and are stratigraphically coincident with the negative isotopic excursions of organic carbon (～ 10‰ VPDB in magnitude) and sulfide sulfur (between 0 and 10‰ CDT), i.e., in bases of Nemakit–Daldynian and Tommotian stages in the Lower Cambrian. In this case, a causal link could have existed between which the hydrothermal venting could have released huge amounts of reduced silica-rich hydrothermal fluids with abundant ¹³C-depleted greenhouse gases (methane) and volcanic-originated H₂S into the ocean and/or atmosphere, resulting in an extreme warm climate and oceanic anoxia, oceanic chemical perturbation, and subsequent massive precipitation of silica (chert), and large-magnitude negative isotopic excursions of organic carbon and sulfide sulfur. This scenario provides a unique chance to explore the causes of apparent tectono-depositional, oceanic and geochemical perturbations during this critical interval in South China and elsewhere.     

Terrestrial and freshwater carbonates in Hoxnian interglacial deposits, UK: micromorphology, stable isotopic composition and palaeoenvironmental significance

MIS 11 is often considered to be the best climatic analogue for the Holocene. Many studies have suggested, however, that it is a period of extreme climate warmth comparable in temperatures to the Middle and Late Pliocene. In Britain deposits of the Hoxnian interglacial are correlated to MIS 11 and multi-proxy techniques can be used to reconstruct the climate of this interglacial. Soil, groundwater and freshwater carbonates are common in Hoxnian deposits and the stable isotopic composition of these precipitates can be used to increase our understanding of MIS 11 environments in Britain. Carbonates from Marks Tey, Clacton, Swanscombe, Elveden and West Stow are studied, the stratigraphic context of which indicates that their formation is broadly synchronous (in the mid-Hoxnian, pollen zones Ho II to Ho III). The carbon isotopic composition of groundwater and pedogenic carbonates is typically depleted with respect to δ¹³C (ca −9 to −8‰ VPDB) reflecting uptake of plant respired CO₂ during water migration/recharge. The carbon isotopic composition of lacustrine carbonate is more enriched with respect to δ¹³C (ca 0-1‰VPDB) reflecting the equilibration of lake waters with atmospheric CO₂. The δ¹⁸O of groundwater and pedogenic carbonates is slightly more enriched than modern soil carbonates but not as enriched as soil carbonates formed under interglacials that were warmer than the Holocene (i.e. the Cromerian). The stable isotopic composition of Hoxnian carbonates does not, therefore, indicate that this interglacial was characterised by uniquely warm climates in the context of other Middle Pleistocene interglacials and the Holocene. This is contrary to many marine and littoral records from around the world but consistent with environmental records from Britain and Europe.     

Infrared microthermometric and stable isotopic study of fluid inclusions in wolframite at the Xihuashan tungsten deposit,Jiangxi province,China

The Xihuashan tungsten deposit, Jiangxi province, China, is a world-class vein-type ore deposit hosted in Cambrian strata and Mesozoic granitic intrusions. There are two major sets of subparallel ore-bearing quartz veins. The ore mineral assemblage includes wolframite and molybdenite, with minor amounts of arsenopyrite, chalcopyrite, and pyrite. There are only two-phase aqueous-rich inclusions in wolframite but at least three major types of inclusions in quartz: two- or three-phase CO₂-rich inclusions, two-phase pure CO₂ inclusions and two-phase aqueous inclusions, indicating boiling. Fluid inclusions in wolframite have relatively higher homogenization temperatures and salinities (239–380°C, 3.8–13.7 wt.% NaCl equiv) compared with those in quartz (177–329°C, 0.9–8.1 wt.% NaCl equiv). These distinct differences suggest that those conventional microthermometric data from quartz are not adequate to explain the ore formation process. Enthalpy–salinity plot shows a linear relationship, implying mixing of different sources of fluids. Although boiling occurred during vein-type mineralization, it seems negligible for wolframite deposition. Mixing is the dominant mechanism of wolframite precipitation in Xihuashan. δ³⁴S values of the sulfides range from −1.6 to +0.1‰, indicative of a magmatic source of sulfur. δ¹⁸O values of wolframite are relatively homogeneous, ranging from +4.8‰ to +6.3‰. Oxygen isotope modeling of boiling and mixing processes also indicates that mixing of two different fluids was an important mechanism in the precipitation of wolframite.     

北京平原周边基岩水和地表水的水化学及同位素分析

利用北京市平原周边基岩水和地表水样品中的T值和Cl-含量对大气降水的输入进行了定量估计。研究结果表明全部样品均为热核爆炸后的补给输入,Cl-≤6.8mg/L的水样为北京平原区近工业化前(距今约150～200a)的输入值,6.8～20mg/L为北京地区区域大气轻微污染条件下的Cl-输入值。通过对2H和18O同位素的关系研究,认为北京平原区的高程效应远比大陆效应显著,并且提供了一张北京平原区地下水研究用的比对样板。     

金刚石矿物学、包裹体及碳稳定同位素研究综述

金刚石是地球上最坚硬、对形成环境要求最苛刻的矿物之一。金刚石的矿物学特征、包裹体特征及碳稳定同位素组成记录了金刚石生长、熔蚀、搬运等地质过程中的温度、压力及物质成分等信息,是探索金刚石物质来源、形成过程和地球深部物理化学环境的重要研究对象。总结了国内外金刚石矿物学特征、包裹体特征和碳稳定同位素组成的相关研究成果,发现金刚石晶形和组合及其颜色可大致区分金刚石来源; 金刚石表面特征是区分原生金刚石与砂矿金刚石的重要鉴别特征; 金刚石包裹体类型及组合、包裹体年代学及金刚石碳稳定同位素研究,可分析金刚石物质来源和地球深部物理化学环境,确定金刚石形成时代,为研究金刚石成因、地幔岩石圈深部作用过程以及壳幔相互作用提供重要依据。     

金刚石矿物学、包裹体及碳稳定同位素研究综述

金刚石是地球上最坚硬、对形成环境要求最苛刻的矿物之一.金刚石的矿物学特征、包裹体特征及碳稳定同位素组成记录了金刚石生长、熔蚀、搬运等地质过程中的温度、压力及物质成分等信息,是探索金刚石物质来源、形成过程和地球深部物理化学环境的重要研究对象.总结了国内外金刚石矿物学特征、包裹体特征和碳稳定同位素组成的相关研究成果,发现金刚石晶形和组合及其颜色可大致区分金刚石来源;金刚石表面特征是区分原生金刚石与砂矿金刚石的重要鉴别特征;金刚石包裹体类型及组合、包裹体年代学及金刚石碳稳定同位素研究,可分析金刚石物质来源和地球深部物理化学环境,确定金刚石形成时代,为研究金刚石成因、地幔岩石圈深部作用过程以及壳幔相互作用提供重要依据.     

Palæohydrology of the calcsilicate aureole of the Beinn an Dubhaich granite, Skye, Scotland: a stable isotopic study

The contact aureole developed in siliceous carbonates surrounding the Beinn an Dubhaich granite, Skye, shows textural and stable isotope evidence for infiltration of aqueous fluids during both prograde and retrograde metamorphism. Strongly depleted isotope compositions of reaction-product calcite correlate with high silica and fluorine contents, demonstrating a strong link between isotopic alteration and metasomatism by fluids with a significant magmatic component, even at the margins of the aureole. The oxygen and carbon isotope compositions of the carbonates form a linear cluster with a positive slope of about five, consistent with the depletion of isotope compositions by the infiltration of magmatic and/or meteoric fluids. Rayleigh fractionation during devolatilization played a minor role in determining the final isotope composition. Stable isotope compositions of coexisting calcite–dolomite pairs show varying amounts of isotopic disequilibrium, which correlate with the inferred fluid infiltration mechanism. Much of the calcite in dolostones is the product of infiltration-driven reactions along fractures, and is greatly depleted isotopically relative to the host dolomite, especially at talc grade. At higher grades the calcite–dolomite fractionation is smaller, probably due to both increased fluid–rock interaction and a greater tendency for fluid infiltration to be pervasive on the grain-scale. Limestones generally show near-equilibrium fractionation of oxygen and carbon owing to the overwhelming compositional influence of the host calcite. Veins formed during late-stage hydrothermal circulation have strongly ¹⁸O-depleted compositions relative to the host rock. No small-scale spatial patterns to the isotopic depletion were observed, but the extent of fluid infiltration was greatest in the west of the aureole. Fluid infiltration was clearly highly heterogeneous, with no evidence of a consistent flow direction. It is not possible to determine fluid fluxes or flow directions from one-dimensional flow models based on continuum flow in the Beinn an Dubhaich aureole.     

A sedimentological and stable isotopic study of travertines and associated sediments within Upper Triassic lacustrine limestones, South Wales, UK

The Upper Triassic in South Wales is composed of up to 100 m of red, dolomitic mudstones of the Mercia Mudstone Group which overlie and are laterally equivalent to basin margin coarse clastic deposits. In the Sully Island and Dinas Powys areas, a series of carbonate deposits was laid down within small basins adjacent to the main Bristol Channel Basin. The rocks consist of dolomites containing replaced evaporites, overlain by perilittoral freshwater limestones. The limestones are fenestral intrasparites and contain abundant pedogenic and stromatolitic horizons, as well as locally developed travertines. Evidence for vadose diagenesis within the limestones is common. The travertines consist of sheets of fibrous calcite (flowstone) associated with pisoids and flöe calcite. Most of the travertines consist of single sheets several millimetres in thickness although ‘mounds’up to 1 m in height and 5 m in diameter are also present. The topmost metre of the limestones, which has been dolomitized, is deformed into tepee and megapolygonal structures. The carbon and oxygen stable isotopic composition of the limestones suggests that they were precipitated in low salinity waters. Successive samples from individual bands of flowstone show a covariance of δ¹⁸C and δ¹³C which is consistent with the mixing of resurgent groundwaters with pools of more evolved waters at the surface. The sedimentological and geochemical evidence suggests that the limestones were deposited in a small, enclosed basin fed by upwelling meteoric groundwaters in an environment distinct from that in which the laterally equivalent gypsiferous red mudstones were formed.     

A carbon and oxygen stable isotopic study of the siderite alteration in the Black Ridge gold deposit,Clermont, central Queensland

Gold mineralisation in the Black Ridge gold deposit, Clermont, central Queensland is associated with extensive siderite alteration and is most concentrated along a locally sheared unconformity between the Proterozoic? Anakie Metamorphics and the overlying basal conglomerates of the Permian Blair Athol Coal Measures. The carbon and oxygen isotopic compositions of 49 siderite specimens from all rock units show a systematic variation spatially related to the unconformity. The δ ¹³C values of siderite decrease with depth from about 0 to ?19‰, while the siderite δ ¹⁸O values of siderite from the overlying conglomerates are lighter (average 20.5‰) than those from the underlying Anakie Metamorphics (average 23.5‰); both isotopes show the largest variations in the samples from the unconformity itself. The data are best interpreted as the result of the mixing of two isotopically and thermally distinct fluids. The upper, cooler fluid has a marine signature and was derived from the pore water of the conglomerate. The lower, geothermal fluid, which carried most of the gold, was not locally derived, but was probably modified in the upper part of the Anakie Metamorphics as a consequence f geothermal gradients imposed by instrusive rocks common throughout the Clermont area. Mixing of the two fluids along the unconformity led to gold solubility in the geothermal fluid dropping more than four orders of magnitude causing gold mineralisation there.