Ca isotopic compositions of dolomite, phosphorite and the oldest animal embryo fossils from the Neoproterozoic in Weng'an, South China

Deciphering the drastic changes of surface environment and the emergence of animals after the Neoproterozoic Snowball Earth event are important for understanding the changes of surface environment and its influence on the evolution of life through geologic time. Especially, the emergence of two types of Metazoan animals such as animal embryo fossils, cnidarians or sponges, and Ediacaran fauna in the late Neoproterozoic was one of the critical turning points in the biological evolution.Calcium is one of the essential elements for the growth of most animals. In this study, in order to evaluate the Ca cycles in the Neoproterozoic, we have measured Ca isotopic ratios (⁴⁴Ca/⁴²Ca and ⁴³Ca/⁴²Ca) for phosphorite, dolostone and phosphatic animal embryo fossils with a multiple collector, inductively coupled plasma-mass spectrometer (MC-ICP-MS). The resulting ⁴⁴Ca/⁴²Ca ratio defined by the relative deviation from the ratio of NIST SRM915a (δ^44/42Ca_NIST915) for phosphorite and dolostone ranges from 0.83 to 0.95‰, demonstrating that the fractionation between phosphorite/dolostone and seawater was very small. This evidence indicates that at the emergence of the Weng'an biota seawater was deficient in Ca probably due to mass deposition of phosphorite/dolostone and to the beginning of Ca-biomineralization.Three phosphatic animal embryo fossils have lower δ^44/42Ca values than the phosphorite and dolomite, implying that the precursor of the phosphatic embryo fossils was able to fractionate Ca isotopes through Ca-biomineralization, consistent with marine gastropods.     

Hydrogeochemical and Stable Isotope Characteristics of the River Idrijca (Slovenia), the Boundary Watershed Between the Adriatic and Black Seas

The hydrogeochemical and isotope characteristics of the River Idrijca, Slovenia, where the world’s second largest mercury (Hg) mine is located, were investigated. The River Idrijca, a typical steep mountain river, has an HCO₃ ⁻–Ca²⁺–Mg²⁺ chemical composition. Its Ca²⁺/Mg²⁺ molar ratio indicates that dolomite weathering prevails in the watershed. The River Idrijca and its tributaries are oversaturated with respect to calcite and dolomite. The pCO₂ pressure is up to 13 times over atmospheric pressure and represents a source of CO₂ to the atmosphere. δ¹⁸O values in river water indicate primary control from precipitation and enrichment of the heavy oxygen isotope of infiltrating water recharging the River Idrijca from its slopes. The δ¹³C_DIC values range from −10.8 to −6.6‰ and are controlled by biogeochemical processes in terrestrial environments and in the stream: (1) exchange with atmospheric CO₂, (2) degradation of organic matter, (3) dissolution of carbonates, and (4) tributaries. The contributions of these inputs were calculated according to steady state equations and are estimated to be—11%:19%:30%:61% in the autumn and 0%:26%:39%:35% in the spring sampling seasons.     

Isotopes in the Hueco Bolson aquifer, Texas (USA) and Chihuahua (Mexico): local and general implications for recharge sources in alluvial basins

Stable isotope data for the Hueco Bolson aquifer (Texas, USA and Chihuahua, Mexico) distinguish four water types. Two types relate to recharge from the Rio Grande: pre-dam (pre-1916) river water with oxygen-18 and deuterium (δ¹⁸O, δD, ‰) from (?11.9, ?90) to (?10.1, ?82), contrasts with present-day river water (?8.5, ?74) to (?5.3, ?56). Pre-dam water is found beneath the Rio Grande floodplain and Ciudad Juárez, and is mixed with post-dam river water beneath the floodplain. Two other types relate to recharge of local precipitation; evidence of temporal change of precipitation isotopes is present in both types. Recharge from the Franklin and Organ Mountains plots between (?10.9, ?76) and (?8.5, ?60) on the global meteoric water line (GMWL), and is found along the western side of the Hueco Bolson, north of the Rio Grande. Recharge from the Diablo Plateau plots on an evaporation trend originating on the GMWL near (?8.5, ?58). This water is found in the southeastern Hueco Bolson, north of the river; evaporation may be related to slow recharge through fine-grained sediment. Pre-dam water, recognizable by isotope composition, provides information on groundwater residence times in this and other dammed river basins.     

Geochemical and petrological aspects of dike intrusions in the Lycian ophiolites (SW Turkey): a case study for the dike emplacement along the Tauride Belt Ophiolites

Lycian ophiolites located in the Western Taurides, are cut at all structural levels by dolerite and gabbro dikes. The dolerite dikes from this area are both pristine and metamorphosed. The non-metamorphosed dikes are observed both in the peridotites and in the metamorphic sole rocks. Accordingly, the non-metamorphosed dikes cutting the metamorphic sole were generated after cooling of the metamorphic sole rocks. The metamorphosed dolerite dikes are only observed in the peridotites. The physical conditions and timing of the metamorphism for the metamorphosed dolerite dikes are similar to those of the metamorphic sole rocks of the Lycian ophiolites suggesting that the metamorphosed dolerite dikes were metamorphosed together with the metamorphic sole rocks. Therefore, the dike injections in the western part of the Tauride Belt Ophiolites occurred before and after the generation of the metamorphic sole rocks. All metamorphosed and non-metamorphosed dikes are considered to have the same origin and all of them are subduction-related as inferred from whole-rock geochemistry and lead isotopes. Lead isotope compositions of whole rocks of both dike groups cluster in a narrow field in conventional Pb isotope diagrams (²⁰⁶Pb/²⁰⁴Pb = 18.40–18.64; ²⁰⁷Pb/²⁰⁴Pb = 15.56–15.58; ²⁰⁸Pb/²⁰⁴Pb = 38.23–38.56) indicating a derivation from an isotopically homogeneous source. On the ²⁰⁷Pb/²⁰⁴Pb versus ²⁰⁶Pb/²⁰⁴Pb diagram, isotope compositions of the dikes plot slightly below the orogen curve suggesting contributions from mantle reservoir enriched by subducted oceanic lithosphere. Such a signature is typical of island arc magmatic rocks and supports the formation of the investigated rocks in a subduction-related environment.     

Origin of the absarokite–banakite association of the Damavand volcano (Iran): trace elements and Sr,Nd, Pb isotope constraints

The activity of the Damavand volcano (Central Alborz, northern Iran) began 1.8 Ma ago and continued up to 7 ka BP. Although the volcanic suite is clearly of shoshonitic affinity, only two petrographic types can be distinguished in the studied lavas: (1) weakly differentiated absarokites (49 < %SiO₂ < 51), scattered around the volcano but with a regional extension, (2) highly differentiated banakites (59 < %SiO₂ < 63), which form the bulk of the 4,000 m thick volcanic pile. All lavas are alkalic (3.7 < %K₂O < 5), REE and LILE-rich (e.g., 85 < La < 148 ppm; 9 < Th < 32 ppm) and show highly fractionated REE patterns (69 < La/Yb < 115) and pronounced Nb–Ta negative anomalies. The absarokites are characterised by Sr (0.7045–0.7046) and Nd (0.51266–0.51269) isotope compositions close to the Bulk Earth values, and distinct from those of the banakites (0.7047 < ⁸⁷Sr/⁸⁶Sr < 0.7049, 0.51258 < ¹⁴³Nd/¹⁴⁴Nd < 0.51262). The Pb isotope ratios are also slightly lower in the absarokites than in the banakites (18.71 < ²⁰⁶Pb/²⁰⁴Pb < 18.77, 15.62 < ²⁰⁷Pb/²⁰⁴Pb < 15.63, 38.85 < ²⁰⁸Pb/²⁰⁴Pb < 38.91, and 18.77 < ²⁰⁶Pb/²⁰⁴Pb < 18.84, 15.62 < ²⁰⁷Pb/²⁰⁴Pb < 15.64, 38.94 < ²⁰⁸Pb/²⁰⁴Pb < 39.06, respectively). Overall, there is a clear tendency towards higher Sr, Pb and lower Nd isotope ratios with increasing degree of differentiation. This study suggests that the absarokites result from a low degree of partial melting (∼5%) of a highly metasomatized mantle source, which inherited its characteristics from an old subduction setting. The initiation of volcanic activity 1.8 Ma ago results from variations in the lithospheric thermal regime, probably related to lithospheric delamination as proposed for Anatolia (Pearce et al. 1990). The banakites are mainly generated by extensive fractional crystallisation (∼70%) of the absarokitic magma, with a limited amount (a few percents) of assimilation of an old crustal component, in the form of bulk assimilation or AFC processes, which both can explain the Sr, Nd and Pb isotope data.     

Role of basement in epithermal deposits: The Kushikino and Hishikari gold deposits, southwestern Japan

The magma–ore deposit relationship of most low-sulfidation epithermal ore deposits is still unclear, partly because many stable isotopic studies of such deposits have indicated the predominance of meteoric waters within hydrothermal fluids. However, it is certainly true that hydrothermal systems are ultimately driven by magmatic intrusions, and epithermal gold deposits might therefore be produced by magmatic activity even in deposits having has no obvious links to a magma. We re-examine the genesis of two typical low-sulfidation epithermal gold deposits, the Kushikino and Hishikari deposits, using structural simulations and isotope data.Many epithermal gold deposits including the Kushikino and Hishikari deposits have been discovered in Kyushu, southwestern Japan. The Kushikino deposit comprises fissure-filling veins within Neogene andesitic volcanics that overlie unconformably Cretaceous sedimentary basement. The veins consist of gold- and silver-bearing quartz and calcite with minor amounts of adularia, sericite and sulfides. Although carbon and oxygen isotopic data for the veins indicate a meteoric origin of the ore fluid, finite element simulations suggest that the vein system might have formed in direct response to magma intrusion. In particular, geophysical data suggest that intruding magma has uplifted the basement rocks, thereby producing fractures and veins and a positive Bouguer anomaly, and providing the heat necessary to drive an ore-forming hydrothermal system.The second component of this study has been to investigate the nature and evolution of the Kushikino and Hishikari epithermal systems. Isotope data document the geochemical evolution of the hydrothermal fluids. We conclude that the existence of sedimentary basement rocks at depth might have affected the strontium and carbon isotopic ratios of the Kushikino and Hishikari ore fluids. The ⁸⁷Sr/⁸⁶Sr ratios and δ¹³C–δ¹⁸O trend reveal that major ore veins in the Hishikari deposit can be distinguished from shallow barren veins. It was suggested isotopically that fluids responsible for the barren veins in nearby shallow and barren circulation systems were only controlled by the shallow host rocks. Such multi-isotope systematics provide a powerful tool with which to determine the center of hydrothermal activity and thereby document the evolution of hydrothermal fluids.     

多接收器等离子体质谱法Zn同位素比值的高精度测定

详细报道了Zn同位素比值的多接收器等离子体质谱(MC-ICP-MS)高精度测定方法,包括:MC-ICP-MS Zn同位素测量过程中的质量歧视校正、同质异位素干扰评估、基质效应调查和同位素测量的长期重现性检验.研究表明,在测定条件下,运用标样一样品交叉法能有效地进行仪器质量歧视校正.同质异位素干扰的评估通过3种方式进行,即:在高分辨状态下同质异位数干扰信号的直接测定,低分辨状态下Zn同位素原始数据间相关关系的检验和低分辨下浓度梯度效应研究.结果表明,在低分辨模式下,尽管66Zn、67Zn、68Zn的同质异位素干扰信号很小,但的确存在,要获得准确同位素比值,必须使标样和样品的浓度在合适的范围内匹配.在基质效应方面,主要考察Fe对Zn同位素比值测定的影响.结果表明,当溶液中Fe/Zn(质量比)不大于0.2时,Fe对Zn同位素比值测定无影响.重复性测定中,δ66ZnGSB-Romil=6.96‰±0.11‰(2sd),δ67ZnGSB-Romil=10.4‰±0.20‰(2sd),δ68ZnGSB-Romil=13.8‰±0.22‰(2sd),达到国际同类实验室先进水准.运用所建立的方法,对地质岩石成分分析国家标准物质GBW 07270(闪锌矿)进行了Zn同位素平均成分测定为:δ66Zn=6.71‰±0.03‰(20),δ67Zn=10.08‰±0.05‰(20),δ68Zn=13.37‰±0.07‰(2σ).     

Microbial remains in some earliest Earth rocks: Comparison with a potential modern analogue

Carbonaceous matter (CM) from ca. 3.5 Ga hydrothermal black cherts of the Pilbara Craton of Western Australia and the Barberton Greenstone Belt of South Africa yielded transmission electron microscopy (TEM) images that are suggestive of microbial remains and possible remnants of microbial cell walls. These are compared to a potential modern analogue, the hyperthermophilic Methanocaldococcus jannaschii, derived from an active seafloor hydrothermal environment and cultured under similar conditions. A striking resemblance to the early Archaean forms was evident in wall structure and thermal degradation mode. Cell disintegration of the cultures occurred at 100 °C marking the limits of life. Complete disintegration, deformation and shrinkage occurred at 132 °C. A multidisciplinary approach to the characterisation of the CM was undertaken using organic petrology, TEM coupled with electron dispersive spectral analysis (EDS), high resolution TEM (HRTEM) to determine molecular ordering, and elemental and carbon isotope geochemistry. Reflectance measurements of the CM to determine thermal stress yielded a range of values corresponding to several populations, and pointing to different sources and processes. The δ¹³C values of Dresser Formation CM (−36.5 to −32.1‰) are negatively correlated with TOC (0.13–0.75%) and positively correlated with C/N ratio (134–569), which is interpreted to reflect the relative abundance of high R_o/oxidised/recycled CM and preferential loss of ¹²C and N during thermal maturation. TEM observations, inferred carbon isotopic heterogeneity and isotope fractionations of −27 to −32‰ are consistent with the activity of chemosynthetic microbes in a seafloor hydrothermal system where rapid silicification at relatively low temperature preserved the CM.     

Identification of the origin of salinization in groundwater using multivariate statistical analysis and geochemical modeling: a case study of Kaohsiung,Southwest Taiwan

The study of brine aquifers in southern Taiwan is highly complicated by hybrid geochemical reactions, which obscure important geochemical information. Using multivariate analysis on major and minor ion compositions normalized by Cl⁻ content, chemical constituents were combined into two principal components representing brine mixing and mineral precipitation. Comparing to multivariate analysis on the original data, this procedure reveals more geochemical information. It demonstrates that the brine groundwater of the region is primarily composed of highly evaporated seawater. The evaporation ratio is >70%; a point at which calcite, dolomite and gypsum precipitate. Oxygen and hydrogen isotopic compositions confirm this inference; and further, geochemical modeling quantitatively determined the evaporation ratio to be about 85%. Natural boron contamination is a consequence of brine groundwater. Two evolutionary trends in the plotting of the Cl/B ratio versus Cl⁻ can be identified: (1) Cl/B ratio decreases with boron being released from clay minerals when brine aquifers are flushed with freshwater; and (2) Cl/B ratio increases when seawater of a high Cl/B ratio infiltrates coastal aquifers.