Elemental and isotopic fractionation of Type B calcium-, aluminum-rich inclusions: experiments, theoretical considerations, and constraints on their thermal evolution

Experiments exposing Type B calcium-, aluminum-rich inclusion (CAI)-like melts at high temperatures to high vacuum or reducing hydrogen-rich gas mixtures were used to determine the rates and consequences of elemental and isotopic fractionation by evaporation. Silicon and magnesium were found to evaporate much faster than calcium and aluminum, and the resulting residual liquid trajectories in composition space are reproduced via a thermodynamic model for the saturation vapor pressure of the evaporating species. Isotopic fractionations associated with evaporation were measured for magnesium. The resulting relationship between fraction of magnesium lost and enrichment of the residue in the heavy isotopes of magnesium follows a Rayleigh fractionation curve with a fractionation factor that is close to, but not exactly, the theoretically expected value. The rate of evaporation is found to be a strong function of temperature, oxygen fugacity, and melt composition, which can be understood and modeled in terms of the dependence of the saturation vapor pressures on these variables. The relationship between evaporation rate, which we measure, and calculated saturation vapor involves empirical evaporation coefficients that we find to be significantly less than one (∼0.1). Analytical and numerical models are used to characterize how diffusion in both the melt and in the surrounding gas affects evaporation rates and the degree of chemical and isotopic fractionation. The experimental data and theoretical considerations are combined to give a parameterization of the rates and consequences of evaporation of Type B CAI-like liquids, which is then used to translate the measured isotopic fractionation of Type B CAIs into constraints on their thermal history. Cooling rates of the order of 10°C per hour are indicated.     

A new technique for precise uranium-series dating of travertine micro-samples

Secondary carbonate formations, such as travertine and calcareous tufa deposits, are important archives for quaternary continental climate studies and archaeology. The extremely complex growth mechanisms result in some serious problems for precise mass spectrometric uranium-series dating. Often, detrital and organic particles contaminate the carbonate and large pore volumes yield a great potential for open system behavior. We utilized microscopic, mineralogical and geochemical methods prior to sample selection to determine the abundance of primary calcite, i.e. micrite and spar. Furthermore, the state of alteration was characterized by cathodoluminescence and trace-element analysis. We conclude that travertine and calcareous tufa are appropriate for precise U-series age determination if a) micrite and/or spar are the dominant phases; b) cathodoluminescence of both phases is weak or absent; c) Fe and Al levels are low; and d) Sr concentrations are close to the average of the studied site. We mapped and sampled solely areas of major micrite/spar abundance having minor alteration for accurate U-series dating. When this new method was applied, travertines located in eastern Germany (sites Bad Langensalza, Burgtonna and Weimar-Ehringsdorf) gave single ²³⁰Th/²³⁸U-ages consistent with the lithological growth sequence and greatly improved compared to previously published chronologies. In addition, we determined ²³⁰Th/U isochron ages on bulk samples that confirm our single ages. In contrast to primary calcite, pore cements are homogeneously distributed throughout the travertine fabric and reflect early diagenetic processes and/or weathering.     

Jurassic strike slip versus subduction in the Eastern Alps

Late Jurassic formations of the Northern Calcareous Alps (NCA) contain ample evidence of synsedimentary tectonics in the form of elongate basins filled with turbidites, debris flows and slumps. Clasts are derived from the Mesozoic of the NCA; they commonly measure tens of metres in diameter and occasionally form kilometre-size bodies. These sedimentologic observations and the presumed evidence of Late Jurassic high-pressure metamorphism recently led to the hypothesis of a south-dipping Jurassic subduction zone with accretionary wedge in the southern parts of the NCA. We present new ⁴⁰Ar/³⁹Ar dates from the location of the postulated high-pressure metamorphism that bracket the age of this crystallization not earlier than 114–120 Ma. The event is therefore part of the well-documented mid-Cretaceous metamorphism of the Austro-alpine domain. Thus, there is currently no evidence of Late Jurassic high-pressure metamorphism to support the subduction hypothesis. The sediment record of the Late Jurassic deformation in the NCA, including the formation of local thrust sheets, is no conclusive evidence for subduction. All these phenomena are perfectly compatible with synsedimentary strike-slip tectonics. Large strike-slip fault zones with restraining and releasing bends and associated flower structures and pull-apart basins are a perfectly viable alternative to the subduction model for the Late Jurassic history of the NCA. However, in contrast to the Eastern Alps transect, where arguments for a Jurassic subduction are missing, a glaucophane bearing Jurassic high-pressure metamorphism in the Meliatic realm of the West Carpathians is well documented. There, the high-pressure/low-temperature slices occur between the Gemeric unit and the Silica nappe system (including the Aggtelek-Rudabanya units), which corresponds in facies with the Juvavic units in the southern part of the NCA. To solve the contrasting palaeogeographic reconstructions we propose that the upper Jurassic left lateral strike-slip system proposed here for the Eastern Alps continued eastwards and caused the eastward displacement of the Silica units into the Meliatic accretionary wedge.     

Barium uptake into the shells of the common mussel (Mytilus edulis) and the potential for estuarine paleo-chemistry reconstruction

In this study we test if calcite shells of the common mussel, Mytilus edulis, contain barium in proportion to the water in which they grew. Similar to all bivalves analyzed to date, the [Ba/Ca]_shell profiles are characterized by a relatively flat background [Ba/Ca]_shell, interrupted by sharp [Ba/Ca]_shell peaks. Previous studies have focused on these [Ba/Ca]_shell peaks, but not on the background [Ba/Ca]_shell. We show that in both laboratory and field experiments, there is a direct relationship between the background [Ba/Ca]_shell and [Ba/Ca]_water in M. edulis shells. The laboratory and field data provided background Ba/Ca partition coefficients (D_Ba) of 0.10 ± 0.02 and 0.071 ± 0.001, respectively. This range is slightly higher than the D_Ba previously determined for inorganic calcite, and slightly lower than foraminiferal calcite. These data suggest that M. edulis shells can be used as an indicator of [Ba/Ca]_water, and therefore, fossil or archaeological M. edulis shells could be used to extend knowledge of estuarine dissolved Ba throughputs back in time. Moreover, considering the inverse relationship between [Ba/Ca]_water and salinity, background [Ba/Ca]_shell data could be used as an estuary specific indicator of salinity. The cause of the [Ba/Ca]_shell peaks is more confusing, both the laboratory and field experiments indicate that they cannot be used as a direct proxy of [Ba/Ca]_water or phytoplankton production, but may possibly be caused by barite ingestion.     

Natural geobatteries associated with sulphide ore deposits, II. Field studies at the viburnum trend, southeast Missouri, U.S.A.

Any conductive sulphide ore body can generate electrical ore potentials and this can be regarded as a geobattery, with an upper positive cathode and a lower negative anode. Two mechanisms which can occur simultaneously and which appear to explain these potentials are the oxygen concentration cell (OCC) and the sulphide galvanic cell (SGC). When there is a difference of O₂ concentration between the cathode and anode, the OCC operates by contributing oxygen to the anode, and ceases when the difference is diminished. However, gradients of pH, temperature or pressure can keep the cell operating. In the SGC the sulphides dissolve at the anode (producing metal ions, sulphur and electrons), while at the cathode, either sulphides dissolve producing metal and sulphur ions, or reaction is as in the OCC. The ore potential measured in the field is the sum of the oxygen concentration cell and at times locally dominant sulphide galvanic cells.     

Scattered Data Approximation on the Bisphere and Application to Texture Analysis

The paper deals with the approximation and optimal interpolation of functions defined on the bisphere \mathbb S²×\mathbb S²\mathbb {S}^{2}\times \mathbb {S}^{2} from scattered data. We demonstrate how the least square approximation to the function can be computed in a stable and efficient manner. The analysis of this problem is based on Marcinkiewicz–Zygmund inequalities for scattered data which we present here for the bisphere. The complementary problem of optimal interpolation is also solved by using well-localized kernels for our setting. Finally, we discuss the application of the developed methods to problems of texture analysis in material science.     

The Gibbs method and Duhem's theorem: The quantitative relationships among P,T, chemical potential,phase composition and reaction progress in igneous and metamorphic systems

The Gibbs method permits simultaneous evaluation of the relationships among all intensive thermodynamic variables of a heterogeneous system in equilibrium. Addition of mass balance constraints permits simultaneous evaluation of both intensive and extensive variables so that changes in phase chemistry and modes may be monitored. Assumption of closed system behavior results in a system of equations with two degrees of freedom, regardless of the thermodynamic variance, as specified by Duhem's theorem. Open system behavior increases the number of degrees of freedom by the number of components to which the system is open. The methodology presented is therefore a formal statement of the constraints among the differential of all of the intensive and extensive variables of a heterogeneous system.Examples of the application of this formalism include contouring pressure-temperature space for mineral composition, modal changes and reaction progress; contouring reaction space with pressure, temperature and mineral composition; and calculation of compositional and modal changes of phases for prescribed changes in pressure and temperature, as, for example, in the calculation of synthetic garnet zoning profiles or liquid lines of descent in crystallizing magmas.     

The early Caledonian (Finnmarkian) event reassessed in Finnmark: Ar/Ar cleavage age data from NW Varangerhalvøya, N. Norway

The relative significance of early (Finnmarkian) and late (Scandian) Caledonian deformation in N. Norway is uncertain. Early studies suggested pervasive Finnmarkian deformation whilst later results indicated a restricted Finnmarkian domain. The present work suggests it was more widespread than accepted and that inter Finnmarkian–Scandian deformation occurred. ⁴⁰Ar/³⁹Ar dating of 2–6 and 6–11 μm pelitic fractions from the lower to mid-greenschist facies Tanahorn Nappe (five samples; base Middle Allochthon) and the epizone Løkvikfjellet and Barents Sea Groups (three samples; North Varanger Region) in the north Scandinavian Caledonides show slightly discordant spectra. Most spectra from the Tanahorn Nappe preserve possible evidence of an early Caledonian event in the high temperature steps, with recoil/excess Ar effects in the low temperature steps; no pre-Caledonian relict component has been recorded. The results indicate Finnmarkian deformation continued to 460 Ma, with Scandian reactivation at 425–415 Ma. From the North Varanger Region, a strongly crenulated sample yielded plateau ages (444–442 Ma); means of combined young steps from weakly to uncrenulated samples gave 470–450 Ma, suggesting penetrative strike-slip deformation occurred in the late Finnmarkian to inter-Finnmarkian–Scandian period. No Scandian ages were recorded in the North Varanger Region. Reassessment of published data from the Laksefjord Nappe and Gaissa Thrust Belt suggests they were affected by Finnmarkian deformation.     

干旱半干旱区土壤含水量反演与验证

基于MODIS遥感影像和表观热惯量法,以新疆为研究区,建立了适用于干旱半干旱区1 m土体的土壤含水量反演模型。模型根据高表观热惯量,高土壤含水量,低表观热惯量,低土壤含水量这一理论,通过日地表温差和宽波段反照率确定土壤含水量的时空变化。假设通过1 m土体的土壤水通量正比于上下底层土壤含水量的差值,利用水平衡方程建立土壤表面和底层土壤含水量关系方程,并利用中国土壤类型特点确定优化模型。通过验证结果表明,壤土和壤质粘土这两类土壤含水量接近真实值,砂土在区域验证中,模拟与实测差值为2.16%,整个模型模拟精度较好,能够准确地从时空上反演干旱半干旱地区1 m土体的土壤水分情况。     

Oxidation of pyrite during extraction of carbonate associated sulfate

The sulfur isotopic composition of carbonate associated sulfate (CAS) has been used to investigate the geochemistry of ancient seawater sulfate. However, few studies have quantified the reliability of δ³⁴S of CAS as a seawater sulfate proxy, especially with respect to later diagenetic overprinting. Pyrite, which typically has depleted δ³⁴S values due to authigenic fractionation associated with bacterial sulfate reduction, is a common constituent of marine sedimentary rocks. The oxidation of pyrite, whether during diagenesis or sample preparation, could thus adversely influence the sulfur isotopic composition of CAS. Here, we report the results of CAS extractions using HCl and acetic acid with samples spiked with varying amounts of pyrite. The results show a very strong linear relationship between the abundance of fine-grained pyrite added to the sample and the resultant abundance and δ³⁴S value of CAS. This data represents the first unequivocal evidence that pyrite is oxidized during the CAS extraction process. Our mixing models indicate that in samples with much less than 1 wt.% pyrite and relatively high δ³⁴S_pyrite values, the isotopic offset imparted by oxidation of pyrite should be much less than ? 4‰. A wealth of literature exists on the oxidation of pyrite by Fe³⁺ and we believe this mechanism drives the oxidation of pyrite during CAS extraction, during which the oxygen used to form sulfate is taken from H₂O, not O₂. Consequently, extracting CAS under anaerobic conditions would only slow, but not halt, the oxidation of pyrite. Future studies of CAS should attempt to quantify pyrite abundance and isotopic composition.