Cadmium stable isotope cosmochemistry

Cadmium stable isotope compositions are reported for a comprehensive suite of carbonaceous, ordinary, enstatite, and Rumuruti chondrites as well as achondrites and lunar samples (soils, breccias, pristine anorthosite). The Cd isotope analyses were performed by multiple collector ICP-MS with an external reproducibility of ±0.43‰ (2 sd) for δ^114/110Cd. None of the samples shows evidence of nucleosynthetic anomalies and cosmogenic isotope effects from neutron-capture by ¹¹³Cd were only observed for two lunar samples.The Cd stable isotope compositions of type 1, 2, and some type 3 carbonaceous chondrites, EH4 enstatite chondrites, eucrites, and the Earth are essentially identical at δ^114/110Cd ≈ 0.0 ± 0.4. This suggests that the portion of the solar nebula from which the inner solar system bodies accreted was homogeneous with respect to its Cd isotope composition. It also indicates that the primary volatile element depletion of the inner solar system did not involve partial kinetic Rayleigh evaporation or condensation. Furthermore no resolvable Cd isotope effects were generated during the accretion and initial differentiation of the planetary bodies.In contrast, the analyses reveal large Cd isotope effects for ordinary and some enstatite chondrites, which display δ^114/110Cd values between about −8 and +16. Smaller fractionations are observed for the Rumuruti and some type 3 to 5 carbonaceous chondrites. These Cd isotope variations are thought to reflect secondary depletion or redistribution of Cd, due to open system thermal metamorphism on the meteorite parent bodies.One CAI and chondrule separates from the Allende meteorite have unexpectedly high Cd concentrations and fractionated light Cd isotope compositions with δ^114/110Cd ≈ −1 to −4. These characteristics may have been established by the interaction of originally Cd-poor materials with a volatile-rich gas prior to the final accretion of the Allende parent body. The general Cd enrichment of the lunar soil and regolith mainly reflects early volcanic activity. However, decreasing Cd abundances in lunar soils correlate well with an enrichment of the heavy Cd isotopes. This relationship is best explained by suppressed Rayleigh fractionation in response to space weathering.     

Response of Freezing/Thawing Indexes to the Wetting Trend under Warming Climate Conditions over the Qinghai–Tibetan Plateau during 1961–2010: A Numerical Simulation

Since the 1990s, the Qinghai–Tibetan Plateau(QTP) has experienced a strikingly warming and wetter climate that alters the thermal and hydrological properties of frozen ground. A positive correlation between the warming and thermal degradation in permafrost or seasonally frozen ground(SFG) has long been recognized. Still, a predictive relationship between historical wetting under warming climate conditions and frozen ground has not yet been well demonstrated,despite the expectation that it will b...     

When timing matters-considering changing temporal structures in runoff response surfaces

Scenario-neutral response surfaces illustrate the sensitivity of a simulated natural system, represented by a specific impact variable, to systematic perturbations of climatic parameters. This type of approach has recently been developed as an alternative to top-down approaches for the assessment of climate change impacts. A major limitation of this approach is the underrepresentation of changes in the temporal structure of the climate input data (i.e., the seasonal and day-to-day variability) since this is not altered by the perturbation. This paper presents a framework that aims to examine this limitation by perturbing both observed and projected climate data time series for a future period, which both serve as input into a hydrological model (the HBV model). The resulting multiple response surfaces are compared at a common domain, the standardized runoff response surface (SRRS). We apply this approach in a case study catchment in Norway to (i) analyze possible changes in mean and extreme runoff and (ii) quantify the influence of changes in the temporal structure represented by 17 different climate input sets using linear mixed-effect models. Results suggest that climate change induced increases in mean and peak flow runoff and only small changes in low flow. They further suggest that the effect of the different temporal structures of the climate input data considerably affects low flows and floods (at least 21% influence), while it is negligible for mean runoff.     

A stochastic inversion workflow for monitoring the distribution of CO<Subscript>2</Subscript> injected into deep saline aquifers

We present a two-step stochastic inversion approach for monitoring the distribution of CO₂ injected into deep saline aquifers for the typical scenario of one single injection well and a database comprising a common suite of well logs as well as time-lapse vertical seismic profiling (VSP) data. In the first step, we compute several sets of stochastic models of the elastic properties using conventional sequential Gaussian co-simulations (SGCS) representing the considered reservoir before CO₂ injection. All realizations within a set of models are then iteratively combined using a modified gradual deformation algorithm aiming at reducing the mismatch between the observed and simulated VSP data. In the second step, these optimal static models then serve as input for a history matching approach using the same modified gradual deformation algorithm for minimizing the mismatch between the observed and simulated VSP data following the injection of CO₂. At each gradual deformation step, the injection and migration of CO₂ is simulated and the corresponding seismic traces are computed and compared with the observed ones. The proposed stochastic inversion approach has been tested for a realistic, and arguably particularly challenging, synthetic case study mimicking the geological environment of a potential CO₂ injection site in the Cambrian-Ordivician sedimentary sequence of the St. Lawrence platform in Southern Québec. The results demonstrate that the proposed two-step reservoir characterization approach is capable of adequately resolving and monitoring the distribution of the injected CO₂. This finds its expression in optimized models of P- and S-wave velocities, density, and porosity, which, compared to conventional stochastic reservoir models, exhibit a significantly improved structural similarity with regard to the corresponding reference models. The proposed approach is therefore expected to allow for an optimal injection forecast by using a quantitative assimilation of all available data from the appraisal stage of a CO₂ injection site.     

Acapulcoite-lodranite meteorites: Ultramafic asteroidal partial melt residues

Acapulcoites (most ancient Hf-W ages are 4,563.1?±?0.8 Ma), lodranites (most ancient Hf-W ages are 4,562.6?±?0.9 Ma) and rocks transitional between them are ancient residues of different degrees of partial melting of a chondritic source lithology (e.g., as indicated by the occurrence of relict chondrules in 9 acapulcoites), although the precise chondrite type is unknown. Acapulcoites are relatively fine- grained (～150–230?μm) rocks with equigranular, achondritic textures and consist of olivine, orthopyroxene, Ca-rich clinopyroxene, plagioclase, metallic Fe,Ni, troilite, chromite and phosphates. Lodranites are coarser grained (540–700?μm), with similar equigranular, recrystallized textures, mineral compositions and contents, although some are significantly depleted in eutectic Fe,Ni-FeS and plagioclase- clinopyroxene partial melts. The acapulcoite-lodranite clan is most readily distinguished from other groups of primitive achondrites (e.g., winoanites/IAB irons) by oxygen isotopic compositions, although more than 50% of meteorites classified as acapulcoites currently lack supporting oxygen isotopic data. The heat source for melting of acapulcoites-lodranites was internal to the parent body, most likely ²⁶Al, although some authors suggest it was shock melting. Acapulcoites experienced lower temperatures of ～980–1170?°C and lower degrees of partial melting (～1–4?vol.%) and lodranites higher temperatures of ～1150–1200?°C and higher degrees (～5?≥?10?vol.%) of partial melting. Hand-specimen and thin section observations indicate movement of Fe,Ni-FeS, basaltic, and phosphate melts in veins over micrometer to centimeter distances. Mineralogical, chemical and isotopic properties, Cosmic Ray Exposure (CRE) ages which cluster around 4–6 Ma and the occurrence of some meteorites consisting of both acapulcoite and lodranite material, indicate that these meteorites come from one parent body and were most likely ejected in one impact event. Whereas the precise parent asteroid of these meteorites is unknown, there is general agreement that it was an S-type object. There is nearly total agreement that the acapulcoite-lodranite parent body was <～100?km in radius and, based on the precise Pb–Pb age for Acapulco of 4555.9?±?0.6 Ma, combined with the Hf/W and U/Pb records and cooling rates deduced from mineralogical and other investigations, that the parent body was fragmented during its cooling which the U/Pb system dates at precisely 4556?±?1 Ma. Hf-W chronometry suggests that the parent body of the acapulcoites-lodranites and, in fact, the parent bodies of all “primitive achondrites” accreted slightly later than those of the differentiated achondrites and, thus, had lower contents of ²⁶Al, the heat producing radionuclide largely responsible for heating of both primitive and differentiated achondrites. Thus, the acapulcoite-lodranite parent body never experienced the high degrees of melting responsible for the formation of the differentiated meteorites, but arrested its melting history at relatively low degrees of ～15?vol.%.     

Calcium Carbonate and Phosphate Reference Materials for Monitoring Bulk and Microanalytical Determination of Sr Isotopes

In situ laser ablation analyses rely on the microanalytical homogeneity of reference materials (RMs) and a similar matrix and mass fraction between unknown samples and RMs to obtain reliable results. Suitable carbonate and phosphate RMs for determination of Sr isotope ratios in such materials are limited. Thus, we determined ⁸⁷Sr/⁸⁶Sr ratios of several carbonate (JCt‐1, JCp‐1, MACS‐1, MACS‐3) and phosphate (MAPS‐4, MAPS‐5, NIST SRM 1400, NIST SRM 1486) international RMs using dissolved samples and two different multi‐collector inductively coupled plasma‐mass spectrometers (MC‐ICP‐MS). Our Sr isotope data are in agreement with published data and have an improved measurement precision for some RMs. For MACS‐1, we present the first ⁸⁷Sr/⁸⁶Sr value. We tested the suitability of these materials for microanalytical analyses by LA‐MC‐ICP‐MS, with two different laser ablation systems: a conventional nanosecond laser and a state‐of‐the‐art femtosecond laser. We investigated the RMs micro‐homogeneity and compared the data with our solution data. Both laser ablation systems yielded identical ⁸⁷Sr/⁸⁶Sr ratios within uncertainty to the solution data for RMs with low interferences of REEs. Therefore, these carbonate and phosphate RMs can be used to achieve accurate and precise results for in situ Sr isotope investigations by LA‐MC‐ICP‐MS of similar materials.     

Age constraints on faulting and fault reactivation: a multi-chronological approach

Movement within the Earth’s upper crust is commonly accommodated by faults or shear zones, ranging in scale from micro-displacements to regional tectonic lineaments. Since faults are active on different time scales and can be repeatedly reactivated, their displacement chronology is difficult to reconstruct. This study represents a multi-geochronological approach to unravel the evolution of an intracontinental fault zone locality along the Danube Fault, central Europe. At the investigated fault locality, ancient motion has produced a cataclastic deformation zone in which the cataclastic material was subjected to hydrothermal alteration and K-feldspar was almost completely replaced by illite and other phyllosilicates. Five different geochronological techniques (zircon Pb-evaporation, K–Ar and Rb–Sr illite, apatite fission track and fluorite (U-Th)/He) have been applied to explore the temporal fault activity. The upper time limit for initiation of faulting is constrained by the crystallization age of the primary rock type (known as “Kristallgranit”) at 325 ± 7 Ma, whereas the K–Ar and Rb–Sr ages of two illite fractions <2 μm (266–255 Ma) are interpreted to date fluid infiltration events during the final stage of the cataclastic deformation period. During this time, the “Kristallgranit” was already at or near the Earth’s surface as indicated by the sedimentary record and thermal modelling results of apatite fission track data. (U–Th)/He thermochronology of two single fluorite grains from a fluorite–quartz vein within the fault zone yield Cretaceous ages that clearly postdate their Late-Variscan mineralization age. We propose that later reactivation of the fault caused loss of helium in the fluorites. This assertion is supported by geological evidence, i.e. offsets of Jurassic and Cretaceous sediments along the fault and apatite fission track thermal modelling results are consistent with the prevalence of elevated temperatures (50–80°C) in the fault zone during the Cretaceous.     

GGR Biennial Review: Reference Materials in Geoanalytical and Environmental Research – Review for 2008 and 2009

This review gives an overview of the literature on reference materials of geochemical and environmental interest for the two-year period 2008–2009. Reference materials play an increasingly important role in all fields of geoanalytical research. This is demonstrated by the large number of publications containing data on reference materials. Although many reference materials exist, there is still a great need for certified samples, so-called delta zero materials for stable isotopic work and homogeneous microanalytical reference materials. This review focuses on six topics: developments of certification processes of reference materials mainly postulated in ISO guidelines and the IAG protocol, new developments of the GeoReM database, investigations of powdered rock reference materials, Chinese reference materials published in Chinese journals, microanalytical reference materials and isotopic reference materials.