In situ iron isotope ratio determination using UV-femtosecond laser ablation with application to hydrothermal ore formation processes

The feasibility of in situ stable Fe isotope ratio measurements using UV-femtosecond laser ablation connected to a multiple-collector inductively coupled plasma mass spectrometer (MC-ICP-MS) has been investigated. Different types of matrices, independently determined by solution MC-ICP-MS after chromatographic separation of Fe, have been analysed by laser ablation using the isotopically certified iron reference material IRMM-014 as the bracketing standard. The samples have been pure iron metal (JM Puratronic), Fe-meteorites (North Chile, Glenormiston and Toluca), the meteorite phases kamacite and taenite in Toluca and Fe-sulphides. Furthermore, Fe isotope ratios from hydrothermal hematite, siderite and goethite from an old mining area in the Schwarzwald, Germany, and of magnetite from the metamorphic Biwabik iron formation have been determined. The results show that a precision of better than 0.1‰ (2 sigma) can be achieved with laser ablation and that all the results obtained agree with those determined by solution ICP to better than 0.1‰. This precision and accuracy is achievable in both raster and spot ablation mode. A matrix-matched bracketing standard is not required , and all these materials can be measured accurately against a metal standard. The hydrothermal minerals show significant Fe isotope zonations. In some samples the range of δ⁵⁶Fe in a single aggregate encompasses the entire spectrum of ratios found by bulk solution analyses in multiple samples distributed over the whole mining district. For example, isotopic zonations found in secondary fibrous hematites show a continuous change in the δ⁵⁶Fe values from −0.5‰ in the core to −1.8‰ in the rim. Primary hydrothermal siderite shows the reverse pattern with lighter values in the core than in the rim. While the siderite is thought to record primary fluid histories, the hematite pattern is interpreted as a reworked isotopic signature generated by oxic dissolution of primary zoned siderite and immediate close range re-precipitation of the oxidized Fe. Abrupt changes are documented for secondary goethite showing a distinct overgrowth that is 0.4‰ lighter than the core of the grain. If indeed Fe isotopes in secondary minerals from hydrothermal ore deposits record the initial isotopic signatures of their precursor minerals, and these in turn record hydrothermal fluid histories, then the tools are in place for a detailed reconstruction of the deposit‘s genesis. We expect similar observations from other Fe-rich deposits formed at intermediate and low-temperatures (e.g. banded iron formations). Laser ablation now provides us with the spatial resolution that adds a further dimension to our interpretation of stable Fe-isotope fractionation.     

Accuracy of the linearized standard balance and asymmetric balance systems in a shallow-water numerical model

A numerical evaluation of the accuracy of the standard balance equations (BE) and the asymmetric balance equations (AB) in strong vortex applications is presented. Linearized equations for the evolution of disturbances on a symmetric hurricane-like vortex in a shallow-water model are used to compare forecasts using the AB and BE formulations with benchmark primitive equation forecasts. The validity of the BE and AB models is formally determined by the square of the Froude number, F², and the square of the local Rossby number for disturbances with azimuthal wavenumber n, , respectively. The numerical experiments demonstrate that accurate results can be achieved with BE and AB in situations where F² and , respectively, are not necessarily small. When the divergence of the asymmetric disturbance is not much smaller than its vorticity, and the azimuthal wavenumber of the disturbance is low, the AB system proves to be a useful alternative to BE.     

New model calculations for the production rates of cosmogenic nuclides in iron meteorites

Abstract— Here we present the first purely physical model for cosmogenic production rates in iron meteorites with radii from 5 cm to 120 cm and for the outermost 1.3 m of an object having a radius of 10 m. The calculations are based on our current best knowledge of the particle spectra and the cross sections for the relevant nuclear reactions. The model usually describes the production rates for cosmogenic radionuclides within their uncertainties; exceptions are ⁵³Mn and ⁶⁰Fe, possibly due to normalization problems. When an average S content of about 1 ± 0.5% is assumed for Grant and Carbo samples, which is consistent with our earlier study, the model predictions for ³He, ²¹Ne, and ³⁸Ar are in agreement. For ⁴He the model has to be adjusted by 24%, possibly a result of our rather crude approximation for the primary galactic α particles. For reasons not yet understood the modeled ³⁶Ar/³⁸Ar ratio is about 30–40% higher than the ratio typically measured in iron meteorites. Currently, the only reasonable explanation for this discrepancy is the lack of experimentally determined neutron induced cross sections and therefore the uncertainties of the model itself. However, the new model predictions, though not yet perfect, enable determining the radius of the meteoroid, the exposure age, the sulphur content of the studied sample as well as the terrestrial residence time. The determination of exposure ages is of special interest because of the still open question whether the GCR was constant over long time scales. Therefore we will discuss in detail the differences between exposure ages determined with different cosmogenic nuclides. With the new model we can calculate exposure ages that are based on the production rates (cm³STP/(gMa)) of noble gases only. These exposure ages, referred to as noble gas exposure ages or simply ^3,4He, ²¹Ne, or ^36,38Ar ages, are calculated assuming the current GCR flux. Besides calculating noble gas ages we were also able to improve the ⁴¹K‐⁴⁰K‐and the ³⁶Cl‐³⁶Ar dating methods with the new model. Note that we distinguish between ³⁶Ar ages (calculated via ³⁶Ar production rates only) and ³⁶Cl‐³⁶Ar ages. Exposure ages for Grant and Carbo, calculated with the revised ⁴¹K‐⁴⁰K method, are 628 ± 30 Ma and 841 ± 19 Ma, respectively. For Grant this is equal to the ages obtained using ³He, ²¹Ne, and ³⁸Ar but higher than the 3⁶Ar‐ and ³⁶Cl‐³⁶Ar ages by ?30%. For Carbo the ⁴¹K‐⁴⁰K age is ?40% lower than the ages obtained using ³He, ²¹Ne, and ³⁸Ar but equal to the ³⁶Ar age. These differences can either be explained by our still insufficient knowledge of the neutron‐induced cross sections or by a long‐term variation of the GCR.     

On the origin of equatorial Atlantic biases in coupled general circulation models

Many coupled ocean–atmosphere general circulation models (GCMs) suffer serious biases in the tropical Atlantic including a southward shift of the intertropical convergence zone (ITCZ) in the annual mean, a westerly bias in equatorial surface winds, and a failure to reproduce the eastern equatorial cold tongue in boreal summer. The present study examines an ensemble of coupled GCMs and their uncoupled atmospheric component to identify common sources of error. It is found that the westerly wind bias also exists in the atmospheric GCMs forced with observed sea surface temperature, but only in boreal spring. During this time sea-level pressure is anomalously high (low) in the western (eastern) equatorial Atlantic, which appears to be related to deficient (excessive) precipitation over tropical South America (Africa). In coupled simulations, this westerly bias leads to a deepening of the thermocline in the east, which prevents the equatorial cold tongue from developing in boreal summer. Thus reducing atmospheric model errors during boreal spring may lead to improved coupled simulations of tropical Atlantic climate.     

Noble gases in Grant and Carbo and the influence of S‐ and P‐rich mineral inclusions on the 41K‐40K dating system

Abstract— Cosmogenic He, Ne, and Ar were measured in the iron meteorites Grant (IIIAB) and Carbo (IID) to re‐determine their preatmospheric geometries and exposure histories. We also investigated the influence of sulphur‐ and/or phosphorus‐rich inclusions on the production rates of cosmogenic Ne. Depth profiles measured in Grant indicate a preatmospheric center location 117 mm left from the reference line and 9 mm below bar B, which is clearly different (?10 cm) from earlier results (?165 mm left from the reference line on bar F). For Carbo the preatmospheric center location was found to be 120 mm right of the reference line and 15 mm above bar J, which is in agreement with literature data. The new measurements indicate a spherical preatmospheric shape for both meteorites and, based on literature ³⁶C1 data, the radii were estimated to be about 32 cm and 70 cm for Grant and Carbo, respectively. We demonstrate that minor elements like S and P have a significant influence on the production rates of cosmogenic Ne. In our samples, containing on average 0.5% S and/or P, about 20% of ²¹Ne was produced from these minor elements. Using measured ²¹Ne concentrations and endmember ²²Ne/²¹Ne ratios for Fe + Ni and S + P, respectively, we show that it is possible to correct for ²¹Ne produced from S and/or P. The thus corrected data are then used to calculate new ⁴¹K‐⁴⁰K exposure ages—using published K data—which results in 564 ± 78 Ma for Grant and 725 ± 100 Ma for Carbo. The correction always lowers the ²¹Ne concentrations and consequently decreases the ⁴¹K‐⁴⁰K exposure ages. The discrepancies between ³⁶Cl‐³⁶Ar and ⁴¹K‐⁴⁰K ages are accordingly reduced. The existence of a significant long‐term variation of the GCR, which is based on a former 30–50% difference between ⁴¹K‐⁴⁰K and ³⁶Cl‐³⁶Ar ages, may warrant re‐investigation.     

Noble gas studies in CAIs from CV3 chondrites: No evidence for primordial noble gases

Abstract— Calcium‐aluminum‐rich inclusions (CAIs) were among the first solids in the solar system and were, similar to chondrules, created at very high temperatures. While in chondrules, trapped noble gases have recently been detected, the presence of trapped gases in CAIs is unclear but could have important implications for CAI formation and for early solar system evolution in general. To reassess this question, He, Ne, and Ar isotopes were measured in small, carefully separated and, thus, uncontaminated samples of CAIs from the CV3 chondrites Allende, Axtell, and Efremovka. The ²⁰Ne/²²Ne ratios of all CAIs studied here are <0.9, indicating the absence of trapped Ne as, e.g., Ne‐HL, Ne‐Q, or solar wind Ne. The ²¹Ne/²²Ne ratios range from 0.86 to 0.72, with fine‐grained, more altered CAIs usually showing lower values than coarse‐grained, less altered CAIs. This is attributed to variable amounts of cosmogenic Ne produced from Na‐rich alteration phases rather than to the presence of Ne‐G or Ne‐R (essentially pure ²²Ne) in the samples. Our interpretation is supported by model calculations of the isotopic composition of cosmogenic Ne in minerals common in CAIs. The ³⁶Ar/³⁸Ar ratios are between 0.7 and 4.8, with fine‐grained CAIs within one meteorite showing higher ratios than the coarse‐grained ones. This agrees with higher concentrations of cosmogenic ³⁶Ar produced by neutron capture on ³⁵Cl with subsequent β^?‐decay in finer‐grained, more altered, and thus, more Cl‐rich CAIs than in coarser‐grained, less altered ones. Although our data do not strictly contradict the presence of small amounts of Ne‐G, Ne‐R, or trapped Ar in the CAIs, our noble gas signatures are most simply explained by cosmogenic production, mainly from Na‐, Ca‐, and Cl‐rich minerals.     

Fluid–Rock Interactions in Geothermal Reservoirs,Germany: Thermal Autoclave Experiments Using Sandstones and Natural Hydrothermal Brines

As renewable energy, geothermal can contribute substantially to the energy transition. To generate electricity or to harvest heat, high-saline fluids are tapped by wells of a few kilometres and extracted from hydrothermal reservoirs. After the heat exchanger units have been passed by, these fluids are reinjected into the reservoir. Due to the pressure and temperature differences between the subsurface and the surface, as well as the cooling of the fluids in the power plant, unwanted chemical reactions can occur within the reservoir, in the borehole, and within the power plant itself. This can reduce the permeability of the reservoir as well as the output of the geothermal power plant. This study aims to simulate real subsurface reactions using batch and leaching experiments with sandstone or sandstone powder as solid phase, and deionised water or natural brine as liquid phase. It is demonstrated that fluid composition changes after only a few days. In particular, calcite, aragonite, clay minerals, and zinc phases precipitate from the natural brine. In contrast, in particular minerals containing potassium, arsenic, barium, and silica are dissolved. Due to the experimental set-up, these mineral reactions mainly took place on the surface of the samples, which is why no substantial changes in petrophysical properties could be observed. However, it is assumed that the observed reactions on the reservoir scale have a relevant influence on parameters such as permeability.

     

The spatial configuration of innovation networks in China

China is rising and gradually developing into an innovation-oriented economy. This transition is fueled by public and private investment in education and by increasing inputs into science and technology. Little attention, however, has been paid to the great differences in China-specific context peculiarity. Hence, the paper assesses Chinese innovation networks using a comprehensive analytical model that includes network configuration, regional environment, government interference and firm attributes. The empirical analysis examines China’s machinery manufacturing industry to test the determinants of the spatial character of Chinese innovation networks based on questionnaire surveys and illustrative cases. Our study finds that Chinese innovation networks are affected not only by innovation resource endowments and firm attributes, but also by government interference and regional culture. Regarding the influence of regional culture, the typical Northern culture with the importance of guanxi plays an important role in the process of searching for partners and makes the innovation network and interpersonal network interwoven. Firms’ ownership and innovation ability are the two essential variables to determine whether any of the regional elements are of significance.