Determination of Zr and Hf in a Flux-Free Fusion of Whole Rock Samples using Laser Ablation Inductively Coupled Plasma-Mass Spectrometry (LA-ICP-MS) with Isotope Dilution Calibration

Isotope dilution calibration has been applied to the determination of Zr and Hf in whole rocks by laser ablation (LA)-ICP-MS. Enriched isotopes were added during the preparation of flux-free, synthetic whole rock glasses and homogenised through a combination of grinding and fusion. This method avoids problems, such as solution instability and the chemical resistance of minerals such as zircon, inherent in acid digestion sample preparation. The use of isotope dilution removes the need for external calibration using certified reference material glasses such as NIST SRM 612 for which certified Zr and Hf values are not available. The precision of Zr and Hf determinations were found to be < 1% and 3.5% respectively, limited by Poisson counting statistics which contributed to 50% of the final precision of analysis. Measured values correlate closely with compiled literature values.     

Petrology,mineralogy, porosity,and cosmic‐ray exposure history of Huaxi ordinary chondrite

A meteorite fall was heard and collected on July 13, 2010 at about 18:00 (local time) in the Shibanjing village of the Huaxi district of Guiyang, Guizhou province, China. The total mass of the fall is estimated to be at least 1.6 kg; some fragments are missing. The meteorite consists mainly of olivine, low‐Ca pyroxene, high‐Ca pyroxene, plagioclase, kamacite, taenite, and troilite. Minor phases include chromite and apatite. Various textural types of chondrules exist in this meteorite: most chondrule textures can be easily defined. The grain sizes of secondary plagioclase in this meteorite range from 2 to 50 μm. The chemical composition of olivine and low‐Ca pyroxene are uniform; Fa in olivine and Fs in low‐Ca pyroxene are, respectively, 19.6 ± 0.2 and 17.0 ± 0.3 (mole%). Huaxi has been classified as an H5 ordinary chondrite, with a shock grade S2, and weathering W0. The weak shock features, rare fractures, and the high porosity (17.6%) indicates that Huaxi is a less compacted meteorite. The preatmospheric radius of Huaxi is ~11 cm, corresponding to ~21 kg. The meteorite experienced a relatively short cosmic‐ray exposure of about 1.6 ± 0.1 Ma. The ⁴He and ⁴⁰Ar retention ages are older than 4.6 Ga implying that Huaxi did not degas after thermal metamorphism on its parent body.     

Numerical investigation into the application of response conditioned waves for long-term nonlinear fatigue analyses of rigid hulls

Previous studies of response conditioned wave methods have been focused on their applicability to the prediction of extreme nonlinear wave-induced load effects. The results showed that theses methods can be used to accurately and efficiently predict the nonlinear short-term probability distributions for rigid hull responses. This has led us to investigate how response conditioned wave methods can be used for long-term nonlinear fatigue analyses, and with which accuracy this can be done. In this paper we present the results from our investigation. The studies were performed using a container vessel with a length between perpendiculars of 281 m. Calculations were done with a nonlinear strip theory method in which the hull of the vessel was assumed to be rigid. The most likely response wave (MLRW) method was used to condition the waves. Only head seas were considered. We found that the MLRW method under-predicted the long-term fatigue damage by 3%. The method, however, required a simulation time that was approximately three orders of magnitude less than that required for a conventional long-term nonlinear analysis based on random irregular waves. A preliminary investigation showed that due to lacking springing and whipping contributions the MLRW method under-predicted the fatigue damage for a flexible hull by approximately 50%. Several comments about a more accurate extension of the proposed method to flexible hulls are included.     

Improved representation of topographic effects by a vertical adaptive grid in Vector-Ocean-Model (VOM). Part II: Simulations in unstructured adaptive grids

A static adaptive grid approximates the topography and defines the vertical resolution in Vector-Ocean-Model (VOM). The adaptation to topography creates unstructured grids, which are organised in a one-dimensional vector by column-wise storage of only wet cells. The model’s name reflects this data structure. The intention of VOM is better resolving flow and stratification near topographic boundaries in Z-coordinates. This is the second part of a publication that describes the generation of adaptive grids (part I), and simulations with VOM in unstructured grids (this part). Adaptive grids generated for a synthetic topography in part I include shelf, continental slope, and ocean. Three of those grids are here utilised in upwelling simulations. Under the same forcing increased vertical resolution at seabed and slopes yields a significant increase in flow energy as compared to coarser grids. Results allow explaining the surface intensification of a continental slope jet by vertical displacements of water masses in the seabed Ekman layer. Results in unstructured grids are almost identical to reference simulations in equidistant grids where the respective smallest grid size of unstructured grids was used. Negative effects of grids on predicted flow and stratification are absent also over particularly rough topography, as demonstrated by using vertical velocity as most sensitive indicator. In a further simulation an overflow governed by the advection of water mass properties is presented to demonstrate the conservation properties of the model. After 5 months of simulation the predicted domain average temperature deviated by 10⁻⁸ from the initial temperature field. Compared to equidistant grids the advection/diffusion scheme looses about one order of magnitude in accuracy when used in an unstructured grid. The results of VOM, being defined in Z-coordinates, are void of coordinate transformation errors. In an arbitrary topography unforced zero-flow remains quiescent in a stratification that only varies in the vertical. VOM due to its depth-independent vertical resolution appears particularly suitable for simulations of ocean-shelf exchange.     

Deciphering formation processes of banded iron formations from the Transvaal and the Hamersley successions by combined Si and Fe isotope analysis using UV femtosecond laser ablation

To investigate the genesis of BIFs, we have determined the Fe and Si isotope composition of coexisting mineral phases in samples from the ∼2.5 billion year old Kuruman Iron Formation (Transvaal Supergroup, South Africa) and Dales Gorges Member of the Brockman Iron Formation (Hamersley Group, Australia) by UV femtosecond laser ablation coupled to a MC-ICP-MS. Chert yields a total range of δ³⁰Si between −1.3‰ and −0.8‰, but the Si isotope compositions are uniform in each core section examined. This uniformity suggests that Si precipitated from well-mixed seawater far removed from its sources such as hydrothermal vents or continental drainage. The Fe isotope composition of Fe-bearing mineral phases is much more heterogeneous compared to Si with δ⁵⁶Fe values of −2.2‰ to 0‰. This heterogeneity is likely due to variable degrees of partial Fe(II) oxidation in surface waters, precipitation of different mineral phases and post-depositional Fe redistribution. Magnetite exhibits negative δ⁵⁶Fe values, which can be attributed to a variety of diagenetic pathways: the light Fe isotope composition was inherited from the Fe(III) precursor, heavy Fe(II) was lost by abiotic reduction of the Fe(III) precursor or light Fe(II) was gained from external fluids. Micrometer-scale heterogeneities of δ⁵⁶Fe in Fe oxides are attributed to variable degrees of Fe(II) oxidation or to isotope exchange upon Fe(II) adsorption within the water column and to Fe redistribution during diagenesis. Diagenetic Fe(III) reduction caused by oxidation of organic matter and Fe redistribution is supported by the C isotope composition of a carbonate-rich sample containing primary siderite. These carbonates yield δ¹³C values of ∼−10‰, which hints at a mixed carbon source in the seawater of both organic and inorganic carbon. The ancient seawater composition is estimated to have a minimum range in δ⁵⁶Fe of −0.8‰ to 0‰, assuming that hematite and siderite have preserved their primary Fe isotope signature. The long-term near-zero Fe isotope composition of the Hamersley and Transvaal BIFs is in balance with the assumed composition of the Fe sources. The negative Fe isotope composition of the investigated BIF samples, however, indicates either a perturbation of the steady state, or they have to be balanced spatially by deposition of isotopically heavy Fe. In the case of Si, the negative Si isotope signature of these BIFs stands in marked contrast to the assumed source composition. The deviation from potential source composition requires a complementary sink of isotopically heavy Si in order to maintain steady state in the basin. Perturbing the steady state by extraordinary hydrothermal activity or continental weathering in contrast would have led to precipitation of light Si isotopes from seawater. Combining an explanation for both elements, a likely scenario is a steady state ocean basin with two sinks. When all published Fe isotope records including BIFs, microbial carbonates, shales and sedimentary pyrites, are considered, a complementary sink for heavy Fe isotopes must have existed in Precambrian ocean basins. This Fe sink could have been pelagic sediments, which however are not preserved. For Si, such a complementary sink for heavy Si isotopes might have been provided by other chert deposits within the basin.     

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.