Determination of Precise and Accurate 51V/50V Isotope Ratios by Multi‐Collector ICP‐MS,Part 2: Isotopic Composition of Six Reference Materials plus the Allende Chondrite and Verification Tests

We present the first measurements of vanadium (V) stable isotopes for six reference materials – USGS PCC‐1, BHVO‐2, BCR‐2, BIR‐1a, GSP‐2 and AGV‐2 – plus the widely available carbonaceous chondrite Allende. We present standard addition and matrix spiking tests to assess the robustness and reproducibility of our data. Standard addition utilised an enriched ⁵⁰V solution designated VISSOX (Vanadium Isotope Standard Solution OXford). We further assessed the veracity of the method by spiking collected sample matrices with the same amount of a V standard solution, whose isotopic composition was defined as 0‰. Standard addition and matrix spiking tests recorded no appreciable artificial isotope fractionation. We estimate that the best currently attainable long‐term reproducibility of stable ⁵¹V/⁵⁰V isotope measurements in complex matrices is 0.15‰, which is in the same order as the reproducibility achievable with standard solutions. Finally, a large range of ～ 1.2‰ in stable V isotopic composition was documented, with ～ 0.5‰ of that variation in high temperature igneous materials alone. The range and resolving power of V stable isotopes, with respect to igneous material, compared favourably with the magnitude of fractionation reported for other non‐traditional stable isotope systems, which bodes well for the utility of this new system.     

Postglacial relative sea‐level rise in the Limfjord region,northern Jutland,Denmark

A new core drilled at Nørrekær Enge, Løgstør, Denmark, shows terrestrial lake and bog sediments lying beneath 10 m of marine sediments. Pollen analysis, ¹⁴C dating and sedimentary observations show that these sediments relate to an ancient lake basin that was flooded when the rising sea levels reached 8.0 m b.s.l. This new study has allowed a review of previous data relating to shoreline displacement from the Limfjord region of northern Jutland, Denmark. Here we present a new shoreline displacement curve spanning the period between c. 11 700 and 7700 cal. a BP and built upon the Nørrekær Enge data and data from seven other boreholes and excavations from the Limfjord region. A previous shoreline displacement curve for this region suggested a very rapid relative sea‐level rise of 3 to 5 m 100 a^?1 whereas this new curve suggests a much slower rise of around 1 m 100 a^?1, similar to global rates.     

Equilibrium H/H fractionations in organic molecules. II: Linear alkanes, alkenes, ketones, carboxylic acids, esters, alcohols and ethers

Equilibrium ²H/¹H fractionation factors (α_eq) for various H positions in alkanes, alkenes, ketones, carboxylic acids, esters, alcohols, and ethers were calculated between 0 and 100 °C using vibrational frequencies from ab initio QM calculations (B3LYP/6-311G**). Results were then corrected using a temperature-dependent linear calibration curve based on experimental data for H_α in ketones (Wang et al., 2009). The total uncertainty in reported α_eq values is estimated at 10–20‰. The effects of functional groups were found to increase the value of α_eq for H next to electron-donating groups, e.g. OR, OH or O(CO)R, and to decrease the value of α_eq for H next to electron-withdrawing groups, e.g. (CO)R or (CO)OR. Smaller but significant functional group effects are also observed for H_β and sometimes H_γ. By summing over individual H positions, we estimate the equilibrium fractionation relative to water to be −90‰ to −70‰ for n-alkanes and around −100‰ for pristane and phytane. The temperature dependence of these fractionations is very weak between 0 and 100 °C. Our estimates of α_eq agree well with field data for thermally mature hydrocarbons (δ²H values between −80‰ and −110‰ relative to water). Therefore the observed δ²H increase of individual hydrocarbons and the disappearance of the biosynthetic δ²H offset between n-alkyl and linear isoprenoid lipids during maturation of organic matter can be confidently attributed to H exchange towards an equilibrium state. Our results also indicate that many n-alkyl lipids are biosynthesized with δ²H values that are close to equilibrium with water. In these cases, constant down-core δ²H values for n-alkyl lipids cannot be reliably used to infer a lack of isotopic exchange.     

Lower crustal intrusions beneath the southern Baikal Rift Zone: Evidence from full-waveform modelling of wide-angle seismic data

The Cenozoic Baikal Rift Zone (BRZ) is situated in south-central Siberia in the suture between the Precambrian Siberian Platform and the Amurian plate. This more than 2000-km long rift zone is composed of several individual basement depressions and half-grabens with the deep Lake Baikal at its centre. The BEST (Baikal Explosion Seismic Transect) project acquired a 360-km long, deep seismic, refraction/wide-angle reflection profile in 2002 across southern Lake Baikal. The data from this project is used for identification of large-scale crustal structures and modelling of the seismic velocities of the crust and uppermost mantle. Previous interpretation and velocity modelling of P-wave arrivals in the BEST data has revealed a multi layered crust with smooth variation in Moho depth between the Siberian Platform (41 km) and the Sayan-Baikal fold belt (46 km). The lower crust exhibits normal seismic velocities around the rift structure, except for beneath the rift axis where a distinct 50–80-km wide high-velocity anomaly (7.4–7.6 ± 0.2 km/s) is observed. Reverberant or “ringing” reflections with strong amplitude and low frequency originate from this zone, whereas the lower crust is non-reflective outside the rift zone. Synthetic full-waveform reflectivity modelling of the high-velocity anomaly suggests the presence of a layered sequence with a typical layer thickness of 300–500 m coinciding with the velocity anomaly. The P-wave velocity of the individual layers is modelled to range between 7.4 km/s and 7.9 km/s. We interpret this feature as resulting from mafic to ultra-mafic intrusions in the form of sills. Petrological interpretation of the velocity values suggests that the intrusions are sorted by fractional crystallization into plagioclase-rich low-velocity layers and pyroxene- and olivine-rich high-velocity layers. The mafic intrusions were probably intruded into the ductile lower crust during the main rift phase in the Late Pliocene. As such, the intrusive material has thickened the lower crust during rifting, which may explain the lack of Moho uplift across southern BRZ.     

Using the pseudospectral method on curved grids for 2D elastic forward modelling1

When applying the conventional Fourier pseudospectral method (FSM) on a Cartesian grid that has a sufficient size to propagate a pulse, spurious diffractions from the staircase representation of the curved interfaces appear in the wavefield. It is demonstrated that these non-physical diffractions can be eliminated by using curved grids that conform to all the interfaces of the subsurface. Methods for solving the 2D acoustic wave equation using such curved grids have been published previously by the authors. Here the extensions to the full 2D elastic wave equations are presented. The curved grids are generated by using the so-called multiblock strategy which is a well-known concept in computational fluid dynamics. In principle the sub-surface is divided into a number of contiguous subdomains. A separate grid is generated for each subdomain patching the grid lines across domain boundaries to obtain a globally continuous grid. Using this approach, even configurations with pinch outs can be handled. The curved grid is taken to constitute a generalized curvilinear coordinate system. Thus, the elastic equations have to be written in a curvilinear frame before applying the numerical scheme. The method implies that twice the number of spatial derivatives have to be evaluated compared to the conventional FSM on a Cartesian grid. However, it is demonstrated that the extra terms are more than compensated for by the fewer grid points needed in the curved approach.     

An application of least-squares inverse analysis in kinetic interpretations of hydrous pyrolysis experiments

A least-squares inverse method is applied to the estimation of optimum kinetic parameters with statistical error bounds from concentration data obtained in isothermal hydrous pyrolysis experiments. The inverse method requires the specification of a data-parameter relationship (e.g., classical kinetic theory), the prior covariance matrices of data and parameter errors, as well as the prior central estimates of data and parameters. The reaction scheme considered is the common case of kerogen breakdown by Gaussian-weighted independent parallel first-order reactions and bitumen cracking by a single first-order reaction. The nonlinearity of the problem is reduced by a logarithmic transformation, which suggests a parameterization in terms of logarithmic concentrations, activation energies, and logarithmic Arrhenius factors. The linearized variance analysis is valid for the case studied, and the posterior covariance matrix reveals which parameters are constrained by the data. We find that the statistical errors in the average activation energy and the associated Arrhenius factor are strongly correlated. Hence, the parameters which determine the temperature dependence of the reaction rate have not been resolved independently. Furthermore, the kinetic results are very sensitive to the presence of a distribution of activation energies in kerogen breakdown. This distribution is not constrained by the data. As a consequence, neglecting the consideration of distributions of activation energies results in activation parameter values which are much too low. This is the major reason for the commonly encountered discrepancy between kinetic parameter values obtained from hydrous pyrolysis and micropyrolysis experiments, respectively.