Stable isotope profiles (Ca,O, C) through modern brachiopod shells of T. septentrionalis and G. vitreus: Implications for calcium isotope paleo-ocean chemistry

Brachiopod shells are widely used as an archive to reconstruct elemental and isotopic composition of seawater. Studies, focused on oxygen and carbon isotopes over the last decades, are increasingly extending to the emerging calcium isotope system. To date, only little attention has been paid to test the reliability of fossil brachiopods on their modern counterparts.In this context, the present study investigates two modern brachiopods, Terebratulina septentrionalis (eastern Canada, 5–30 m depth, 7.1 °C seasonal temperature variation, two-layer shell) and Gryphus vitreus (northern Mediterranean, 200 m depth, constant all-year round temperature, three-layer shell). Both species were sampled along the ontogenetic growth direction and calcium, oxygen, and carbon isotopes as well as elemental concentration were measured. Calcium isotopes were analyzed on TIMS. The elemental composition was analyzed by LA-ICP-MS and ICP-AES.The results indicate an intra-specimen δ^44/40Ca variation ranging from 0.16 to 0.33‰, pointing to a fairly homogenous distribution of calcium isotopes in brachiopod shells. However, in the light of the suggested 0.7‰ increase in calcium isotopes over the Phanerozoic such intra-specimen variations constrain ocean reconstruction. δ^44/40Ca values of T. septentrionalis do not seem to be affected by growth rate. Calcium isotopic values of G. vitreus are heavy in the central part of the shell and trend towards lighter values in peripheral areas approaching the maximum isotopic composition of T. septentrionalis. The maximum inter-species δ^44/40Ca difference of 0.62‰ between T. septentrionalis and G. vitreus indicates that care should be taken when using different taxa, species with different strontium content or brachiopods with specialized shell structure, such as G. vitreus, for ocean water reconstruction in terms of Ca isotopic composition. T. septentrionalis may record Ca isotopic fractionation related to seasonal seawater temperature variations in its shell but this is difficult to resolve at the current analytical precision. Average δ¹⁸O-derived temperatures of the two investigated species are close to on-site measured temperatures.     

An evaluation of the surface radiation budget over North America for a suite of regional climate models against surface station observations

Components of the surface radiation budget (SRB) [incoming shortwave radiation (ISR) and downwelling longwave radiation (DLR)] and cloud cover are assessed for three regional climate models (RCM) forced by analysed boundary conditions, over North America. We present a comparison of the mean seasonal and diurnal cycles of surface radiation between the three RCMs, and surface observations. This aids in identifying in what type of sky situation simulated surface radiation budget errors arise. We present results for total-sky conditions as well as overcast and clear-sky conditions separately. Through the analysis of normalised frequency distributions we show the impact of varying cloud cover on the simulated and observed surface radiation budget, from which we derive observed and model estimates of surface cloud radiative forcing. Surface observations are from the NOAA SURFRAD network. For all models DLR all-sky biases are significantly influenced by cloud-free radiation, cloud emissivity and cloud cover errors. Simulated cloud-free DLR exhibits a systematic negative bias during cold, dry conditions, probably due to a combination of omission of trace gas contributions to the DLR and a poor treatment of the water vapor continuum at low water vapor concentrations. Overall, models overestimate ISR all-sky in summer, which is primarily linked to an underestimate of cloud cover. Cloud-free ISR is relatively well simulated by all RCMs. We show that cloud cover and cloud-free ISR biases can often compensate to result in an accurate total-sky ISR, emphasizing the need to evaluate the individual components making up the total simulated SRB.     

Isotropic and anisotropic correlations in turbulent wind speed data

The correlations in turbulent wind speed data from the open ocean are studied. They are calculated as Fourier transforms of the spectraldensities, which are computed from Fourier transforms of the measured windspeed components. All correlations are found to decay within a few seconds.It is shown that the spectra are most efficiently calculated using data sections whose length does not exceed the observed correlation decay time.Longer runs include more random noise without containing more information.The ratio of the along-wind to transverse spectral levels is investigatedand found to be in excellent agreement with the assumption of isotropy inthe inertial wave number range.     

An Empirical Method to Derive Ocean Waves From Second-Order Bragg Scattering: Prospects and Limitations

High-frequency (HF) radar wave processing is often based on the inversion of the Barrick-Weber equations, introduced in 1977. This theory reaches its limitations if the length of the Bragg-scattering wave raises to the order of the significant waveheight, because some assumptions are no longer met. In this case, the only solution is moving to lower radar frequencies, which is not possible or desirable in all cases. This paper describes work on an empirical solution which intends to overcome this limitation. However, during high sea state, the first-order Bragg peaks sometimes could not be clearly identified which avoids the access to the second-order sidebands. These cases cause problems to the algorithm which have not been solved yet and currently limit the maximum significant waveheight to about the same values as reported for the integral inversion method. The regression parameters of the empirical solution calibrated from the European Radar Ocean Sensing (EuroROSE) data set are constant values for the complete experiment and when applied to the HF radar data they reconstruct the measurements by a colocated wave buoy quite well. When including a radar-frequency-dependent scaling factor to the regression parameters, the new algorithm can also be used at different radar frequencies. The second-order frequency bands used for the empirical solution are sometimes disturbed by radio interference and ship echoes. Investigations are presented to identify and solve these situations     

In situ hydrocarbon concentrations from pressurized cores in surface sediments, Northern Gulf of Mexico

Two newly developed coring devices, the Multi-Autoclave-Corer and the Dynamic Autoclave Piston Corer were deployed in shallow gas hydrate-bearing sediments in the northern Gulf of Mexico during research cruise SO174 (Oct–Nov 2003). For the first time, they enable the retrieval of near-surface sediment cores under ambient pressure. This enables the determination of in situ methane concentrations and amounts of gas hydrate in sediment depths where bottom water temperature and pressure changes most strongly influence gas/hydrate relationships. At seep sites of GC185 (Bush Hill) and the newly discovered sites at GC415, we determined the volume of low-weight hydrocarbons (C₁ through C₅) from nine pressurized cores via controlled degassing. The resulting in situ methane concentrations vary by two orders of magnitudes between 0.031 and 0.985 mol kg^− 1 pore water below the zone of sulfate depletion. This includes dissolved, free, and hydrate-bound CH₄. Combined with results from conventional cores, this establishes a variability of methane concentrations in close proximity to seep sites of five orders of magnitude. In total four out of nine pressure cores had CH₄ concentrations above equilibrium with gas hydrates. Two of them contain gas hydrate volumes of 15% (GC185) and 18% (GC415) of pore space. The measurements prove that the highest methane concentrations are not necessarily related to the highest advection rates. Brine advection inhibits gas hydrate stability a few centimeters below the sediment surface at the depth of anaerobic oxidation of methane and thus inhibits the storage of enhanced methane volumes. Here, computerized tomography (CT) of the pressure cores detected small amounts of free gas. This finding has major implications for methane distribution, possible consumption, and escape into the bottom water in fluid flow systems related to halokinesis.     

Thermodynamic mixing behavior of synthetic Ca-Tschermak–diopside pyroxene solid solutions: I. Volume and heat capacity of mixing

The unite cell parameters and heat capacities of a series of synthetic clinopyroxenes on the join Ca-Tschermak (CaTs)−diopside (Di) were measured using X-ray powder diffraction and calorimetric methods, respectively. The volume of mixing at 298 K shows a negative asymmetric deviation from ideality. A two-parameter Margules fit to the data yields W _CaTs−Di ^V = −0.29 ± 0.11 cm³ mol⁻¹ and W _Di−CaTs ^V = −1.14 ± 0.14 cm³ mol⁻¹. Heat capacities were determined between 5 and 923 K by heat-pulse at 5−302 K and differential-scanning calorimetry at 143−923 K. The precision of the low and high temperature C _p data is better than ±1%. Polynomials of the form C _p = a + bT ^−1/2 + cT ⁻² + dT ⁻³ were fitted to the C _p data in the temperature range between 250 and 925 K. Thermal entropy values [S ₂₉₈ − S ₀] and [S ₉₀₀ −S ₀] as well as enthalpies [H ₂₉₈ − H ₀] and [H ₉₀₀ − H ₀] were calculated for all members of the solid solution series. No significant deviation from ideal mixing behavior was observed.     

Justification of the Inertial Dissipation Technique in Anisotropic Mean Flow

The inertial dissipation technique has been successfully employed for many years to measure the wind stress, especially over the open ocean. This method is based on Kolmogorov's theoretical prediction of universality in the inertial wavenumber range. The theory was developed under the assumption of locally isotropic turbulence, and the dissipation technique has been criticized as lacking justification in a boundary-layer shear flow. In this paper, Kolmogorov's theory is explicitly applied to the anisotropic conditions prevailing in the atmosphere. It is shown that the inertial dissipation method relies on the homogeneity and isotropy of the spectrum _ii(k) for k in the inertial range. This is a weaker condition than Kolmogorov's assumption of isotropy of the correlation function B_ij(r). In high-Reynolds-number shear flows, isotropy of _ii(k) is realized to a good approximation, whereas isotropy of B_ij(r) is not. Some consequences for the experimental implementation are discussed; in particular, sampling times (block lengths) not exceeding the order of the eddy life time are recommended in the calculation of spectra.     

Overcoming Challenges Associated with the Analysis of Nacre by Atom Probe Tomography

In this study atom probe tomography was used to study nacre, an important biocomposite material that is challenging to prepare and analyse by atom probe and, when successful, yields data that is challenging to interpret. It was found that these challenges mainly arise from the insulating and heterogeneous nano‐scale properties of nacre. We outline our current best practice for preparing and running atom probe tips, such as using a low acceleration voltage (< 3 kV) and current (≤ 50 pA) to avoid damage to the microstructure, and using transmission electron microscopy to confirm that the region of interest is located close to the apex of the atom probe tip. Optimisation of the preparation parameters led to several successful atom probe experiments, with one of the data sets containing part of an organic membrane and others showing organic inclusions within the reconstruction.