Fe–Mg diffusion in olivine I: experimental determination between 700 and 1,200<Emphasis Type="Bold">°</Emphasis>C as a function of composition,crystal orientation and oxygen fugacity

We have determined Fe–Mg diffusion coefficients in olivines from different sources (Nanga Parbat, Pakistan and San Carlos, Arizona, USA) at atmospheric pressure as a function of composition, oxygen fugacity (10⁻⁵–10⁻¹² Pa) and temperature (700–1200°C) using thin films produced by pulsed laser deposition and RBS to analyze the concentration profiles. We have characterized the nano-scale structure and composition of the thin films annealed at various conditions and shown that the nature of the film (e.g. crystallinity, wetting behavior) depends strongly on the annealing conditions. If these variations are not taken into account in the form of boundary conditions for modeling the diffusion profiles, artifacts would result in the diffusion data. The diffusion coefficients obtained from 75 experiments reveal that (i) between fO₂ of 10⁻⁵ and 10⁻¹⁰ Pa, diffusion along all three principal crystallographic directions in olivine, [100], [010] and [001], are described by a constant activation energy of ∼200 kJ/mol, precluding any temperature dependence of diffusion anisotropy and change of mechanism of diffusion at temperatures between 950 and 1200°C, (ii) diffusion coefficients increase with oxygen fugacity at fO₂ > 10⁻¹⁰ Pa, with an fO₂ exponent that lies between 1/4 and 1/7, and (iii) at fO₂ below 10⁻¹⁰ Pa, and consequently at temperatures below ∼900°C, diffusion becomes weakly dependent/independent of fO₂, indicating a change of diffusion mechanism. Activation energy of diffusion at these conditions is slightly higher, ∼220 kJ/mol. The data, including the change of mechanism, are analyzed in terms of point defect chemistry in Part II of this work to derive an equation that allows calculation of diffusivities in olivine over its entire field of stability. Availability of directly measured data at temperatures down to 700°C imply that for the first time diffusion coefficients can be interpolated, rather than extrapolated, for modeling most natural systems.     

Tropospheric parameters: combination studies based on homogeneous VLBI and GPS data

The combination of tropospheric parameters derived from different space-geodetic techniques has not been of large interest in geodesy so far. However, due to the high correlation between station coordinates and tropospheric parameters, the latter should not be neglected in combinations. This paper deals with the comparison and combination of tropospheric parameters derived from global positioning system (GPS) and very long baseline interferometry (VLBI) observations stemming from a 15-day campaign of continuous VLBI observations in 2002 (CONT02). The observation data of both techniques were processed homogeneously to avoid systematic differences between the solutions. We compared the tropospheric estimates of GPS and VLBI at eight co-location sites and found a very good agreement in the temporal behavior of the tropospheric zenith path delays (ZPD), reflected by correlation factors up to 0.98. Following this, a combination of the tropospheric parameters was performed. We demonstrate that the combination of tropospheric parameters leads to a stabilization of combined station networks. This becomes visible in the improvement of the repeatabilities of the station height components. Furthermore, the potential use of independent data from water vapor radiometers (WVRs) to validate space-technique-derived tropospheric parameters was investigated. Correlation coefficients of 0.95 or better were estimated between the tropospheric parameters of WVR and GPS or VLBI. Additionally, the utility of the tropospheric parameters for validation of local tie vectors was investigated. Both tropospheric zenith delays and tropospheric gradients were found to be very suitable to validate the height component and the horizontal components of the local tie, respectively.     

Tourmaline Reference Materials for the In Situ Analysis of Oxygen and Lithium Isotope Ratio Compositions

Three tourmaline reference materials sourced from the Harvard Mineralogical and Geological Museum (schorl 112566, dravite 108796 and elbaite 98144), which are already widely used for the calibration of in situ boron isotope measurements, are characterised here for their oxygen and lithium isotope compositions. Homogeneity tests by secondary ion mass spectrometry (SIMS) showed that at sub‐nanogram test portion masses, their ¹⁸O/¹⁶O and ⁷Li/⁶Li isotope ratios are constant within ± 0.27‰ and ± 2.2‰ (1s), respectively. The lithium mass fractions of the three materials vary over three orders of magnitude. SIMS homogeneity tests showed variations in ⁷Li/²⁸Si between 8% and 14% (1s), which provides a measure of the heterogeneity of the Li contents in these three materials. Here, we provide recommended values for δ¹⁸O, Δ’¹⁷O and δ⁷Li for the three Harvard tourmaline reference materials based on results from bulk mineral analyses from multiple, independent laboratories using laser‐ and stepwise fluorination gas mass spectrometry (for O), and solution multi‐collector inductively coupled plasma‐mass spectroscopy (for Li). These bulk data also allow us to assess the degree of inter‐laboratory bias that might be present in such data sets. This work also re‐evaluates the major element chemical composition of the materials by electron probe microanalysis and investigates these presence of a chemical matrix effect on SIMS instrumental mass fractionation with regard to δ¹⁸O determinations, which was found to be < 1.6‰ between these three materials. The final table presented here provides a summary of the isotope ratio values that we have determined for these three materials. Depending on their starting mass, either 128 or 512 splits have been produced of each material, assuring their availability for many years into the future.     

Fe–Mg diffusion in olivine II: point defect chemistry,change of diffusion mechanisms and a model for calculation of diffusion coefficients in natural olivine

Analysis of existing data and models on point defects in pure (Fe,Mg)-olivine (Phys Chem Miner 10:27–37,1983; Phys Chem Miner 29:680–694, 2002) shows that it is necessary to consider thermodynamic non-ideality of mixing to adequately describe the concentration of point defects over the range of measurement. In spite of different sources of uncertainties, the concentrations of vacancies in octahedral sites in (Fe,Mg)-olivine are on the order of 10⁻⁴ per atomic formula unit at 1,000–1,200 °C according to both the studies. We provide the first explicit plots of vacancy concentrations in olivine as a function of temperature and oxygen fugacity according to the two models. It is found that in contrast to absolute concentrations at ∼1,100 °C and dependence on fO₂, there is considerable uncertainty in our knowledge of temperature dependence of vacancy concentrations. This needs to be considered in discussing the transport properties such as diffusion coefficients. Moreover, these defect models in pure (Fe,Mg)-olivine need to be extended by considering aliovalent impurities such as Al, Cr to describe the behavior of natural olivine. We have developed such a formulation, and used it to analyze the considerable database of diffusion coefficients in olivine from Dohmen et al. (Phys Chem Miner this volume, 2007) (Part - I) and older data in the literature. The analysis documents unequivocally for the first time a change of diffusion mechanism in a silicate mineral—from the transition metal extrinsic (TaMED) to the purely extrinsic (PED) domain, at fO₂ below 10⁻¹⁰  Pa, and consequently, temperatures below 900 °C. The change of diffusion mechanism manifests itself in a change in fO₂ dependence of diffusivity and a slight change in activation energy of diffusion—the activation energy increases at lower temperatures. These are consistent with the predictions of Chakraborty (J Geophys Res 102(B6):12317–12331, 1997). Defect formation enthalpies in the TaMED regime (distinct from intrinsic defect formation) lie between −66 and + 15 kJ/mol and migration energies of octahedral cations in olivine are most likely ∼ 260 kJ/mol, consistent with previous inferences (Phys Chem 207:147–162, 1998). Plots are shown for diffusion at various constant fO₂ as well as along fO₂ buffers, to highlight the difference in behavior between the two. Considering all the diffusion data and constraints from the point defect models, (Fe–Mg) diffusion in olivine along [001] is best described by the Master equations: (1) At oxygen fugacities greater than 10⁻¹⁰ Pa:

Interacting Loop Current variability and Mississippi River discharge over the past 400 kyr

The Loop Current mediating the oceanic heat and salt flux from the Caribbean Sea into the Atlantic Ocean and its interference with the Mississippi River discharge are critical for both the regional climate in the Gulf of Mexico area and the water vapor transport towards high northern latitudes. We present a 400-kyr record of sea surface temperature and local surface salinity from the northeastern Gulf of Mexico (IMAGES core MD02-2575) approximated from combined planktonic foraminiferal δ¹⁸O and Mg/Ca, which reflects the temporal dynamics of the Loop Current and its relationship to both varying Mississippi discharge and evolution of the Western Hemisphere Warm pool. The reconstructed sea surface temperature and salinity reveal glacial/interglacial amplitudes that are significantly larger than in the Western Hemisphere Warm pool. Sea surface freshening is observed during the extreme cool periods of Marine Isotope Stages 2, 8, and 10, caused by the strengthened Mississippi discharge which spread widely across the Gulf favored by the less established Loop Current. Interglacial and interstadial sea-surface conditions, instead, point to a strengthened, northward flowing Loop Current in line with the northward position of the Intertropical Convergence Zone, allowing northeastern Gulf of Mexico surface hydrographic conditions to approach those of the Caribbean. At these times, the Mississippi discharge was low and deflected westward, promoted by the extended Loop Current. Previously described deglacial megadischarge events further to the west did not affect the northeastern Gulf of Mexico hydrography, implying that meltwater routing from the Laurentide Ice Sheet via the Mississippi River is unlikely to have affected Atlantic Meridional Overturning Circulation.     

Quantifying river incision into low‐relief surfaces using local and catchment‐wide 10Be denudation rates

Relief generation in non‐glaciated regions is largely controlled by river incision into bedrock but datable fluvial terraces that allow quantifying incision rates are not always present. Here we suggest a new method to determine river incision rates in regions where low‐relief surfaces are dissected by streams. The approach consists of three steps and requires the ¹⁰Be concentrations of a stream sediment sample and a regolith sample from the low‐relief surface. In the first step, the spatial distribution of ¹⁰Be surface concentrations in the given catchment is modelled by assuming that denudation rates are controlled by the local hillslope angles. The slope–denudation rate relation for this catchment is then quantified by adjusting the relation between slope angle and denudation rate until the average ¹⁰Be concentration in the model is equal to the one measured in the stream sediment sample. In the second step, curved swath profiles are used to measure hillslope angles adjacent to the main river channel. Third, the mean slope angle derived from these swath profiles and the slope–denudation relation are used to quantify the river incision rate (assuming that the incision rate equals the denudation rate on adjacent hillslopes). We apply our approach to two study areas in southern Tibet and central Europe (Black Forest). In both regions, local ¹⁰Be denudation rates on flat parts of the incised low‐relief surface are lower than catchment‐wide denudation rates. As the latter integrate across the entire landscape, river incision rates must exceed these spatially averaged denudation rates. Our approach yields river incision rates between ~15 and ~30 m/Ma for the Tibetan study area and incision rates of ~70 to ~100 m/Ma in the Black Forest. Taking the lowering of the low‐relief surfaces into account suggests that relief in the two study areas increases at rates of 10–20 and 40–70 m/Ma, respectively. Copyright © 2018 John Wiley & Sons, Ltd.     

Identification of extreme storm surges with high-impact potential along the German North Sea coastline

Planning and design of coastal protection rely on information about the probabilities of very severe storm tides and the possible changes that may occur in the course of climate change. So far, this information is mostly provided in the form of high percentiles obtained from frequency distributions or return values. More detailed information and assessments of events that may cause extreme damages or have extreme consequences at the coast are so far still unavailable. We describe and compare two different approaches that may be used to identify highly unlikely but still physically possible and plausible events from model simulations. Firstly, in the case when consistent wind and tide-surge data are available, different metrics such as the height of the storm surge can be derived directly from the simulated water levels. Secondly, in cases where only atmospheric data are available, the so called effective wind may be used. The latter is the projection of the horizontal wind vector on that direction which is most effective in producing surges at the coast. Comparison of events identified by both methods show that they can identify extreme events but that knowledge of the effective wind alone does not provide sufficient information to identify the highest storm surges. Tracks of the low-pressure systems over the North Sea need to be investigated to find those cases, where the duration of the high wind is too short to induce extreme storm tides. On the other hand, factors such as external surges or variability in mean sea level may enhance surge heights and are not accounted for in estimates based on effective winds only. Results from the analysis of an extended data set suggest that unprecedented storm surges at the German North Sea coast are possible even without taking effects from rising mean sea level into account. The work presented is part of the ongoing project “Extreme North Sea Storm Surges and Their Consequences” (EXTREMENESS) and represents the first step towards an impact assessment for very severe storm surges which will serve as a basis for development of adaptation options and evaluation criteria.     

Sparsity‐enhanced wavelet deconvolution

We propose a three‐step bandwidth enhancing wavelet deconvolution process, combining linear inverse filtering and non‐linear reflectivity construction based on a sparseness assumption. The first step is conventional Wiener deconvolution. The second step consists of further spectral whitening outside the spectral bandwidth of the residual wavelet after Wiener deconvolution, i.e., the wavelet resulting from application of the Wiener deconvolution filter to the original wavelet, which usually is not a perfect spike due to band limitations of the original wavelet. We specifically propose a zero‐phase filtered sparse‐spike deconvolution as the second step to recover the reflectivity dominantly outside of the bandwidth of the residual wavelet after Wiener deconvolution. The filter applied to the sparse‐spike deconvolution result is proportional to the deviation of the amplitude spectrum of the residual wavelet from unity, i.e., it is of higher amplitude; the closer the amplitude spectrum of the residual wavelet is to zero, but of very low amplitude, the closer it is to unity. The third step consists of summation of the data from the two first steps, basically adding gradually the contribution from the sparse‐spike deconvolution result at those frequencies at which the residual wavelet after Wiener deconvolution has small amplitudes. We propose to call this technique “sparsity‐enhanced wavelet deconvolution”. We demonstrate the technique on real data with the deconvolution of the (normal‐incidence) source side sea‐surface ghost of marine towed streamer data. We also present the extension of the proposed technique to time‐varying wavelet deconvolution.     

Localized shock-induced melting of sandstone at low shock pressures (<17.5 GPa): An experimental study

Shock-induced recovery experiments were performed to investigate melt formation in porous sandstones in the low shock pressure regime between 2.5 and 17.5 GPa. The sandstone shocked at 2.5 and 5 GPa is characterized by pore closure, fracturing of quartz (Qtz), and compression and deformation of phyllosilicates; no melting was observed. At higher pressures, five different types of melts were generated around pores and alongside fractures in the sandstone. Melting of kaolinite (Kln), illite (Ill), and muscovite (Ms) starts at 7.5, 12, and 15 GPa, respectively. The larger the amount of water in these minerals (Kln ~14 wt%, Ill ~6–10 wt%, and Ms ~4 wt% H₂O), the higher the shock compressibility and the lower the shock pressure required to induce melting. Vesicles in the almost dry silicate glasses attest to the loss of structural water during the short shock duration of the experiment. The compositions of the phyllosilicate-based glasses are identical to the composition of the parental minerals or their mixtures. Thus, this study has demonstrated that phyllosilicates in shocked sandstone undergo congruent melting during shock loading. In experiments at 10 GPa and higher, iron melt from the driver plate was injected into the phyllosilicate melts. During this process, Fe is partitioned from the metal droplets into the surrounding silicate melts, which induced unmixing of silicate melts with different chemical properties (liquid immiscibility). At pressures between 7.5 and 15 GPa, a pure SiO₂ glass was formed, which is located as short and thin bands within Qtz grains. These bands were shown to contain tiny crystals of experimentally generated stishovite.