The Influence of Path Corrections and a Three-dimensional Global <Emphasis Type="Italic">P</Emphasis>-wave Velocity Model on Seismic Event Location in Kazakhstan

We relocate 81 large nuclear explosions that were detonated at the Balapan and Degelen Mountain subregions of the Semipalatinsk test site in Kazakhstan during the years 1978 to 1989. The absolute locations of these explosions are available, as well as very accurate estimates of their origin times. This ground truth information allows us to perform a detailed analysis of location capability. We use a sparse network of stations with highly accurate first arrival picks measured using a waveform cross-correlation method. These high quality data facilitate very accurate location estimates with only a few phases per event. We contrast two different approaches: 1) a calibration-based approach, where we achieve improved locations by using path corrections, and 2) a model-based approach, where we achieve improved locations by relocating in a recently published global 3-D P-velocity model. Both methods result in large improvements in accuracy of the obtained absolute locations, compared to locations obtained in a 1-D reference earth model (ak135). The calibration-based approach gives superior results for this test site, in particular when arrival times from regional stations are included. Estimated locations remain well within a 1000 km² region surrounding the ground truth locations when the path corrections for the Balapan and Degelen Mountain subregions are interchanged, but even for the short separation between these two regions, we find variations in the path corrections that cause systematic mislocations. The model-based approach also results in substantially reduced mislocation distances and has the distinct advantage that it is, in principle, transportable to other source regions around the world.     

Titanium in subduction zone fluids: First insights from abinitio molecular metadynamics simulations

The preferential incorporation of High-Field-Strength Elements (HFSE) in rutile (TiO₂), combined with its supposed stability in subduction zone settings, make it an ideal candidate to explain the low HFSE concentrations in subduction-derived magmas. The solubility behaviour of rutile is key to these arguments, but at present experimental and field-based evidence are contradictory.We have used abinitio molecular (meta)dynamics to investigate the coordination environment of Ti(IV) in pure water at 300 and 1000 K and densities ranging from 900-1260 kg m⁻³ (approximate pressures 0.9-3.6 GPa). In all high temperature simulations, the long-range structure of the solvent indicates a breakdown of the hydrogen bonding network as expected for supercritical water. The five-fold coordination of titanium to water is energetically most favourable in aqueous fluids at room temperature and pressure, separated from four and six-fold configurations by ∼175 and ∼200 kJ mol⁻¹, respectively. The average first shell Ti-O distance is 2.00 Å, in excellent agreement with bond lengths obtained from experiments. At similar densities and 1000 K, titanium is on average six-fold coordinate with water, and shows some degree of water dissociation in the first hydration shell. This coordination environment is remarkably persistent with increasing density from 1021 to 1260 kg m⁻³ at constant temperature (1000 K). At lower densities, however, (900 kg m⁻³ at 1000 K), the coordination with first shell water molecules is less than five. The observed coordination changes could promote association of titanium with peralkaline or peraluminous domains in the aqueous fluid, and thereby explain field-and laboratory based evidence of enhanced HFSE concentrations.This study demonstrates that abinitio molecular dynamics has considerable potential to access details of element behaviour in aqueous fluids at geologically relevant conditions that are impossible to examine otherwise. Changes in the solvent structure due to density variations lead to differences in solvent behaviour allowing access to new domains for fluid-solid interaction. Moreover, changes in the solvent structure are strongly linked to the effectiveness of element solvation.     

A map-view restoration of the Alpine-Carpathian-Dinaridic system for the Early Miocene

A map-view palinspastic restoration of tectonic units in the Alps, Carpathians and Dinarides reveals the plate tectonic configuration before the onset of Miocene to recent deformations. Estimates of shortening and extension from the entire orogenic system allow for a semi-quantitative restoration of translations and rotations of tectonic units during the last 20 Ma. Our restoration yielded the following results: (1) The Balaton Fault and its eastern extension along the northern margin of the Mid-Hungarian Fault Zone align with the Periadriatic Fault, a geometry that allows for the eastward lateral extrusion of the Alpine-Carpathian-Pannonian (ALCAPA) Mega-Unit. The Mid-Hungarian Fault Zone accommodated simultaneous strike-perpendicular shortening and strike-slip movements, concomitant with strike-parallel extension. (2) The Mid-Hungarian Fault Zone is also the locus of a former plate boundary transforming opposed subduction polarities between Alps (including Western Carpathians) and Dinarides. (3) The ALCAPA Mega-Unit was affected by 290 km extension and fits into an area W of present-day Budapest in its restored position, while the Tisza-Dacia Mega-Unit was affected by up to 180 km extension during its emplacement into the Carpathian embayment. (4) The external Dinarides experienced Neogene shortening of over 200 km in the south, contemporaneous with dextral wrench movements in the internal Dinarides and the easterly adjacent Carpatho-Balkan orogen. (5) N–S convergence between the European and Adriatic plates amounts to some 200 km at a longitude of 14° E, in line with post-20 Ma subduction of Adriatic lithosphere underneath the Eastern Alps, corroborating the discussion of results based on high-resolution teleseismic tomography.The displacement of the Adriatic Plate indenter led to a change in subduction polarity along a transect through the easternmost Alps and to substantial Neogene shortening in the eastern Southern Alps and external Dinarides. While we confirm that slab-pull and rollback of oceanic lithosphere subducted beneath the Carpathians triggered back-arc extension in the Pannonian Basin and much of the concomitant folding and thrusting in the Carpathians, we propose that the rotational displacement of this indenter provided a second important driving force for the severe Neogene modifications of the Alpine-Carpathian-Dinaridic orogenic system.     

Experimental and computational study of trace element distribution between orthopyroxene and anhydrous silicate melt: substitution mechanisms and the effect of iron

Although orthopyroxene (Opx) is present during a wide range of magmatic differentiation processes in the terrestrial and lunar mantle, its effect on melt trace element contents is not well quantified. We present results of a combined experimental and computational study of trace element partitioning between Opx and anhydrous silicate melts. Experiments were performed in air at atmospheric pressure and temperatures ranging from 1,326 to 1,420°C in the system CaO–MgO–Al₂O₃–SiO₂ and subsystem CaO–MgO–SiO₂. We provide experimental partition coefficients for a wide range of trace elements (large ion lithophile: Li, Be, B, K, Rb, Sr, Cs, Ba, Th, U; rare earth elements, REE: La, Ce, Nd, Sm, Y, Yb, Lu; high field strength: Zr, Nb, Hf, Ta, Ti; transition metals: Sc, V, Cr, Co) for use in petrogenetic modelling. REE partition coefficients increase from $ D_{\text{La}}^{{\text{Opx}} {\hbox{-}} {\text{melt}}} \sim 0.0005 Although orthopyroxene (Opx) is present during a wide range of magmatic differentiation processes in the terrestrial and lunar mantle, its effect on melt trace element contents is not well quantified. We present results of a combined experimental and computational study of trace element partitioning between Opx and anhydrous silicate melts. Experiments were performed in air at atmospheric pressure and temperatures ranging from 1,326 to 1,420°C in the system CaO–MgO–Al₂O₃–SiO₂ and subsystem CaO–MgO–SiO₂. We provide experimental partition coefficients for a wide range of trace elements (large ion lithophile: Li, Be, B, K, Rb, Sr, Cs, Ba, Th, U; rare earth elements, REE: La, Ce, Nd, Sm, Y, Yb, Lu; high field strength: Zr, Nb, Hf, Ta, Ti; transition metals: Sc, V, Cr, Co) for use in petrogenetic modelling. REE partition coefficients increase from $ D_{\text{La}}^{{\text{Opx}} {\hbox{-}} {\text{melt}}} \sim 0.0005 $ D_{\text{La}}^{{\text{Opx}} {\hbox{-}} {\text{melt}}} \sim 0.0005 to $ D_{\text{Lu}}^{{{\text{Opx}} {\hbox{-}} {\text{melt}}}} \sim 0.109 $ D_{\text{Lu}}^{{{\text{Opx}} {\hbox{-}} {\text{melt}}}} \sim 0.109 , D values for highly charged elements vary from $ D_{\text{Th}}^{{{\text{Opx}} {\hbox{-}} {\text{melt}}}} \sim 0.0026 $ D_{\text{Th}}^{{{\text{Opx}} {\hbox{-}} {\text{melt}}}} \sim 0.0026 through $ D_{\text{Nb}}^{{{\text{Opx}} {\hbox{-}} {\text{melt}}}} \sim 0.0033 $ D_{\text{Nb}}^{{{\text{Opx}} {\hbox{-}} {\text{melt}}}} \sim 0.0033 and $ D_{\text{U}}^{{{\text{Opx}} {\hbox{-}} {\text{melt}}}} \sim 0.0066 $ D_{\text{U}}^{{{\text{Opx}} {\hbox{-}} {\text{melt}}}} \sim 0.0066 to $ D_{\text{Ti}}^{{\text{Opx}} {\hbox{-}} {\text{melt}}} \sim 0.058 $ D_{\text{Ti}}^{{\text{Opx}} {\hbox{-}} {\text{melt}}} \sim 0.058 , and are all virtually independent of temperature. Cr and Co are the only compatible trace elements at the studied conditions. To elucidate charge-balancing mechanisms for incorporation of REE into Opx and to assess the possible influence of Fe on Opx-melt partitioning, we compare our experimental results with computer simulations. In these simulations, we examine major and minor trace element incorporation into the end-members enstatite (Mg₂Si₂O₆) and ferrosilite (Fe₂Si₂O₆). Calculated solution energies show that R²⁺ cations are more soluble in Opx than R³⁺ cations of similar size, consistent with experimental partitioning data. In addition, simulations show charge balancing of R³⁺ cations by coupled substitution with Li⁺ on the M1 site that is energetically favoured over coupled substitution involving Al–Si exchange on the tetrahedrally coordinated site. We derived best-fit values for ideal ionic radii r ₀, maximum partition coefficients D ₀, and apparent Young’s moduli E for substitutions onto the Opx M1 and M2 sites. Experimental r ₀ values for R³⁺ substitutions are 0.66–0.67 ? for M1 and 0.82–0.87 ? for M2. Simulations for enstatite result in r ₀ = 0.71–0.73 ? for M1 and ~0.79–0.87 ? for M2. Ferrosilite r ₀ values are systematically larger by ~0.05 ? for both M1 and M2. The latter is opposite to experimental literature data, which appear to show a slight decrease in $ r_{0}^{{{\text{M}}2}} $ r_{0}^{{{\text{M}}2}} in the presence of Fe. Additional systematic studies in Fe-bearing systems are required to resolve this inconsistency and to develop predictive Opx-melt partitioning models for use in terrestrial and lunar magmatic differentiation models.     

The Energy Balance Experiment EBEX-2000. Part I: overview and energy balance

An overview of the Energy Balance Experiment (EBEX-2000) is given. This experiment studied the ability of state-of-the-art measurements to close the surface energy balance over a surface (a vegetative canopy with large evapotranspiration) where closure has been difficult to obtain. A flood-irrigated cotton field over uniform terrain was used, though aerial imagery and direct flux measurements showed that the surface still was inhomogeneous. All major terms of the surface energy balance were measured at nine sites to characterize the spatial variability across the field. Included in these observations was an estimate of heat storage in the plant canopy. The resultant imbalance still was 10%, which exceeds the estimated measurement error. We speculate that horizontal advection in the layer between the canopy top and our flux measurement height may cause this imbalance, though our estimates of this term using our measurements resulted in values less than what would be required to balance the budget. The National Center for Atmospheric Research is supported by the National Science Foundation     

Quantifying garnet-melt trace element partitioning using lattice-strain theory: assessment of statistically significant controls and a new predictive model

As a complement to our efforts to update and revise the thermodynamic basis for predicting garnet-melt trace element partitioning using lattice-strain theory (van Westrenen and Draper in Contrib Mineral Petrol, this issue), we have performed detailed statistical evaluations of possible correlations between intensive and extensive variables and experimentally determined garnet-melt partitioning values for trivalent cations (rare earth elements, Y, and Sc) entering the dodecahedral garnet X-site. We applied these evaluations to a database containing over 300 partition coefficient determinations, compiled both from literature values and from our own work designed in part to expand that database. Available data include partitioning measurements in ultramafic to basaltic to intermediate bulk compositions, and recent studies in Fe-rich systems relevant to extraterrestrial petrogenesis, at pressures sufficiently high such that a significant component of majorite, the high-pressure form of garnet, is present. Through the application of lattice-strain theory, we obtained best-fit values for the ideal ionic radius of the dodecahedral garnet X-site, r ₀(3+), its apparent Young’s modulus E(3+), and the strain-free partition coefficient D ₀(3+) for a fictive REE element J of ionic radius r ₀(3+). Resulting values of E, D ₀, and r ₀ were used in multiple linear regressions involving sixteen variables that reflect the possible influence of garnet composition and stoichiometry, melt composition and structure, major-element partitioning, pressure, and temperature. We find no statistically significant correlations between fitted r ₀ and E values and any combination of variables. However, a highly robust correlation between fitted D ₀ and garnet-melt Fe–Mg exchange and D _Mg is identified. The identification of more explicit melt-compositional influence is a first for this type of predictive modeling. We combine this statistically-derived expression for predicting D ₀ with the new expressions for predicting E and r ₀ outlined in the first of our pair of companion papers into an updated set of formulae that use easy-to-measure quantities (e.g. garnet composition, pressure, temperature) to predict variations in E, r ₀, and D ₀. These values are used in turn to calculate D values for those garnets. The updated model substantially improves upon a previous model (van Westrenen et al. in Contrib Mineral Petrol 142:219–234, 2001), and accounts well for trivalent cation partitioning in nominally anhydrous systems up to at least 15 GPa, including for eclogitic bulk compositions and for Fe-rich systems appropriate to magmagenesis on the Moon and Mars. The new model is slightly less successful in predicting partitioning with strongly majoritic garnets, although the mismatch is much less than with the original 2001 model. Although it also improves upon the 2001 model in predicting partitioning in hydrous systems, the mismatch between model and observation is still unacceptably large. The same statistical tools were applied in an attempt to predict tetravalent partitioning as well, because lattice-strain based techniques are not applicable to such partitioning. However, no statistically significant predictive relationships emerged from that effort. Our analyses show that future efforts should focus on filling the gap in partitioning data between ∼10 and 25 GPa to evaluate more closely the gradual transition of garnet to majorite, and on systematically expanding the hydrous partitioning database to allow extension of our model to water-bearing systems.     

Pleistocene Rhine–Thames landscapes: geological background for hominin occupation of the southern North Sea region

This paper links research questions in Quaternary geology with those in Palaeolithic archaeology. A detailed geological reconstruction of The Netherlands' south‐west offshore area provides a stratigraphical context for archaeological and palaeontological finds. Progressive environmental developments have left a strong imprint on the area's Palaeolithic record. We highlight aspects of landscape evolution and related taphonomical changes, visualized in maps for critical periods of the Pleistocene in the wider southern North Sea region. The Middle Pleistocene record is divided into two palaeogeographical stages: the pre‐Anglian/Elsterian stage, during which a wide land bridge existed between England and Belgium even during marine highstands; and the Anglian/Elsterian to Saalian interglacial, with a narrower land bridge, lowered by proglacial erosion but not yet fully eroded. The Late Pleistocene landscape was very different, with the land bridge fully dissected by an axial Rhine–Thames valley, eroded deep enough to fully connect the English Channel and the North Sea during periods of highstand. This tripartite staging implies great differences in (i) possible migration routes of herds of herbivores as well as hominins preying upon them, (ii) the erosion base of axial and tributary rivers causing an increase in the availability of flint raw materials and (iii) conditions for loess accumulation in northern France and Belgium and the resulting preservation of Middle Palaeolithic sites. Copyright © 2011 John Wiley & Sons, Ltd.     

The impact of summer temperature changes on vegetation development in Ireland during the Weichselian Lateglacial Interstadial

We analysed pollen from a sediment core from Fiddaun, a small Lateglacial lake basin in western Ireland. Results reflect the general Lateglacial vegetation development in Ireland, as reconstructed from other pollen records. The Fiddaun diagram shows a number of short‐lived regressive vegetation phases during the Interstadial. The close similarity between two pollen records from the same region (Fiddaun and Lurga) indicates that these fluctuations probably reflect regional rather than local changes. Comparison with a previously published climate reconstruction, based on a chironomid‐inferred mean July air temperature reconstruction, lithology, and oxygen and carbon isotopes of lake marl from the Fiddaun record, allowed us to establish the relationship between summer temperature and vegetation changes. Results reveal that two temporary regressive shifts in the pollen record correspond to cold oscillations, which have been correlated to Greenland Interstadial 1b and 1d. It seems that the first cold oscillation (GI‐1d) had the most distinct effect on vegetation in Ireland. In contrast, it appears that the transition from Juniperus shrubland and Empetrum heath to grassland, which is estimated at ～13.7 ka BP, was not caused by decreasing summer temperatures, as no substantial change is observed in the climate proxies. Copyright © 2012 John Wiley & Sons, Ltd.     

Trace element partitioning between ilmenite, armalcolite and anhydrous silicate melt: Implications for the formation of lunar high-Ti mare basalts

We performed a series of experiments at high pressures and temperatures to determine the partitioning of a wide range of trace elements between ilmenite (Ilm), armalcolite (Arm) and anhydrous lunar silicate melt, to constrain geochemical models of the formation of titanium-rich melts in the Moon. Experiments were performed in graphite-lined platinum capsules at pressures and temperatures ranging from 1.1 to 2.3 GPa and 1300-1400 °C using a synthetic Ti-enriched Apollo ‘black glass’ composition in the CaO-FeO-MgO-Al₂O₃-TiO₂-SiO₂ system. Ilmenite-melt and armalcolite-melt partition coefficients (D) show highly incompatible values for the rare earth elements (REE) with the light REE more incompatible compared to the heavy REE ( 0.0020 ± 0.0010 to 0.069 ± 0.010 for ilmenite; 0.0048 ± 0.0023 to 0.041 ± 0.008 for armalcolite). D values for the high field strength elements vary from highly incompatible for Th, U and to a lesser extent W (for ilmenite: 0.0013 ± 0.0008, 0.0035 ± 0.0015 and 0.039 ± 0.005, and for armalcolite 0.008 ± 0.003, 0.0048 ± 0.0022 and 0.062 ± 0.03), to mildly incompatible for Nb, Ta, Zr, and Hf (e.g. 0.28 ± 0.05 and : 0.76 ± 0.07). Both minerals fractionate the high field strength elements with D_Ta/D_Nb and D_Hf/D_Zr between 1.3 and 1.6 for ilmenite and 1.3 and 1.4 for armalcolite. Armalcolite is slightly more efficient at fractionating Hf from W during lunar magma ocean crystallisation, with D_Hf/D_W = 12-13 compared to 6.7-7.5 for ilmenite. The transition metals vary from mildly incompatible to compatible, with the highest compatibilities for Cr in ilmenite (D ∼ 7.5) and V in armalcolite (D ∼ 8.1). D values show no clear variation with pressure in the small range covered.Crystal lattice strain modelling of D values for di-, tri- and tetravalent trace elements shows that in ilmenite, divalent elements prefer to substitute for Fe while armalcolite data suggest REE replacing Mg. Tetravalent cations appear to preferentially substitute for Ti in both minerals, with the exception of Th and U that likely substitute for the larger Fe or Mg cations. Crystal lattice strain modelling is also used to identify and correct for very small (∼0.3 wt.%) melt contamination of trace element concentration determinations in crystals.Our results are used to model the Lu-Hf-Ti concentrations of lunar high-Ti mare basalts. The combination of their subchondritic Lu/Hf ratios and high TiO₂ contents requires preferential dissolution of ilmenite or armalcolite from late-stage, lunar magma ocean cumulates into low-Ti partial melts of deeper pyroxene-rich cumulates.     

Impact of India–Asia collision on SE Asia: The record in Borneo

Borneo occupies a central position in the Sundaland promontory of SE Asia. It has a complex Cenozoic geological history of sedimentation and deformation which began at about the same time that India is commonly suggested to have started to collide with Asia. Some tectonic reconstructions of east and SE Asia interpret a large SE Asian block with Borneo at its centre which has been rotated clockwise and displaced southwards along major strike–slip faults during the Cenozoic due to the indentation of Asia by India. However, the geological history of Borneo is not consistent with the island simply forming part of a large block extruded from Asia. The large clockwise rotations and displacements predicted by the indentor model for Borneo are incompatible with palaeomagnetic evidence and there is no evidence that the major strike–slip faults of the Asian mainland reach Borneo. Seismic tomography shows there is a deep high velocity anomaly in the lower mantle beneath SE Asia interpreted as subducted lithosphere but it can be explained just as well by alternative tectonic models as by the indentor model. Very great thicknesses of Cenozoic sediments are present in Borneo and circum-Borneo basins, and large amounts of sediment were transported to the Crocker turbidite fan of north Borneo from the Eocene to the Early Miocene, but all evidence indicates that these sediments were derived from local sources and not from distant sources in Asia elevated by India–Asia collision. The Cenozoic geological history of Borneo records subduction of the proto-South China Sea and Miocene collision after this ocean lithosphere was eliminated, and a variety of effects resulting from long-term subduction beneath SE Asia. There is little to indicate that India–Asia collision has influenced the Cenozoic geological record in Borneo.