Dissolved organic carbon in the freshwater tidal reaches of the Schelde estuary

To unravel the factors that regulate DOC dynamics in the freshwater tidal reaches of the Schelde estuary, DOC concentration and biodegradability were monitored in the upper Schelde estuary and its major tributaries. Although the Schelde estuary possesses a densely populated and industrialized catchment, our data suggest that the bulk of DOC in the freshwater tidal reaches is not derived from waste water. This was concluded from the low biodegradability of DOC (on average 9%), DOC concentrations that are close to the mean for European rivers (4.61 mg l⁻¹) and the absence of an inverse relationship between DOC and discharge. Most DOC originating from waste water being discharged in tributaries of the estuary appears to be remineralised before these tributaries reach the main estuary. Although dense phytoplankton blooms were observed in the upper estuary during summer (up to 700 μg chl a l⁻¹), these blooms did not appear to produce large quantities of DOC in the freshwater tidal reaches as DOC concentrations were low when phytoplankton biomass was high. The fact that DOC concentrations were high in winter and decreased in summer suggests a predominantly terrestrial source of DOC in the freshwater tidal reaches of the Schelde estuary.     

Formal definition and dating of the GSSP (Global Stratotype Section and Point) for the base of the Holocene using the Greenland NGRIP ice core,and selected auxiliary records

The Greenland ice core from NorthGRIP (NGRIP) contains a proxy climate record across the Pleistocene–Holocene boundary of unprecedented clarity and resolution. Analysis of an array of physical and chemical parameters within the ice enables the base of the Holocene, as reflected in the first signs of climatic warming at the end of the Younger Dryas/Greenland Stadial 1 cold phase, to be located with a high degree of precision. This climatic event is most clearly reflected in an abrupt shift in deuterium excess values, accompanied by more gradual changes in δ¹⁸O, dust concentration, a range of chemical species, and annual layer thickness. A timescale based on multi‐parameter annual layer counting provides an age of 11 700 calendar yr b2 k (before AD 2000) for the base of the Holocene, with a maximum counting error of 99 yr. A proposal that an archived core from this unique sequence should constitute the Global Stratotype Section and Point (GSSP) for the base of the Holocene Series/Epoch (Quaternary System/Period) has been ratified by the International Union of Geological Sciences. Five auxiliary stratotypes for the Pleistocene–Holocene boundary have also been recognised. Copyright © 2008 John Wiley & Sons, Ltd.     

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 nature of hydroxyl groups in aluminosilicate glasses: Quantifying Si-OH and Al-OH abundances along the SiO2-NaAlSiO4 join by H, Al-H and Si-H NMR spectroscopy

The combined results of ²⁷Al-¹H and ¹H-²⁹Si-¹H cross polarization NMR experiments for hydrous glasses (containing 0.5-2 wt% water) along the SiO₂-NaAlSiO₄ join confirm that the dissolution mechanism of water in aluminosilicate glasses is fundamentally the same as for Al-free systems, i.e. the dissolved water ruptures oxygen bridges and creates Si-OH and Al-OH groups, in addition to forming molecular water (H₂O_mol). The fraction of Al-OH increases non-linearly as the Al content increases with up to half of the OH groups as Al-OH for compositions close to NaAlSiO₄. The relative abundances of the different species are controlled by the degree of Al-avoidance and the relative tendency of hydrolysis of the different types of oxygen bridges, Si-O-Si, Si-O-Al and Al-O-Al. A set of homogeneous reactions is derived to model the measured Al-OH/Si-OH speciation, and the obtained equilibrium constants are in agreement with literature data on the degree of Al-avoidance. With these equilibrium constants, the abundance of the different oxygen species, i.e. Si-O-Si, Si-O-Al, Al-O-Al, Si-OH, Al-OH and H₂O_mol, can be predicted for the entire range of water and Al contents.     

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.     

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 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.     

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.     

Effects of an oil spill in outdoor model tidal flat ecosystems

For several reasons the fate and effects of oil pollution are not easily studied in natural ecosystems. Furthermore, the results of laboratory tests cannot easily be extrapolated to natural systems. A logical objective of ecotoxicological research is, therefore, to simulate natural systems in model ecosystem experiments. A one-year feasibility study was carried out with MOdel TIdal Flat ecosystems (MOTIFs), designed to represent tidal flat systems typical of the Wadden Sea and other temperate estuarine areas. During the first 6 months the 4 MOTIFs studied developed very similarly. After this period an oil spill was simulated by exposing two of the four MOTIFs to a floating oil mousse for one week. During this week part of the oil was buried in the sediment by bioturbation. This sediment-bound fraction caused a prolonged exposure of the MOTIFs to oil compounds. Short- and long-term effects resulted in large differences between oil-treated and control MOTIFs. These differences persisted to the end of the experiment, 7 months after the removal of most of the oil.     

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.