Modeling the binding of fulvic acid by goethite: the speciation of adsorbed FA molecules

Under natural conditions, the adsorption of ions at the solid-water interface may be strongly influenced by the adsorption of organic matter. In this paper, we describe the adsorption of fulvic acid (FA) by metal(hydr)oxide surfaces with a heterogeneous surface complexation model, the ligand and charge distribution (LCD) model. The model is a self-consistent combination of the nonideal competitive adsorption (NICA) equation and the CD-MUSIC model. The LCD model can describe simultaneously the concentration, pH, and salt dependency of the adsorption with a minimum of only three adjustable parameters. Furthermore, the model predicts the coadsorption of protons accurately for an extended range of conditions. Surface speciation calculations show that almost all hydroxyl groups of the adsorbed FA molecules are involved in outer sphere complexation reactions. The carboxylic groups of the adsorbed FA molecule form inner and outer sphere complexes. Furthermore, part of the carboxylate groups remain noncoordinated and deprotonated.     

Detection of sinkholes using 2D electrical resistivity imaging

Sinkholes in dolomitic areas are notoriously difficult geophysical targets, and selecting an appropriate geophysical solution is not straightforward. Electrical resistivity imaging, or tomography (RESTOM) is well suited to mapping sinkholes because of the ability of the technique for detecting resistive features and discriminating subtle resistivity variations. RESTOM surveys were conducted at two sinkhole sites near Pretoria, South Africa. The survey areas are located in the dolomites of the Lyttelton Formation, which forms part of the Malamani Subgroup and Chuniespoort Group of the Transvaal Supergroup. The survey results suggest that RESTOM is an ideal geophysical tool to aid in the detection and monitoring of sinkholes and other subsurface cavities.     

Quasi-conservative behaviour of Be in deep waters of the Weddell Sea and the Atlantic sector of the Antarctic Circumpolar Current

We present the first transect of dissolved ¹⁰Be depth profiles across the Antarctic Circumpolar Current (ACC) in the Atlantic sector. North of the Polar Front the ¹⁰Be concentrations increase continuously from very low values at the surface to values of up to 1600 atoms/g at depth. Deep water ¹⁰Be concentrations of particular water masses are consistent with earlier results obtained further north. South of the Polar Front and in the Weddell Sea the distribution of ¹⁰Be is also characterised by low surface concentrations but below 1000 m depth the concentrations are relatively constant and significantly higher (up to 2000 atoms/g) than further north, probably as a result of mixing and advection of water masses of Pacific origin. Overall the deep water ¹⁰Be distribution is obviously not significantly affected by scavenging processes or ice melt and comparison with the density distribution suggests that ¹⁰Be can be viewed as a quasi-conservative tracer. This provides a tool for an improved understanding of the behaviour of other more particle reactive trace metals in the Southern Ocean such as ²³⁰Th: in deep waters north of the ACC/Weddell Gyre boundary (AWB) ¹⁰Be/²³⁰Th has a relatively constant value (1.7±0.3×10⁹ atoms/dpm) over a wide density range whereas south of the AWB the ratio is significantly lower (1.1±0.2×10⁹ atoms/dpm). This normalisation to ¹⁰Be corroborates that ²³⁰Th is enriched by 50% due to accumulation south of the AWB as a consequence of minimal particulate fluxes. The quasi-conservative behaviour deduced from our results also implies that ¹⁰Be can only be used as a tracer for Southern Ocean particle fluxes in the past if ocean circulation patterns and water mass residence times did not change significantly.     

Palynological evidence for the astronomical origin of lignite-detritus sequence in the Middle Pleistocene Marathousa Member, Megalopolis, SW Greece

The Marathousa Member, Middle Pleistocene strata in the fluvio-lacustrine Megalopolis basin, southwest Greece, displays distinct but complicated lithological cycles comprising first-order alternation of lignites and detrital muds and second-order alternation expressed by frequent intercalation of organic layers. Palynological evidence indicates that the lithological cycles are driven by the Earth’s orbital forcing. All the lignite seams yield temperate oak forest whereas the detrital beds provide semi-arid steppe mainly of Artemisia. This means that the first-order lithological cycle represents the glacial/interglacial cycle (i.e., the 100-kyr eccentricity cycle), providing a timescale of at least 350 kyr to the Marathousa Member. Pollen also detects smaller-scale climate fluctuations in many of the subordinate organic layers, with the total number of fluctuations being five in a complete lignite-detritus couplet. This means that the second-order lithological cycle reflects the 21-kyr insolation cycle. A tentative phase relation between the lithological cycles and the astronomical cycles is shown based on palynostratigraphy and electron spin resonance dating. Lacustrine environments with increased water tables are implied for the glacial periods sedimentologically, in contrast to local swamp vegetation for the interglacial periods. The subordinate organic layers were formed under intermediate environments (climate, water depth, etc.) between full glacials and interglacials.     

Relative hotspot motions versus True Polar Wander

The fixity of hotspots and mantle plume locations has long been axiomatic. If the assumption of fixed hotspots is granted, ‘absolute’ plate motions and movements of the spin axis with respect to the hotspot framework, defined by some as True Polar Wander (TPW), can be determined. However, this assumption can be tested by paleomagnetic data, and such tests are gradually raising some doubts about the fixity of hotspots. The result is that discrepancies between Cretaceous and Tertiary hotspot and paleomagnetic reference frames are now beginning to be interpreted as the result of plume drift within a convective mantle. In the Indo-Atlantic, hotspots have remained relatively stationary with respect to the spin axis for the last 95 million yr. However, the Pacific hotspots, notably Hawaii, appear to have undergone large-scale southward drift with respect to the spin axis during the Early Tertiary. Global paleomagnetic data do not indicate that any TPW occurred during the Late Cretaceous or Tertiary. Although the Early Cretaceous paleomagnetic and hotspot frames for the Indo-Atlantic realm can be interpreted as slow TPW, direct estimates of paleolatitude and hotspot motion, in particular the Kerguelen hotspot, challenge TPW as a global phenomenon. At present, we consider that the large Early Cretaceous discrepancy between hotspot and paleomagnetic data is best explained by southward drift of the Atlantic hotspots prior to ∼95 Ma.     

High-resolution estimates of lithospheric thickness from Missouri to Massachusetts, USA

This paper presents a new three-dimensional (3-D) model, NA00, of the S-velocity of the upper mantle beneath North America. The model differs from its predecessor NA95 in that it exploits seismograms recorded by a recent dense, broadband array, MOMA, and from independent measurements of North American crustal thickness. Model NA00 is derived by fitting the waveforms of broadband seismic S and surface waves recorded by the MOMA array and inverting them together with the database of waveform fits used for NA95 and the crustal thickness estimates. It is demonstrated that including data from the dense, broadband MOMA array yields a resolving power beneath the array that is of unprecedented quality and relatively constant over a large depth range. This improved resolution provides a unique opportunity for quantifying the structure of the upper mantle in and below the lower, thick Precambrian lithosphere. The high-resolution seismic structure of the imaged high-velocity lithosphere is compared with the thermal structure (estimated from heat flow), compositional structure (estimated from xenoliths and electrical conductivity) and the elastic structure (estimated from gravity and topography). There is a remarkable agreement between the seismic, thermal, and compositional estimates. The seismic lithosphere is 180 km thick below Missouri and Illinois, 200 km thick below Indiana, Ohio and Pennsylvania, practically undefined below New York, and 80 km below Massachusetts and the Atlantic continental shelf. The thick lithosphere is underlain by a layer with lower S-velocities that could represent a relatively low-viscosity channel. However, the S-velocities in this layer are much higher than those of typical oceanic asthenosphere.     

Imagining difference: the experiences of 'transnational' Indian IT professionals in Germany

In this paper we explore the motivations to migrate and the migration experiences of 22 Indian IT professionals in Germany. When studying skilled migration, Germany is an interesting case as it struggled with waves of extreme right activities whilst trying to attract IT professionals from outside the European Union at the same time. In this context, we are interested in the conflicts that the migrants may experience as a result of their desire or obligation to move, their specific cultural baggage and the way in which they encounter the different sides of German society.