Spatial distribution and bonding forms of heavy metals in sediments along the middle course of the River Elbe (km 287ċ390)

Sediments of eight groyne fields along the middle course of the River Elbe (river km 287?390) were geochemically studied. The 78 sediment samples were analysed for pH and grain size distribution. The grain size fraction < 2 μm was used for mineralogical and chemical analysis: semiquantitative clay mineral analysis; total element content (Al, Ca, Fe, K, Mn, Cd, Cr, Cu, Ni, Pb, Zn), total inorganic and organic C, and bonding form fractionation with a six‐step sequential chemical extraction. The latter was performed on selected samples (n = 32). The sediments along the Elbe's course are still contaminated with heavy metals far above the local geogenic background level. An enrichment factor of more than 15 was calculated for zinc. Cr and Ni are the elements with the lowest enrichment. The bonding form analysis of selected heavy metals shows a dominance of relatively immobile bonding forms, e. g. the moderately reducible and the residual fraction, which implies a relative low mobility potential. Only Zn poses a higher potential threat to the environment, since it has a higher percentage of the first three extracted phases: adsorbed, carbonate, and easily reducible fraction.     

Free cupric ion concentrations and Cu complexation in selected Swiss lakes and rivers

[Cu²⁺] and Cu complexation parameters in some selected freshwater systems in Switzerland were determined by the technique of ligand-exchange and DPCSV. Results from the water columns of some eutrophic and oligotrophic lakes are presented and compared to small acid lakes. Cu is strongly complexed by organic ligands which with very high stability constants at low concentrations are probably biologically produced, as indicated by the seasonal variations in the eutrophic lakes and by the relationship between Cu complexation and algal activity in the eutrophic (pCu=15–16), oligotrophic (pCu=13–14) and acidic (pCu=9–10) lakes. The extent of Cu complexation in river waters was generally lower than in the eutrophic lakes, at similar DOC levels. No obvious correlation between Cu complexation and DOC was observed, indicating that Cu complexing ligands are specific organic compounds.     

The effect of crystallization on the rheology and dynamics of lava flows

The dynamics of a lava flow is studied by a two-dimensional model describing a viscous fluid with Bingham rheology, flowing down a slope. The temperature in the flow is calculated assuming that heat is transferred through the plug by conduction and is lost by radiation to the atmosphere at the top of the flow. Taken into account is that the increasing crystallization takes place in the flow as a consequence of cooling. The lava viscosity and yield stress are expressed as a function of crystallization degree as well as of temperature: in particular it is assumed that yield stress reaches a maximum value above the solidus temperature, according to experimental data. Dynamical variables, such as velocity and thickness of the flow, are calculated for different values of the maximum crystallization degree and the flow rate. The model shows how the lava flow dynamics is affected by cooling and crystallization. The cooling of the flow is controlled by the increase of yield stress, which produces a thicker plug and makes the heat loss slower. The increasing crystallization has two opposing effects on viscosity: it produces an increase of viscosity, but at the same time produces an increase of yield stress and hence reduces the heat loss and keeps the internal temperature high. As a consequence, lava flows are significantly affected by the dependence of yield stress on temperature and scarcely by the maximum crystallization degree.     

Contributions to the Ring Current Energy During Geomagnetic Storms

The purpose of this research was to study the complexity of the energization of the ring current during a geomagnetic storm, produced during southern Bz(IMF) by the injection of plasma sheet ions, accelerated by enhanced convective electric fields. This model assumes that the plasma sheet is continuously populated by H⁺ from the sun and the ionosphere, and sporadically by ionospheric O⁺, making the ring current a coupled system whose energy can hardly be expressed analytically. When Bz(IMF) turns north, the ring current becomes uncoupled, and the energy decays exponentially if the storm is weak, or can be expressed as a combination of exponentials during strong storms representing the quick decay of O⁺ and the slower decay of H⁺, as has been shown.     

Bromine cycle in subduction zones through in situ Br monitoring in diamond anvil cells

The geochemical partitioning of bromine between hydrous haplogranitic melts, initially enriched with respect to Br and aqueous fluids, has been continuously monitored in situ during decompression. Experiments were carried out in diamond anvil cells from 890 °C to room temperature and from 1.7 GPa to room pressure, typically from high P, T conditions corresponding to total miscibility (presence of a supercritical fluid). Br contents were measured in aqueous fluids, hydrous melts and supercritical fluids. Partition coefficients of bromine were characterized at pressure and temperature between fluids, hydrous melts and/or glasses, as appropriate: D^Br_fluid/melt = (Br)_fluid/(Br)_melt, ranges from 2.18 to 9.2 ± 0.5 for conditions within the ranges 0.66-1.7 GPa, 590-890 °C; and D^Br_fluid/glass = (Br)_fluid/(Br)_glass ranges from 60 to 375 at room conditions. The results suggest that because high pressure melts and fluids are capable of accepting high concentrations of bromine, this element may be efficiently removed from the slab to the mantle source of arc magmas. We show that Br may be highly concentrated in subduction zone magmas and strongly enriched in subduction-related volcanic gases, because its mobility is strongly correlated with that of water during magma degassing. Furthermore, our experimental results suggest that a non negligible part of Br present in the subducted slab may remain in the down-going slab, being transported toward the transition zone. This indicates that the Br cycle in subduction zones is in fact divided in two related but independent parts: (1) a shallower one where recycled Br may leave the slab with a water and silica-bearing “fluid” leading to enriched arc magmas that return Br to the atmosphere. (2) A deeper cycle where Br may be recycled back to the mantle maybe to the transition zone, where it may be present in high pressure water-rich metasomatic fluids.     

Magnetic properties and cation ordering of nanopowders of the synthetic analogue of kuramite, Cu3SnS4

An extensive characterisation of the magnetic properties of synthetic powders of kuramite, with formal composition Cu₃SnS₄, was performed. Powders were investigated through superconducting quantum interference device (SQUID) magnetometry, electron paramagnetic resonance (EPR) spectroscopy, X-ray powder diffraction (XRPD), scanning and transmission electron microscopies (SEM and TEM) and microanalysis. SEM and TEM reveal the presence of nanodimensioned particles. XRPD clearly shows that Cu₃SnS₄ crystallised in a cubic sphalerite-type structural model, in spite of the stannite-type tetragonal structure described for the natural phase. This difference arises from a full random distribution of cations. Synthetic kuramite nanopowders exhibit a marked paramagnetism, originated by the presence of Cu(II), definitely assessed by EPR measurements. Moreover, the overall magnetic behaviour of the sample cannot be simply ascribed to diluted paramagnetism, and this suggests the presence of strong superexchange interactions among Cu(II) ions even at room temperature. The main consequences of these results are the definitive assessment of the chemical formula Cu(I)₂Cu(II)SnS₄ and of a random distribution of Cu(II), Cu(I) and Sn(IV) ions within the available tetrahedral sites.     

Investigation of groundwater residence times during bank filtration in Berlin: a multi‐tracer approach

Berlin relies on induced bank filtration from a broad‐scale, lake‐type surface water system. Because the surface water contains treated sewage, wastewater residues are present in surface water and groundwater. Multiple environmental tracers, including tritium and helium isotopes (³H, ³He, ⁴He), stable isotopes (δ¹⁸O and δ²H) and a number of persistent sewage indicators, such as chloride, boron and a selection of pharmaceutical residues (phenazone‐type analgesics and their metabolites, carbamazepine and anthropogenic gadolinium, Gd_excess), were used to estimate travel times from the surface water to individual production and observation wells at two sites. The study revealed a strong vertical age stratification throughout the upper aquifer, with travel times varying from a few months to several decades in greater depth. Whereas the shallow bank filtrate is characterized by the reflection of the time‐variant tracer input concentrations and young ³H/³He ages, the deeper, older bank filtrate displays no tracer seasonality, ³H/³He ages of a few years to decades and strongly deviating concentrations of several pharmaceutical residues, reflecting concentrations of the source surface water over time. The phenazone‐type pharmaceuticals persist in the aquatic environments for decades. Bank filtration in Berlin is only possible at the sandy lakeshores. In greater water depth, impermeable lacustrine sapropels inhibit infiltration. The young bank filtrate originates from the nearest shore, whereas the older bank filtrate infiltrates at more distant shores. This paper illustrates the importance of using multiple tracer methods, capable of resolving a broad range of residence times, to gain a comprehensive understanding of time‐scales and infiltration characteristics in a bank filtration system. Copyright © 2007 John Wiley & Sons, Ltd.