Modelling the equilibrium speciation of nickel in the Tweed Estuary, UK: Voltammetric determinations and simulations using WHAM

The complexation of dissolved Ni has been evaluated in a rapidly-flushed, rural estuary (Tweed, UK) by ligand exchange-adsorptive cathodic stripping voltammetry. Results suggest the presence of strongly binding ligands, L, throughout, with average stability constants of about 10¹⁹ and which are saturated by ambient Ni concentrations. Equilibrium speciation calculations incorporating these constants in WHAM, version 6, predict an increase in Ni complexation (as NiL) from about 50% of total dissolved Ni in fresh water to over 90% in sea water. Equivalent calculations using the default-mode fulvic and humic substances (FS and HS, respectively) encoded in the WHAM database predict a reduction in complexation (as NiFS + NiHS) from about 20% in fresh water to less than 1% in sea water. Discrepancies arising from the two approaches are largely attributed to the different analytical detection windows employed. Thus, a better representation of Ni complexation is derived from including both types of complexant in the speciation calculations, resulting in estimates of net complexation in excess of 60% of total dissolved Ni throughout the estuary. The uncertainties and assumptions inherent in all computations illustrate the difficulty in measuring or predicting metal complexation in estuaries.     

Some chemical characteristics of the brines in Bannock and Tyro Basins: salinity, sulphur compounds, Ca, F, pH, At, PO4, SiO2, NH3

Results of the chemical investigation on the Bannock and Tyro Basins are reported.Both basins were found to be hypersaline ( 10 times higher than salinity of normal seawater) and anoxic. In all investigated basins a region of transition, a few meters thick, was identified at depths > 3327 dbar. It is characterized by a sharp gradient of salinity, and all concentrations of analysed species increase strongly except for dissolved oxygen and nitrate, which immediately drop to zero. This region appears as a sharp boundary that prevents mixing. As a result, in the presence of organic matter, an anoxic condition developed with the complete depletion of dissolved oxygen. At the same time, hydrogen sulphide and ammonium accumulated within the brine. Between the Bannock and the Tyro brines differences occur in the measured concentrations of H₂S, SO²⁻₄, Ca²⁺ and NH₃. There are some differences also within the Bannock area sub-basins.The Libeccio sub-basin, in the Bannock area, contains a double-layered brine: the upper layer is 140 dbar thick and the lower layer is 300 dbar thick. A second interface between upper and lower brines develops at a depth of 3500 dbar. Nearly all of the measured concentrations vs. depth show the double layer, with the exception of ammonium, the concentration of which remains nearly constant throughout the anoxic column. Profiles of the other species analyzed show remarkable differences on passing from the upper to the lower brine. Hydrogen sulphide, sulphate and fluoride concentrations appear constant and then increase at the second interface. The calcium concentration is also constant in the upper brine, but decreases at the second interface. Total alkalinity and phosphate concentrations show a maximum peak just below the first interface. However, after passing through the second interface all the chemical parameters exhibit an almost constant behaviour down to the bottom.Hypersaline conditions are attributed to the dissolution of Messinian evaporite, and anoxia is suggested to originate from the oxidation of organic matter present in sediments and from the absence of bottom water circulation in such a deep and enclosed environment.The chemical conditions can be summarized as follows: in the Libeccio Basin the values for the species analysed have the ranges: 39–321 psu for ‘salinity’, 8.2−6.5 for pH, 2.7–4.0 mM for total alkalinity, 0.2-0 mM for dissolved oxygen, 0–1669 μM for hydrogen sulphide, 0–198 μM for thiol, 31–99 mM for sulphate, 11–21 mM for calcium, 7–100 μM for fluoride, 0.2–3080 μM for ammonium, 5.8-0 μM for nitrite, 0.2–12 μM for phosphate and 8–130 μM for silicate.     

Light curves of SZ Piscium for 1977 and 1978

We present a relatively completeV-band light curve of SZ Psc for 1978 and a partial light curve for 1977. From the 1978 light curve we derive a new time of primary minimum, JD2443823.674±0.001, and a Russell-model solution,i=75°.8±0°.1,r _h =0.096±0.003,r _c =0.351±0.001, andL _h =0.253±0.002. The hotter component of this system is a F5-8 main-sequence star, the cooler component a K3-4 star well above the main sequence. The system is detached with the larger component filling only 82% of its Roche lobe. The distortion wave in this RS CVn-type binary seems not to migrate regularly as do those in many other such systems, but rather seems to change phase and amplitude more erratically. Between 1977 and 1978 its phase stayed practically constant while its amplitude decreased by a factor of three. We discuss the implications of this behavior for the spot model of RS CVn-type activity. We find that the traditional comparison star for SZ Psc, HD 219018, is very likely a constant star contrary to a recent suggestion that it is variable. Its brightness and colors,V=7.705, (B-V)=0.628, and (V-I) _c =0.688, are those of a G2V star.Visiting Astronomer, Kitt Peak National Observatory, which is operated by AURA, Inc., under contract with the National Science Foundation, and Visiting Astronomer, Prarie Observatory, University of Illinois.     

On the secular variations of Io and Titan

A long-term variation of the magnitude at mean opposition is shown to exist for Io and Titan. The variation of Io seems to be correlated with the orbital period of Jupiter, the maximum light occurring at perihelion.     

Search for nucleosynthetic and radiogenic tellurium isotope anomalies in carbonaceous chondrites

Tellurium isotope data acquired by multiple-collector inductively coupled plasma-mass spectrometry (MC-ICPMS) are presented for sequential acid leachates of the carbonaceous chondrites Orgueil, Murchison, and Allende. Tellurium isotopes are produced by a broad range of nucleosynthetic pathways and they are therefore of particular interest given the isotopic anomalies previously identified for other elements in these meteorites. In addition, the data provide new constraints on the initial solar system abundance of the r-process nuclide ¹²⁶Sn, which decays to ¹²⁶Te with a half-life of 234,500 years. The ¹²⁶Te/¹²⁸Te ratios of all leachates were found to be identical, within uncertainty, despite variations in ¹²⁴Sn/¹²⁸Te of between about 0.002 and 1.4. The data define a ¹²⁶Sn/¹²⁴Sn ratio of <7.7 × 10⁻⁵ at the time of last isotopic closure, consistent with the value of <18 × 10⁻⁵ previously reported for bulk carbonaceous chondrites. How close this is to the initial ¹²⁶Sn/¹²⁴Sn ratio of the solar system depends on when the investigated samples last experienced redistribution of Sn and Te. No clear evidence is found for nucleosynthetic anomalies in the abundances of p-, s-, and r-process nuclides. The largest effect detected in this study is a small excess of the r-process nuclide ¹³⁰Te in a nitric acid leachate of Murchison. This fraction displays an anomalous ε¹³⁰Te of +3.5 ± 2.5. Although barely resolvable given the analytical uncertainties, this is consistent with the presence of a small excess r-process component or an s-process deficit. The general absence of anomalies contrasts with previous results obtained for K, Cr, Zr, Mo, and Ba isotopes in similar leachates, which display nucleosynthetic anomalies of up to 3.8%. The reason for this discrepancy is unclear but it may reflect volatility and more efficient mixing of Te in the solar nebula.     

Beyond world cities: Central America in a global space of flows

Central America is a region without a world city. Traditionally, the region's national projects have been based upon openness to the world economy: how do the region's contemporary transnational projects connect to the world economy under the new conditions of openness that is contemporary globalization? Focusing upon advanced producer services, three connections into the world city network are identified: global service firms operating directly in Central American cities, local service firms operating indirectly through extra-regional world cities and global service firms operating through Latin American regional offices. Miami is confirmed as the primary world city through which Central America connects into the world economy     

The BEAM-project: prediction and assessment of mixture toxicities in the aquatic environment

Freshwater and marine ecosystems are exposed to various multi-component mixtures of pollutants. Nevertheless, most ecotoxicological research and chemicals regulation focus on hazard and exposure assessment of individual substances only, the problem of chemical mixtures in the environment is ignored to a large extent. In contrast, the assessment of combination effects has a long tradition in pharmacology, where mixtures of chemicals are specifically designed to develop new products, e.g. human and veterinary drugs or agricultural and non-agricultural pesticides. In this area, two concepts are frequently used and are thought to describe fundamental relationships between single substance and mixture effects: Independent Action (Response Addition) and Concentration Addition. The question, to what extent these concepts may also be applied in an ecotoxicological and regulatory context may be considered a research topic of major importance, as the concepts would allow to make use of already existing single substance toxicity data for the predictive assessment of mixture toxicities. Two critical knowledge gaps are identified: (a) There is a lack of environmental realism, as a huge part of our current knowledge about the applicability of the concepts is restricted to artificial situations with respect to mixture composition or biological effect assessment. (b) The knowledge on what exactly is needed for using the concepts as tools for the predictive mixture toxicity assessment is insufficient. Both gaps seriously hamper the necessary, scientifically sound consideration of mixture toxicities in a regulatory context.In this paper, the two concepts will be briefly introduced, the necessity of considering the toxicities of chemical mixtures in the environment will be demonstrated and the applicability of Independent Action and Concentration Addition as tools for the prediction and assessment of mixture toxicities will be discussed. An overview of the specific aims and approaches of the BEAM project to fill in the identified knowledge gaps is given and first results are outlined.     

Paleogeography and structure of the central Mediterranean: Sicily and its offshore area

The geology of the mainland and offshore of Sicily is illustrated by a few geologic sections and seismic profiles across the late Cenozoic orogenic belt of central and western Sicily and across the Sardinia Channel and Sicily Straits. This belt is the result of several tectonic events. Deformation involved mainly the sedimentary cover of the old African continental margin characterized by a broad basinal domain, flanked along its external (southern) margin by a shallow-water carbonate platform attached to Africa in the Triassic. Compressional deformation started in the more internal basinal rock assemblages overlying a thinned crust. The most important structural characteristic of the early phase of thrusting is the duplex pile forming the bulk of the chain in Central Western Sicily. The structure consists of a basal allochthon, made up of Permian to Middle Triassic layers, an intermediate duplex wedge, composed of competent Mesozoic carbonates, and a roof complex, including Upper Mesozoic-Lower Tertiary less competent rocks. Large-scale clockwise rotation of the thrusts accompanied transpressional movements in the hinterland during the Pliocene. Right oblique reverse faults modified the previous tectonic contacts between the allochthons in the hinterland zones. Contemporaneous south-directed imbrications affected the southern external areas, progressively incorporating foreland and piggyback basins. Development of the Gela Thrust System appears to be linked to the transpressional event; its accretion is also related to contemporaneous underthrusting at deeper levels of Mesozoic carbonate substratum. The older buried thrust sheets were pushed up to the surface breaching the deformed Tertiary cover of the Gela TS. Northwards in the belt post-Messinian normal growth faults opened half graben whose sedimentary fill underwent structural inversion. Alternation of extension and compression tectonics characterizes the Sicilian continental margin in the last million years.     

Uranyl adsorption onto montmorillonite: Evaluation of binding sites and carbonate complexation

The fate and transport of uranium in contaminated soils and sediments may be affected by adsorption onto the surface of minerals such as montmorillonite. Extended X-ray absorption fine structure (EXAFS) spectroscopy has been used to investigate the adsorption of uranyl (UO₂²⁺) onto Wyoming montmorillonite. At low pH (∼4) and low ionic strength (10⁻³ M), uranyl has an EXAFS spectrum indistinguishable from the aqueous uranyl cation, indicating binding via cation exchange. At near-neutral pH (∼7) and high ionic strength (1 M), the equatorial oxygen shell of uranyl is split, indicating inner-sphere binding to edge sites. Linear-combination fitting of the spectra of samples reacted under conditions where both types of binding are possible reveals that cation exchange at low ionic strengths on SWy-2 may be more important than predicted by past surface complexation models of U(VI) adsorption on related montmorillonites. Analysis of the binding site on the edges of montmorillonite suggests that U(VI) sorbs preferentially to [Fe(O,OH)₆] octahedral sites over [Al(O,OH)₆] sites. When bound to edge sites, U(VI) occurs as uranyl-carbonato ternary surface complexes in systems equilibrated with atmospheric CO₂. Polymeric surface complexes were not observed under any of the conditions studied. Current surface complexation models of uranyl sorption on clay minerals may need to be reevaluated to account for the possible increased importance of cation exchange reactions at low ionic strengths, the presence of reactive octahedral iron surface sites, and the formation of uranyl-carbonato ternary surface complexes. Considering the adsorption mechanisms observed in this study, future studies of U(VI) transport in the environment should consider how uranium retardation will be affected by changes in key solution parameters, such as pH, ionic strength, exchangeable cation composition, and the presence or absence of CO₂.