Potentiometric and F nuclear magnetic resonance spectroscopic study of fluoride substitution in the GaAl12 polyoxocation: implications for aluminum (hydr)oxide mineral surfaces

Fluoride replacement of oxygens in the GaO₄Al₁₂(OH)₂₄(H₂O)127+(aq) molecule [GaAl₁₂] was studied via ¹⁹F nuclear magnetic resonance (NMR) at 4 < pH < 5 and 278 K in order to elucidate similar reactions at the surfaces of clays. Peaks are identified in the ¹⁹F-NMR spectra that correspond to both terminal and bridging fluorides on the GaAl₁₂ molecule, with relative peak positions similar to those previously identified in fluoridated aluminum (hydr)oxide mineral surfaces (Nordin, J. P., Sullivan, D. J., Phillips, B. L., and Casey, W. H. [1999], “Mechanisms for fluoride-promoted dissolution of bayerite [β-Al(OH)₃(s)] and boehmite [γ-AlOOH(s)]-¹⁹F-NMR spectroscopy and aqueous surface chemistry,” Geochim. Cosmochim. Acta63, 3513-3524). Fluoride substitutes for oxygen at three different sites in the GaAl₁₂ molecule, but at dramatically different rates.The kinetics of fluoride substitution follow a rate law that includes parallel and reversible transfer of fluoride from nonbridging sites to the two bridging sites. The essential features of the rate law are as follows: (1) fluoride replaces bound water molecules (η-OH₂) within minutes at 278 K at rates that are quantitatively similar to fluoride uptake by Al(H₂O)63+(aq) to form AlF²⁺(aq) at similar conditions; (2) fluoride substitutes onto the two topologically distinct μ₂-OH sites at different rates, as was previously observed for oxygen exchange, but here, the reaction is complete in hours to days at 278 K. Most importantly, rates of fluoride substitution onto μ₂-OH sites are 10² times more rapid than the corresponding rates of oxygen exchange with bulk waters, indicating that fluoride considerably labilizes the molecule, as is also observed at the surfaces of minerals. The largest cause of this labilization is the reduced molecular charge on the GaAl₁₂ upon replacement of bound waters by fluoride, which for mineral surfaces corresponds to a reduction in surface charge density.     

Some general relations of the development of complex molecular objects at early stages of biosphere formation as a consequence of the physical properties of condensed medium

We analyzed the character of molecular transformations under conditions of condensed media, in which intermolecular interactions always occur. It was shown that, instead of discrete transfer of external energy into the molecule, the energy characteristics of the condensed medium (appearance of zones) could result in gradual accumulation of internal energy in reaction centers owing to sequential thermal collisions with particles of the medium initiating the chemical reaction. This does not require high temperatures. The established physical properties related to the energy characteristics of condensed media could play an important role in molecular transformations and, consequently, formation of complex molecular objects at early stages of biosphere formation.     

Zonal flows,Rossby waves,and vortex transport in laboratory experiments with rotating annular channel

Results of experiments are considered for flows generated by different sources-sinks of mass in the rotating annular channel with beta-effect simulation using the inclined bottom. Diagrams of regimes are presented in parameters of the dimensionless angular velocity of the zonal flow averaged over the channel width and the dimensionless angular velocity of transport of vortex perturbations of cyclonic and anticyclonic types. In experiments and the simplest linear theories, most attention is paid to diagram regions with a slow motion of vortices relative to the rotating coordinate system near the parameters for stationary Rossby waves.     

The concentration and composition of polyaromatic hydrocarbons in small rivers in the drainage area of the eastern Gulf of Finland

The results of examining the concentrations of 16 major polycyclic aromatic hydrocarbons are given. The examined samples were taken in the territory of Leningrad province and in the eastern Gulf of Finland in different seasons. Two seasonal natural profiles of polycyclic aromatic hydrocarbons were constructed, conventionally, for the spring and the autumn. The dominating effect on the formation of the profile of polycyclic aromatic hydrocarbons is exerted by pyrogenous pollution sources in winter and petrogenic pollution sources in summer.     

Fossil brines preserved in the St-Lawrence Lowlands, Québec, Canada as revealed by their chemistry and noble gas isotopes

Brines in Cambrian sandstones and Ordovician dolostones of the St-Lawrence Lowlands at Bécancour, Québec, Canada were sampled for analysis of all stable noble gases in order to trace their origin and migration path, in addition to quantifying their residence time. Major ion chemistry indicates that the brines are of Na-Ca-Cl type, possibly derived from halite dissolution. ⁸⁷Sr/⁸⁶Sr ratios and Ca excess indicate prolonged interactions with silicate rocks of the Proterozoic Grenville basement or the Cambrian Potsdam sandstone. The brines constrain a 2-3% contribution of mantle ³He and large amounts of nucleogenic ²¹Ne^∗ and ³⁸Ar^∗ and radiogenic ⁴He and ⁴⁰Ar^∗. ⁴He/⁴⁰Ar^∗ and ²¹Ne^∗/⁴⁰Ar^∗ ratios, corrected for mass fractionation during incomplete brine degassing, are identical to their production ratios in rocks. The source of salinity (halite dissolution), plus the occurrence of large amounts of ⁴⁰Ar^∗ in brines constrain the residence time of Bécancour brines as being older than the Cretaceous. Evaporites in the St-Lawrence Lowlands likely existed only during Devonian-Silurian time. Brines might result from infiltration of Devonian water leaching halite, penetrating into or below the deeper Cambrian-Ordovician aquifers. During the Devonian, the basin reached temperatures higher than 250 °C, allowing for thermal maturation of local gas-prone source rocks (Utica shales) and possibly facilitating the release of radiogenic ⁴⁰Ar^∗ into the brines. The last thermal event that could have facilitated the liberation of ⁴⁰Ar^∗ into fluids and contributed to mantle ³He is the Cretaceous Monteregian Hills magmatic episode. For residence times younger than the Cretaceous, it is difficult to find an appropriate source of salinity and of nucleogenic/radiogenic gases to the Bécancour brines.     

The Salamón gold deposit (León, Spain)

Located 55 km NE of the provincial capital León, Salamón deposit, discovered in 1985, is located on the southern slope of the Cantabrian Mountains, in the north of the Iberian Peninsula. The deposit is located on the León fault, which is a late-Variscan, E–W trending, deep structure extending for more than 100 km. The León fault has a complex history, and many mines and occurrences are located near it. The deposit is also close to small stocks and dykes of igneous rocks with intermediate to basic composition to which the mineralisation is related. The mineralisation is hosted mainly by the limestones and bituminous shales of the Lena Group (Namurian–Westphalian). There is also some mineralisation in other stratigraphic units of the Upper Carboniferous, such as the Maraña Group or the Stephanian B sediments.Apart from local and regional exploration, a detailed mineralogical and metallogenic research has been carried out. The epithermal mineralisation of Salamón was developed in two phases: an early dominant and extensive stage, with very fine crystalline gold-bearing sulphides, mainly pyrite, arsenic-bearing pyrite and arsenopyrite, in a matrix of quartz–chalcedony (jasperoid) and dolomite, and a later stage, of a larger crystal size, which occurs replacing the early stage or in pockets and veins, with greater mineralogical variety. Last of all there is a stage of supergene mineralisation, a product of the oxidant action of meteoric waters over the previous minerals. The hydrothermal alterations of the host rocks related to the orebodies are fundamentally decarbonatisation–dolomitisation, silicification and argillitisation. The early stages of mineralisation were produced in a temperature of 148–241°C, while that in the later stages occurred at 86–123°C. The early stage has been dated as 269±5 Ma, and this agrees with the ages of the other deposits of the district, which lay between 292 and 263 Ma, and the igneous rocks of the Peña Prieta stock (277±1 Ma), all which are of Permian age.The results of the studies carried out until now lead to the conclusion that Salamón is a Carlin-type gold deposit.