Inhibition of the reduction of Cr(VI) at the magnetite–water interface by calcium carbonate coatings

The effect of calcium carbonate coatings on the reduction of aqueous chromate on the magnetite(1 1 1) surface has been investigated using a combination of synchrotron based X-ray photoemission spectroscopy (PES) and X-ray absorption near edge structure (XANES) spectroscopy, along with laboratory-based powder X-ray diffraction (XRD) and scanning electron microscopy (SEM). CaCO₃ coatings (dominantly calcite with minor quantities of aragonite and vaterite) of thicknesses ranging from 10 Å to 20 m were grown on magnetite(1 1 1) surfaces by exposure to supersaturated aqueous solutions followed by evaporation of the solution—a process that mimics pore-water evaporation in vadose zones leading to the formation of caliche and calcium carbonate coatings on mineral grains. Coating thicknesses were determined from attenuation of the Fe 2p photoemission signal by the carbonate coating. For coatings less than 15 Å thick, Cr 2p photoemission and Cr L_II, L_III-edge XANES spectra show that chromate is reduced by the underlying magnetite surface; however, as the minimum coating thickness increases beyond 15 Å, the magnetite surface becomes passivated and further chromate reduction ceases. Our findings suggest that carbonate coatings on natural magnetite grains can significantly reduce or eliminate their ability to reduce Cr(VI), which is a toxic and highly mobile environmental contaminant.     

Fluorinations with complex metal fluorides. Part 6 [1] fluorination of yridine and related compounds with caesium tetrafluorocobaltate(III) [2]

Pyridine has been fluorinated over caesium tetrafluorocobaltate(III) (CsCo^IIIF₄) at 300–400°C to give a mixture of undecafluoro-N-methylpyrrolidine, bis(trifluoromethyl)amine, pentafluoropyridine and several polyfluoropyridines; the product composition depended to some extent on the geometry of the reactor. The fluorinations of pentafluoropyridine, piperidine and undecafluoropiperidine were also investigated.     

On the evolution of islands

Letn cells be arranged in a ring, or alternatively, in a row. Initially, all cells are unmarked. Sequentially, one of the unmarked cells is chosen at random and marked until, aftern steps, each cell is marked. After thekth cell has been marked the configuration of marked cells defines some number of islands: maximal sets of adjacent marked cells. Let ξ _k denote the random number of islands afterk cells have been marked. We give explicit expressions for moments of products of ξ _k ’s and for moments of products of 1/ξ _k ’s. These are used in a companion paper to prove that if a random graph on the natural number is made by drawing an edge betweeni≧1 andj>i with probabilityλ/j, then the graph is almost surely connected ifλ>1/4 and almost surely disconnected ifλ≦1/4.     

Concentration for self‐bounding functions and an inequality of Talagrand

We see that the entropy method yields strong concentration results for general self‐bounding functions of independent random variables. These give an improvement of a concentration result of Talagrand much used in discrete mathematics. © 2006 Wiley Periodicals, Inc. Random Struct. Alg., 2006     

Computational investigations of the Prouhet-Tarry-Escott Problem

We describe a method for searching for ideal symmetric solutions to the Prouhet-Tarry-Escott Problem. We report results of extensive searches for solutions of sizes up to 12. We found two solutions of size 10 that are smaller by two orders of magnitude than the solution found by A. Letac in the 1940s, which was the smallest size 10 solution known before our search.

     

Nonlinear dynamics of charged particles interacting with combined ac-dc electromagnetic fields

A nonlinear Lorenz model describing interactions between charged particles and combined ac-dc electromagnetic fields is studied for various combinations of frequencies, field strengths and relative angle (θ) between the ac and dc magnetic fields. Strong directional effects on the magnitude and location of resonant particle motion are observed when θ is varied and the regular resonance windows in the aligned field (θ = 0) and linear version of the model studied previously by Durney etaal., break up to form irregular and less well pronounced regions of large and small particle displacements when nonlinearities are taken into account. The length of time takne to achieve resonant behaviour also becomes larger and more variable when nonlinearities are present. The possible relevance of these effects to interactions between electromagnetic fields and biological media is briefly discussed.