Separation and Detection of Arsenic and Selenium Species in Environmental Samples by HPLC-ICP-MS

A method is presented for arsenic speciation analysis of an oyster sample using ion chromatography coupled with an inductively coupled plasma mass spectrometry (ICP-MS) instrument. A strong anion exchange resin was employed with a step gradient elution of 0.1 mM/0.1 M K 2 SO 4 at pH 10.2. Arsenobetaine and dimethylarsinic acid were determined following extraction based on trypsin enzymolysis with 95-100% extraction efficiency. Limits of detection in the range 0.1-0.3 mg kg m 1 of arsenic were obtained for organic arsenic species. No inorganic arsenic was detected. Validation was performed using TORT-2 as a certified reference material. Although high performance liquid chromatography (HPLC) coupled to ICP-MS is an effective method for speciation analysis it is not always necessary to obtain such a detailed picture. A simple liquid chromatographic separation technique based upon mini-column technology is presented. It was developed to obtain a fast, efficient and reliable separation of inorganic from organic, i.e. assumed toxic from non-toxic, arsenic and selenium species suitable for use as an initial screening method for environmental analysis. Two types of strong anion exchange resin were tested. Excellent separation was obtained for both min-column resins and analysis times were within 7 min. Limits of detection obtained for inorganic arsenic, organic arsenic, selenomethionine, Se IV and Se VI were 1.6, 1.8, 66, 32 and 22 µg kg m 1 , respectively.     

Links between microscopic and macroscopic fluid mechanics

The microscopic and macroscopic versions of fluid mechanics differ qualitatively. Microscopic particles obey time-reversible ordinary differential equations. The resulting particle trajectories {q(t)} may be time-averaged or ensemble-averaged so as to generate field quantities corresponding to macroscopic variables. On the other hand, the macroscopic continuum fields described by fluid mechanics follow irreversible partial differential equations. Smooth particle methods bridge the gap separating these two views of fluids by solving the macroscopic field equations with particle dynamics that resemble molecular dynamics. Recently, nonlinear dynamics have provided some useful tools for understanding the relationship between the microscopic and macroscopic points of view. Chaos and fractals play key roles in this new understanding. Non-equilibrium phase-space averages look very different from their equilibrium counterparts. Away from equilibrium the smooth phase-space distributions are replaced by fractional-dimensional singular distributions that exhibit time irreversibility.     

Gaussian Property of the Rings R(X) and R〈X〉

The content of a polynomial f over a commutative ring R is the ideal c(f) of R generated by the coefficients of f. A commutative ring R is said to be Gaussian if c(fg) = c(f)c(g) for every polynomials f and g in R[X]. A number of authors have formulated necessary and sufficient conditions for R(X) (respectively, R?X?) to be semihereditary, have weak global dimension at most one, be arithmetical, or be Prüfer. An open question raised by Glaz is to formulate necessary and sufficient conditions that R(X) (respectively, R?X?) have the Gaussian property. We give a necessary and sufficient condition for the rings R(X) and R?X? in terms of the ring R in case the square of the nilradical of R is zero.     

Accurate and efficient method for the treatment of exchange in a plane-wave basis

We describe an accurate and efficient extension of Chawla and Voth's [J. Chem. Phys. 108, 4697 (1998)] plane-wave based algorithm for calculating exchange energies, exchange energy densities, and exchange energy gradients with respect to wave-function parameters in systems of electrons subject to periodic boundary conditions. The theory and numerical results show that the computational effort scales almost linearly with the number of plane waves and quadratically with the number of k vectors. To obtain high accuracy with relatively few k vectors, we use an adaptation of Gygi and Baldereschi's [Phys. Rev. B 34, 4405 (1986)] method for reducing Brillouin-zone integration errors.     

Eulerian numbers,Newcomb's problem and representations of symmetric groups

Consider a set of n positive integers consisting of μ₁ 1's, μ₂ 2's,…, μ_rr's. If the integer in the ith place in an arrangement σ of this set is σ(i), and a non-rise in σ is defined as σ(i+1)?σ(i), a problem that suggests itself is the determination of the number of arrangements σ with k non-rises. When each μ_i is unity, the problem is that of finding the number A(n, k) of permutations of distinct integers 1, 2,…, n with k descents, a descent being defined as σ(i+1)<σ(i). The number A(n, k) is known as an Eulerian number. The problem of finding the number of arrangements with k non-rises of the more general set, when not all of μ_i are unity, has appeared in the literature as one part of a problem on dealing a pack of cards, this having been proposed by the American astronomer Simon Newcomb (1835–1909).Both the Eulerian numbers and Newcomb's problem have accumulated a substantial literature. The present paper considers these topics from an entirely new stand-point, that of representations of the symmetric group. This approach yields a well-known recurrence for the Eulerian numbers and a known formula for them in terms of Stirling numbers. It also gives the solutions of the Newcomb problem and some recurrences between these solutions, not all of which have been found earlier. A simple connection is found between Stirling numbers and the Kostka numbers of symmetric group representation theory. The Eulerian numbers can also be expressed in terms of the Kostka numbers.The idea which is novel in this treatment and recurs almost as a motif throughout the paper is that of a skew-hook. This occurs in the first place in a very natural way as a picture of the rises and non-rises of σ, with the nodes of the skew-hook labelled successively as σ(1), σ(2),…. As the paper develops, a new form of skew-hook associated with σ emerges. This does not in general depict the rises and non-rises of σ, and it is now the edges, not the nodes, which carry integer labels. A new type of combinatorial number, here called a ψ-function, arises from these edge-labelled skew-hooks. The ψ-functions are intimately related to the Eulerian numbers and the Newcomb solutions and may have further combinatorial applications. The skew-hook treatment casts fresh light on MacMahon's solution of the Newcomb problem and on his “new symmetric functions”, and, if σ(i)?σ(i+1)?s defines an s-descent in σ, on the enumeration of permutations with ks-descents.Also some characters of the symmetric group with interesting properties and recurrences arise in the course of the paper.