Determination of lewisite constituents in aqueous samples using hollow-fibre liquid-phase microextraction followed by gas chromatography-mass spectrometry

The applicability of hollow-fibre liquid-phase microextraction for extracting 2-chlorovinyldichloroarsine (lewisite 1), bis(2-chlorovinyl)chloroarsine (lewisite 2), tris(2-chlorovinyl)arsine (lewisite 3) and arsenic trichloride from aqueous samples is reported. Parameters affecting the extraction efficiency of these chemicals were optimised. These parameters included the type of derivatising agent, extraction solvent, derivatisation method, pH, ionic strength, stirring speed and extraction time. A linear range between 0.002 and 0.2 μg/mL was established for the lewisites with good square regression coefficients (0.9955–0.9992). Good reproducibility with relative standard deviations (RSDs) from 8 to 10 % was achieved. The limit of detection was 0.002 μg/mL for the lewisites and 0.005 μg/mL for arsenic trichloride (3:1 signal-to-noise ratio). The extraction method was validated with a proficiency test sample issued by the Organisation for the Prohibition of Chemical Weapons (OPCW). The rapidity and precision of the new method should help deter against the employment of lewisite as a chemical warfare agent: its use could be confirmed easily from analysis of aqueous samples.     

Upper bound for neutron emission from sonoluminescing bubbles in deuterated acetone

An experimental search for nuclear fusion inside imploding bubbles of degassed deuterated acetone at 0 degrees C driven by a 15 atm sound field and seeded with a neutron generator reveals an upper bound that is a factor of 10 000 less than the signal reported by Taleyarkhan et al. The strength of our upper bound is limited by the weakness of sonoluminescence, which we ascribe to the relatively high vapor pressure of acetone.     

Trace element speciation in largemouth bass ( Micropterus salmoides) from a fly ash settling basin by liquid chromatography-ICP-MS

Analytical techniques used to examine the chemical speciation of multiple trace elements are important for the investigation of biological systems. Size exclusion chromatography (SEC) coupled to ICP-MS was used to investigate the speciation of Se, As, Cu, Cd and Zn in tissue extracts from a largemouth bass (Micropterus salmoides) collected from a coal fly ash basin and results were compared to a largemouth bass collected at a reference site. Using a Biosil SEC column, with an effective separation range of 100-7 KDa, Cu, Zn and Cd were shown to be bound to metallothionein (MT) in the liver, gill and, to a lesser extent, gonad tissue extract. In liver, muscle and gill of the ash basin bass, Se was predominantly present as low molecular weight species. Only in the gonad extract was the major fraction of Se associated with high molecular weight species. For the liver and gill extracts, further SEC-ICP-MS on a column with an effective separation range of 7000-500 Da was performed, but Se species still eluted near the total volume of the column suggesting a low molecular weight organic or inorganic species. Ion chromatography (IC)-ICP-MS using an AS7 column and HNO(3) gradient elution indicated that the Se and As species in the liver and gill extracts had similar retention times but these retention times did not correspond to retention times for As(III), As(V), dimethylarsenate, arsenobetaine, Se(IV), Se(VI), seleno-methionine, or seleno-cystine.     

Auger and electron energy loss spectra of adsorbed species: α and β states of carbon monoxide and nitrogen on W(100)

Auger and electron energy loss spectra have been recorded for both α and β chemisorbed states of carbon monoxide and nitrogen on W(100). The α state spectra have been analysed with reference to results for the gas phase molecules, those for the β states have been analysed following a quasi-atomic final state model. The results illustrate both the potential and the limitations of AES and ELS in surface chemical analysis.     

On the dynamics of plastic circular plates

The paper is concerned with the dynamics of a thin circular plate made of a plastic-rigid material that obeys the yield condition ofTresca and the associated flow rule. The basic equations are established in the case of rotational symmetry, and their complete solution is given for a simply supported plate subjected to a uniformly distributed load which is brought on suddenly and, after a certain time interval, removed suddenly.

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Résumé Cet article étudie la dynamique d'une plaque circulaire infiniment mince fabriquée avec un matériau plastique qui obéit à la condition de plasticité deTresca et à la loi d'écoulement associée. Les équations fondamentales sont établies dans le cas où existe une symétrie de révolution. Leur solution complète est donnée pour une plaque reposant sur des appuis simples, soumise à une charge uniformément répartie qui est appliquée rapidement et demeure constante pendant un certain temps, après lequel elle est rapidement retirée.

     

Dynamic strain-birefringence apparatus for polymer films

A new apparatus for investigating dynamic strain birefringence in polymer films at frequencies up to 10 Hz and at various degrees of internal sample orientation is described. Samples are elongated at constant low rates while simultaneously being strained sinusoidally. Fast changes in sample retardance are recorded while slow changes are automatically compensated with a servo-controlled Soleil-Babinet compensator. The signal-to-noise ratio of the system is greatly enhanced by incorporating a highly monochromatic laser light source, a synchronous amplifier, and a light beam modulator based on a rotating polarizer. Data obtained from this apparatus can be used to elucidate polymer relaxation mechanisms at various frequencies over a wide range of static strains.     

The diffusion of carbon to and from W(100)

The equilibrium segregation in the system W(100) plus two monolayers of total carbon content has been studied in the range 1600 to 2073 K. The energy of segregation is ?56(±2) kcal mole^?1. The kinetics of carbon segregation at 1350 and 1420 K were observed. From a semi-empirical treatment an upper limit to the activation energy for volume diffision is deduced to be 59 (±8) kcal mole^?1.     

Theoretical and Empirical Relationships Between the Redox Potentials and <Superscript>1</Superscript>(<Emphasis Type="Italic">δ</Emphasis>→<Emphasis Type="Italic">δ</Emphasis>*) Transition Energies of Quadruply Bonded Complexes

An analysis of the available electrochemical and electronic-sectroscopic data for quadruply metal–metal bonded complexes reveals that the ¹(*) transition energy is an approximately linear function of the difference between the electrode potentials at which they are reduced and oxidized to the bond-order 3. 5 complexes. A theoretical framework for interpreting this correlation is provided by extending to the redox potentials a simple zero-differential-overlap model previously applied to ¹(*) transition energies. It is suggested on the basis of this model that the simplicity of the empirical relationship between ¹(*) energies and redox potentials is a consequence of the particular one- and two-electron energy terms that characterize these complexes; a linear relationship is not required by theory.