The analysis of volatile trace compounds in landfill gases,compost heaps and forest air

Landfill gas, cryotrapped on a loop fashioned from a length of a capillary gas chromatography (GC) column, was examined for volatile organometallic compounds (VOMCs) and for volatile organic compounds (VOCs) by using GC–mass spectrometry (MS). A large number of organic components were present and many were identified, but the only VOMCs present in high enough concentrations to be detected were trimethylstibine and tetramethyltin. The use of inductively coupled plasma (ICP)‐MS as an element‐specific detector allowed the identification of a number of other organometallic species in the landfill gas, including trimethylarsine and trimethylbismuth, and, for the first time, butyltrimethyltin and dibutyldimethyltin. The presence of molybdenum hexacarbonyl was confirmed. Gas from a large‐scale compost heap and from compost incubated in the laboratory contained iodomethane but no common VOMCs (GC–ICP‐MS). Only VOCs were present in forest air (GC–MS). Copyright © 2003 John Wiley & Sons, Ltd.     

Bioaccumulation and excretion of arsenic compounds by a marine unicellular alga,polyphysa peniculus

Polyphysa peniculus was grown in artificial seawater in the presence of arsenate, arsenite, monomethylarsonate and dimethylarsinic acid. The separation and identification of some of the arsenic species produced in the cells as well as in the growth medium were achieved by using hydride generation–gas chromatography–atomic absorption spectrometry methodology. Arsenite and dimethylarsinate were detected following incubation with arsenate. When the alga was treated with arsenite, dimethylarsinate was the major metabolite in the cells and in the growth medium; trace amounts of monomethylarsonate were also detected in the cells. With monomethylarsonate as a substrate, the metabolite is dimethylarsinate. Polyphysa peniculus did not metabolize dimethylarsinic acid when it was used as a substrate. Significant amounts of more complex arsenic species, such as arsenosungars, were not observed in the cells or medium on the evidence of flow injection–microwave digestion–hydride generation–atomic absorption spectrometry methodology. Transfer of the exposed cells to fresh medium caused release of most cell–associated arsenicals to the surrounding environment.     

Simplex optimisation of conditions for the determination of antimony in environmental samples by using electrothermal atomic absorption spectrometry

Analysis of the total antimony in plant material was unsuccessful using the electrothermal atomic absorption spectrometry (ETAAS) conditions recommended by the instrument manufacturer. For this reason, an optimisation procedure utilising the Plackett-Burman method, simplex optimisation and visualisation of the generated response surface via principal components analysis, was carried out. The Plackett-Burman method was used to eliminate four of the initial variables chosen. Four variables (atomisation temperature, atomisation time, ash temperature and modifier concentration) were subsequently optimised using the composite modified simplex method and the results were visualised as a contour diagram, after reduction to two principal components. The optimised conditions were used for the analysis of both an acid digested pine needle standard reference material (NIST 1575) and a pond weed sample, collected from a contaminated site at Yellowknife Bay, Yellowknife, NWT, Canada. The total concentration of antimony present in the pine needles was statistically indistinguishable from the non-certified value, as was the value for the pond weed sample, compared with a value determined by neutron activation analysis (NAA). The results for the analysis of the pond weed sample by ETAAS agreed with those obtained from a subsequent analysis by inductively coupled plasma-mass spectrometry.     

Preparation of some complexes of the type (C6H5)3P[(CH3)2AsCH2CH(R)CH2As(CH3)2] M(CO)3 (M = Mo or W,R = H or C(CH3)3)

The title compounds, which contain six-membered chelate rings locked in the chair conformation, have been prepared by the reaction of (C₆H₅)₃P with the appropriate tetracarbonyl derivative in refluxing mesitylene.