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.     

The reaction of 1,2-dilithiotetrafluorobenzene with group V halides

Although the arsenic containing analogue of triptycene, 5,10-$\text{o}$-benzenoarsanthrene $\text{A}$ (E=As) was isolated some time ago [1] the related derivatives of antimony and bismuth are unknown. We now find that when 1,2-diiodotetrafluorobenzene is treated with methyllithium at -78/dg, to afford the little studied dilithiotetrafluorobenzene [2], and the appropriate metal chloride is added to the resulting solution, perfluorinated analogues of $\text{A}$ (E = As, Sb, or Bi) are obtained in good yield. These are stable volatile solids.

     

In situ extraction/preconcentration of PCBs and PAHs from aqueous samples using polytetrafluoroethylene tubing

In situ extraction/preconcentration of organics from water samples was accomplished using polytetrafluoroethylene (PTFE) tubing. Polychlorinated biphenyls (PCBs) and polycyclic aromatic hydrocarbons (PAHs) were concentrated inside the tubing by flowing aqueous samples through it. The adsorbed PCBs and PAHs were then recovered by solvent desorption. The eluent was subsequently analyzed using gas chromatography with electron capture detection (GC-ECD) or gas chromatography with flame ionization detection (GC-FID). Multiple samples were simultaneously processed to concentrate organics onto several PTFE tubings. Analyses of seawater and surface microlayers using this technique demonstrated that organics in the surface microlayers were elevated with respect to those in the water column, consistent with previous findings.     

Determination of urinary arsenic and impact of dietary arsenic intake

An analytical method based on microwave decomposition and flow injection analysis (FIA) coupled to hydride generation atomic absorption spectrometry (HGAAS) is described. This is used to differentiate arsenite [As(III)], arsenate [As(V)], monomethylarsonic acid (MMA) and dimethylarsinic acid (DMA) from organoarsenic compounds usually present in seafood. Without microwave digestion, direct analysis of urine by HGAAS gives the total concentration of As(III), As(V), MMA and DMA because organoarsenic compounds such as arsenobetaine, usually found in most seafood, are not reducible upon treatment with borohydride and therefore cannot be determined by using the hydride generation technique. The microwave oven digestion procedure with potassium persulfate and sodium hydroxide as decomposition reagents completely decomposes all arsenicals to arsenate and this can be measured by HGASS. Microwave decomposition parameters were studied to achieve efficient decomposition and quantitative recovery of arsenobetaine spiked into urine samples. The method is applied to the determination of urinary arsenic and is useful for the assessment of occupational exposure to arsenic without intereference from excess organoarsenicals due to the consumption of seafood. Analysis of urine samples collected from an individual who ingested some seafood revealed that organoarsenicals were rapidly excreted in urine. After the ingestion of a 500-g crab, a 10-fold increase of total urinary arsenic was observed, due to the excretion of organoarsenicals. The maximum arsenic concentration was found in the urine samples collected approximately between 4 to 17 hr after eating seafood. However, the ingestion of organoarsenic-containing seafoods such as crab, shrimp and salmon showed no effect on the urinary excretion of inorganic arsenic, MMA and DMA.     

Fifth-order constant denominator perturbation theory within a localized bond model: Contributions from triple and quadruple excitations

The contributions of the triple and quadruple excitations to the fifth-order perturbation energy for the perturbation configuration interaction using localized orbitals (PCILO ) method are derived. This completes the development of a fifth-order constant denominator perturbation theory initiated in a previous paper [5] with the single and double excitations. This theory is tested on molecules containing strained ring geometries, stretched bonds, strongly polarized bonds, and delocalized pi systems: cases where the starting zero order reference wave function poorly describes the system. Although the perturbation expansions turn out to be slowly convergent, the Padé approximant taken from an energy series which itself is constructed from Padé approximants provides results accurate to within a few kilocalories/mole of benchmark calculations. Computational times as in the original PCILO procedure remain proportional to N³, where N is the number of bonds.