Mulinane and Azorellane Diterpenoid Biomarkers by GC-MS from a Representative Apiaceae (Umbelliferae) Species of the Andes.

Extracts of bled resin from Azorella compacta, of the Azorelloideae family from the Andes (>4000 m), were analyzed by gas chromatography-mass spectrometry. The mass spectra of the dominant compounds of the resin and its hydrogenation products were documented. The most abundant compounds were oxygenated diterpenoids, namely mulinadien-20-oic (Δ11,13 and Δ11,14) acids, azorell-13-en-20-oic acid, 13α,14ß-dihydroxymulin-11-en-20-oic acid, and azorellanol, with a group of azorellenes and mulinadienes. The mass spectra of the novel diterpenoid hydrocarbons with the azorellane and mulinane skeletons were also presented. This study documents the molecular diversity of these diterpenoid classes, and could be of great utility for future organic geochemical, environmental, archeological, pharmaceutical, and forensic chemistry studies.

Combustion products of plastics as indicators for refuse burning in the atmosphere.

Despite all of the economic problems and environmental discussions on the dangers and hazards of plastic materials, plastic production worldwide is growing at a rate of about 5% per year. Increasing techniques for recycling polymeric materials have been developed during the last few years; however, a large fraction of plastics are still being discarded in landfills or subjected to intentional or incidental open-fire burning. To identify specific tracer compounds generated during such open-fire combustion, both smoke particles from burning and plastic materials from shopping bags, roadside trash, and landfill garbage were extracted for gas chromatography-mass spectrometry analyses. Samples were collected in Concón, Chile, an area frequently affected by wildfire incidents and garbage burning, and the United States for comparison. Atmospheric samples from various aerosol sampling programs are also presented as supportive data. The major components of plastic extracts were even-carbon-chain n-alkanes (C16-C40), the plasticizer di-2-ethylhexyl phthalate, and the antioxidants and lubricants/antiadhesives Irganox 1076, Irgafos 168, and its oxidation product tris(2,4-di-tertbutylphenyl) phosphate. Major compounds in smoke from burning plastics include the non-source-specific n-alkanes (mainly even predominance), terephthalic acid, phthalates, and 4-hydroxybenzoic acid, with minor amounts of polycyclic aromatic hydrocarbons (including triphenylbenzenes) and tris(2,4-di-tert-butylphenyl)phosphate. 1,3,5-Triphenylbenzene and tris(2,4-di-tert-butylphenyl)- phosphate were found in detectable amounts in atmospheric samples where plastics and refuse were burned in open fires, and thus we propose these two compounds as specific tracers for the open-burning of plastics.

Sugars--dominant water-soluble organic compounds in soils and characterization as tracers in atmospheric particulate matter.

The presence of saccharides is being reported for aerosols taken in urban, rural, and marine locales. The commonly found primary saccharides are alpha- and beta-glucose, alpha- and beta-fructose, sucrose, and mycose with lesser amounts of other monosaccharides. Saccharide polyols are also found in some airsheds and consist mainly of sorbitol, xylitol, mannitol, erythritol, and glycerol. In temperate climate areas these compounds increase from negligible concentrations in winter aerosols (usually dominated by levoglucosan and related anhydrosaccharides from biomass burning) to a maximum in late spring-summer, followed by a decrease to winter. The composition of the saccharide mixtures suggests soil and associated microbiota as the source. Saccharide analyses of soils confirmed these compositions. Therefore, we propose resuspension of soil (also unpaved road dust) from agricultural activities as a major component of aerosol particles and the saccharides are the source specific tracers. In addition, the saccharides as well as the anhydrosaccharide derivatives from biomass burning are completely water soluble and thus contribute significantly to the total water-soluble mass of aerosols.