A review of biomarker compounds as source indicators and tracers for air pollution

An overview of the application of organic geochemistry to the analysis of organic matter on aerosol particles is presented here. This organic matter is analyzed as solvent extractable bitumen/ lipids by gas chromatography-mass spectrometry. The organic geochemical approach assesses the origin, the environmental history and the nature of secondary products of organic matter by using the data derived from specific molecular analyses. Evaluations of production and fluxes, with cross-correlations can thus be made by the application of the same separation and analytical procedures to samples from point source emissions and the ambient atmosphere. This will be illustrated here with typical examples from the ambient atmosphere (aerosol particles) and from emissions of biomass burning (smoke). Organic matter in aerosols is derived from two major sources and is admixed depending on the geographic relief of the air shed. These sources are biogenic detritus (e.g., plant wax, microbes, etc.) and anthropogenic particle emissions (e.g., oils, soot, synthetics, etc.). Both biogenic detritus and some of the anthropogenic particle emissions contain organic materials which have unique and distinguishable compound distribution patterns (C₁₄-C₄₀). Microbial and vascular plant lipids are the dominant biogenic residues and petroleum hydrocarbons, with lesser amounts of the pyrogenic polynuclear aromatic hydrocarbons (PAH) and synthetics (e.g., chlorinated compounds), are the major anthropogenic residues. Biomass combustion is another important primary source of particles injected into the global atmosphere. It contributes many trace substances which are reactants in atmospheric chemistry and soot paniculate matter with adsorbed biomarker compounds, most of which are unknown chemical structures. The injection of natural product organic compounds into smoke occurs primarily by direct volatilization/steam stripping and by thermal alteration based on combustion temperature. Although the molecular composition of organic matter in smoke particles is highly variable, the molecular tracers are generally still source specific. Retene has been utilized as a tracer for conifer smoke in urban aerosols, but is not always detectable. Dehydroabietic acid is generally more concentrated in the atmosphere from the same emission sources. Degradation products from biopolymers (e.g., levoglucosan from cellulose) are also excellent tracers. An overview of the biomarker compositions of biomass smoke types is presented here. Defining additional tracers of thermally-altered and directly-emitted natural products in smoke aids the assessment of the organic matter type and input from biomass combustion to aerosols. The precursor to product approach of compound characterization by organic geochemistry can be applied successfully to provide tracers for studying the chemistry and dispersion of ambient aerosols and smoke plumes. Presented at the 6th FECS Conference on Chemistry and the Environment, Atmospheric Chemistry and Air Pollution, August 26–28, 1998, Copenhagen.     

车内空气中挥发性有机物的研究

采用热脱附-气相色谱/质谱联用法对4辆处于静止状态下的车辆内部空气中挥发性有机物（VOCs）进行了研究,共定性检出了48种有机物,其中C6～C9之间的组分较多;并对VOCs的总浓度进行了定量,1#～4#车分别为1846、2289、1104和3146 μg/m^3;其中BTEX占VOCs总量的20%～30%;车内VOCs浓度与温度及车辆使用年限密切相关.     

Distribution of endocrine disruptors in the Llobregat River basin (Catalonia, NE Spain)

The Llobregat basin is a Mediterranean fluvial system with major agricultural, urban and industrial impacts. We combined chemical quantification by liquid chromatography–mass spectrometry with electrospray interface (LC-ESI-MS) and the recombinant yeast assay (RYA) assays to estimate the loads of endocrine disrupting compounds (EDCs) along the basin. Chemical analysis revealed maximum concentrations (at μg l⁻¹ level) of alkylphenols at the lower course of the Llobregat River, which correlated with high levels of estrogenic activity detected by RYA. Analysis by RYA and LC-ESI-MS of influent and effluent waters from four sewage treatment plants (STP) discharging into the basin showed the removal of 80–95% of EDCs by STP treatment. Chemical analysis data and RYA data showed a quasi-linear correlation, demonstrating the complementariness of both methods. Our data suggest that the concentrations of the analysed compounds were enough to explain the total estrogenicity of water and STP samples from the Llobregat basin.     

Levels of organochlorine pesticides and polychlorinated biphenyls in the critically endangered Iberian lynx and other sympatric carnivores in Spain

Accumulation of organochlorine compounds is well studied in aquatic food chains whereas little information is available from terrestrial food chains. This study presents data of organochlorine levels in tissue and plasma samples of 15 critically endangered Iberian lynx (Lynx pardinus) and other 55 wild carnivores belonging to five species from three natural areas of Spain (Doñana National Park, Sierra Morena and Lozoya River) and explores their relationship with species diet. The Iberian lynx, with a diet based on the consumption of rabbit, had lower PCB levels (geometric means, plasma: <0.01 ng mL⁻¹, liver: 0.4 ng g⁻¹ wet weight, fat: 87 ng g⁻¹ lipid weight) than other carnivores with more anthropic and opportunistic foraging behavior, such as the red fox (Vulpes vulpes; plasma: 1.11 ng mL⁻¹, liver: 459 ng g⁻¹, fat: 1984 ng g⁻¹), or with diets including reptiles at higher proportion, such as the Egyptian mongoose (Herpestes ichneumon; plasma: 7.15 ng mL⁻¹, liver: 216 ng g⁻¹, fat: 540 ng g⁻¹), or the common genet (Genetta genetta; liver: 466 ng g⁻¹, fat: 3854 ng g⁻¹). Chlorinated pesticides showed interspecific variations similar to PCBs. Organochlorine levels have declined since the 80s in carnivores from Doñana National Park, but PCB levels are still of concern in Eurasian otters (Lutra lutra; liver: 3873-5426 ng g⁻¹) from the industrialized region of Madrid.     

Mass flows of perfluorinated compounds (PFCs) in central wastewater treatment plants of industrial zones in Thailand

Perfluorinated compounds (PFCs) are fully fluorinated organic compounds, which have been used in many industrial processes and have been detected in wastewater and sludge from municipal wastewater treatment plants (WWTPs) around the world. This study focused on the occurrences of PFCs and PFCs mass flows in the industrial wastewater treatment plants, which reported to be the important sources of PFCs. Surveys were conducted in central wastewater treatment plant in two industrial zones in Thailand. Samples were collected from influent, aeration tank, secondary clarifier effluent, effluent and sludge. The major purpose of this field study was to identify PFCs occurrences and mass flow during industrial WWTP. Solid-phase extraction (SPE) coupled with HPLC-ESI-MS/MS were used for the analysis. Total 10 PFCs including perfluorooctane sulfonate (PFOS), perfluorooctanoic acid (PFOA), perfluoropropanoic acid (PFPA), perfluorohexanoic acid (PFHxA), perfluoroheptanoic acid (PFHpA), perfluorohexane sulfonate (PFHxS), perfluoronanoic acid (PFNA), perfluordecanoic acid (PFDA), perfluoroundecanoic acid (PFUnA), and perfluorododecanoic acid (PFDoA) were measured to identify their occurrences. PFCs were detected in both liquid and solid phase in most samples. The exceptionally high level of PFCs was detected in the treatment plant of IZ1 and IZ2 ranging between 662-847 ng L⁻¹ and 674-1383 ng L⁻¹, respectively, which greater than PFCs found in most domestic wastewater. Due to PFCs non-biodegradable property, both WWTPs were found ineffective in removing PFCs using activated sludge processes. Bio-accumulation in sludge could be the major removal mechanism of PFCs in the process. The increasing amount of PFCs after activated sludge processes were identified which could be due to the degradation of PFCs precursors. PFCs concentration found in the effluent were very high comparing to those in river water of the area. Industrial activity could be the one of major sources of PFCs contamination in the water environment.     

Partitioning behaviour of perfluorinated alkyl contaminants between water, sediment and fish in the Orge River (nearby Paris, France)

This paper reports on the partitioning behaviour of 15 perfluorinated compounds (PFCs), including C₄-C₁₀ sulfonates and C₅-C₁₄ carboxylic acids, between water, sediment and fish (European chub, Leuciscus cephalus) in the Orge River (nearby Paris). Total PFC levels were 73.0 ± 3.0 ng L⁻¹ in water and 8.4 ± 0.5 ng g⁻¹ in sediment. They were in the range 43.1-4997.2 ng g⁻¹ in fish, in which PFC tissue distribution followed the order plasma > liver > gills > gonads > muscle. Sediment-water distribution coefficients (log K_d) and bioaccumulation factors (log BAF) were in the range 0.8-4.3 and 0.9-6.7, respectively. Both distribution coefficients positively correlated with perfluoroalkyl chain length. Field-based biota-sediment accumulation factors (BSAFs) are also reported, for the first time for PFCs other than perfluorooctane sulfonate. log BSAF ranged between −1.3 and 1.5 and was negatively correlated with the perfluoroalkyl chain length in the case of carboxylic acids.     

Biodegradation during contaminant transport in porous media: 4. Impact of microbial lag and bacterial cell growth

Miscible-displacement experiments were conducted to examine the impact of microbial lag and bacterial cell growth on the transport of salicylate, a model hydrocarbon compound. The impacts of these processes were examined separately, as well as jointly, to determine their relative effects on biodegradation dynamics. For each experiment, a column was packed with porous medium that was first inoculated with bacteria that contained the NAH plasmid encoding genes for the degradation of naphthalene and salicylate, and then subjected to a step input of salicylate solution. The transport behavior of salicylate was non-steady for all cases examined, and was clearly influenced by a delay (lag) in the onset of biodegradation. This microbial lag, which was consistent with the results of batch experiments, is attributed to the induction and synthesis of the enzymes required for biodegradation of salicylate. The effect of microbial lag on salicylate transport was eliminated by exposing the column to two successive pulses of salicylate, thereby allowing the cells to acclimate to the carbon source during the first pulse. Elimination of microbial lag effects allowed the impact of bacterial growth on salicylate transport to be quantified, which was accomplished by determining a cell mass balance. Conversely, the impact of microbial lag was further investigated by performing a similar double-pulse experiment under no-growth conditions. Significant cell elution was observed and quantified for all conditions/systems. The results of these experiments allowed us to differentiate the effects associated with microbial lag and growth, two coupled processes whose impacts on the biodegradation and transport of contaminants can be difficult to distinguish.     

Sorption of polar and nonpolar aromatic compounds to four surface soils of eastern China

Improved predictions on the fate of organic pollutants in surface environments require a better understanding of the underlying sorption mechanisms that control their uptake by soils. In this study, we monitored sorption of nine aromatic compounds with varying physicochemical properties (hydrophobicity, electron-donor/acceptor ability and polarity), including two polycyclic aromatic hydrocarbons, two chlorobenzenes, two nitroaromatic compounds, dichlobenil, carbaryl and 2,4-dichlorophenol in aqueous suspension of four surface soils of eastern China. The tested soils were characterized with respect to organic carbon (OC) content, black carbon content, mineralogy, morphology and size fraction to assess the role of the diverse soil characteristics in sorption. The results of this study show that not only the solute hydrophobicity and the OC content of soil are important to the retention of organic pollutants, but also the solute molecular structure and the soil nature.     

Characterization of Organic Compounds in Compost-Amended Soil

Samples of compost-amended soil from waste dumping sites in Lagos Metropolis were extracted with dichloromethane (3 × 20 cm³) and the extract was evaporated at 35 °>C. The residue was extracted with 2,2,4-trimethylpentane, and portions of the solution were applied to a column containing silica gel from which aliphatic and aromatic hydrocarbons were eluted with n-hexane and toluene respectively. Analysis of the n-hexane fraction using gas chromatography showed the presence of a mixture of aliphatic hydrocarbons, ranging from C₉ to C₂₅, while ultraviolet analysis of the toluene fraction suggested 1,2-benzanthracene; 2,3-benzphenanthrene, chrysene and pyrene as polyaromatic compounds present in samples analyzed. The crude extracts were highly coloured and viscous. Total extractable organic residues in the 2,2,4-trimethylpentane extracts ranged from 36 to 89 mg g^-1 of soil.