Complex mixtures, PAHs

Actual water treatment challenges are multicomponent. For example, contamination of groundwater by creosote [8021-39-4], a wood (qv) preservative, is a recurring problem in the vicinity of wood-preserving faciUties. Creosote is a complex mixture of 85 wt % polycycHc aromatic hydrocarbons (PAHs) 10 wt % phenohc compounds, including methylated phenols and the remaining 5 wt % N—, S—, and O— heterocycHcs (38). Aqueous solutions of creosote are therefore, in many ways, typical of the multicomponent samples found in polluted aquifers. 

The theory and development of a solvent-extraction scheme for polynuclear aromatic hydrocarbons (PAHs) is described. The use of y-cyclodextrin (CDx) as an aqueous phase modifier makes this scheme unique since it allows for the extraction of PAHs from ether to the aqueous phase. Generally, the extraction of PAHS into water is not feasible due to the low solubility of these compounds in aqueous media. Water-soluble cyclodextrins, which act as hosts in the formation of inclusion complexes, promote this type of extraction by partitioning PAHs into the aqueous phase through the formation of complexes. The stereoselective nature of CDx inclusion-complex formation enhances the separation of different sized PAH molecules present in a mixture. For example, perylene is extracted into the aqueous phase from an organic phase anthracene-perylene mixture in the presence of CDx modifier. Extraction results for a variety of PAHs are presented, and the potential of this method for separation of more complex mixtures is discussed. 

Cyclodextrin-modified solvent extraction has been used to extract several PAHs from ether to an aqueous phase. Data evaluation shows that the degree of extraction is related to the size of the potential guest molecule and that the method successfully separates simple binary mixtures in which one component does not complex strongly with CDx. The most useful application of cyclodextrin-modified solvent extraction is for the simplification of complex mixtures. The combined use of CDx modifier and data-analysis techniques may simplify the qualitative analysis of PAH mixtures. 

The relative biodegradability of components in complex mixtures such as PAHs and PCBs, since some of the less readily degraded components may be the least desirable from an environmental and toxicological viewpoint. 

Complex Mixture of PAHs from Coal Tar PAHs (12) PAHs (18)... 

Kline WF, Wise SA, and May WE (1985) The apphcation of perdeuterated polycydic aromatic hydrocarbons (PAH) as internal standards for the liquid chromatc aphic determination of PAH in petroleum crude oil and other complex mixtures. J Liq Chromatogr 8 223-237. 

Chemicals degraded by WRF include pesticides such as organochlorines DDT and its very toxic metabolite DDE [8, 9] and organophosphate pesticides such as chlorpyrifos, fonofos and terbufos [10] polychlorinated biphenyls (PCBs) of different degrees of chlorine substitution [11-13], some even to mineralization [14, 15] diverse polycyclic aromatic hydrocarbons (PAHs) in liquid media and from contaminated soils or in complex mixtures such as creosote [16-18] components of munition wastes including TNT and its metabolites DNT [19-23], nitroglycerin [24] and RDX [25]. 

The most refractory compounds in the resids may be the PAHs. Those present in residues consists of fused rings of more than six cycles, with molecular weight above 600. Some of the complex larger PAHs isolated and identified are collected in Table 10. These examples probably correspond to the smallest PAH compounds in a resid cut, but worth to set the lowest limit to the level of complexity, from where the reacting mixture starts. 

Human exposure to complex mixtures of polycyclic aromatic hydrocarbons (PAH) occurs through inhalation of tobacco smoke and polluted indoor or outdoor air, through ingestion of certain foods and polluted water, and by dermal contact with soots, tars, and oils CO. Methylated PAH are always components of these mixtures and in some cases, as in tobacco smoke and in emissions from certain fuel processes, their concentrations can be in the same range as some unsubstituted PAH. The estimated emission of methylated PAH from mobile sources in the U.S. in 1979 was approximately 1700 metric tons (2). The occurrence of methylated and unsubstituted PAH has been recently reviewed (1, 2). In addition to their environmental occurrence, methylated PAH are among the most important model compounds in experimental carcinogenesis. 7,12-Dimethylbenz[a]anthracene, one of... 

Petty et al. (1998, 2000) used a vitellogenin (VGT) assay to assess the endocrine disrupting potential of contaminants in purified SPMD extracts. VGT is an egg yolk phosphoprotein precursor that is synthesized in the liver of female teleosts in response to estrogen from the ovary (Bailey, 1957). A wide variety of environmental contaminants have been shown to have estrogenic activity (Colborn et al., 1993). Equal portions of purified extracts from SPMDs, exposed in the Missouri River after the flood of 1993 and from the IWWTP at the Nogales Wash deployment were individually injected into immature rainbow trout (Oncorhynchus mykiss) as described in Section 6.4. The SPMD extracts contained elevated levels of complex mixtures of contaminants, including PAHs and pesticides. The fish injected with these sample extracts exhibited VGT induction, while no induction was observed in fish injected with any of the blank sample extracts. 

Fuel oils are complex mixtures of aliphatic and aromatic hydrocarbons whose exposure potentials are based on the environmental fate of the individual components of the mixtures, particularly -alkanes, branched alkanes, benzene and alkylbenzenes, naphthalenes, and PAHs. 

When epidemiological studies form the basis for the risk assessment of a single chemical or even complex mixtures, such as various combustion emissions, it may be stated that in those cases the effects of combined action of chemicals have been incorporated. Examples can, for instance, be found in the updated WHO Air Quality guidelines (WHO 2000). Thus, the guideline value for, e.g., ozone was derived from epidemiological studies of persons exposed to ozone as part of the total mixture of chemicals in polluted ambient air. In addition, the risk estimate for exposure to polycyclic aromatic hydrocarbons was derived from studies on coke-oven workers heavily exposed to benzo[fl]pyrene as a component of a mixture of PAH and possibly many other chemicals at the workplace. Therefore, in some instances the derivation of a tolerable intake for a single compound can be based on studies where the compound was part of a complex chemical mixture. 

Increased cancer mortality has been associated with exposure to the PAH present in used metal-work cutting oils and mineral oils. The carcinogenic potential of these complex mixtures was related to their PAH... 

Throughout this chapter, we cite examples of the use of the NIST Standard Reference Material SRM 1649, which is referred to as Air Particles or Urban Air Particulate Matter, (a) to validate analytical procedures for determination of PAHs and PACs in samples of complex mixtures of particulate matter in ambient air and (b) for laboratory intercomparisons of methodologies for bacterial bioassays and bioassay-directed fractionations of organic extracts of such mixtures (e.g., see Claxton et al., 1992a Lewtas et al., 1990a, 1992 and May et al., 1992). 

Clearly, a sound evaluation of the total mutagenic/carcinogenic potencies of a complex mixture of POM emissions (e.g., diesel exhaust) should include not only the PEFs of the primary particle- and vapor-phase PAHs and PACs but also those of the mutagens formed in atmospheric reactions of precursor PAHs (see, for example, Arey et al. (1992), Lewtas (1993b), Atkinson and Arey (1994), Nielsen et al. (1996), Arey (1998a), and Section F). For examples of such formal scientific health risk assessments prepared by the State of California Air Resources Board and Office of Environmental Health Hazard Assessment, see Benzo[ ]pyrene as a Toxic Air Contaminant (CARB, 1994) and Identification of Diesel Exhaust as a Toxic Air Contaminant (CARB, 1998). 

Complex mixtures of oxidized products are produced in the ozonolysis of BaP on solid substrates. For example, BaP deposited on a glass fiber filter and exposed to 1 ppm 03 in air primarily formed products characteristic of the ring-opening mechanism, e.g., dialdehydes and dicarboxylic and ketocarboxylic acids. However, some quinones and phenols, were also formed. For details on the mechanisms and O-PAH products of these BaP-Ov gas-solid substrate reactions, see Van Cauwenberghe et al. (1979) and Van Cauwenberghe and Van Vaeck (1983 and references therein). 

The PAH pollution found in these cases consists of an extremely complex mixture of individual PAH compounds. In some cases more than 100 compounds have been identified in the particulate matter from workplace environments (13). This means that, for a complete characterization of the potential hazardous compounds in some of these workplace environments, analytical techniques with very high resolving power, high sensitivity and good reproducibi- lity for quantitative determinations are necessary. At present GC seems to be the best method to meet these requirements (14). 

Often, many simultaneously occurring pollutants or contaminants determine an environmental problem. In industry, agriculture, and households, products are often mixtures of many compounds. The process of production and consumption is accompanied by emissions and consequently by contamination. One example is the use of toxaphene in the past, a very complex mixture of polychlorinated camphenes, as a pesticide. Technical toxaphene consists of more than 175 individual compounds. A second example is industrial and domestic emissions resulting from the combustion of fossil fuels. The emissions contain both a mixture of gases (SO2, NOx, CO2, etc.) and airborne particulate matter which itself contains a broad range of heavy metals and also polycyclic aromatic hydrocarbons (PAH). 

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