Abstract
In recent decades. an exponential increase in the concentration of anthropogenic Polycyclic Aromatic Hydrocarbons (PAHs; see Table I for a li st of PAH abbreviations) has been observed worldwide. Regulators need to know the sources if concentrations are to be reduced and appropriate remediation measures taken. "Source characterization of PAHs" involves linking these contaminants to their sources. Scientists place PAH sources into three classes: pyrogenic, petrogenic. and natural. In this review. we investigate the possibility of using PAH molecular ratios individually or in combination for the purpose of deducing the petrogenic or pyrogenic origin of the contamination in sediments. We do this by reviewing the characteristic PAH patterns of the sources and by taking into account the fate of PAHs in the aquatic environment. Many PAH indicators have been developed for the purpose of discriminating different PAH sources. In Table 4 we summarize the applicability of different PAH ratios and threshold values. The analysis of two- to four-ringed alkylated PAH soilers the possibility to distinguish two or more single sources or categories of pollution in greater detail. For example. the FLO/PYO. the PPI. and PO/AO ratios can be used to discriminate between pyrogenic and petrogcnic sources of contamination. When petrogenic contamination is suspected. chrysenes. PAHs lighter than CO. and in particular. alkylated PAHs can usually be of use. For unburned coal PAHs. The methylphenanthrenic ratios (MP!s). the 1-D I/4- DI. and BbF/BkF are promising, since they are sometimes correlated with vitrinite rellectance (coal ranks). Alkylphenanthrenes can be used to detect biomass combustion. Higher molecular weight parent and alkylated PAHs are appropriate for pyrogenic discriminations. When PAH indices are coupled with discriminant analysis techniques such as PMF (positive matrix factorization),the origin of multiple sources in even the most complex environments can be traced and measured. Even so. the most stable isomer pairs degrade differentially. depending on their thermodynamic stability, the environmental conditions, and the type of degradation. If PAH ratios are to be used, it is usually necessary to have pri or knowledge of the degradation state of the matrices examined (air, sediment, etc.) and of how the PAH ratio behaves under such conditions. PAH ind ices (e.g ., NO/CO or LPAH/HPAH ) can be app lied for distinguishing differential degradation gradients (photodegradation, biodegradation, etc.). Degradation does not significantly affect the ratio of parent to alkylated PAHs and the PI. The degradation arrow in Table 4 and Figs. 9. I 0. II . 12. 13, 14. 15. 17. 18. 19, 20, 2 1, 22. 23. and 24 shows how the ratio usually changes with degradation. Merely detecting the six PAHs of Borneff6 is not enough to establish petrogenic contamination, because Borneff6 includes main ly HMW PAHs. The LPAH 16 appears to be the most suitable for identify ing pyrogenic and petrogenic sources. For more specific information on sources and their discrimination it is recommended to further take into account important parent PAHs such as NO. BeP. PER. DO. and-most importantly- alkylatcd PAHs.
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