On the composition of dissolved and particle-associated fossil fuel residues in Mediterranean surface water

Abstract

Gas chromatography-mass spectrometry (GC-MS) analyses of organic concentrates from eastern Mediterranean surface water show that dissolved fossil fuel residues are dominated by unsubstituted aromatic hydrocarbons and heterocyclic aromatics and thus resemble products of incomplete combustion. Deviating from this interpretation, preferential photochemical oxidation of alkyl-substituted aromatics is suggested as the principal causative mechanism, although, especially near land-based sources. the influence of combustion-derived unsubstituted aromatics is not defined. Total concentrations of dissolved aromatics as determined by GC-FID (flame ionization detection) and GC-MS from a limited data subset were in reasonable agreement with UV fluorescence measurements of dissolved/dispersed oil residues. The same preponderance of unsubstituted aromatics over their alkyl derivatives was found in extracts of the particulate phase, but concentrations were small relative to alkanes and/or alkenes of recent marine biosynthetic origin. CPI (carbon preference index) values of higher molecular weight n-alkanes indicated varying contributions of plant waxes to the particulate hydrocarbon pool. CPI values of corresponding dissolved n-alkanes were found to be near unity, indicating fossil fuel origin. Despite differences in higher molecular weight n-alkane CPI values and the predominance of recent biosynthetic aliphatics, the similarity of dissolved and particulate aromatic fractions suggests limited adsorption by particles of fossil fuel derived hydrocarbons and heterocyclics.