Comprehensive two-dimensional gas chromatography (GC x GC) was used to investigate the chemical composition of the unresolved complex mixture (UCM) of hydrocarbons in petroleum-contaminated marine sediments. The UCM hydrocarbons were extracted and separated with silica and silver-impregnated silica gel chromatography to yield four fractions (branched alkanes and cycloalkanes, monoaromatics, naphthalenes, and multi-ring PAHs) prior to GC x GC analysis. GC x GC separations used a poly-(dimethylsiloxane) stationary phase for volatility selectivity on the first dimension and a 14% cyanopropylphenyl polysiloxane phase for polarity selectivity on the second dimension to fully resolve monoaromatic, naphthalene, and multi-ring PAH compounds from the UCM. A chiral gamma-cyclodextrin phase was used for shape selectivity on the second GC x GC dimension to resolve individual branched alkanes and cycloalkanes in the saturates fraction of the UCM. The ability of GC x GC to resolve thousands of individual chemical components from the UCM will facilitate an understanding of the sources, weathering, and toxicity of UCM hydrocarbons.

The long-term fate of petroleum hydrocarbons in marsh sediments (West Falmouth, MA) contaminated in 1969 by the spill of the barge Florida was investigated. A 36-cm-long sediment core was collected in August 2000, and sediment extracts were analyzed by gas chromatography (GC) and comprehensive two-dimensional gas chromatography (GC x GC). The latter technique is capable of separating 1 order of magnitude more compounds than the former and was used to observe whether any compositional changes in the unresolved complex mixture (UCM) occurred. No evidence of petroleum residues was detected in the top 6 cm (0-6 cm) and the lower 8 cm (28-36 cm) of the core. However, the central sections 16-28 cm) were dominated by a UCM in the boiling range of n-C13-n-C25 alkanes, consistent with a No. 2 fuel oil source. The 12-14- and 14-16-cm sections had the highest concentrations of UCM approximately 8 mg g(-1)). These values are similar to concentrations observed shortly after the spill. Initial GC x GC analysis revealed that only the n-alkanes were completely degraded, and contrary to previous studies, pristane and phytane as well as numerous other branched alkanes are still present in the sediments. These results suggestthatatthis site hydrocarbon contamination will persist indefinitely in the sedimentary record.

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