Biodegradation preference for isomers of alkylated naphthalenes and benzothiophenes in marine sediment contaminated with crude oil

Abstract

Contamination of coastal marine sediments with polycyclic aromatic hydrocarbons is pervasive, with major sources including anthropogenic activity and natural seepage. Biodegradation serves as a major hydrocarbon sink with evaporation and dissolution responsible for the removal of low boiling range compounds and photo-oxidation acting on many multi-substituted aromatic compounds. In this work, first-order rate constants for aerobic biodegradation were quantified for naphthalene (N), benzothiophene (BT) and their alkylated congeners (1–4 carbon substituents (C1–C4)) in laboratory experiments with oil laden marine sediments from a natural seep. Rate constants were used as proxies for microbial preference, which follows the order: naphthalene > C1N > C2N > C1BT > C2BT > benzothiophene > C3BT > C3N > C4BT > C4N, with some overlap. The application of comprehensive two dimensional gas chromatography further enabled separation and quantification of multiple structural isomers for C2N–C4N and C2BT–C4BT, with 7–12 isomers resolved for each C2N–C4N and 4–7 isomers resolved for each C2BT–C4BT. A strong isomeric biodegradation preference was noted within each of these compound classes, with rate constants varying as much as a factor of 2 for structural isomers of the same compound class. Each isomer was consumed to a low, but non-zero concentration, suggesting that their residual load in sediment may be proportional to the number of structural isomers originally present, in addition to the pattern and the number of alkyl substitutions. The simultaneous first-order biodegradation rates observed for 52 aromatic hydrocarbons resolved in this study, along with reference compounds such as n-alkanes, lends support to the concept of broad scale metabolic specificity during aerobic biodegradation of petroleum.