Sources and composition of natural and anthropogenic hydrocarbons in sediments from an impacted estuary

Hydrocarbons in estuarine sediments provide information on sources of sedimentary organic matter (OM), and they are thus useful for tracing natural and anthropogenic OM inputs to the estuary. Here, we assessed the amounts, compositions and sources of natural and anthropogenic hydrocarbons from the sediments of a large, ecologically important estuary, Mobile Bay in Southeast USA. TOC/TN ratios and δ¹³C of organic carbon suggest that the bulk natural OM was sourced from marine phytoplankton and bacteria mixed with marsh and terrigenous C3 plants. Normal alkanes show high proportions of long-chain compounds with a high Carbon Preference Index, indicating the importance of C3 plants-derived OM in Mobile Bay. High concentrations of biogenic hopanes and perylene indicate microbial sources and degradation played an important role in shaping OM compositions. Anthropogenic hydrocarbons, αβ-hopanes and polycyclic aromatic hydrocarbons (PAHs), were widely detected in Mobile Bay sediments. The source diagnostic ratios of hopanes and steranes suggest they were sourced from coal and diesel combustions. The source diagnostic ratios of PAHs, together with a positive correlation between PAHs and total mercury, suggests that PAHs originated primarily from coal combustion. We proposed two ratios, αβ-hopanes/(ββ-hopanes+hopenes) and 16 PAHs/perylene, to evaluate anthropogenic versus natural contributions of hydrocarbons. These ratios were higher in the western estuary than in the eastern estuary, suggesting elevated anthropogenic hydrocarbon inputs to the western estuary. Correspondingly, the toxic equivalent quantity (TEQ_BaQ) of PAHs showed a higher ecological risk for the western estuary. This spatially uneven distribution of hydrocarbon pollutants can be attributed to more concentrated urban and industrial areas on the western shore, suggesting the importance of adjacent pollution sources. Collectively, our results provide new insights into the origins and dynamics of natural and anthropogenic OM and highlight the significance of coal combustion in contributing hydrocarbon pollutants in Mobile Bay sediments.