Fingerprint and weathering characteristics of crude oils after Dalian oil spill, China

Highlights: • Discuss the weathering characteristics of spilled oil in the natural coastal zone environments of Dalian Bay. • Determine the effects of natural weathering processes on the isotopic composition of individual n-alkanes. • A variety of diagnostic ratios were developed and evaluated for spill source identification and differentiation. -- Abstract: In an attempt to analyze the chemical characterization of oil residues and examine the suitability of chemical fingerprinting methods in oil spill investigations, multiple parameters sensitive to both sources and degree of weathering were used to characterize oil residues from "7–16" Dalian oil spill, China. Oil residues collected 90 days to 120 days after the spill showed a weathering pattern where significant amounts of light to middle molecular weight normal alkanes were depleted with pristane and phytane as dominant peaks. Diagnostic ratios developed from n-alkane and selected isoprenoids (e.g. Pr/Ph, n-C17/Pr, n-C18/Ph, carbon preference index, LMW/HMW-alkanes ratio), all display obvious changes over weathering time, indicating that these ratios are not valid for oil source identification. Furthermore, the biomarker ratios of hopanes and steranes with relative standard deviations (RSDs) of 0.88–4.08% were useful for source identification even for severely weathered oil residues. In addition, RSD of δ13C values of individual n-alkanes in oil residue varied from 0.07% to 0.20%, which suggest that stable carbon isotope profile of n-alkanes can also be a useful tool for tracing the source of an oil spill