[Compositions and diagnostic ratios of heavily degraded crude oil residues in contaminated soil in oilfields].

The aims of this study were to determine the rate of degradation of crude oil in soil, to reveal the fingerprints of residual oil after long-term biodegradation, and to screen parameters for evaluation of the biodegradability residual oil. A total of 18 contaminated soil samples containing heavily degraded crude oil residuals from Daqing, Shengli and Baise oilfields were analyzed. More than 100 individual target compounds including straight-and branched-chain alkanes (n-alkanes, pristane and phytane), polycyclic aromatic hydrocarbons (PAHs), terpanes, steranes and triaromatic steranes (TAS) in residual oil were determined by gas chromatography-mass spectrometry (GC-MS). For all the soil samples, less than 10% and 30% of alkanes and PAHs remained in the residual oils relative to crude oils. Terpanes, steranes and TAS were found to be less biodegradable. Depletions decreased with increasing carbon number of n-alkanes. However, average depletions > 80% were found in n-alkanes with carbon numbers < 37. Average depletions were > 70% for 2-4 ring PAHs, while 5-6 ring PAHs were more resistant. Increase in alkylation level decreased depletion within homologues of naphthalene, phenanthrene, chrysene and Benzo[e] pyrene. GC-MS could only reveal less than 3% of the compounds of residual oils, which were mainly comprised of n-alkanes with carbon number > 20, alkylated naphthalenes and phenanthrenes, terpanes, steranes and TAS. Based on compositional characteristics of alkanes and PAHs in residual oils, 6 diagnostic ratios, which were ratios of susceptible compounds to resistant compounds or to the amounts residual oil, were proposed as the parameters for characterization of residual oils and determining the biodegradability of oils contaminated soils.