Molecular Transformation of Crude Oil Contaminated Soil after Bioelectrochemical Degradation Revealed by FT-ICR Mass Spectrometry.

Abstract

Bioremediation is a low-cost approach for crude oil spill remediation, but it is often limited by electron acceptor availability. In addition, the biodegradation products of crude oil contaminants are complex, and transformation pathways are difficult to decipher. This study demonstrates that bioelectrochemical systems (BESs) can be effective in crude oil degradation by integrating biological and electrochemical pathways, and more importantly, it provides the first understanding on the daughter products of bioelectrochemical hydrocarbon degradation. Using electrospray ionization (ESI) Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) and two-dimensional gas chromatography (GC × GC), the results showed that the active BES reactor improved the total petroleum hydrocarbon (TPH) degradation by ∼70% than open circuit control reactors. After separating the daughter products into nine fractions (MA1-MA9) according to the molecular weight (m/z 200-1000) by modified aminopropyl silica (MAPS) fractionation, we found that active BES remediation resulted in 50% more polar, oxygen-containing naphthenic (NAP) acids. The MA4 fraction (centered at ∼550 Da) increased by 47%, and MA5 and MA7 fractions with higher molucular weight increased by a maximum of ∼7- and 9-fold, respectively. These results are in accordance with the variation of bulk elemental compositions in O2 species, where daughter transformation products doubled relative to parent oil extract. The contribution of newly generated NAP acids was mainly from higher-order oxygen species (O5-O6) with increased hydrophobicity in conjunction with a decreased abundance in lower-order oxygen species (O1). Overall, the study suggests that n-alkane degradation occurred via β-oxidation to oxygenated transformation products with lower molecular weight, such as n-alcohols in O1 class and subsequently to n-fatty acids in O2 class.