Determination and characterization of oxy-naphthenic acids in oilfield wastewater

Oxy-naphthenic acids (oxy-NAs) are one of the major components of NA mixtures in wastewaters from petroleum industries. The limited available data indicated that oxy-NAs were considered as a potential marker for the degradation of NAs, and some oxy-NAs exhibited endocrine disrupting activities. However, the lack of information on the structures and occurrences of oxy-NAs in oilfield wastewaters limited the interpretations of the biotransformation pathways of NAs and structure-specific toxicity. A sensitive method for simultaneous determination of oxy-NAs together with NAs was developed by combining MAX extraction column and UPLC-ESI(-)-QTOF-MS. The 2000-fold SPE preconcentration step was highly specific for acids and the prewash solvent greatly reduced matrix effects in the UPLC-ESI(-)-QTOF-MS analysis, resulting in an increase in sensitivity down to detection limits in the ng/L range. To provide structural information within each oxy-NA isomer class, a new method was developed by derivatizing oxy-NAs with dansyl chloride by UPLC-ESI(+)-QTOF-MS. The molecular ion dansyl derivatives from the corresponding oxy-NAs and characteristic fragmentation ions, not detected before derivatization, were observed in the extracts of oilfield wastewater, providing evidence that O3-NAs and O4-NAs were mainly composed of OH-NAs and (OH)2-NAs, respectively. Semiquantification of oxy-NAs and NAs in various oilfield wastewaters revealed NAs, O3-NAs, and O4-NAs present at concentrations of 187-397, 44-146, and 40-108 μg/L, respectively. Significantly different profiles of NA mixtures were observed in petroleum refinery wastewater and oil sands extraction water, but the profile of oxy-NAs was similar to NAs in different wastewaters suggesting the existence of biotransformation between NAs and oxy-NAs in the environment, and hydroxylation could be one of the major biotransformation pathways of NAs.