Biodegradation and detoxification of naphthenic acids in oil sands process affected waters Siqing Yue a , Bruce A. Ramsay a , Jiaxi Wang b , Juliana A. Ramsay a, ⁎ a Chemical Engineering, Queen's University, Kingston, ON K7L 3N6, Canada b Chemistry, Queen's University, Kingston, ON K7L 3N6, Canada HIGHLIGHTS • Toxicity/estrogenicity of SPE/HPLC frac- tions of biologically treated OSPW using EDA • Relate compositional change of key fractions with biodegradation and de- toxification • C12–14 bicyclic, tricyclic O2 NAs linked to toxicity decrease • O3, O4, C16 DBE = 5–6, C16–17 DBE = 7, C19 DBE O2 NAs linked to estrogenicity decrease GRAPHICAL ABSTRACT abstract article info Article history: Received 24 June 2016 Received in revised form 22 July 2016 Accepted 23 July 2016 Available online xxxx Editor: D. Barcelo After oil sands process affected water (OSPW) was treated in a continuous flow biofilm reactor, about 40% of the organic compounds in the acid extractable fraction (AEF) including naphthenic acids (NAs) were degraded resulting in a reduction of 73% in the Microtox acute toxicity and of 22% in the yeast estrogenic assay. Using effect directed analysis, treated and untreated OSPW were fractionated by solid phase extraction and the fractions with the largest decrease in toxicity and estrogenicity were selected for analysis by electrospray ionization combined with linear ion trap and a high-resolution Orbitrap mass spectrometer (negative ion mode). The aim of this study was to determine whether compositional changes between the untreated and treated fractions provide insight related to biodegradation and detoxification of NAs. The O2S, O3S and O4S compounds were either not major contributors of toxicity or estrogenicity or the more toxic or estrogenic ones were biodegraded. The O3- and O4-NAs seem to be more readily metabolized than O2NAs and their degradation would contribute to detoxifica- tion. The decrease in acute toxicity may be associated with the degradation of C12 and C13 bicyclic and C12–C14 tricyclic NAs while the decrease in estrogenicity may be linked to the degradation of C16 O2-NAs with double bond equivalents (DBE) = 5 and 6, C16 and 17 O2-NAs with DBE = 7, and C19-O2-NAs with DBE = 8. The re- sidual acute toxicity may be caused by recalcitrant components and/or degradation products such as the O2 bi- cyclic and tricyclic NAs, particularly the C14 and C15 bicyclic and C14–C16 tricyclic NAs as well as the polycyclic aromatic NAs (DBE ≥ 5 compounds). The decrease in estrogenicity may be linked to the degradation of the O3 and O4 oxidized NAs while much of the residual estrogenicity may be due to the recalcitrant polycyclic aromatic O2- NAs. Hence, treatment to further detoxify OSPW should target these compounds. © 2016 Elsevier B.V. All rights reserved. Keywords: Biodegradation Estrogenicity Naphthenic acids NAs OSPW Acute toxicity Science of the Total Environment 572 (2016) 273–279 ⁎ Corresponding author. E-mail address: juliana.ramsay@queensu.ca (J.A. Ramsay). http://dx.doi.org/10.1016/j.scitotenv.2016.07.163 0048-9697/© 2016 Elsevier B.V. All rights reserved. Contents lists available at ScienceDirect Science of the Total Environment journal homepage: www.elsevier.com/locate/scitotenv