Identification of halogenated polycyclic aromatic hydrocarbons in biological samples from Alberta Oil-Sands Region

Zhe Xia; Ifeoluwa Idowu; Chris Marvin; Philippe J Thomas; Wesley Johnson; Olga Francisco; Jorg Stetefeld; Bernard Crimmins; Mark Fry; Gregg T Tomy

doi:10.1016/j.chemosphere.2018.10.050

Identification of halogenated polycyclic aromatic hydrocarbons in biological samples from Alberta Oil-Sands Region

Chemosphere. 2019 Jan:215:206-213. doi: 10.1016/j.chemosphere.2018.10.050. Epub 2018 Oct 8.

Authors

Affiliations

¹ University of Manitoba, Centre for Oil and Gas Research and Development, Department of Chemistry, Winnipeg, Manitoba, Canada.
² Environment and Climate Change Canada, National Water Research Institute, Burlington, ON, Canada.
³ Environment and Climate Change Canada, National Wildlife Research Centre, Ottawa, ON, Canada.
⁴ Clarkson University, Department of Civil and Environmental Engineering, Potsdam, NY, USA; Academic Environmental/Analytical Consulting Services, LLC, Alliance, OH, USA.
⁵ University of Manitoba, Department of Biological Sciences, Winnipeg, Manitoba, Canada.
⁶ University of Manitoba, Centre for Oil and Gas Research and Development, Department of Chemistry, Winnipeg, Manitoba, Canada. Electronic address: Gregg.tomy@umanitoba.ca.

PMID: 30317091
DOI: 10.1016/j.chemosphere.2018.10.050

Abstract

Halogenated polycyclic aromatic hydrocarbons (HPAHs) were identified in biological samples from the Alberta Oil-Sands Region (AOSR) using gas chromatography coupled with high-resolution time-of-flight mass spectrometry (GC-HRTOF-MS) at a resolving power of 25,000. Knowledge of the electron ionization (EI) fragmentation behavior of individual HPAH isomers, achieved by injecting authentic standards in full-scan MS mode, was paramount in identifying a suite of HPAHs in samples from the AOSR. Confirmation of compounds in biological samples was based on the measured mass accuracy (±3 ppm) of 2 characteristic ions prominent in the EI mass spectra of each compound. Numerous compounds were detected in the high resolution total ion chromatogram in liver extracts of 4 biological species from the AOSR: river otter (Lontra Canadensis), northern pike (Esox lucius), lake whitefish (Coregonus clupeaformis) and snails (Gastropod sp.) many of which remain unidentified. Careful examination of the high-resolution accurate mass data suggests that dichloro-anthracene/phenanthrene, bromo-anthracene/phenanthrene and dibromo-fluorene were present in the biological samples. Lipid corrected concentrations of dichloro-PAHs were estimated to be 16.3 ± 11.4 (n = 4) and 5.5 (n = 1) ng/g in lake whitefish and river otter, respectively. Concentrations of mono-bromo-PAHs were an order of magnitude greater in snails (170.5 ng/g) than in northern pike (12.5 ng/g) while concentrations of dibromo-PAHs were 4 times greater in snails than in northern pike. The detection of these compounds in biota implies that these compounds are bioaccumulative. The liver-based biomagnification factor of the dichloro-PAH congener in the river otter/lake whitefish feeding relationship is much smaller than 1 implying that this compound does not biomagnify.

Keywords: Alkylated polycyclic aromatic hydrocarbons; Bioaccumulation; Biomagnification; Halogenated polycyclic aromatic hydrocarbons; Polycyclic aromatic hydrocarbons.

MeSH terms

Alberta
Animal Population Groups
Animals
Anthracenes / analysis
Biota*
Fluorenes / analysis
Gas Chromatography-Mass Spectrometry / methods*
Halogenation
Liver / metabolism
Phenanthrenes / analysis
Polycyclic Aromatic Hydrocarbons / analysis*

Substances

Anthracenes
Fluorenes
Phenanthrenes
Polycyclic Aromatic Hydrocarbons