Determination of polybrominated biphenyls in Tasmanian devils (Sarcophilus harrisii) by gas chromatography coupled to electron capture negative ion tandem mass spectrometry or electron ionization high‐resolution mass spectrometry

Abstract

Two gas chromatography/mass spectrometry (GC/MS) methods for the determination of polybrominated biphenyls (PBBs) by isotope dilution analysis (IDA) using 13 C 12 -PBB 153 in the presence of polybrominated diphenyl ethers (PBDEs) were compared. Recovery of 13 C 12 -PBB 153 which was added to the extracted lipids before sample purification was commenced ranged from 88-117% (mean value 98.2 W 8.9%). Nevertheless, IDA analysis of PBBs using 13 C 12 -labelled congeners is limited by the potential co-elution of PBBs with polybrominated diphenyl ethers (PBDEs). The pair PBB 153 and BDE 154 was inspected since M R and [M-2Br] R ions of 13 C 12 -PBB 153 and BDE 154 were only separated by 4 u. Gas chromatography/electron ionization high-resolution mass spectrometry with selected ion monitoring (GC/EI-HRMS-SIM) was suitable when m/z 475.7449 and m/z 477.7429 were used for 13 C 12 -PBB 153 because they are below the monoisotopic peak of the [M-2Br] R fragment ion of hexaBDEs at m/z 479.7. Gas chromatography/electron capture negative ion tandem mass spectrometry selected reaction monitoring (GC/ECNI-MS/MS-SRM) measurements could be applied because 13 C 12 -PBB 153 and BDE 154 were separated by GC on a 25-m Factor Four CP-Sil 8MS column. Comparative measurements with GC/EI-HRMS-SIM and GC/ECNI-MSMS-SRM were carried out with samples of Tasmanian devils from Tasmania (Australia), an endangered species due to a virus epidemy which has already proved fatal for half of the population. Both techniques verified concentrations of PBB 153 in the range 0.3-11 ng/g lipids with excellent agreement of the levels in all but two samples. The PBB residue pattern demonstrated that PBB pollution originated from the previous discharge with technical hexabromobiphenyl which is dominated by PBB 153. Other congeners such as PBB 132 and PBB 138 were detected in the Tasmanian devils but the proportions relative to PBB 153 were lower than in the technical product. Samples of healthy and affected Tasmanian devils showed no significant difference in the PBB pollution level. The PBB concentrations in the Tasmanian devils were significantly below those causing toxic effects. On the other hand, PBB concentrations were one level or even higher than PBDEs.

Researching new diseases: assumptions and trajectories

“…DFTD has been described as a neuro-endocrine tumor of unknown origin (Loh 2006). A viral cause was initially suspected but remains unconfirmed (TDPIWE 2005). Research has investigated hematology, blood biochemistry, immunology, endocrinology, and identification of the etiology of the disease, including a trial to test for a range of environmental toxins (TDPIWE 2005).…”

“…A viral cause was initially suspected but remains unconfirmed (TDPIWE 2005). Research has investigated hematology, blood biochemistry, immunology, endocrinology, and identification of the etiology of the disease, including a trial to test for a range of environmental toxins (TDPIWE 2005). In 2006 the novel hypothesis that DFTD was an allograft-an infectious cell line passed between individuals through biting-was proposed (Pearse and Swift 2006).…”

“…The dominant research trajectory has been built on the assumption that the cancer is a natural phenomenon originating in and spread by Tasmanian devils (for example, as presented by Ujvari et al 2017). An early finding contrary to this assumption was reported in an abstract by Steve Marvanek, a Commonwealth Scientific and Industrial Research Organisation (CSIRO) expert in applying geographic information systems (GIS).…”

“…By 2007 many of the waterways in Tasmania were polluted by pesticides used in forestry plantations (Bleaney 2007). A preliminary study of toxins used in Tasmania (Vetter et al 2008), which found evidence of flame retardants, has not been followed up. Tasmania's economic development has relied heavily on an expansion in forestry plantations (Parsons et al 2006).…”

Improved derivatization protocol for simultaneous determination of alkylphenol ethoxylates and brominated flame retardants followed by gas chromatography – mass spectrometry analyses

“…Studies have shown that APE metabolites are more toxic than their parent compounds, are persistent, and accumulate in fatty tissues (Ying et al, 2002;Petrovic et al, 2003;Gatidou et al, 2007;Sibali et al, 2010). Despite their benefits for reducing fire-related injury and property damage, concern about BFRs is growing because of their occurrence and persistence, and they have been detected in the environment, biota and humans (Alaee et al, 2001;Hyötyläinen and Hartonen, 2002;Polder et al, 2008;Vetter et al, 2008;Yu et al, 2008;Odusanya et al, 2009;Segev et al, 2009;Olukunle et al, 2012). Determination of low volatility polar compounds such as phenolic analytes has been achieved by indirect analysis using derivatization techniques because such compounds show low sensitivity and tailing in gas chromatographic analysis (Ding and Tzing, 1998;Cathum and Sabik, 2001;Hoai et al, 2003;Esperanza et al, 2004;Stehmann and Schröder, 2004;Fiedler et al, 2007;Gatidou et al, 2007;Dirtu et al, 2008).…”