Complementary Nontargeted and Targeted Mass Spectrometry Techniques to Determine Bioaccumulation of Halogenated Contaminants in Freshwater Species
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abstract
Assessing the toxicological significance of complex environmental mixtures is challenging due to the large number of unidentified contaminants. Nontargeted analytical techniques may serve to identify bioaccumulative contaminants within complex contaminant mixtures without the use of analytical standards. This study exposed three freshwater organisms (Lumbriculus variegatus, Hexagenia spp., and Pimephales promelas) to a highly contaminated soil collected from a recycling plant fire site. Biota extracts were analyzed by Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) and mass defect filtering to identify bioaccumulative halogenated contaminants. Specific bioaccumulative isomers were identified by comprehensive two-dimensional gas chromatography high-resolution time-of-flight mass spectrometry (GCxGC-HRToF). Targeted analysis of mixed brominated/chlorinated dibenzo-p-dioxins and dibenzofurans (PXDD/PXDFs, X = Br and Cl) was performed by atmospheric pressure gas chromatography tandem mass spectrometry (APGC-MS/MS). Relative sediment and biota instrument responses were used to estimate biota-sediment accumulation factors (BSAFs). Bioaccumulating contaminants varied among species and included polychlorinated naphthalenes (PCNs), polychlorinated dibenzofurans (PCDFs), chlorinated and mixed brominated/chlorinated anthracenes/phenanthrenes, and pyrenes/fluoranthenes (Cl-PAHs and X-PAHs, X = Br and Cl), as well as PXDD/PXDFs. Bioaccumulation potential among isomers also varied. This study demonstrates how complementary high-resolution mass spectrometry techniques identify persistent and bioaccumulative contaminants (and specific isomers) of environmental concern.
