Nontargeted Screening of Halogenated Organic Compounds in Fish Fillet Tissues from the Great Lakes

Abstract

Fish have been used for decades as bioindicators for assessing toxic contaminants in the Great Lakes ecosystem. Routine environmental monitoring programs target predetermined compounds that do not reflect the complete exposure of chemicals to biota and do not provide the complete halogenated fingerprint of the biota. In the current work, a nontargeted screening method was developed using a two-dimensional gas chromatograph coupled to a high-resolution time-of-flight mass spectrometer and was applied to 149 edible fish fillets from different species in the Great Lakes to characterize a more robust set of halogenated organic compounds across species and among lakes. Lake Ontario had the largest number of novel halogenated organic compounds (NHOCs). Seven NHOCs were observed in species from all lakes, indicating that this regional signature was not species-dependent. Hierarchical cluster analysis showed identical NHOC profiles between bottom dwelling and pelagic species. The NHOCs were grouped into seven clusters with similar structures and potentially similar environmental behaviors. Seven of the 29 NHOCs likely containing methoxy or ethoxy groups on a benzene or benzene−methanol backbone were clustered into one group with similar retention times. Five NHOCs were clustered with legacy contaminants that likely have similar structures or are their degradation products.

Nontargeted Discovery of Novel Contaminants in the Great Lakes Region: A Comparison of Fish Fillets and Fish Consumers

“…Archived full scan HRMS data from eight human serum samples collected from older (50+ years) male anglers with the highest PFAS concentration (based on the previous targeted analysis) was investigated in a hybrid targeted and nontargeted analyses workflow. , Additionally, three Lake Superior and three Lake Michigan fish fillet samples were used to study the potential linkages between unknown PBT substances on these frequent fish consumers that may be coextracted with samples slated for PFAS analysis. The sera samples and fish fillets were collected from the same geographical region around Lakes Superior and Michigan in 2014–2015 in several projects. , Fish fillet and sera cohort collection and storage were described by Renaguli et al and Christensen et al., respectively.…”

“…Fish fillets were collected as part of the Great Lakes Human Health Fish Fillet Tissue Study (GLHHFFTS) with the goal of understanding the potential exposure of fish consumers to toxic chemicals through fish consumption. , Human serum was collected during the same time frame (2014–2015) from a cohort of fish consumers in Wisconsin described by Christensen et al Years earlier, this cohort was characterized for several chemical classes, including polychlorinated biphenyls, polybrominated diphenyl ethers, and perfluoroalkyl substances. Contaminant levels in the sera were found to be correlated with fish consumption. − The 2014–2015 samples (sera and fillets) were previously analyzed in our laboratory for PFAS using a hybrid targeted/nontargeted method for perfluoroalkyl acids (unpublished data) . In the current study, the available archived data files from (1) Lakes Michigan and Superior GLHHFTS fish fillets and (2) fish consumer sera from Wisconsin were screened using the IPDC algorithm .…”

“…Contaminant levels in the sera were found to be correlated with fish consumption. − The 2014–2015 samples (sera and fillets) were previously analyzed in our laboratory for PFAS using a hybrid targeted/nontargeted method for perfluoroalkyl acids (unpublished data) . In the current study, the available archived data files from (1) Lakes Michigan and Superior GLHHFTS fish fillets and (2) fish consumer sera from Wisconsin were screened using the IPDC algorithm . While two separate projects presented in this study have the same collection region (Lakes Superior and Michigan), sampling period (2014–2015), analytical and CENTS methodology providing a unique opportunity for the first colocated nontargeted screening of edible fish tissue and fish consumers for contaminant profiles in the Great Lakes region. ,, …”

“…The sera samples and fish fillets were collected from the same geographical region around Lakes Superior and Michigan in 2014−2015 in several projects. 20,21 Fish fillet and sera cohort collection and storage were described by Renaguli et al 20 and Christensen et al, 21 respectively.…”

Characterization of Halogenated Organic Compounds in Pelagic Sharks and Sea Turtles Using a Nontargeted Approach

“…Alternatively, nontargeted analysis (NTA) detects a wider range of compounds and provides a better understanding of broad-spectrum chemical burdens in the biota. NTA of HOCs in biological samples has become possible with the implementation of advanced technologies including two-dimensional gas chromatography (GC × GC) and high-resolution mass spectrometry (HRMS). − Several NTA studies on marine mammals near the southern California Bight in the eastern North Pacific Ocean have established a chemical database containing hundreds of anthropogenic and naturally occurring bioaccumulative HOCs. ,− A comprehensive HOC analysis performed on the freshwater Laurentian Great Lakes detected dozens of novel contaminants in top predator fish, with their total concentration accounting for more than 60% of the total HOC burden. , A nontargeted screening experiment using mussels from Hiroshima Bay, Japan, revealed several novel mixed halogenated congeners of 3-chloro-allyl-polybromophenyl ethers at levels comparable to, or higher than, the legacy compounds detected …”