Nontarget Screening of Organohalogen Compounds in the Liver of Wild Birds from Osaka, Japan: Specific Accumulation of Highly Chlorinated POP Homologues in Raptors

Abstract

Nontarget screening studies have recently revealed the accumulation of typically unmonitored organohalogen compounds (OHCs) in various marine animals, but information for terrestrial food chains is still lacking. This study investigated the accumulation profiles of known and unknown OHCs in the liver of representative wild bird specimens from Osaka, Japan using nontarget analysis based on twodimensional gas chromatography−time-of-flight mass spectrometry. A large number of unmonitored OHCs were identified, including anthropogenic contaminants and marine halogenated natural products (HNPs), and their accumulation profiles were considered to be influenced by terrestrial and brackish water-based diets. Anthropogenic OHCs were highly accumulated in terrestrial predator species (peregrine falcon, hawks, and black kite), and some unmonitored highly chlorinated contaminants reached the levels of microgram per gram lipid in the liver, i.e., C 10 -/C 15 -based chlordane related compounds (CHLs) and their epoxides, dichlorodiphenyldichloroethylene (DDE) homologues, and polychlorinated terphenyls (PCTs). In contrast, HNPs were accumulated at higher levels in piscivorous birds (gray heron and common cormorant). Considering the enrichment of the unmonitored C 10 -/C 15 -based CHLs, PCTs, and DDE homologues relative to structurally similar persistent organic pollutants (POPs) in high trophic-level species such as raptors, further studies are needed to elucidate their environmental levels, behavior in terrestrial food chains, and ecotoxicological impacts.

Assessing Marine Endocrine-Disrupting Chemicals in the Critically Endangered California Condor: Implications for Reintroduction to Coastal Environments

“…Identification of HOCs in inland condors was expected, as some legacy contaminants, such as p,p′-DDE, are ubiquitous in most biota including terrestrial birds and humans. 34,35 Consistent with our study, DDTs, PCBs, PBDEs, and other chlorinated pesticides have been previously detected in inland condors but at concentrations 12−100 times lower than coastal condors. 8 Notably, in our analysis, inland condors lacked the halogenated natural product (HNP) classes MBP and DMBP that are produced by marine organisms and detected regularly in cetacean species due to their bioaccumulative nature.…”

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

“…While the formulas C 15 H 8 Cl 9 , C 15 H 7 Cl 10 , and C 15 H 6 Cl 11 were assigned, the mass spectra of these compounds are identical to the compounds reported as Chlordene Plus (CP, C 15 H 6 Cl 12 ) and its analogues (C 15 H 7 Cl 11 , C 15 H 8 Cl 10 ) in the wild birds from Japan, indicating missing of the molecular ion. 74 Fragment ion cluster (m/z 269.813) is close to the theoretical values of C 5 Cl 6 + (<1 ppm) that is a common fragment in most hexachloronorbornene moiety-containing compounds, such as chlordane, mirex, and Dechlorane 602. Chlordene Plus was detected in technical chlordane and human adipose tissue in the 1990s by Dearth and Hites.…”

“…The observed MS fragments represented the subsequent loss of chlorines. The EI MS of C 10 Cl 10 is similar to an unknown feature reported in the livers of wild birds from Japan, but no additional information was available . Features with molecular formulas C 14 H 7 Cl 5 , C 14 H 6 Cl 6 , and C 14 H 5 Cl 7 were part of one noticeable array of markers observed in the KMD plots (Figures S5 and ) across the x -axis at an MD of 0.30.…”

“…The EI MS of C 10 Cl 10 is similar to an unknown feature reported in the livers of wild birds from Japan, but no additional information was available. 74 Features with molecular formulas C 14 H 7 Cl 5 , C 14 H 6 Cl 6 , and C 14 H 5 Cl 7 were part of one noticeable array of markers observed in the KMD plots (Figures S5 and 3) across the x-axis at an MD of 0.30. The exact masses and isotope ratios suggest that these markers correspond to a homologous series with the elemental compositions C 14 H 12−n Cl n (n = 2−8).…”

Discovery of Iodinated Polyfluoroalkyl Acids by Nontarget Mass-Spectrometric Analysis

“…21,22 By means of state-of-the-art analytical technologies in terms of chromatography and high-resolution mass spectrometry (HRMS), many nontarget analysis methods for environmental pollutants have been developed in recent years. [23][24][25][26] The advanced technologies employed in nontarget analysis mainly include liquid chromatographyquadrupole-Orbitrap HRMS (LC-Q-Orbitrap-HRMS), [27][28][29][30][31] gas chromatography-Q-Orbitrap-HRMS (GC-Q-Orbitrap-HRMS), 32,33 LC-quadrupole time-of-flight MS (LC-QTOF-MS), [34][35][36] GC-QTOF-MS, 37,38 and Fourier transform ion cyclotron resonance MS (FT-ICR-MS). 39,40 In many studies concerning identification of PFASs, nontarget analysis has also been used, and > 1000 previously unrecognized PFASs have been continuously found in various matrices, 41 such as commercial products, 2,[42][43][44] environmental matrices, [45][46][47] and biological samples.…”