Nontargeted LC/ESI-HRMS Detection of Polyhalogenated Compounds in Marine Mammals Stranded on French Atlantic Coasts

Abstract

Up to now, non-targeted analysis (NTA) of halogenated organic compounds in biota has mostly been performed using GC/MS based instruments. We intended to broaden the spectrum of physicochemical properties of amenable substances by taking advantage of liquid chromatography-high resolution mass spectrometry coupling fitted with electrospray ionisation source. Thus, a NTA strategy was applied to a set of twelve blubber samples belonging to five marine mammal sentinel species stranded on the French Atlantic coasts. It involved specific postacquisition data interpretation using open-source software HaloSeeker 1.0 for annotating chemical formulas. A total of 135 distinct unequivocal molecular formulas were assigned to 466 polyhalogenated ion clusters of interest. The most intense representative ions were identified as bioaccumulative heptachloro-1,2′-bipyrrole (Cl 7 -BP), α-hexabromocyclododecane and (1R,2S,4R,5R,1'E)-2-bromo-1-bromomethyl-1,4-dichloro-5-(2'-chloroethenyl)-5methylcyclohexane (MHC-1) in the μg/g lipids weight range. To the best of our knowledge, it is the first time that Cl 7 -BP, the most intense signal observed, is reported in biota. A dozen other compound families will require further in-depth work to gain structural information.

Data Analytics for Environmental Science and Engineering Research

“…The application of NTA and advanced postacquisition data treatment will continue to enhance our ability to discover emerging contaminants in the environment, including those that bioaccumulate and pose risks to humans and wildlife. For instance, new polyhalogenated compounds were detected for the first time in blubber samples from marine mammal sentinel species using both LC-HRMS and GC-HRMS for analysis, and an open-source data mining software in the R programming environment that detected halogenated signatures in full scan HRMS . Finally, NTA combined with personal passive samplers and proper sample preparation techniques can be used to unlock the composition of chemical mixtures that humans are exposed to on a daily basis, which can be used in investigating the human exposome …”

“…For instance, new polyhalogenated compounds were detected for the first time in blubber samples from marine mammal sentinel species using both LC-HRMS and GC-HRMS for analysis, and an open-source data mining software in the R programming environment that detected halogenated signatures in full scan HRMS. 91 Finally, NTA combined with personal passive samplers and proper sample preparation techniques can be used to unlock the composition of chemical mixtures that humans are exposed to on a daily basis, which can be used in investigating the human exposome. 92 Akin to metagenomic data, NTA data pose a similar HDLSS challenge, as each mass spectrum constitutes a large number of peaks representing potential compounds present in a given sample.…”

First Discovery of Iodinated Polyfluoroalkyl Acids by Nontarget Mass-Spectrometric Analysis and Iodine-Specific Screening Algorithm

“…Nontarget analysis has become a practicable and reliable approach for screening and identification of environmental pollutants, which can alleviate the dilemma in lack of reference standards. , 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. − The advanced technologies employed in nontarget analysis mainly include liquid chromatography-quadrupole-Orbitrap HRMS (LC-Q-Orbitrap-HRMS), − gas chromatography-Q-Orbitrap-HRMS (GC-Q-Orbitrap-HRMS), , LC-quadrupole time-of-flight MS (LC-QTOF-MS), − GC-QTOF-MS, , and Fourier transform ion cyclotron resonance MS (FT-ICR-MS). , In many studies concerning the identification of PFASs, nontarget analysis has also been used, and >1000 previously unrecognized PFASs have been continuously found in various matrices, such as commercial products, ,− environmental matrices, − and biological samples. ,− These nontarget analysis methods mainly utilized LC-Q-Orbitrap-HRMS ,− and LC-QTOF-MS, ,, with data acquisition modes in full scan, , data-dependent acquisition (DDA) and data-independent acquisition (DIA). ,, Characteristic fragment ions such as C 2 F 5 – , C 3 F 5 – , FSO 3 – , HSO 4 – , PO 3 – , and NSO 2 – were used for tracing quasi-molecular ions, , thus identifying PFASs. Moreover, carbon and sulfur isotopologue distributions are also useful features for the screening and identification of PFASs as some previous studies have applied isotopic patterns to facilitating nontarget identification of PFAS pollutants. ,, …”

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.…”