Institut für Lebensmittelchemie

Permanent URI for this collectionhttps://hohpublica.uni-hohenheim.de/handle/123456789/8

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Hydroxylated transformation products obtained after UV irradiation of the current-use brominated flame retardants hexabromobenzene, pentabromotoluene, and pentabromoethylbenzene
(2023) Klimm, Alexandra; Vetter, Walter
Hexabromobenzene (HBB), pentabromotoluene (PBT), and pentabromoethylbenzene (PBEB) are current-use brominated flame retardants (cuBFRs) which have been repeatedly detected in environmental samples. Since information on hydroxylated transformation products (OH-TPs) was scarcely available, the three polybrominated compounds were UV irradiated for 10 min in benzotrifluoride. Fractionation on silica gel enabled the separate collection and identification of OH-TPs. For more insights, aliquots of the separated OH-TPs were UV irradiated for another 50 min (60 min total UV irradiation time). The present investigation of polar UV irradiation products of HBB, PBT, and PBEB was successful in each case. Altogether, eight bromophenols were detected in the case of HBB (three Br3-, four Br4-, and one Br5-isomer), and nine OH-TPs were observed in the case of PBT/PBEB (six Br3- and three Br4-congeners). In either case, Br➔OH exchange was more relevant than H➔OH exchange. Also, such exchange was most relevant in meta- and ortho-positions. As a further point, and in agreement with other studies, the transformation rate decreased with decreasing degree of bromination. UV irradiation of HBB additionally resulted in the formation of tri- and tetrabrominated dihydroxylated compounds (brominated diphenols) that were subsequently identified. These dihydroxylated transformation products were found to be more stable than OH-TPs.
The natural product 2,4,6-tribromoanisole is the predominant polyhalogenated compound in representative Australian passive air samples
(2025) Schweizer, Sina; Wang, Xianyu; Paxman, Chris; Mueller, Jochen F.; Vetter, Walter
Passive air samplers are well-suited for monitoring persistent organic pollutants (POPs) in ambient air. While the presence of POPs had been documented in Australian air, no data existed on structurally similar, halogenated natural products (HNPs), although these were frequently found in marine biota samples from Australia at levels exceeding those of anthropogenic POPs. This study reports quantitative data of the HNP 2,4,6-tribromoanisole (2,4,6-TBA) along with three POPs (polychlorinated biphenyls (PCBs) 153 and 138 as well as hexachlorobenzene (HCB)) in six selected passive air samples from different Australian regions (islands, coastal cities, and inland). For the most abundant HNP, 2,4,6-TBA, time-averaged concentrations for one year were determined at up to 420 pg/m 3 (One Tree Island), indicating its predominant natural production in the Great Barrier Reef (GBR). High concentrations of 2,4,6-TBA (17 pg/m 3 ), even in the remote inland sample (~ 800 km from the sea), led to the conclusion that the marine-derived 2,4,6-TBA was transported over long distances in air and can be found ubiquitously in Australian air. Even in the coastal cities of Brisbane and Darwin, 2,4,6-TBA levels were comparable to those of the PCBs. The HNP 2,3,3',4,4',5,5'-heptachloro-1'-methyl-1,2'-bipyrrole (Q1) was also detected in air from two islands. Its presence in air from One Tree Island was in line with expectations, given the high levels in marine mammal samples from the GBR. In direct comparison, the ~15 times higher ratio of Q1/2,4,6-TBA in air from Phillip Island indicated Q1 could be even more abundant in this marine region than in the GBR.
NMR and GC/MS analysis of industrial chloroparaffin mixtures
(2020) Sprengel, Jannik; Vetter, Walter
Chlorinated paraffins (CPs) are high-volume chemicals used worldwide in various industries as plasticizers, lubricants, and flame retardants. CPs are produced by chlorination of alkane mixtures which leads to complex products of thousands of homologs and congeners. Classic mass spectrometric analyses of CPs allow determining carbon chain lengths and degrees of chlorination while information on the substitution patterns cannot be derived. Therefore, we performed different one- and two-dimensional nuclear magnetic resonance spectroscopy (NMR) experiments, elemental analysis (EA), and gas chromatography coupled with electron capture negative ion mass spectrometry (GC/ECNI-MS) for the analysis of ten technical CP products with 42%, 52%, and 70% chlorine content from four producers. Slight differences in chlorine content but varying chain length compositions were observed for similarly labeled products from different manufacturers. Two-dimensional heteronuclear spectral quantum coherence (HSQC) measurements helped to evaluate ten structural elements in the products and confirmed the presence of geminal chlorine atoms in primary and secondary carbons in products with 70% chlorine. The variation of signal groups increased with increasing chlorine content of the products. Two-dimensional heteronuclear multiple bond coherence (HMBC) analysis of one sample and GC/ECNI-MS measurements indicated the presence of impurities (e.g., C9-CPs, iso-alkanes) in different technical CP products. These methods could in future allow for better distinction of CP mixtures, and an improved trace-back of environmental CPs to the source, based on specific structural features. Additionally, further structural characterization could help in the development of more accurate analysis processes.

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