Thorough study of persistent organic pollutants and halogenated natural products in sperm whale blubber through preparative sample cleanup followed by fractionation with countercurrent chromatography.

Marine mammals are top predators of the marine food chain and thus known to bioaccumulate high concentrations of polyhalogenated compounds. Yet, details of the organohalogen pattern are largely unknown. For this reason, we isolated the polyhalogenated compounds from 750 g blubber of a sperm whale (Physeter catodon), which deceased at the German North Sea coast in January 2016. The sample matrix was decomposed by sulfuric acid treatment and the polyhalogenated compounds were then fractionated by countercurrent chromatography (CCC). Seventy-three CCC fractions were taken and analyzed by gas chromatography with electron capture negative ion mass spectrometry (GC/ECNI-MS). The bulk of the polyhalogenated compounds in the sample originated from classic persistent organic pollutants (POPs). Altogether 90 polychlorinated biphenyl (PCB) congeners were detected in the sample including all possible octa- to decachloro congeners except one. The sample also featured 105 toxaphene congeners including 30 chlorobornenes (contribution ∼14% of the total toxaphene content) which were only detected after the CCC fractionation. In addition, several chlordane and mirex related compounds were detected which were never or very scarcely described before in biota. Classic POPs (PCBs, DDT, toxaphene, chlordane, mirex) were predominant, while new emerging contaminants were scarcely detected. The sample featured several halogenated natural products (HNPs) some of which were less stable and destroyed during the sample cleanup involving treatment with sulfuric acid. Sample fractionation by means of CCC was crucial for the detection and assignment of many of the uncommon polyhalogenated compounds.

Brominated flame retardants (BFRs) in eggs from birds of prey from Southern Germany, 2014.

In Southern Germany, peregrine falcons (Falco peregrinus), which almost exclusively prey on other birds, are top predators of the terrestrial food chain. These animals accumulate persistent organic pollutants (POPs) and halogenated flame retardants (HFRs) with mothers transferring these lipophilic contaminants to their eggs. Here we analyzed unhatched eggs of eleven peregrine falcons and six of other species, and report concentrations of polybrominated diphenyl ethers (PBDEs), hexabromocyclododecane (HBCD), hexabromobenzene (HBB), 2,3-dibromopropyl-2,4,6-tribromophenyl ether (DPTE) and its metabolites, pentabromoethylbenzene (PBEB), pentabromotoluene (PBT), and tribromophenol (TBP). The extract of one purified peregrine falcon egg sample was comprehensively analyzed in a non-target (NT) approach by gas chromatography with mass spectrometry in the electron capture negative ion mode. A total of ∼400 polyhalogenated compounds were detected, among them dechloranes and possibly transformation products, two tetrabrominated metabolites of PBT and several compounds unknown to us which could not be identified.

Polyhalogenated compounds (chlorinated paraffins, novel and classic flame retardants, POPs) in dishcloths after their regular use in households.

Dishcloths are routinely used in the clean-up process following daily kitchen activities and are thus subject to contamination commensurate with their frequent use. Here we analyzed dishcloths for the occurrence of polyhalogenated compounds after 14days of use in household kitchens. Analysis of 19 dishcloths revealed the presence of 29 polyhalogenated contaminants with total mean/median concentrations of 6,900/3,600ng/dishcloth, respectively. The spectrum featured classic and novel halogenated flame-retardants (HFRs) like polybrominated diphenyl ethers (PBDEs), hexabromocyclododecane (HBCD), decabromodiphenyl ethane (DBDPE), pentabromoethylbenzene (PBEB), chlordene plus and dechlorane plus, as well as typical chloropesticides and background contaminants (e.g. hexachlorobenzene (HCB), p,p'-dichlorodiphenyldichloroethene (p,p'-DDE), polychlorinated biphenyls (PCBs) and lindane). The individual dishcloths showed highly variable fingerprints of polyhalogenated compounds. If present, medium-chain chlorinated paraffins (MCCPs) were by far the most prominent compound class with up to 55,400ng/dishcloth. Without consideration of chlorinated paraffins, the mean concentration of other polychlorinated compounds (270ng/dishcloth) was generally one order of magnitude lower than the mean concentration of brominated flame retardants (BFRs) (1,700ng/dishcloth). Our study verified that a wide range of polyhalogenated compounds is readily available in the kitchen environment. Furthermore, dishcloths are ordinarily handled without gloves or hand protection, given the observed concentrations of polyhalogenated compounds in dishcloths, such handling may serve as an additional exposure pathway for human users. Evaluation of this thesis was supported by conduction of a dermal uptake assessment.