First assessment of pollutant exposure in two balaenopterid whale populations sampled in the Svalbard Archipelago, Norway.

Pollutant concentrations are poorly known for the largest animals on Earth, blue whales Balaenoptera musculus and fin whales Balaenoptera physalus. In this study, concentrations of persistent organic pollutants (POPs) were determined in blubber biopsies and stable isotope values for nitrogen (δ15N) and carbon (δ13C) were measured using skin biopsies for 18 blue whales and 12 fin whales sampled in waters surrounding the Svalbard Archipelago, Norway. The samples were collected in summer during the period 2014-2018. POPs were dominated by DDTs, PCBs and toxaphenes, with median concentrations in blue/fin whales being 208/341, 127/275 and 133/233 ng/g lipid weight, respectively. Linear models indicated that pollutant concentrations were 1.6-3 times higher in fin whales than in blue whales, which is likely related to the higher trophic positions of fin whales, as indicated by their higher δ15N. Lower δ13C in fin whales suggests that they feed at higher latitudes than blue whales; these values were not correlated with pollutant concentrations. Pollutant levels were approximately twice as high in males compared to females (intraspecifically), which indicates that females of these species offload pollutants to their offspring during gestation and lactation, similar to many other mammalian species. Pollutant concentrations in balaenopterid whales from Svalbard waters were generally much lower than in conspecific whales from the Mediterranean Sea or the Gulf of California, but higher than those in conspecifics from the Antarctic Peninsula.

Negligible Impact of Ingested Microplastics on Tissue Concentrations of Persistent Organic Pollutants in Northern Fulmars off Coastal Norway.

The northern fulmar (Fulmarus glacialis) is defined as an indicator species of plastic pollution by the Oslo-Paris Convention for the North-East Atlantic, but few data exist for fulmars from Norway. Moreover, the relationship between uptake of plastic and pollutants in seabirds is poorly understood. We analyzed samples of fulmars from Norwegian waters and compared the POP concentrations in their liver and muscle tissue with the corresponding concentrations in the loads of ingested plastic in their stomachs, grouped as "no", "medium" (0.01-0.21 g; 1-14 pieces of plastic), or "high" (0.11-0.59 g; 15-106 pieces of plastic). POP concentrations in the plastic did not differ significantly between the high and medium plastic ingestion group for sumPCBs, sumDDTs, and sumPBDEs. By combining correlations among POP concentrations, differences in tissue concentrations of POPs between plastic ingestion subgroups, fugacity calculations, and bioaccumulation modeling, we showed that plastic is more likely to act as a passive sampler than as a vector of POPs, thus reflecting the POP profiles of simultaneously ingested prey.

Determination of the enantiomer fraction of PBB 149 by gas chromatography/electron capture negative ionization tandem mass spectrometry in the selected reaction monitoring mode.

Enantioselective determination of the atropisomers of 2,2',3,4',5',6-hexabromobiphenyl (PBB 149) in a purified sample from a bird egg was attempted in this work. By application of the classic method for PBB determination, i.e. gas chromatography coupled to electron capture negative ionization mass spectrometry (GC/ECNI-MS) using the bromide ions, the enantiomers interfered with another brominated compound. Subsequent measurements clarified that this interference did not occur in the mass chromatogram of the molecular ion of PBB 149. Therefore, a GC/ECNI tandem mass spectrometry (MS/MS) method was developed, based on the fragmentation of [M]-. A suitable precursor-product ion transition was found for m/z 627.5 --> 80 +/- 1.5, representing the most abundant ion trace of the molecular ion and the bromide ions. Optimization of the ion source temperature, the methane gas pressure, and the collision voltages resulted in a robust method that could solve the problem. Subsequent injections of a technical PBB product (Firemaster BP-6) resulted in the anticipated racemic proportion (enantiomer fraction (EF) = 0.50 +/- 0.02 (n = 8)). By contrast, the EF in the purified extract of a bird egg was found to be 0.42 +/- 0.02 (n = 10), indicative of a significant enantioenrichment of the second eluting atropisomer. Additional measurements were performed on a non-chiral column. These measurements allowed for the detection of 16 hexabromobiphenyls (hexa-BBs) in Firemaster BP-6. These comparisons verified that PBB 149 enantiomers did not interfere with an isomer that could falsify the enantiomer fraction in the sample. The novel method using GC/ECNI-MS/MS in the selected reaction monitoring (SRM) mode was eight times more sensitive than application of conventional GC/ECNI-MS selected ion monitoring (SIM) analysis of the molecular ion.

Analytical strategies for successful enantioselective separation of atropisomeric polybrominated biphenyls 132 and 149 in environmental samples.

Some of the polybrominated biphenyls (PBBs) found in the environment are axially chiral, due to hindered rotation about the interannular phenyl-phenyl bond. This applies for PBB congeners having two or more bromine substituents in ortho-position to this bond. In this study analytical methods were developed that allow determining the enantiomer fraction (EF) of axially chiral (atropisomeric) PBBs in environmental samples. A white-tailed sea eagle egg was used as test sample. The egg extract was purified and further fractionated by normal phase (NP) high performance liquid chromatography (HPLC), yielding enriched fractions of axially chiral PBB 132 and PBB 149. Gas chromatographic (GC) enantioseparation of the atropisomers of PBB 149 was achieved on one of nine tested modified cyclodextrin phases. Due to coelution with an unknown brominated compound, conventional GC/ECNI-MS, which is based on the detection of the bromide ion, did not allow for the establishment of the EF. However, by means of GC/EI-MS-MS it was possible to verify an EF of 0.42-0.43, i.e. a significant enantiomeric enrichment of the second eluting atropisomer of PBB 149 in the white-tailed sea eagle egg. This is the first proof of non-racemic proportions of a chiral PBB in environmental samples. Despite the testing of nine different chiral stationary phases, GC enantioseparation of PBB 132 or other atropisomeric PBB congeners failed. For this reason, an enantioselective reversed-phase HPLC method was developed. This method proved to be a powerful tool for the separation of PBB atropisomers. It was found that even a standard of the di-ortho substituted PBB 153 could be partially separated into atropisomers at 0 degrees C but already enantiomerized at 5 degrees C. For establishing the EF of PBB 132 in the bird egg sample a combination of enantioselective HPLC followed by non-chiral gas chromatography was employed. Using enantioselective HPLC, the atropisomers of PBB 132 were quantitatively targeted into two separate fractions at room temperature (20 degrees C). After addition of internal standards for volume adjustment the relative amounts of the atropisomers in the isolated fractions were quantified by using non-chiral GC/EI-MS analysis. A deviation from the racemic mixture of the atropisomers of PBB 132 in the egg extract could not be statistically proven.

Chromatographic enrichment and enantiomer separation of axially chiral polybrominated biphenyls in a technical mixture.

The separation properties of different chromatographic methods regarding the enantioselective separation of axially chiral (atropisomeric) polybrominated biphenyls (PBB) were studied. For this purpose, the technical hexabromobiphenyl product Firemaster BP-6 was characterised by gas-chromatography coupled to electron capture detection (GC/ECD) and electron-capture negative ion mass spectrometry (GC/ECNI-MS) as well as by liquid chromatographic fractionating on active carbon and celite. Twelve individual PBBs including potential atropisomeric PBBs were isolated from Firemaster BP-6 by reversed-phase high-performance liquid chromatography (HPLC) on three serially coupled octadecylsilane columns. Six of the 12 isolated PBBs (three tri-ortho and di-ortho substituted PBBs, respectively) were separated into atropisomers on a HPLC column containing permethylated beta-cyclodextrin on silica. Moreover, the temperature dependency of the enantiomer separations is discussed. Gas chromatographic enantiomer separation of PBBs is a very demanding task due to high elution temperatures. However, the atropisomers of one tri-ortho substituted PBB congener (PBB 149) could be resolved on a column coated with randomly modified heptakis(6-O-tert.-butyldimethylsilyl-2,3-di-O-methyl)-beta-cyclodextrin in OV 1701.