Halogenated natural products (MHC-1, TriBHD, TetraBHD, MeO-PBDEs, Q1, and related PMBPs) and halogenated flame retardants (PBDEs, HBB, Dec 602, Dec 603, and DP) in blubber and brain are reported from five Alboran Sea delphinids (Spain). Both HNPs and HFRs were detected in brain, implying that they are able to surpass the blood-brain barrier and reach the brain, which represents a new finding for some compounds, such as Q1 and PMBPs, MHC-1, TriBHD, TetraBHD, or Dec 603. Moreover, some compounds (TetraBHD, BDE-153, or HBB) presented higher levels in brain than in blubber. This study evidence the high concentrations of HNPs in the marine environment, especially in top predators. It shows the importance of further monitoring these natural compounds and evaluating their potential toxicity, when most studies focus on anthropogenic compounds only. While no bioaccumulation was found for ∑HNPs, ∑HFRs increased significantly with body size for both common and striped dolphins. Studies evaluating BBB permeation mechanisms of these compounds together with their potential neurotoxic effects in dolphins are recommended.

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Since eight GC runs are required per sample, the method is not aimed for routine analysis. It is recommended as an initial screening method for the analysis of new sample matrices or samples from new regions. The non-targeted GC/ECNI-MS-SIM method benefits from the fact that it can be used with standard equipment.

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Polyhalogenated N-methylpyrroles (PMPs) are halogenated natural products (HNPs) recently detected in seagrass, blue mussels, and other marine organisms. In this study, we synthesized 2,3,4,5-tetrachloro-N-methylpyrrole (Cl-MP), 2,3,4,5-tetrabrominated-N-methylpyrrole (Br-MP, aka TBMP), and mixed tetrahalogenated (Cl and Br) N-methylpyrrole congeners. Use of one- and two-dimensional H andC NMR verified the structures of isolated/enriched 3,4-dibromo-2,5-dichloro-N-methylpyrrole (3,4-Br-2,5-Cl-MP), 2,3,4-tribromo-5-chloro-N-methylpyrrole (2,3,4-Br-5-Cl-MP), and 3-bromo-2,4,5-trichloro-N-methylpyrrole (3-Br-2,4,5-Cl-MP). GC/EI-MS and GC/ECNI-MS mass spectra of the five PMPs were studied with regard to fragmentation pattern and individual responses which were strongly affected by the presence (or absence) of Br in α-position(s). Quantitative solutions of the synthesized standards were used to determine the elution order of isomers and to quantify PMPs in selected blue mussel samples (Mytilus sp.) from the European Atlantic coast (Spain, France), the North Sea (the Netherlands, Germany) and Baltic Sea (Germany). PMPs were detected in all samples and the concentrations ranged between 0.6 and 52 μg/kg lipids with Br-MP being the most abundant representative of this substance class.