Polyhalogenated 1,1′-dimethyl-2,2′-bipyrroles (PDBPs) are halogenated natural products (HNPs) previously shown to bioaccumulate in marine mammals and birds. Since their discovery in 1999, six hexahalogenated and a few lesser halogenated congeners have been identified in diverse marine mammal samples. Here we report the identification of 17 additional hexahalogenated PDBPs in the blubber extract of a humpback dolphin (Sousa chinensis) from Queensland, Australia. Thirteen of these new PDBPs were also detected in an Australian sea cucumber (Holothuria sp.). Additional samples were also tested positive on several new PDBPs, including an Australian venus tuskfish (Choerodon venustus) as well as a white whale (Delphinapterus leucas) and a sperm whale (Physeter macrocephalus) from the Northern Hemisphere. GC/ECNI-MS-SIM quantification of the molecular ions was carried out with the help of synthesized standards. The sum concentration of PDBPs was 1.1 mg/kg lipid in the humpback dolphin and 0.48 mg/kg lipid in the sea cucumber.

The objective of the present study was to investigate recent concentrations of perfluoroalkyl substances (PFASs) in white whales (Delphinapterus leucas) from Svalbard and compare them to concentrations found in white whales sampled from that same area 15 years ago. Plasma collected from live-captured white whales from two time periods (2013–2014, n = 9, and 1996–2001, n = 11) were analysed for 19 different PFASs. The 11 PFASs detected included seven C₈–C₁₄ perfluoroalkyl carboxylates (PFCAs) and three C₆–C₈ perfluoroalkyl sulfonates (PFSAs) as well as perfluorooctane sulfonamide (FOSA). Recent plasma concentrations (2013–2014) of the dominant PFAS in white whales, perfluorooctane sulfonate (PFOS; geometric mean = 22.8 ng/mL), was close to an order of magnitude lower than reported in polar bears (Ursus maritimus) from Svalbard. PFOS concentrations in white whales were about half the concentrations in harbour (Phoca vitulina) and ringed (Pusa hispida) seals, similar to hooded seals (Cystophora cristata) and higher than in walruses (Odobenus rosmarus) from that same area. From 1996 to 2001 to 2013–2014, plasma concentrations of PFOS decreased by 44%, whereas four C₉₋₁₂ PFCAs and total PFCAs increased by 35–141%. These results follow a similar trend to what has been reported in other studies of Arctic marine mammals from Svalbard. The most dramatic change has been the decline of PFOS concentrations since 2000, corresponding to the production phase-out of PFOS and related compounds in many countries around the year 2000 and a global restriction on these substances in 2009. Still, the continued dominance of PFOS in white whales, and increasing concentration trends for several PFCAs, even though exposure is relatively low, calls for continued monitoring of concentrations of both PFCAs and PFSAs and investigation of biological effects.

The impact that microplastics have on baleen whales is a question that remains largely unexplored. This study examined the interaction between free-ranging fin whales (Balaenoptera physalus) and microplastics by comparing populations living in two semi-enclosed basins, the Mediterranean Sea and the Sea of Cortez (Gulf of California, Mexico). The results indicate that a considerable abundance of microplastics and plastic additives exists in the neustonic samples from Pelagos Sanctuary of the Mediterranean Sea, and that pelagic areas containing high densities of microplastics overlap with whale feeding grounds, suggesting that whales are exposed to microplastics during foraging; this was confirmed by the observation of a temporal increase in toxicological stress in whales. Given the abundance of microplastics in the Mediterranean environment, along with the high concentrations of Persistent Bioaccumulative and Toxic (PBT) chemicals, plastic additives and biomarker responses detected in the biopsies of Mediterranean whales as compared to those in whales inhabiting the Sea of Cortez, we believe that exposure to microplastics because of direct ingestion and consumption of contaminated prey poses a major threat to the health of fin whales in the Mediterranean Sea.

Occurrence and behaviour of classical (PBDEs) and alternative (HNs, HBB, PBEB, DBDPE and HBCD) flame retardants, together with naturally produced MeO-PBDEs, were studied in short-beaked common dolphin (Delphinus delphis), bottlenose dolphin (Tursiops truncatus) and long-finned pilot whale (Globicephala melas) in two sampling locations from Southern European waters. PBDEs, Dec 602, Dec 603, DP, α-HBCD and two MeO-PBDEs were detected in all three species. ∑PBDEs were between 17 and 2680 ng/g lw; ∑HNs were between 1.1 and 59 ng/g lw; α-HBCD levels ranged between 3.2 and 641 ng/g lw; ∑MeO-PBDEs were between 34 and 1966 ng/g lw. Bottlenose dolphins were the most contaminated species and some individuals could present health risk for endocrine disruption since levels found were above the reported threshold (1500 ng/g lw). Stable isotope analysis was used to evaluate the biomagnification capacity of these compounds. PBDEs, MeO-PBDEs and Dec 602 showed a significant positive correlation with trophic position.

When mammals strand, they present a unique opportunity to obtain insights into their ecology. In May 2013, three True's beaked whales (two adult females and a female calf) stranded on the north and west coasts of Ireland and the contents of their stomachs and intestines were analysed for anthropogenic debris. A method for identifying microplastics ingested by larger marine organisms was developed. Microplastics were identified throughout the digestive tract of the single whale that was examined for the presence of microplastics. The two adult females had macroplastic items in their stomachs. Food remains recovered from the adult whales consisted of mesopelagic fish (Benthosema glaciale, Nansenia spp., Chauliodius sloani) and cephalopods, although trophic transfer has been discussed, it was not possible to ascertain whether prey were the source of microplastics. This is the first study to directly identify microplastics <5 mm in a cetacean species.

Plastic pollution is ubiquitous and not even remote protected islands are safe from it. Floating debris can adsorb toxic compounds that concentrate on their surface, being available to the animals that ingest them. For this reason, a baseline study of plastic pollution was conducted in the remote Revillagigedo Archipelago, in the Mexican Pacific Ocean. In 47 manta net samples an average of 4.8 plastics/1000m² was found, 73% of the pieces being <5 mm. Polyethylene and polypropylene were the most common polymers found. The chemical analysis of organic pollutants revealed that organochlorine pesticides, polycyclic aromatic hydrocarbons and polychlorinated biphenyls are adsorbed on the plastics collected in the area. Filter feeding megafauna such as humpback whales, manta rays and whale sharks could ingest contaminated micro and macroplastics. Plastics were found also on the beach, where they are available to the ingestion by terrestrial animals, including endemic species endangered to extinction.

Plastic pollution is an omnipresent problem that threatens marine animals through ingestion and entanglement. Marine mammals are no exception to this rule but their interaction with plastic remains understudied in the Mediterranean Sea. Here we highlight this problem by analyzing the stomach contents of 34 individuals from seven odontocete species stranded in Greece. Macroplastic (>5 mm) was found in the stomachs of nine individuals from four species (harbour porpoise Phocoena phocoena, Risso's dolphin Grampus griseus, Cuvier's beaked whale Ziphius cavirostris and sperm whale Physeter macrocephalus) with the highest frequency of occurrence in sperm whales (60%). Gastric blockage from plastic was presumably lethal in three cases, with plastic bags being the most common finding (46%). Plastic ingestion is of particular conservation concern for the endangered Mediterranean sperm whales. A regular examination of stranded cetaceans with a standardised protocol is critical for allowing spatiotemporal comparisons within and across species.