Levels of persistent organic pollutants (POPs) and the role of anthropic subsidies in the diet of avian scavengers tracked by stable isotopes.

Persistent Organic Pollutants (POPs) have been identified as a significant factor driving declines in wildlife populations. These contaminants exhibit a dual tendency to biomagnify up the food chains and persist within tissues, rendering long-lived vertebrates, such as raptors, highly vulnerable to their adverse effects. We assessed the concentrations of polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) in fledglings of two vulture species, the Egyptian vulture (Neophron percnopterus) and the griffon vulture (Gyps fulvus), coexisting in northern Spain. Vultures, currently facing a severe threat with a population decline exceeding 90%, represent one of the most critically endangered avian groups in the Old World. Despite this critical situation, there remains a scarcity of research examining the intricate relationship between contaminant levels and individual foraging behaviors. In parallel, we analyzed stable isotope levels (δ15N and δ13C) in fledgling's feathers and prey hair to determine the association between individual dietary and contaminant burdens. Our findings revealed higher levels of PCBs in Egyptian vultures, while pesticide concentrations remained very similar between focal species. Furthermore, higher individual values of δ13C, indicating a diet based on intensive farming carcasses and landfills, were associated with higher levels of PCBs. While the levels of POPs found do not raise immediate alarm, the presence of individuals with unusually high values reveals the existence of accessible contamination sources in the environment for avian scavengers. The increasing reliance of these birds on intensive livestock farming and landfills, due to the decline of extensive livestock farming, necessitates long-term monitoring of potential contaminant effects on their populations.

Relevance of current PCB concentrations in edible fish species from the Mediterranean Sea.

Legal restrictions and bans have led to a steady decrease in PCB environmental concentrations. Yet, in recent years PCBs have been found at very high levels in the Mediterranean Sea, for instance, in some apex predators. This work aimed to investigate current PCB (eighteen congeners: #28,52,77,81,101,105,114,118,123,126,138,153,156,157,167,169,180,189) concentrations in the Mediterranean Sea and their relevance today, focusing on their occurrence in edible fish species typically consumed in the Mediterranean diet. In spring 2017, a total of 48 fish samples from the Northern Thyrrenian Sea were collected: 16 specimens of sardine (Sardina pilchardus), 16 of anchovy (Engraulis encrasicolus) and 16 of bogue (Boops boops). PCBs were quantified in the muscle of the animals by means of GC-QqQ-MS. They were found in all samples at the greatest concentrations (ng/g w.w.) in sardine (4.15-17.9, range), and very similar values between anchovy (1.01-7.08) and bogue (1.46-7.22). WHO-TEQ PCB values followed the same order, i.e. sardine (0.410-1.24, range in pg/g w.w.) > anchovy (0.0778-0.396) ~ bogue (0.0726-0.268). These concentrations lied below the European limits of 75 ng/g (w.w.) for the six indicator PCBs and 6.5 pg/g WHO-TEQ for dioxins and dioxin-like PCBs in muscle meat of fish. Additionally, estimated weekly intakes (EWI, in pg WHO-TEQ/Kg/week) for sardine (1.2), anchovy (0.29) and bogue (0.35) scored below the safe value proposed by EFSA of 2 pg WHO-TEQ/Kg/week. When comparing with data reported for the same species in previous Mediterranean studies, values found here were lower than those surveyed in the late 90s and early 2000s; however, they were often not notably different from concentrations reported in last years. This builds up on the concept of a current slow decrease of PCBs in the Mediterranean Sea, likely linked to new inputs and/or remobilization of burdens, and reinforces the need of continous monitoring of these legacy contaminants still ubiquitous today.

Evaluation of PCDD/Fs, dioxin-like PCBs and PBDEs in sperm whales from the Mediterranean Sea.

Numerous studies to date have reported concentrations of Persistent Organic Pollutants (POPs) in different marine mammal species worldwide. Yet data on sperm whales are scarce from rich and unique biodiverse areas such as the Mediterranean Sea. This work aimed to assess levels of dioxin-like polychlorinated biphenyls (dl-PCBs), polybrominated diphenyl ethers (PBDEs), and polychlorodibenzo-p-dioxins and furans (PCDD/Fs) in blubber of sperm whales stranded along the Italian coast between 2008 and 2016. POP mean concentrations (dl-PCBs: 6410 ng/g l.w.; PBDEs: 612 ng/g l.w.; PCDD/Fs: 57.8 pg/g l.w.) were mostly in line with what has been previously reported on the same species in the Mediterranean environment and tended to be higher than those reported from other geographical regions. The relative abundance followed the order dl-PCBs > PBDEs ≫ PCDD/Fs. Interestingly, the non-ortho dl-PCB pattern (126 > 169 > 77) was similar to that described in other studies worldwide and different from what is described in its main prey. This could be linked to particular metabolic activities in sperm whales against these highly toxic contaminants. Total TEQs ranged from 275 to 987 pg/g l.w. and showed the pattern Σnon-ortho-dl-PCBs > Σortho-dl-PCBs > PCDDs > PCDFs, with PCBs' contribution about 96%. These findings highlight the high abundance of PCBs still found in the Mediterranean environment despite having been banned for decades. All sperm whales analyzed in this study surpassed the threshold of 210 pg WHO-TEQ/g l.w. proposed as starting point of immunosuppression in harbour seals; a level of contamination that may have contributed to an impairment of their immune system.

First assessment of persistent organic pollutant contamination in blubber of Chilean blue whales from Isla de Chiloé, southern Chile.

Persistent organic pollutants (POPs) were assessed for the first time in blue whales from the South Pacific Ocean. Concentrations of polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), hexachlorobenzene (HCB) and dichlorodiphenyltrichloroethane and its main metabolites (DDTs), were determined in 40 blubber samples from 36 free-ranging individuals and one stranded, dead animal along the coast of southern Chile between 2011 and 2013. PCBs were the most abundant pollutants (2.97-975 ng/g l.w.), followed by DDTs (3.50-537 ng/g l.w.), HCB (nd-77.5 ng/g l.w.) and PBDEs (nd-33.4 ng/g l.w). There was evidence of differences between sexes, with lower loads in females potentially due to pollutants passing to calves. POP concentrations were higher in specimens sampled in 2013; yet, between-year differences were only statistically significant for HCB and PBDEs. Lower chlorinated (penta > tetra > tri) and brominated (tetra > tri) congeners were the most prevalent among PCBs and PBDEs, respectively, mostly in agreement with findings previously reported in blue and other baleen whales. The present study provides evidence of lower levels of contamination by POPs in eastern South Pacific blue whales in comparison to those reported for the Northern Hemisphere.

Could feeding habit and migratory behaviour be the causes of different toxicological hazard to cetaceans of Gulf of California (Mexico)?

In this work, a suite of diagnostic biomarkers was applied to seven cetacean species to evaluate the role of the feeding habits and migratory behavior in the toxicological status of these species from the Gulf of California, Mexico. We investigate the interspecific differences in cytochrome P450 1A1 and 2B (CYP1A1 and CYP2B, respectively), aryl hydrocarbon receptor and E2F transcription factor 1 and the contaminants levels [organochlorine compounds, polybrominated diphenyl ethers (PBDEs) and polycyclic aromatic hydrocarbons (PAHs)] in four odontocete species (common bottlenose dolphin, long-beaked common dolphin, sperm whale and killer whale) and three mysticete species (blue whale, fin whale, and Bryde's whale) using skin biopsy. Differences in contaminant levels and molecular biomarker responses between the odontocete and mysticete species have been pointed out. The canonical discriminant analysis on principal component analysis factors, performed to reveal clustering variables, shows that odontocete are characterised by the highest levels of lipophilic contaminants compared to the mysticete, with the highest levels of polychlorinated biphenyls, dichlorodiphenyltrichloroethanes and PBDEs detected in killer whale and the lowest levels in Bryde's whale. The biomarker data show interspecific differences amongst the seven species, revealing highest CYP1A and CYP2B protein levels in the mysticete fish-eating species (Bryde's whale). In conclusion, three main factors seem to regulate the biomarker responses in these species: (a) the inductive ability of persistent organic pollutants and PAHs; (b) the different evolutionary process of the two CYPs related to the different feeding habits of the species; (c) the migratory/resident behaviour of the mysticete species in this area.

Seasonal and spatial variation of organic tracers for biomass burning in PM1 aerosols from highly insolated urban areas.

PM1 aerosol characterization on organic tracers for biomass burning (levoglucosan and its isomers and dehydroabietic acid) was conducted within the AERTRANS project. PM1 filters (N = 90) were sampled from 2010 to 2012 in busy streets in the urban centre of Madrid and Barcelona (Spain) at ground-level and at roof sites. In both urban areas, biomass burning was not expected to be an important local emission source, but regional emissions from wildfires, residential heating or biomass removal may influence the air quality in the cities. Although both areas are under influence of high solar radiation, Madrid is situated in the centre of the Iberian Peninsula, while Barcelona is located at the Mediterranean Coast and under influence of marine atmospheres. Two extraction methods were applied, i.e. Soxhlet and ASE, which showed equivalent results after GC-MS analyses. The ambient air concentrations of the organic tracers for biomass burning increased by an order of magnitude at both sites during winter compared to summer. An exception was observed during a PM event in summer 2012, when the atmosphere in Barcelona was directly affected by regional wildfire smoke and levels were four times higher as those observed in winter. Overall, there was little variation between the street and roof sites in both cities, suggesting that regional biomass burning sources influence the urban areas after atmospheric transport. Despite the different atmospheric characteristics in terms of air relative humidity, Madrid and Barcelona exhibit very similar composition and concentrations of biomass burning organic tracers. Nevertheless, levoglucosan and its isomers seem to be more suitable for source apportionment purposes than dehydroabietic acid. In both urban areas, biomass burning contributions to PM were generally low (2 %) in summer, except on the day when wildfire smoke arrive to the urban area. In the colder periods the contribution increase to around 30 %, indicating that regional biomass burning has a substantial influence on the urban air quality.

Evaluation of the possible adverse effects of legacy persistent organic pollutants (POPs) on the brown booby (Sula leucogaster) along the Brazilian coast.

This study aimed to investigate the impact of contamination by persistent organic pollutants (POPs) on Brazilian wildlife. The concentrations of certain POPs, including dichlorodiphenyltrichloroethane (DDT) and polychlorinated biphenyls (PCBs), in the eggs of the brown booby (Sula leucogaster) were measured. The eggs were collected from breeding colonies located on three archipelagos (Saint Peter and Saint Paul, Abrolhos and Cagarras Islands) in the Atlantic Ocean, which are located at different distances from the Brazilian coast (range 4-1010 km). In addition, possible alterations in eggshell characteristics were evaluated. The average values of POPs found in eggs from the archipelago of Saint Peter and Saint Paul (0.05µgg(-1) of ΣPCBs and 0.01 µg g(-1) of ΣDDT) and the archipelago of Abrolhos (0.19 µg g(-1) of ΣPCBs and 0.03 µg g(-1) of ΣDDT) were low compared to the reference values reported in the literature. In contrast, the concentrations measured in eggs from Cagarras (8.4 µg g(-1) of ΣPCBs and 1.8 µg g(-1) of ΣDDT) were the highest, and this total PCB level is close to the threshold values considered to be harmful to birds. Our findings indicate that the brown booby colony closest to the Rio de Janeiro coast has recently been exposed to DDT. Despite the high pollution levels found on the Cagarras Islands, no alterations in the eggshell weight or the thickness of the analyzed eggs were detected. Hence, more detailed studies are recommended to determine the actual effects of the selected POPs on the Cagarras breeding colony.