Enantiomeric signatures of chiral polychlorinated biphenyl atropisomers in livers of harbour porpoises (Phocoena phocoena) from the southern North Sea

The enantiomeric composition of polychlorinated biphenyl (PCB) atropisomers, including PCB 95, PCB 149 and PCB 132, was measured in 11 livers of harbour porpoises (Phocoena phocoena) from the southern North Sea. Non-racemic enantiomeric ratios (ERs) were found in some samples. The value of ERs in three of the four juvenile porpoises was equal or almost equal to one, while the ERs in all adults differed from racemic and ranged from 1.31 to 2.54 for PCB 95; from 1.19 to 1.81 for PCB 149 and from 0.45 to 0.94 for PCB 132. There were no relationships between the total concentration of PCBs and ERs. To understand the phenomena, the relationships between the ER value of individual chiral congener with age, concentration of total PCBs and PCB congener pattern were discussed. A model of intake and elimination kinetics was set up and it was tested using the ratio between concentration of PCB 153 and PCB 101 in the liver samples. There was a clear trend between the enantiomeric ratios and the ratio between PCB 153 and PCB 101. Considering that PCB 153 is one of the most persistent PCB congeners in marine mammals and PCB 101 is a relatively easy metabolised congener, this trend means that the enantiomeric ratio most likely reflects the proportion of the metabolised congener. The exposure period in contaminated conditions has a strong impact on ERs, and it is suggested that ERs in wildlife, combined with information on their anthropometric data, health status, diet and habitat conditions, might be good indicators of pollution in coastal ecosystems.     

Brominated flame retardants and polychlorinated biphenyls in fish from the river Scheldt, Belgium

Levels of polybrominated diphenyl ethers (PBDEs), hexabromocyclododecanes (HBCDs), and polychlorinated biphenyls (PCBs) were measured in several fish species originating from the river Scheldt (Belgium). Five sampling locations were chosen in a highly industrialized area along the river, while two ponds in the vicinity of the river served as reference sites. The present study is a follow-up of a survey performed in 2000 which reported extremely high levels of PBDEs and HBCDs in eel (Anguilla anguilla) collected from the same region (Oudenaarde, Flanders). The sum of tri- to hepta-BDE congeners (2270+/-2260 ng/g lipid weight (lw), range 660-11500 ng/g lw) and total HBCDs (4500+/-3000 ng/g lw, range 390-12100 ng/g lw) were one order of magnitude higher than levels usually reported from freshwater systems, indicating the presence of point sources. In most samples, levels of total HBCDs were higher than those of PBDEs, probably due to the high density of factories using HBCD as an additive brominated flame retardant (BFR). The high values of HBCDs were confirmed by both gas- and liquid-chromatography-mass spectrometry. Although BFR levels were between the highest ever reported in freshwater ecosystems, PCBs could be detected at even higher concentrations (16000+/-14300 ng/g lw, range 3900-66600 ng/g lw), being among the highest levels recorded in Belgium. The inter-sampling site variation of PBDEs, HBCDs and PCBs was comparable. All locations presented similar PBDE congener profiles, with BDE 47 being the dominant congener, followed by BDE 100, BDE 99 and BDE 49, probably originating from the former use of the penta-BDE technical mixture. In order to estimate the impact of these point sources on human exposure, we further focussed on eels which showed a considerable decrease in the PBDE and HBCD levels between 2000 and 2006. Due to the wide span in concentrations between the different sampling locations, a variable contribution to the total human exposure through local eel consumption was estimated. The calculated daily intake ranged from 3 ng to 330 ng PBDEs/day for normal eel consumers, but was as high as 9800 ng PBDEs/day for anglers, which may be considered at risk.     

Perfluorooctane sulfonic acid and organohalogen pollutants in liver of three freshwater fish species in Flanders (Belgium): relationships with biochemical and organismal effects

A perfluorooctane sulfonic acid (PFOS) assessment was conducted on gibel carp (Carassius auratus gibelio), carp (Cyprinus carpio), and eel (Anguilla anguilla) in Flanders (Belgium). The liver PFOS concentrations in fish from the Ieperlee canal (Boezinge, 250-9031 ng/g wet weight, respectively) and the Blokkersdijk pond (Antwerp, 633-1822 ng/g wet weight) were higher than at the Zuun basin (Sint-Pieters-Leeuw, 11.2-162 ng/g wet weight) and among the highest in feral fish worldwide. Eel from the Oude Maas pond (Dilsen-Stokkem) and Watersportbaan basin (Ghent) had PFOS concentrations ranging between 212 and 857 ng/g wet weight. The hepatic PFOS concentration was significantly and positively related with the serum alanine aminotransferase activity, and negatively with the serum protein content in eel and carp. The hepatic PFOS concentration in carp correlated significantly and negatively with the serum electrolyte concentrations whereas a significant positive relation was found with the hematocrit in eel. Although 13 organochlorine pesticides, 22 polychlorinated biphenyl (PCB) congeners and 7 polybrominated diphenyl ethers (PBDEs) were also measured in the liver tissue, only PCB 28, PCB 74, gamma-hexachlorocyclohexane (gamma-HCH) and hexachlorobenzene (HCB) were suggested to contribute to the observed serological alterations in eel.     

Polybrominated diphenyl ethers (PBDEs) in freshwater mussels and fish from Flanders, Belgium

The levels and distribution of PBDEs in zebra mussels and several freshwater fish species (eel, carp and gibel carp) were investigated for different sites in Flanders, Belgium. In parallel, other organohalogenated contaminants, such as polychlorinated biphenyls (PCBs), p,p[prime or minute]-DDE and hexachlorobenzene (HCB) were also measured and their relationship with PBDEs was investigated. At most sites, individual PBDE congeners were present at detectable levels in mussel tissue, with the mean [summation operator]PBDE concentration ranging from 0.15 to 1.8 ng g(-1) wet weight (ww). The PCB concentrations in mussels ranged from 6.2 to 102 ng g(-1) ww. HCB and p,p[prime or minute]-DDE could be measured in mussels from most sites, mean values ranging from below the limit of quantification (LOQ) to 0.58 ng g(-1) ww and from 0.66 to 6.5 ng g(-1) ww, respectively. Except for one site (Blokkersdijk, Antwerp) where PBDEs were below the LOQ in carp muscle, all fish samples from other sites contained detectable PBDE levels, with the highest concentrations (14 +/- 14 ng g(-1) ww) being measured in eel liver from Watersportbaan (Ghent). The sampled sites covered a broad concentration range of organohalogenated pollutants with the highest values being consistently measured in eel liver. With few exceptions, all correlations between PBDEs and organochlorine pollutants for each species were low (r < 0.50) and most were statistically not significant (p > 0.05). This suggests that the exposure to contaminants arises from local sources possessing different signatures of PBDEs and organochlorine pollutants.     

Penguin colonies as secondary sources of contamination with persistent organic pollutants

Although long-range atmospheric transport has been described as the predominant mechanism for exposing polar regions to persistent organic pollutants (POPs), recent studies have suggested that bird activity can also contribute substantially to contaminant levels in some environments. However, because the species so far reported have all been migratory, it has not been demonstrated conclusively whether locally elevated contamination represents transport from lower latitudes by the migrating birds or, alternatively, redistribution and concentration of contaminants that were already present in the high-latitude environments. The present study demonstrates, for the first time, that several POPs are present in elevated concentrations in an environment frequented by a non-migratory species (Adélie penguins) that spends its entire life in the Antarctic. Levels of POPs, such as p,p'-DDE, hexachlorobenzene (HCB), chlordanes (CHLs) and polychlorinated biphenyls (PCBs), were 10 to 100-fold higher in soil samples from penguin colonies than from reference areas. This significant difference is likely related to local penguin activity, such as a higher abundance of guano and the presence of bird carcasses. This hypothesis is also supported by a higher percentage of persistent congeners (PCB 99, 118, 138 and 153) in the soil from the colonies compared to the reference areas. This profile of PCB congeners closely matched profiles seen in penguin eggs or penguin blood.     

Effects of heavy metal exposure on the condition and health of nestlings of the great tit (Parus major), a small songbird species

In this study we examined the possible effects of heavy metal exposure on the condition and health of great tit nestlings (Parus major) at four study sites along a pollution gradient near a large non-ferrous smelter in Belgium during three consecutive breeding seasons. Our results showed that nestlings were indeed exposed to large amounts of heavy metals. Excrements contained significantly higher concentrations of several heavy metals (silver, arsenic, cadmium, mercury, lead) near the pollution source than at study sites farther away. When taking into account the number of young in the nest at the time of sampling, nestling body mass and condition were significantly reduced at the most polluted site. Nestlings at the two most polluted sites fledged significantly later than at the least polluted site. We also observed growth abnormalities of the legs near the pollution source. Tarsus length, wing length and haematocrit values did not differ significantly among study sites.     

The importance of exogenous contamination on heavy metal levels in bird feathers. A field experiment with free-living great tits, Parus major

Feathers have been used extensively as non-destructive biomonitors for heavy metal pollution. Birds excrete heavy metals into growing feathers during moult. After feather formation, the feathers become isolated from the rest of the body, suggesting that the feathers contain information of circulating heavy metal concentrations in the blood at the time of their development. However, heavy metal levels may change due to exogenous contamination, resulting in higher concentrations in feathers that are exposed most to exogenous conditions. We studied the effect of exogenous contamination in free-living adult great tits (Parus major) by measuring--within the same individual--the concentrations of twelve heavy metals (Ag, Al, As, Cd, Co, Cu, Fe, Hg, Mn, Pb, Tl and Zn) in three outermost tail feathers that were exposed to exogenous contamination for different periods of time. In particular, for each individual heavy metal levels in the removed left outermost tail feather were compared with levels in the regrown left and the right outermost tail feather, that were both removed 40 days after removal of the original left feather. This study revealed that, with the exception of mercury, the concentration of all heavy metals was significantly different among the three outermost tail feathers. Our results suggest that concentrations of most heavy metals build up with increasing age of the feather, indicating that exogenous contamination may be an important source of heavy metals in feathers. However, we found no significant differences in Hg concentrations and we found only small differences in Zn concentrations among tail feathers. Consequently, the concentrations of zinc and mercury in feathers are probably primarily due to endogenous deposition.     

Climate, icing, and wild arctic reindeer: past relationships and future prospects

Across the Arctic, heavy rain-on-snow (ROS) is an "extreme" climatic event that is expected to become increasingly frequent with global warming. This has potentially large ecosystem implications through changes in snowpack properties and ground-icing, which can block the access to herbivores' winter food and thereby suppress their population growth rates. However, the supporting empirical evidence for this is still limited. We monitored late winter snowpack properties to examine the causes and consequences of ground-icing in a Svalbard reindeer (Rangifer tarandus platyrhynchus) metapopulation. In this high-arctic area, heavy ROS occurred annually, and ground-ice covered from 25% to 96% of low-altitude habitat in the sampling period (2000-2010). The extent of ground-icing increased with the annual number of days with heavy ROS (> or = 10 mm) and had a strong negative effect on reindeer population growth rates. Our results have important implications as a downscaled climate projection (2021-2050) suggests a substantial future increase in ROS and icing. The present study is the first to demonstrate empirically that warmer and wetter winter climate influences large herbivore population dynamics by generating ice-locked pastures. This may serve as an early warning of the importance of changes in winter climate and extreme weather events in arctic ecosystems.