Simonetta Corsolini

CONGENER PROFILE AND TOXICITY ASSESSMENT OF POLYCHLORINATED BIPHENYLS IN DOLPHINS, SHARKS AND TUNA COLLECTED FROM ITALIAN COASTAL WATERS

Abstract Bottlenose and Rissos dolphins found dead along the Italian coast in 1992 were analysed for the presence of PCB isomers and DDT. High concentrations of PCBs (90–1400 μg/g wet wt) were detected in the blubber of stranded carcasses. The concentrations were higher than those found in animals showing reproductive failure and physiological impairment following prolonged PCB exposure, suggesting that the contamination by PCBs as well as DDT may be a major causative factor for the large-scale deaths of dolphins in the Mediterranean Sea. The 2,3,7,8-TCDD toxic equivalents estimated for bottlenose and Rissos dolphins were 18.8 and 20.8 ng/g, respectively, with a major contribution from mono-ortho PCBs. The monoortho congeners of IUPAC Nos 105, 118 and 156 accounted for most of the toxicity exerted by PCBs in these dead dolphins. An increase in the proportion of non-ortho coplanar PCB congener of IUPAC No. 169 to No. 126 with an increase in the total PCB concentration in the blubber suggested a strong induction of drug metabolizing enzymes. It is possible to use CB-169 CB-126 concentration ratio to indicate whether there has been a strong activation of cytochrome P450 enzyme system in severely exposed/contaminated dolphin populations. The total PCB concentrations in the adipose fat of sharks from Italian coasts ranged from 70 to 4000 ng/g wet wt and that of DDT from 14 to 300 ng/g wet wt. In bluefin tuna, the total PCB and DDT concentrations were 170–2200 and 56–780 ng/g wet wt, respectively. These values were comparable to those reported for the same species in the Mediterranean Sea during the 1970s, suggesting the existence of PCB sources near this marine ecosystem.

Sex differences in Adélie penguin foraging strategies

Abstract Consistent sex differences in foraging trip duration, feeding locality and diet of breeding Adélie penguins (Pygoscelis adeliae) were demonstrated at two widely separated locations over several breeding seasons. Differences in foraging behaviour were most pronounced during the guard stage of chick rearing. Female penguins made on average longer foraging trips than males, ranged greater distances more frequently and consumed larger quantities of krill. In contrast, males made shorter journeys to closer foraging grounds during the guard period and fed more extensively on fish throughout chick rearing. Mean guard stage foraging trip durations over four seasons at Béchervaise Island, Eastern Antarctica and over two seasons at Edmonson Point, Ross Sea ranged between 31 and 73 h for females and 25 and 36 h for males. Ninety percent of males tracked from Béchervaise Island by satellite during the first 3 weeks post-hatch foraged within 20 km of the colony, while the majority (60%) of females travelled to the edge of the continental shelf (80–120 km from the colony) to feed during this period.

Accumulation Pattern of Butyltin Compounds in Dolphin, Tuna, and Shark Collected from Italian Coastal Waters

Tributyltin (TBT) and its breakdown products, mono-(MBT) and dibutyltin (DBT) were determined in bottlenose dolphin (Tursiops truncatus), bluefin tuna (Thunnus thynnus thynnus) and blue shark (Prionace glauca) collected from the Italian coast of the Mediterranean Sea in 1992–1993. Concentrations of total butyltin (BTs) in the liver of dolphin (1,200–2,200 ng/g wet wt) were an order of magnitude higher than in the blubber (48–320 ng/g wet wt). TBT was the predominant butyltin species in the blubber while DBT accounted for an higher proportion in the liver of dolphins. Butyltin concentrations in bluefin tuna were lower than those in dolphins, with TBT highest in the muscle and DBT in the liver. Concentrations of BTs in blue sharks were lower than those in dolphin and tuna, with kidney having the highest concentrations. TBT was the predominant form of butyltin derivatives in all the tissues of shark. Accumulation of butyltin compounds in liver/kidney seems to be associated with the presence of proteins such as glutathione.

Industrial contaminants in Antarctic biota

A critical review of the levels and patterns of industrial contaminants in biota from Antarctica and the Southern Ocean revealed that concentrations are low with respect to other regions of the world, although in some specimens/species (e.g. leopard seal, some invertebrates) they are occasionally high and comparable to those found in regions with a strong human impact; the highest levels of persistent organic pollutants (POPs) were detected in the vicinity of scientific stations. Bioconcentration prevails at the lower trophic levels of pelagic food webs, while biomagnification can become the main route of contamination at higher levels. In a benthic food web, biomagnification poses a major risk for organisms that accumulate lipids to overwinter, compared to those that accumulate glycogen. Hexachlorobenzene, DDTs and chlordanes showed similar concentrations and patterns in the 1980s-1990s period in organisms from Western and Eastern Antarctica, while the polychlorinated biphenyls time trend was different in a variety of species from the two regions.

Interactive effects of n-TiO2 and 2,3,7,8-TCDD on the marine bivalve Mytilus galloprovincialis

Despite the growing concern over the potential biological impact of nanoparticles (NPs) in the aquatic environment, little is known about their interactions with other pollutants. The bivalve Mytilus sp, largely utilized as a sentinel for marine contamination, has been shown to represent a significant target for different types of NP, including n-TiO2, one of the most widespread in use. In this work, the possible interactive effects of n-TiO2 and 2,3,7,8-TCDD, chosen as models of NP and organic contaminant, respectively, were investigated in Mytilus galloprovincialis. In vitro experiments with n-TiO2 and TCDD, alone and in combination, were carried out in different conditions (concentrations and times of exposure), depending on the target (hemocytes, gill cells and biopsies) and the endpoint measured. Mussels were also exposed in vivo to n-TiO2 (100 μg L(-1)) or to TCDD (0.25 μg L(-1)), alone and in combination, for 96 h. A wide range of biomarkers, from molecular to tissue level, were measured: lysosomal membrane stability and phagocytosis in hemocytes, ATP-binding cassette efflux transporters in gills (gene transcription and efflux activity), several biomarkers of genotoxicity in gill and digestive cells (DNA damage, random amplified polymorphic DNA-RAPD changes), lysosomal biomarkers and transcription of selected genes in the digestive gland. The results demonstrate that n-TiO2 and TCDD can exert synergistic or antagonistic effects, depending on experimental condition, cell/tissue and type of measured response. Some of these interactions may result from a significant increase in TCDD accumulation in whole mussel organisms in the presence of n-TiO2, indicating a Trojan horse effect. The results represent the most extensive data obtained so far on the sub-lethal effects of NPs and organic contaminants in aquatic organisms. Moreover, these data extend the knowledge on the molecular and cellular targets of NPs in bivalves.

POPs in key species of marine Antarctic ecosystem

Abstract Remote areas including the Polar regions were considered to be pristine until contamination was first documented in the 1970s. Given the fact that the xenobiotics detected in polar ecosystems are persistent and toxic, investigating the presence of these chemicals in a pristine environment such as Antarctica has become a priority. In specimens of the most important key species of Antarctic marine food web, Euphausia superba and Pleuragramma antarcticum sampled in the Ross Sea, we evaluated concentrations of the following persistent organic pollutants: polychlorinated biphenyls (PCBs), chlorinated pesticides such as hexachlorobenzene (HCB), and p,p′-DDE. Sampling was carried out in the framework of the Italian National Program for Research in Antarctica (PNRA) from 1999 to 2000. PCB concentrations were higher than HCB and p,p′-DDE by two orders of magnitude; levels of HCB and p,p′-DDE, in the range of 1–5 ng/g wet weight, were low compared to those reported for species in lower latitude marine environments. PCBs values were comparable to those determined in moderately contaminated areas. PCB fingerprints and patterns of isomer classes showed a predominance of low-chlorinated PCBs: tri-, tetra- and penta-CB congeners constituted more than 50% of the total residue in krill and larvae and less than 50% in adult silverfish. The pattern seems common to that of Kanechlor, a technical mixture used mostly in Japan and other Eastern Asian countries that are roughly at the same longitude of the Ross Sea.

Polybrominated diphenyl ethers, polychlorinated naphthalenes and polycyclic musks in human fat from Italy: Comparison to polychlorinated biphenyls and organochlorine pesticides

Prior to this study, reports of occurrence of polycyclic musks and polychlorinated naphthalenes (PCNs) in human tissues from Italy were not available. In this study, concentrations of PCNs and polycyclic musks were determined in human adipose tissue from Italy collected during 2005-2006; for comparison, legacy organohalogen pollutants such as organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), and polybrominated diphenyl ethers (PBDEs) were determined. SigmaPCN concentrations ranged from 0.5 to 14 ng/g lipid wt (lw). Polycyclic musks such as HHCB and AHTN were found in 92% and 83% of the human samples, respectively. Concentrations of PBDEs in Italian adipose tissue ranged between 3.2 and 35.6 ng/g lw.

Polychlorinated dibenzo-p-dioxins, dibenzofurans and polychlorinated biphenyls in polar bear, penguin and south polar skua

Concentrations of 2378-substituted polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (DFs) and non- and mono-ortho-substituted polychlorinated biphenyls (dioxin-like PCBs) were measured in livers of polar bears from the Alaskan Arctic and in eggs of Adelie penguin and south polar skua and weddell seal liver, fish and krill from Antarctica. This is one of the first reports to document the concentrations of PCDDs/DFs in polar bear livers from Alaska, and in penguin and skua eggs from Antarctica. Concentrations of total PCDD/DFs in livers of polar bears ranged from 8 to 66 (mean: 26) pg/g, on a lipid weight basis. Concentrations of total PCDD/DFs in Antarctic samples were in the increasing order on a lipid weight basis; weddell seal liver (8.9 pg/g) < fish (11-17 pg/g) < krill (27 pg/g) <penguin eggs (mean: 23 pg/g) < south polar skua eggs (mean: 181 pg/g). Concentrations of dioxin-like PCBs (including two di-ortho congeners) in polar bear livers were in the range of 1,080-3,930 ng/g, lipid wt. Concentrations of dioxin-like PCBs in Antarctic samples were in the following order on a lipid weight basis; south polar skua eggs (mean: 1,440 ng/g) > > penguin eggs (30 ng/g) > seal liver (57 ng/g) > fishes (6.2 ng/g) > krill (0.9 ng/g). Concentrations of 2378-tetrachlorodibenzo-p-dioxin equivalents (TEQs) calculated based on the WHO TEFs were higher in the eggs of polar skua (mean: 344: range: 220-650 pg/g, lipid wt.) from Antarctica than in polar bear livers from Alaska (mean: 120; range: 69-192 pg/g). In general, concentrations of PCDFs were greater than those of PCDDs in polar organisms. 23478-PeCDF is one of the dominant congener found in several samples. Concentrations of TEQs in polar bear livers and skua eggs were close to those that may cause adverse health effects. Dioxin-like PCBs, particularly, non-ortho coplanar PCBs were the major contributors to TEQ concentrations in penguin and skua eggs whereas mono-ortho PCBs accounted for a major portion of TEQs in polar bear livers.

Atlantic Bluefin Tuna (Thunnus thynnus) Population Dynamics Delineated by Organochlorine Tracers

Atlantic bluefin tuna (ABFT) are highly valued and heavily exploited, and critical uncertainties regarding their population structure hinder effective management. Evidence supports the existence of two breeding populations of ABFT; a western population in the Gulf of Mexico and an eastern population in the Mediterranean Sea; both of which migrate and mix in the North Atlantic. Conventional tagging studies suggest low rates of trans-Atlantic migrations; however, electronic tagging and stable isotopes in otoliths indicate stock mixing up to 57% between management zones delineated by 45 degrees W longitude. Here we show that organochlorine pesticides and polychlorinated biphenyls (PCBs) can be used as tracers of bluefin tuna foraging grounds in the North Atlantic and confirm that stock mixing of juvenile tuna within the U.S. Mid Atlantic Bight is indeed high (33-83% eastern origin), and is likely spatially and temporally variable. We further demonstrate that >10% of the Mediterranean population is migratory, that young bluefin tuna migrate from the Mediterranean to western Atlantic foraging grounds as early as age 1, and then return to the Mediterranean Sea as young as age 5, presumably to breed. The tracer method described here provides a novel means for distinguishing bluefin tuna populations and ontogenetic shifts in migration in the North Atlantic.

Levels of polybrominated diphenyl ethers (PBDEs) and organochlorine pollutants in two species of Antarctic fish (Chionodraco hamatus and Trematomus bernacchii).

In the late 1960s the first scientific studies on contamination in Antarctica demonstrated the presence of pollutants in Antarctic ecosystems. Many Persistent Organic Pollutants (POPs) are transported globally from the areas in which they are produced and released into the environment in remote areas, including Antarctica. Here we report results obtained concerning the accumulation of polybrominated diphenyl ethers (PBDEs), mono- and non-ortho-polychlorobiphenyls (PCBs), polychlorodibenzodioxins (PCDDs) and polychlorodibenzofurans (PCDFs) in the tissues of two species of Antarctic fish (Chionodraco hamatus and Trematomus bernacchii). The 2,3,7,8-TCDD toxic equivalents (TEQs) were also calculated to evaluate the potential risk of these compounds for the two species. In general, POP levels were higher in the tissues of T. bernacchii than in C. hamatus and the highest concentrations were found in the liver of both species. The PBDE levels varied from 160.5 pg g(-1) wet wt in C. hamatus muscle to 789.9 pg g(-1) wet wt in T. bernacchii liver and were lower than the levels of PCBs. PCBs were the main organochlorine compounds detected and their concentrations ranged from 0.3 ng g(-1) wet wt in C. hamatus muscle to 15.1 ng g(-1) wet wt in T. bernacchii liver. TEQ concentrations resulted higher in C. hamatus than in T. bernacchii and were due mainly to PCDDs. The presence of PBDEs and organochlorine pollutants in the tissues of Antarctic organisms confirms their global transport and distribution.