Determination of 2,3,7,8-tetrachlorodibenzo-p-dioxin in fresh water fish

Validated sample preparation procedures and high resolution gas chromatography-high resolution mass spectrometry techniques were utilized for the quantitative measurement of 4 to 695 pg/g (ppt) levels of 2,3,7,8-tetrachlorodibenzo-p-dioxin (2378-TCDD) in the edible portions of fish from the state of Michigan. The methodology and the analytical results are presented.     

Polybrominated diphenyl ethers (PBDEs) in grey seals during their first year of life--are they thyroid hormone endocrine disrupters?

Blubber biopsy and blood samples were collected from weaned grey seal pups and juveniles in 1998 and 1999. The relationship between the concentration of total PDBEs in the blubber and the circulating concentrations of serum proteins, minerals and thyroid hormones was investigated. Fifty-four post-weaned pups were sampled and 55 first year juveniles, of which 13 were recaptured post-weaned pups. The median concentration of total PBDEs in the pups' blubber was 170 and 460 ng g(-1) in the first-year animals. Total blubber PBDEs contributed significantly to the prediction of circulating thyroid hormone concentrations, after controlling for age and condition. Cholesterol and albumin concentrations were also positively related to blubber PBDEs. The results of this study suggest a link between thyroid hormones and exposure to PBDEs in grey seals during their first year of life. Such an association is not alone sufficient evidence for a cause and effect relationship, however it is in accordance with the hypothesis that these compounds are endocrine disrupters in grey seal pups.     

Rhizosphere characteristics of indigenously growing nickel hyperaccumulator and excluder plants on serpentine soil

The role of rhizosphere processes in metal hyperaccumulation is largely unexplored and a matter of debate, related field data are virtually not available. We conducted a field survey of rhizosphere characteristics beneath the Ni hyperaccumulator Thlaspi goesingense Hálácsy and the metal-excluder species Silene vulgaris L. and Rumex acetosella L. growing natively on the same serpentine site. Relative to bulk soil and to the rhizosphere of the excluder species, we found significantly increased DOC and Ni concentrations in water extracts of T. goesingense rhizosphere, whereas exchangeable Ni was depleted due to excessive uptake of Ni. Chemical speciation analysis using the MINTEQA2 software package revealed that enhanced Ni solubility in Thlaspi rhizosphere is driven by the formation of Ni-organic complexes. Moreover, ligand-induced dissolution of Ni-bearing minerals is likely to contribute to enhanced Ni solubility. Increased Mg and Ca concentrations and pH in Thlaspi rhizosphere are consistent with ligand-induced dissolution of orthosilicates such as forsterite (Mg(2)SiO(4). Our field data reinforce the hypothesis that exudation of organic ligands may contribute to enhanced solubility and replenishment of metals in the rhizosphere of hyperaccumulating species.     

Age dependence of the accumulation of organochlorine pollutants in brown trout (Salmo trutta) from a remote high mountain lake (Redó, Pyrenees)

Polychlorobiphenyls (PCBs), hexachlorocyclohexanes (HCHs), hexachlorobenzene (HCB) and DDT were examined in the muscle of brown trout (Salmo trutta) from a high mountain lake located in the Pyrenees (Catalonia, Spain) that was used as a model of these lacustrine environments. Results indicate that fish age is the main factor of variability among specimens in this population that is subjected to atmospheric inputs of the organochlorine compounds (OC). Increases of 2- and 20-fold between fish aged 1 year and 15 years old are found. The observed pattern cannot be explained in terms of fish size, condition factor, or muscle lipid content. Higher molecular weight compounds (higher lipophilicity) are better correlated with fish age than low molecular weight compounds. A transformation from 4,4'-DDT to 4,4'-DDE occurs in fish after ingestion; this results in amplified age-dependent signals, especially in male specimens. In contrast, PCB congener #180 has lower age dependence than the general OC group, which could be due to its high hydrophobicity (log K(ow) > 7). In any case, selective accumulation of hydrophobic compounds is already observed among younger fish (age, 1 year). Due to this effect, the relative OC composition does not reflect the main OC pollutants in the lake waters.     

Rat metabolism of polychlorinated dibenzo-p-dioxins

In rats, dibenzo-p-dioxin, 1-chlorodibenzo-p-dioxin, 2-chlorodibenzo-p-dioxin, 2,3-dichlorodibenzo-p-dioxin, 2,7-dichlorodibenzo-p-dioxin, 1,2,4-trichlorodibenzo-p-dioxin and 1,2,3,4-tetrachlorodibenzo-p-dioxin are metabolized to mono- and dihydroxy derivatives, whilst in case of dibenzo-p-dioxin and both the two monochloro isomers, also sulphur containing metabolites are excreted. Primary hydroxylation exclusively takes place at the 2-, 3-, 7- or 8-position in the molecule. In none of the experiments metabolites resulting from fission of the C-O bonds (ortho, ortho'-dihydroxychlorodiphenyl ethers, chlorocatechols) or hydroxylated derivatives thereof, were detected. No metabolites were found from octachlorodibenzo-p-dioxin.     

The role of algae (Isochrysis galbana) enrichment on the bioaccumulation of benzo[a]pyrene and its effects on the blue mussel Mytilus edulis

The role of algal concentration in the transfer of organic contaminants in a food chain has been studied using the ubiquitous model polycyclic aromatic hydrocarbon benzo[a]pyrene (BaP) as the contaminant, Isochrysis galbana as the phytoplankton food source, and the common mussel (Mytilus edulis) as the primary consumer. The effect of algal concentration on BaP uptake by M. edulis was determined by feeding M. edulis daily with I. galbana which had previously been kept in the presence of BaP for 24 h. Four combinations of concentrations of algae and BaP were used to give final exposure concentrations of 30,000 or 150,000 algal cells ml(-1) in combination with either 2 or 50 microg BaP l(-1). BaP concentrations were determined fluorometrically in rest tissues (excluding digestive glands) and digestive gland microsomal fractions of M. edulis after 1, 7 and 15 days exposure, and also in isolated algae. Potentially toxic effects of BaP on M. edulis were examined in terms of blood cell lysosomal membrane damage (neutral red dye retention assay) and induction of digestive gland microsomal mixed-function oxygenase (MFO) parameters [BaP hydroxylase (BPH) and NADPH-cytochrome c (P450) reductase activities]. BaP bioaccumulation in rest tissues (and to a lesser extent in digestive gland microsomes) of M. edulis increased with both increasing BaP and algal exposure concentrations, and over time, producing maximal bioconcentration factors in rest tissues after 15 days exposure to 150,000 algal cells ml(-1) and 50 microg BaP l(-1) of 250,000. The five-fold higher concentration of algae increased BaP bioaccumulation by a factor of approximately 2 for 50 microg BaP l(-1) at day 15. Blood cell neutral red dye retention time decreased linearly with increasing log(10) tissue BaP body burden, indicating an increased biological impact on M. edulis with increasing BaP exposure possibly due to a direct effect of BaP on blood cell lysosomal membrane integrity. An increase was seen in NADPH-cytochrome c reductase activity, and indicated in BPH activity, with 1 but not 7 or 15 days exposure to BaP, indicating a transient response of the digestive gland microsomal MFO system to BaP exposure.     

Empty nests in the great tit (Parus major) and the pied flycatcher (Ficedula hypoleuca) in a polluted area

Great tits (Parus major) are sometimes found to incubate in their nests even though the nests contain no eggs. This phenomenon has been observed in different parts of Europe (Sweden, Finland, UK, Netherlands, Germany) and it has become more common during the 1980s. We analysed the occurrence of empty nests in P. major and in pied flycatcher (Ficedula hypoleuca) in SW Finland from 6-year data collected in a polluted area around a copper smelter which emits large quantities of sulphuric oxides and heavy metals. Among first broods 3.3% of P. major females incubated in empty nests. Incubation on empty nests was not observed in F. hypoleuca, but in this species 2.4% of the nests remained without eggs. In both species empty nests were more common close to the pollution source than farther away. Histopathological analyses in P. major suggest that there are diverse reasons for the incapability of a female to lay. One out of five P. major females captured from incubating in an empty nest had dark cysts in her oviduct. Two P. major females had very scanty medullary bone tissue in their tibiotarsus and tarsometatarsus and one female showed exceptionally high concentrations of lead in her bone tissue. We conclude that air pollutants enhance the number of empty nests especially in F. hypoleuca, but cannot wholly explain the phenomenon in P. major.     

The internal barriers of rotation for the 209 polychlorinated biphenyls

The internal barrier of rotation (Erot) was calculated for all 209 polychlorinated biphenyls (PCBs) by using a semi-empirical method, viz. the Austin Model 1 (AMI) Hamiltonian. The difference in total energy between a forced planar state and an optimised twisted structure was defined as Erot. The Erot values were in the range of 8.33 to 483 kj/mol, and were significantly influenced by the number of chlorine atoms inortho position. An additional structural characteristic of the PCBs influencing Erot ofortho substituted congeners was substitution by chlorine atoms in vicinalmeta positions, which is assumed to prevent outward bending ofortho substituents. This so-called buttressing effect contributed with 4 to 31 kj/mol per added chlorine atom. In conclusion, the internal barrier of rotation, calculated for all 209 PCBs, provides an important structure dependent physico-chemical parameter for multivariate modelling of future quantitative structure-activity and structure-property relationships (QSARs/QSPRs).