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.     

Bioaccumulation of PCBs in the cuttlefish Sepia officinalis from seawater, sediment and food pathways

The cuttlefish Sepia officinalis was selected as a model cephalopod to study PCB bioaccumulation via seawater, sediments and food. Newly hatched, juvenile cuttlefish were exposed for 17 days to environmentally realistic concentrations of (14)C-labeled 2,2',4,4',5,5'-hexachlorobiphenyl (PCB#153) (18 ng PCB l(-1) seawater; 30 ng PCB g(-1) dry wt sediments; Artemia salina exposed to 18 ng PCB l(-1) seawater). Accumulation of PCB#153 was followed in three body compartments: digestive gland, cuttlebone and the combined remaining tissues. Results showed that (1) uptake kinetics were source- and body compartment-dependent, (2) for each body compartment, the accumulation was far greater when S. officinalis was exposed via seawater, (3) the cuttlebone accumulated little of the contaminant regardless of the source, and (4) the PCB congener showed a similar distribution pattern among the different body compartments following exposure to contaminated seawater, sediment or food with the lowest concentrations in the cuttlebone and the highest in the remaining tissues. The use of radiotracer techniques allowed delineating PCB kinetics in small whole organisms as well as in their separate tissues. The results underscore the enhanced ability of cephalopods to concentrate organic pollutants such as PCBs, and raise the question of potential risk to their predators in contaminated areas.     

An evaluation of olive-tree bark for the biological monitoring of airborne trace-elements at ground level

There is a need to start looking into the possibility of tree bark for biomonitoring. Bark from olive trees (Olea europaea Linn.) has been collected over an area in northwestern Portugal, featuring a blend of rural lands, industrial towns and coastal environments. Samples were analysed through INAA and PIXE for their elemental contents. Results from both techniques were reconciled and then compared with an extensive database on 46 trace elements in Parmelia spp. thalli from the same sites and mostly from the very bark substrates. Distribution-free, nonparametric statistics show that, despite signal magnitude, variation patterns of bark and lichen concentrations follow one another in a most significant way. Selected elements in bark also correlate to a superior extent. As far as this investigation goes, there is no reason whatsoever for discarding bark as an alternative to lower epiphytes.     

Das neue Chemikalienprogramm von UNEP Chemicals

Zusammenfassung  UNEP International Register of Potentially Toxic Chemicals (IRPTC) wurde von der ersten VN-Umweltkonferenz 1972 geschaffen. Sein Einfu? und Zusammenwirken in den 80ziger Jahren mit anderen internationalen Programmen der WHO, FAO, OECD und EG in der Chemikalienkontrolle wird beschrieben. Nach dem Erdgipfel von Rio 1992 werden im VN-Rahmen drei neue Gremien gebildet, die das Fachprogramm des Kapitels 19 der Agenda 21 (umweltfreundliches Chemikalienmanagement) umsetzen sollen: die United nations Commission of Sustainable Development, das Intergovernmental Forum on Chemical Safety und das Interorganization Programme for the Sound Management of Chemicals. Der Erdgipfel brachte auch für IRPTC eine Neuorientierung. Seit 1996 hat UNEP Chemicals, wie sich IRPTC nunmehr nennt, drei Aufgaben in sein Arbeitsprogramm aufgenommen, die beschrieben werden: das internationale übereinkommen zum Prior Informed Consent, das internationale übereinkommen zur Kontrolle der Persistent Organic Pollutants, und schlie?lich sein traditionelles Arbeitsgebiet des Informations-austausches über Stoffe wird weitergeführt.

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Die Aussagen dieses Beitrages sind die Meinung des Autors. Sie müssen nicht mit der Auffassung des Umweitbundesamtes oder von UNEP Chemicals übereinstimmen.     

PBDF and PBDD from the combustion of bromine containing flame retarded polymers: A survey

The formation of polybrominated dibenzofurans (PBDF) and dibenzodioxins (PBDD) during the pyrolysis of different polymers containing brominated organic flame retardants was investigated. The pyrolyses were conducted at two different temperatures (600°C and 800°C) using three different oven configurations. Both the pyrolysis gases and the solid residues were analysed for PBDF and PBDD.

PBDF were found in almost all samples, but both the concentration and the degree of bromination varied greatly. The largest yields of PBDF in the percent range were measured in the pyrolysis products of polymers containing brominated diphenyl ethers. The other flame retardants generally yielded only a few ppm of PBDF. PBDD are formed only in a few samples and related to the PBDF in very low concentrations.     

Environmental chemistry of PCB-replacement compounds - V - the metabolism of chloro-isopropylbiphenyls in fish,frogs, fungi and bacteria

The metabolism of 2,5-dichloro-4'-isopropylbiphenyl and 4-chloro-4'-isopropylbiphenyl, two model compounds for alkylated chlorobiphenyls (Chloroalkylenes), has been investigated in fish, frogs, fungi and mixed cultures of bacteria. Fish (Carassius auratus) and frogs (Rana aesculenta) show a very limited metabolism of these compounds. A pure strain of fungus (Cunninghamella echinulata Thaxter) metabolized 2,5-dichloro-4'-isopropylbiphenyl both by stepwise oxidation of the isopropyl group to 2,5-dichloro-4'-biphenylcarboxylic acid and by hydroxylation of the chlorine substituted phenyl ring. A mixed culture of aerobic bacteria from activated sludge shows extensive degradation of 4-chloro-4'-isopropylbiphenyl to p-chlorobenzoic acid via stepwise oxidation of the isopropyl group when using the compound as sole carbon source. However, in the presence of D-glucose as additional carbon source, no metabolism is observed.     

Presence of nitro-chlorinated dioxins on fly ash from municipal incinerators and from laboratory production through reactions between NO2 and T4CDD on fly ash

Treatment of tetrachlorodibenzo-p-dioxin (T₄CDD) on municipal incinerator fly ash at 30 to 150°C for 10 minutes using 5% (Vol/Vol) NO₂ in air resulted in production of nitro-T₄CDD. Percent conversion was between 40% at 50°C to 100% at 150°C. Nitro-T₄CDD produced in the laboratory was unstable in hexane/methanol or hexane/acetone solutions and decomposed at ?5°C with half-lives of 8–10 days^?1 to the original T₄CDD.Fly ash from a municipal incinerator in Toronto, Ontario was extracted using toluene/methanol for 12 hrs in a Soxhlet extractor. Condensate of this extract was analyzed using capillary gas chromatography with flame ionization, nitrogen-selective, and mass spectrometric detectors. Retention times for nitro-T₄CDD, multi-ion selected ion monitoring, and nitrogen detector response were used as supporting evidence for the presence of nitro-chlorinated dioxins as naturally occurring in this sample.     

A new photodegradable molecule as a low impact ballast water biocide: efficacy screening on marine organisms from different trophic levels

Marine species carried by the ships’ ballast waters are a potentially serious environmental problem. Many strategies are being adopted to minimize the transfer of invasive or pathogenic marine species between different aquatic ecosystems. This problem is often addressed by using biocides for ballast water treatment; however, the biocide could be dangerous to native organisms once the ballast water is discharged. Chemical treatments such as chlorination and addition of glutaraldehyde could cause problems related to toxicity and application costs. The search for new effective molecules with a low environmental impact is pressing. This paper presents data from a preliminary efficacy screening of a promising molecule derived from alkylated naphtoquinones on a battery of ballast water model organisms. Results show that this new molecule is very effective in the absence of light and is extremely photodegradable (half-life <6 h). It can thus be easily degraded when released in the environment. Physical and Chemical Impacts on Marine Organisms, a Bilateral Seminar Italy-Japan held in November 2004.