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.     

Influence of the application of sewage sludge on the degradation of pesticides in the soil

A study was made of the influence of the application of sewage sludge on the degradation of pesticides in the soil. Two kinds of sludge were used, with different characteristics, one from an urban treatment plant and one from a food processing plant. Three organophosphorus insecticides, fenitrothion, diazinon and dimethoate, were studied. The relative importance was determined of the chemical and biological degradation processes, which involved experiments on soil and sterile soil samples. A comparative study was also made of the degradation of pesticide residues and the evolution of the microbial population. The application of sludge seems to have a complex effect on the degradation of pesticides, determined by the bioavailability and biodegradability of their active ingredient. The biodegradation of pesticide residues brings about alterations in the microorganism population of the soil.     

Comparison of supercritical fluid extraction and Soxhlet extraction for the determination of PCBs in seaweed samples

The efficiency of supercritical fluid extraction for the determination of 12 polychlorinated biphenyls from algae samples is compared to Soxhlet extraction. Analytical detection limits for the individual congeners ranged from 0.62 microgl(-1) to 19 microgl(-1). Recovery was tested for both methods using standard addition procedure. At maximum spike level of concentration, the mean recoveries were not significantly different (P>0.05) of all PCBs studied, with the exception of PCBs 28, 52, 77 and 169. Method precision for Soxhlet extraction (< or =3.9%) was slightly better than for SFE (< or =9.2%). Although both methods yield comparable results, SFE offers the advantage of detecting all PCBs studied at lower concentrations, reducing extraction time, and reducing the amount of solvents needed. The optimized methods were applied to the analysis of three real seaweed samples, except for PCB101 the concentrations of all PCBs were low or below the detection limits. The levels of PCB101 found in sample 1 were 6.6+/-0.54 ng g(-1) d.w., in sample 2 the levels were 8.2+/-0.86 ng g(-1) d.w. and in sample 3 they were 7.7+/-0.08 ng g(-1) d.w.     

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.     

Wirkung subakuter PCB-Exposition (Aroclor 1254) auf Sauerstoffverbrauch, Schwimmbewegung und Biotransformation (GST-Aktivität) des Karpfens (Cyprinus carpio)

Objective and Background

PCB (polychlorinated biphenyle) are typical man-made environmental pollutants that cause a broad spectrum of effects in vertebrates. Although a lot has been studied about the toxic effects of xenobiotic substances on aquatic organisms, their subacute effects are not yet well known. Fish occupies a central position in freshwater food webs and therefore, carp was chosen to be our test organism. The aim of our study was the investigation of subacute effects of Aroclor 1254 (22μg ^l?1) on respiration, swimming activity, and biotransformation, allowing discussion of changed interaction between the available energy resources.

Methods

The respiration experiments under controlled laboratory conditions were run for 29 days (5 d before, 16 d with and 8 d after chemical exposure) with exposed carp compared to the non-exposed fish. Furthermore, the BehavioQuant system quantitatively monitors the positions of each individual fish before (8 d) and during (21 d) PCB exposure and swimming activity (number of horizontal turnings s^?1) of animals was calculated. Thereafter, liver samples were taken from animals for analysis of the phase 2 enzyme activity (glutathione-S-transferase). In the respiration experiments were 6 exposure, 6 controll, and 3 solubilizer controll groups (12 animals each group); in the behavioral experiments were 9 exposure, 6 controll- und 3 solubilizer controll groups (6 animals each group), and in the enzyme activity measurements were 9 exposure, 6 controll and 3 solubilizer controll groups (6 animals each group) examined.

Results and Discussion

A clearly increased (33%) oxygen consumption due to the PCB-exposure is found to be reversible; after the exposure period the respiration of carp shows a level comparable to the oxygen consumption during non-exposure time. By evaluating quantitative behavioral parameters of animals, it becomes evident that the exposure to PCB also causes a reversible change in their swimming behavior. Chemical stress leads to a decrease of mean daily swimming activity combined with an increase of the mean number of turnings during the night. Thereafter, the swimming activity shifts to the circadian swimming behavior under control conditions. Furthermore, our measurement of soluble and microsomal glutathione-S-transferase activity of fish liver shows a significant elevation after exposure period.

Conclusion

Our results prove that it was feasible to detect sublethal effects of PCB-mixture on all parameters under these conditions successfully. Our findings imply that fish are able to cope with the chemicals and we purse the hypothesis that the higher physiological energy demand caused by increased activity of enzymes, which are involved in biotransformation of foregin substances, may be related to a higher respiration of fish stressed by xenobiotics.

Recommendation and Outlook

Further experiments should investigate the effects of PCB on ecophysiological parameters of carp fed with exposed natural food allowing discussion of ecological consequences.     

Spatial and temporal variability of phytoplankton biomass and taxonomic composition around Elephant Island,Antarctica, during the summers of 1990–1993

During the austral summers of 1990–1993, phytoplankton studies were conducted in the vicinity of Elephant Island, Antarctica, to investigate the spatial and temporal variability of phytoplankton biomass and taxonomic composition. There was much intraannual variability, with a trend for increasing biomass from January–February (Leg I) to February–March (Leg II), except in the 1993 studies. There was also a change in phytoplankton composition between the two legs. During 1990–1991 the increase was due mostly to diatoms, during 1992 mostly to an increase of flagellates; during 1993 there was a decrease in total biomass between the two legs, with diatoms decreasing, so that dinoflagellates, which increased slightly in numbers, dominated the biomass during the second leg. There was also much inter-annual variability, with the summers of 1990–1991 having greater biomass and higher proportions of microplanktonic diatoms than that of 1992–1993, which had a higher proportion of flagellates. Cluster analyses revealed the presence of four major phytoplankton assemblages, with varying geographical distributions. The northwestern portion of the grid (Drake Passage waters), was characterized by nanoplanktonic diatoms during 1990–1991 and 1993, but by nanoplanktonic flagellates during 1992. The central area (Drake-Bransfield confluence) was characterized by microplanktonic diatoms in 1990–1991, but by cryptophytes or flagellates in 1992–1993. The south and southeastern portion of the area (Bransfield Strait waters) was characterized mainly by either cryptophytes or other flagellates during all 4 yr. The spatial and temporal variability of phytoplankton could not be ascribed specifically to the geographical extent of the different water masses found in the study area, but appears to be due to changing growth conditions in the upper water column as influenced by physical mixing and meteorological conditions, as well as to effects of differential grazing.     

The reproductive behavior and energetics of male gray seals (Halichoerus grypus) breeding on a land-fast ice substrate

The reproductive behavior of male gray seals (Halichoerus grypus) breeding on land-fast ice at Amet Island, Nova Scotia, was studied. Data on energy expenditure (rate of mass loss over time) were collected. The average time budget of males at Amet Island was comparable to that of land-breeding males. The behavior of males showed seasonal changes, with a decrease in the proportion of time spent in the water and an increase in agonistic behavior during the peak mating period. The estimated amount of body mass lost over the season ranged between 25.6 and 77.1 kg, and the estimated percent of initial body mass lost ranged between 7.7 and 26.5% (n=10). The maximum number of observed copulations for an individual male was nine. Only 15 out of 42 males observed during 1992 and 1993 were seen copulating. The number of observed copulations per male was strongly correlated with success in remaining close to, or attending, females (r=0.91, P<0.001, n=42). The mean duration of attendance was 4.5 ± 5.54 days (n=42). Large size was not an important factor in determining attendance success, but reproductive effort (the estimated proportion of body mass lost over the season) and success in agonistic interactions with other males were both correlated with male success.