Polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) distributions in the Bay of Marmara sea: Izmit Bay

In 1999, the concentrations of 16 polycyclic aromatic hydrocarbons (PAHs), the total PAH and polychlorinated biphenyls (PCBs) were measured in sea water, sediment and mussels collected along the coast of Izmit Bay, the most important bay of the Marmara Sea. The total-PAH concentrations, measured by Spectrofluorometry were in the range of 1.16-13.68 microg/l in sea water, in the range of 30.0 1670.0 microg/g dry weight in sediments and in the range from 5.67 to 14.81 microg/g wet weight in edible part of mussel. HPLC revealed Phenanthrene (three rings), chrysene (four rings) and benz[a]antracene (five rings) to be the dominant PAHs in sea water, while 16 different PAHs compounds were observed and measured in mussel samples. The most pollution occured at Dogu Kanali and Dil Deresi where were the main rivers containing wastes fall into the the Izmit Bay. Although the maximum mono-ortho PCB concentrations in sea water were measured in the Dil Deresi River (26.33 ng/l) and the Solventa? (22.19 ng/l) stations, maximum PCB concentrations in mussels were measured in the SEKA (28.11 microg/kg) and the Dil Deresi River (25.68 microg/kg). The dominant congeners of PCBs were from tetra to hexachlorobiphenyls. The toxicity equivalent values were very low in sea water and mussels.     

Influence of combustion conditions on the PCDD/F-, PCB-, PCBz- and PAH-concentrations in the post-combustion chamber of a waste incineration pilot plant

Experiments at a pilot scale waste incinerator (0.5 MW thermal power) showed that the conditions in the post-combustion chamber (650-900 degrees C) are strongly influencing the formation of chlorinated and non-chlorinated aromatics. Non-optimal combustion conditions resulted in increased concentrations of mono- to trichlorinated dibenzo-p-dioxins (PCDD), dibenzofurans (PCDF) and polycyclic aromatic hydrocarbons (PAH), while chlorinated benzenes (PCBz), polychlorinated biphenyls (PCB) and the higher chlorinated PCDD/F are only weakly affected or even decrease. The changes in concentration of the compounds investigated over a time span of hours gave hints on 'memory effects' in this combustion zone. For mono- and dichlorinated benzenes, a high correlation (r2 = 0.80) with the international toxicity equivalent (I-TEQ) value of PCDD/F was observed. As recently has been demonstrated, this correlation can be utilized for an indirect on-line measurement of the I-TEQ by a novel laser mass spectrometric technique (REMPI-TO-FMS).     

Bioassay zur Bestimmung von TCDD-Toxizit?ts?quivalenten (TEQ) von Umweltproben und Reststoffen

Zusammenfassung  Polychlorierte aromatische Kohlenwasserstoffe (PHAK), z.B. 2,3,7,8-Tetrachlordibenzo-p-dioxin (TCDD), weisen eine Vielzahl von toxischen Wirkungen und biologischen Effekten auf. Die Substanzklasse der PHAK besitzt die Eigenschaft der Bindung an ein cytosolisches Rezeptor-Protein, gefolgt von der Synthese bestimmter Genprodukte, u.a. von Cytochrom P450 1A1 (CYP 1A1). In dieser Arbeit wird ein Bioassay beschrieben, der erlaubt, die Induktion von CYP 1A1 als Summenparameter für die biologische Wirksamkeit der kritischen, halogenierten Verbindungen in komplexen Umweltmatrizes zu bestimmen. Zur Abtrennung von Substanzen aus den Extrakten von Umweltproben (z. B. Naturstoffe und polyzyklische aromatische Kohlenwasserstoffe), die den Bioassay st?ren k?nnen, wurde ein Ein-S?ulen-Clean-up entwickelt. Die biologisch ermittelten TEQ-Werte stimmen gut mit den Resultaten der chemischen Analytik überein. Der Bioassay in Kombination mit dem Clean-up bietet eine zeitsparende und kostengünstige M?glichkeit zur Untersuchung von Umweltproben.      

Determination of photosynthetic rates for the marine algae Fucus vesiculosus and Laminaria digitata

A continuously recording, flow-through oxygen electrode system for the measurement of oxygen exchange is described and applied to an investigation of photosynthetic rates in the marine algae Fucus vesiculosus L. and Laminaria digitata (Huds.) Lam. The photosynthetic rate (mg O₂.g dry weight^-1.h^-1) at 15°C and 21.5 mW.cm^-2 (usually just saturating) ranges in F. vesiculosus from 1.20 in basal portions of the thallus to 9.27 at the apices and in L. digitata from 1.19 mg O₂ at the thallus base to 3.97 mg O₂ at distances of several centimetres behind the upper thallus margin. This variation is reduced when the photosynthetic rate is expressed in terms of fresh weight or surface area.This research was carried out while one of us (R.J.K.) was an Alexander von Humboldt fellow at the University of Kiel, and is part of the programme Sonderforschungsbereich 95, Wechselwirkung Meer-Meeresboden, Universität Kiel.     

Untersuchungen über den einfluß von ölverschmutzungen auf meeresalgen. I. Die wirkung von rohölfilmen auf den CO2-gaswechsel außerhalb des wassers

Oil pollution in the sea is generally restricted to thin oil films floating on the water surface. Such oil films tend to coat littoral plants or animals during low tide. The effects of coating with crude oil on the CO₂-uptake of various marine algae has been investigated under conditions of emersion. In emersed algae, CO₂-uptake is more or less depressed, depending on the thickness of the oil film (0.1 to 0.0001 mm) and the type of crude oil (Iran, Libya, Venezuela). On the other hand, water loss during exposure is reduced, so that the oil-covered algae are able to photosynthesize over a longer period than algae without oil cover. After retransfer to oil-free sea water, in most cases photosynthesis rates remain depressed throughout the period of observation. There are two effects which probably interfere with gas exchange: (1) lowering of diffusion rates of photosynthetic gases and of water evaporation by the oil films; (2) toxic effects of crude-oil components.     

Degradative fate of 3-chlorocarbazole and 3,6-dichlorocarbazole in soil

Background, aim, and scope  

3-Chlorocarbazole and 3,6-dichlorocarbazole were isolated from Bavarian soils. The stereospecific formation of the isomers of these chlorinated carbazols can be explained by quantum mechanical calculations using the DFT method. It was shown that chlorination of carbazole and 3-chlorocarbazole respectively is preferred via the sigma-complexes 3-chlorocarbazole and 3,6-dichlorocarbazole as the most stable products. The dioxin-like toxicological potential of 3,6-dichlorocarbazole, determined by the Micro-EROD Test, is in the range of some picogram TCDD equivalents per milligram carbazole. The degradative fate of 3-chlorocarbazole and 3,6-dichlorocarbazole was analysed within a long-term study (57 days) in soil.     

Copper-catalyzed chlorination and condensation of acetylene and dichloroacetylene

The chlorination and condensation of acetylene at low temperatures is demonstrated using copper chlorides as chlorinated agents coated to model borosilicate surfaces. Experiments with and without both a chlorine source and borosilicate surfaces indicate the absence of gas-phase and gas-surface reactions. Chlorination and condensation occur only in the presence of the copper catalyst. C₂ through C₈ organic products were observed in the effluent; PCDD/F were only observed from extraction of the borosilicate surfaces. A global reaction model is proposed that is consistent with the observed product distributions. Similar experiments with dichloroacetylene indicate greater reactivity in the absence of the copper catalyst. Reaction is observed in the gas-phase and in the presence of borosilicate surfaces at low temperatures. The formation of hexachlorobenzene is only observed in the presence of a copper catalyst. PCDD/F were only observed from extraction of the borosilicate surfaces. A global reaction model is proposed for the formation of hexachlorobenzene from dichloroacetylene.