The metabolism of some chlorinated dibenzofurans by rats

Rats were given single oral doses of 2-chloro-, 2,8-dichloro-, 2,3,8-trichloro- and octachloro-dibenzofuran. Urine, faeces, fat and liver were analysed for starting materials and metabolites. The mono-, di- and trichlorodibenzofurans yielded mono- and dihydroxy derivatives, but metabolites containing sulphur were detected only with the mono- and dichlorodibenzofuran.Contrary to the chlorodibenzo-p-dioxins, where hydroxylated metabolites with substitution only at the 2,3-positions were isolated, chlorodibenzofuran-metabolites show a wider substitution pattern; five monohydroxy-derivatives were found, for instance, from 2,8-dichlorodibenzofuran.No metabolites were detected in urine, faeces and tissues of rats which were fed with octachlorodibenzofuran.     

Environmental chemistry of PCB-replacement compounds - VI - composition and metabolism of Wemcol ®, an isopropylbiphenyl formulation

Wemcol is a technical isopropylbiphenyl formulation that is used as a substitute for polychlorobiphenyl. According to the producer Wemcol is 4-isopropylbiphenyl, but we found our sample to consist of 60.3% 3-isopropylbiphenyl, 38.6% 4-isopropylbiphenyl and 3,5-, 3,3′-, 3,4′- and 4,4′-diisopropylbiphenyl in amounts of 0.3%, 0.4%, 0.2% and 0.1% respectively. The two major components of the mixture are metabolized in the rat by two routes : oxidation of the isopropyl group and hydroxylation of the aromatic nuclei. Rats fed the technical mixture retained 3- and 4-isopropylbiphenyl in a ratio 4.3 : 1 in their abdominal fat, whilst the ratio in the mixture is 1.6 : 1. One week after the simultaneous feeding of equal amounts of Wemcol, 4,4′-dichlorobiphenyl, 2,4′,5-trichlorobiphenyl and 2,2′,5,5′-tetrachlorobiphenyl, the isopropylbiphenyls, in contrast to the chlorobiphenyls, could no longer be detected in the abdominal fat of rats.     

Environmentally significant photochemistry of chlorinated benzenes and their derivatives in aquatic systems†

The pollution of soil and aquatic environments by chlorinated aromatic pollutants (CAPs) such as polychlorobenzenes (PCBzs), polychlorophenols (PCPs), polychloro‐diphenyl ethers (PCDPEs), phenoxyacetic acids, etc., creates growing public anxiety. Phototransformation is an important process for pollutants in aquatic systems. This article extensively reviews the environmentally significant solution phase photochemistry of PCBzs as well as other CAPs derived therefrom. The paper includes photochemical fate of these CAPs at wavelengths >285 nm on the one hand and their photolysis in solution in aquatic systems on the other. In this article, photolytic reductive dechlorination and isomerization of PCBzs are reviewed together with the photoformation of several products including polychlorobiphenyls (PCBs) from PCBzs. Recently developed phenomena of photoincorporation of PCBzs into humic model monomers is also described. This review also describes the environmental photochemistry of chlorobenzene derivatives, namely, α‐substituted p‐chlorotoluenes of the general structure p‐ClC₆H₄CH₂‐X (X = H, Cl, CN, COOH and OH), di‐through pentachlorophenols, PCDPEs (having Cl_1–5 contents) with and without o‐OH substituents, and 2,4‐di‐ and 2,4,5‐trichlorophenoxyacetic acid (2,4‐D and 2,4,5‐T, respectively) as well as their esters and some formulations.     

Dioxins: Sources of environmental load and human exposure

Polychlorinated dibenzo‐p‐dioxins (PCDD) and polychlorinated dibenzofurans (PCDF) represent a class of tricylic, almost planar, aromatic ethers with 1 to 8 chlorine atoms. Congeners with substituents in the positions 2, 3, 7, and 8 are of special concern due to their toxicity, stability, and persistence. These compounds have been identified in almost all environmental compartments and humans.

Dioxins are a potent carcinogen for animals and—at the moment—considered a probable carcinogen for humans. Actual toxicological risk assessment for humans are based on 2,3,7,8‐Cl4DD carcinogenicity studies on rodents. Tumorigenic effects were found for 2 strains of rats and 2 strains of mice. All dioxins and furans elicit common toxic and biological responses, starting with a specific binding to a protein receptor, but existing epidemiologic data do not provide definitive data on human health effects.

Toxicity equivalency factors (TEFs) have been developed by several agencies as a provisional method of risk assessment for complex mixtures of PCDD/PCDF.

Dioxins have never been produced intentionally and have never served any useful purpose. They are formed in trace amounts as by‐products in industrial processes; for instance within the chemical industry, of the pulp and paper industry, metallurgical processes, processes for reactivation of granular carbon, dry cleaning, and the manufacture of flame‐retarded plastics.

The main pathway for dioxins to enter the environment is via combustion processes. Incineration is of special importance since PCDD/PCDF are directly released to the atmosphere from either stationary sources, such as municipal, hazardous and hospital waste incinerators, the combustion of sewage sludge, and scrap metal recycling, or diffuse sources, e.g. automobile exhausts, private home heating with fossil fuels, forest fires, and cigarette smoking. Furthermore, fires with PCB and PVC have additionally contributed to the total dioxin load. The emission gases can undergo long‐range transport, so that dioxins have been found even in remote areas.

Besides the two primary sources (industrial processes and combustion processes) the release of dioxins from contaminated areas and waste dumps via the leachate and the application of sewage sludge for fertilization represents a third source of PCDD/PCDF.

After more than 10 years of dioxin research the most important sources of PCDD/PCDF have been identified and analytical methods have been developed for their quantification in trace levels and in complex matrices.

Various efforts have been undertaken to reduce the emission of dioxins: for example, optimization of combustion processes for municipal waste incineration, use of unleaded gasoline, ban of chemicals, such as polychlorinated biphenyls (PCBs) and pentachlorophenol (PCP). More detail is provided in the pulp and paper section where changes have been initiated to significantly reduce the sources of PCDD/PCDF.

However, relatively little is known about transport and transformation processes, so only rough estimates can be made. Photodegradation has been found to be the primary process for 2,3,7,8‐Cl4DD breakdown. A half‐life of 3–4 days has been estimated for photochemical degradation under oxidative conditions. Field studies on the fate of 2,3,7,8‐Cl4DD in soil gave a half‐life of 9.1 (Seveso) and 12 years (under special conditions: sand, erosion), respectively. Biodegradation seems to be negligible. Transfer factors soil‐plants for PCDD/PCDF have been determined—with a high degree of uncertainty—to be less than 0.1.

Human exposure primarily occurs via ingestion whereas inhalation is a minor pathway. Dermal absorption can be neglected although skin contact to polluted surfaces may occur. Due to the lipophilicity of PCDD/PCDF and their potential for accumulation, foods such as meat and especially dairy products contribute most to the dioxin body burden of humans.

Both national agencies and international organizations have recognized the significance of this problem and as a result have initiated regulations, recommendations and research programmes (1) to understand where and how PCDD/PCDF are formed, (2) to reduce their impact on the environment and to humans, and (3) to start remedial action on contaminated areas.     

Application of QSARS to predict potential aquatic toxicities of organochlorine pesticides∗

On the basis of physico‐chemical data, such as water solubility and vapour pressure as well as acute toxicity tests we developed an ecotoxicological model for preliminary hazard assessment. By use of the reciprocal product from log H and LC₅₀ we developed a suitable ranking system that allows us to predict potential damage to aquatic organisms through pesticides.     

Microbial metabolism of chlorobiphenyls

Photochemical reactions induced by sunlight contribute to the overall chemistry of natural water systems in many ways. The degradation of pollutants, dissolution of iron and manganese sediments, cycling of trace metal nutrients, and reactions of aquatic nitrogen and oxygen species are some of the many processes having solar photolysis pathways. This paper reviews recent research concerned with photo‐decomposition of pollutants, photolysis of nitrite and nitrate, photosensitization by humic materials and the generation of reactive intermediates. In addition, background material is presented concerning the basic principles of photochemistry and the limited wavelength range of effective solar radiation.