Formation of 2,3,7,8‐tetrabromodibenzodioxin and ‐furan by thermolysis of polymers containing brominated flame retardants

Several plastic products which are used in areas exposed to fire hazards contain flame retardants. A group of important flame retardants are brominated aromatic compounds, and it is believed that they thermally generate polybrominated dibenzodioxins (PBrDD) and dibenzofurans (PBrDF).

The formation of 2,3,7,8‐Tetrabromodibenzodioxin (TBrDD) and ‐Tetrabromodibenzofuran (TBrDF) from various plastics with brominated flame retardants under different thermolysis conditions is presented. At 600 °C, 2,3,7,8‐TBrDD and ‐TBrDF in concentrations of 0.01–7 and 0.01–6 ppm, respectively, are formed from plastics containing decabromodiphenylether or polybromodiphenylether as flame retardant. With increasing temperature the concentration of these isomers decreases until they are no longer detectable above 800 °C (detection limit: 0.01 ppm).

The hypothetical reaction pathways for the formation of 2,3,7,8‐TBrDD and ‐TBrDF by thermolysis of decabromodiphenylether are proposed.

The solubility and photochemical properties of 2,3,7,8‐TBrDD in different solvents are given.     

Free ‐ living animals as indicators of environmental pollution by chlorinated hydrocarbons

As some species of game and free‐living animals promptly respond to ecosystem damage by a reaction that is easy to interpret, they are important ecological indicators in assessing the total contamination of the environment. Consumers of the highest order like predators, predatory and fish‐eating birds are among the most important bioindicators of environmental contamination by chlorinated hydrocarbons and PCB.

Data on chlorinated hydrocarbons and PCB levels were collected throughout 1988–1992 and obtained from 16 species of free‐living animals from 9 protected areas of Slovakia. Muscle tissue, liver, kidney and egg samples were examined for HCB, HCH isomers, DDT and its analogues, and PCB.

Levels of organic chlorinated contaminants reveal a decreasing tendency and thus cease to be a toxicologically important risk factor in game, with the exception of predatory birds, as significant values have been recorded in their eggs and reproductive organs.     

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.     

Accumulation of Organochlorine Compounds in Oysters (Crassostrea Gasar) of an Estuarine Environment: Case of A Tropical Lagoon in the Gulf of Guinea

As part of a pollution monitoring study, oysters (Crassostrea gasar) were sampled in June 1996, in order to determine the concentrations and distribution of chlorinated hydrocarbons in two stations (near Boulay Island and Riviera Golf) of the Ebrie Lagoon, in the Abidjan area.

The chromatographic analysis of the oven dried samples revealed the presence of PCBs (2.13 to 86.22 ppb or ng/g dry weight), DDE (<0.48 to 169.55 ppb), DDD (<1.04 to 60.27 ppb), DDT (1.43 to 77.81 ppb, lindane (<0.22 to 91.64 ppb), aldrin (<0.30 to 154.1 ppb), endrin (<0.23 to 293.31 ppb) and dieldrin (<0.26 to 199.74 ppb). the results indicated high concentrations in oysters sampled near Boulay Island, due to industrial, agricultural and port activities going on in this area.

Compared to DDD/ΣDDT and DDT/ΣDDT, the DDE/ΣDDT ratios were high indicating old DDT inputs. the ΣDDT/PCBs ratios were higher than 1 illustrated the predominance of organochlorine inputs from agriculture activities. the presence of lindane in both stations illustrated the problem of fishing with toxic products.

Negative correlations found between dry tissue weight and organochlorine compounds concentrations showed that young oysters may concentrate more of these substances. More studies are needed in order to make any conclusions on their bioaccumulation trends.     

Pollution from polychlorodibenzo‐p‐dioxins and furans: The case of several foundry plants in the Lombardy region

In 1991 a co‐operation between Public Health Office (U.S.S.L.) n° 18 of Brescia and the Chemical Section Laboratories of U.S.S.L. n° 38 of Milan concerning the possible environmental impact of foundry industrial activities performing metallic scraps recovering, has been undertaken.

Soil and surfaces have been classified in conformity with the National Toxicological Consultative Commission (C.C.T.N.) recommendation dated 12/02/1988'; owing to the characteristics of the processed material, besides heavy metals, polychlorodibenzo‐p‐dioxins (PCDDs), polychlorodibenzofurans (PCDFs) and polychlorobiphenyls (PCBs) have been looked for.

The particulate matter collected from the filters positioned over the arc furnaces in 14 foundry plants has been characterized and classified, according both to C.C.T.N.¹ and to the Interministerial Board regulation dated 27/07/1985 for the first application of the Republic President Decree Law (D.P.R.) n° 915/1982, concerning wastes classification, based, in this case, on these toxic chlorinated compounds concentrations. From the very beginning, high levels of PCDDs and PCDFs have been detected, corroborating the very few literature data from foundry plants². The results obtained on 14 different foundries allow us to draw already some information, acceptable from the point of view of the statistical validity, about the pollution produced by this industry.     

Control of chlorinated aromatic compounds from a municipal solid waste incinerator using limestone addition

In this study, limestone powder was directly added to synthetic MSW, which was fed into a small‐scale fluidized bed incinerator. The concentration of CBzs and CPs in the flue gas were measured before and after a secondary combustion air injection. Finally, the PCDDs and PCDFs concentrations were also measured in the flue gas after the secondary combustion zone. The CaCO₃ added to synthetic MSW not only controls HCl in the flue gas, but suppresses the formation of chlorinated aromatic compounds like CBzs, CPs, PCDDs, and PCDFs. The main mechanisms to control the formation of chlorinated aromatic compounds was more likely related to the suppression of catalytic capability of flyash than the HCl reduction in the flue gas. However, the NO concentration was increased by catalytic reaction of limestone in the fluidized bed.     

Air monitoring of solvent exposed workers with passive samplers in comparison to “biological monitoring (BM)"†

A study was performed comparing ambient air monitoring (AM) and biological monitoring (BM) in order to evaluate the reliability of passive sampling (PS) in occupational medicine.

Five groups of persons (total number = 188) exposed to tetrachloroethene, isopropanol, toluene, xylene and styrene at the workplace were examined.

AM was performed over several hours using one or two brands of passive samplers (Monitor 3500 and/or ORSA 5). BM includes the determination of the solvent and specific metabolites resp. in blood or urine samples taken at the end of workshift. On the basis of our results we recommend that PS can supply relevant data for the estimation of external exposure to several solvents like chlorinated‐ and aromatic‐hydrocarbons.     

Pharmazeutische Wirkstoffe und Umweltschutz

On 26 April this year the German Environmental Advisory Council (SRU) published a statement on ‘Pharmaceuticals in the environment’ and pointed considerable need for action to understand and to reduce the risks from diffuse pharmaceutical inputs in the environment. On the one hand, it is urgently necessary to improve the database for environmental risk assessments; on the other hand measures should already be taken to minimize harmful inputs. Fortunately, the new regulations for an application for an authorization to market new pharmaceuticals require an environmental risk assessment. However, there is a lack of information on possible impacts from long time admitted medicines which may be responsible for harmful active substances detectable in the environment. To remove this data deficit, a European programme for risk evaluation of old pharmaceuticals should be established. It is necessary for an adequate risk assessment to look at all impacts of one active substance or all substances same-directed in their active potential summativ and to generate regularly consumption data in particular for the use of veterinary products. The hot spots of contamination are the introduction of large scale volumes of active pharmaceutical ingredients for human use like diclofenac and carbamazepin as well as hormones into surface waters, as well as the application of antibiotics-loaded economic fertilizers on soils. Not to be neglected is the application of antiparasitics in animals kept on pasture. With the assessment of the use of pharmaceuticals for all purposes special attention is needed on antibiotic resistance. For the mitigation of environmental exposures there are exposures measures necessary to reduce use of antibiotics in farming, for the application of new effective technologies in treatment sewage — as for example ozonation, filtration with activated carbon or membrane filtration — as well as for the labelling of environmentally harmful medicinal products.     

Should consumptive sustainable use of Sika Deer (Ceruus nippon) in Dilijan Reserve,NE Armenia be instituted?

SUMMARY

Numbers of sika deer (Ceruus nippon), resident in the Dilijan Reserve in 1969 (52 animals), 1970 (50), 1972 (1), and 1976 (28) dramatically increased in number until 1981, when the population reached a ceiling, being the number which can subsist in the area—300 individuals (density—11–12.5 deer per 1000 ha). Thus, Dilijan Reserve's C. nippon population develops in a way which resembles an S-like log curve equation.

Actually, Dilijan Reserve no longer has the status of a protected area—nowadays lumbering activities predominate and, inevitably, the unique broadleaf deciduous forest ecosystem will run down to extinction. Such economically valuable species as oak, beech, and sika deer are likely to be the first victims of this large-scale devastation.

The present article does not reject exploitation of any resource (including sika deer), if necessary. The key question is: how C. nippon can be sustainably utilized, so that the number of culled animals is replenished within the same year and and so that eventually the population size will remain constant?     

Untersuchungen zur Charakterisierung von Brandrauch

The aim of this work is to clarify if there is a correlation between fuel and its organic combustion products. To acquire homogenous data sets for our investigations, we analysed only the measurements of the “Forschungsstelle für Brandschutztechnik” at the University of Karlsruhe. All compounds with a similar structure were grouped and structural indices were ascribed to them. This also made it possible to obtain information about the frequency of occurrence of a set of substances in fire smoke. The kind of analytical measurements used by this institute provided no or only little information about inorganic compounds, highly volatile substances like acrolein or vinyl chloride, and very poorly volatile substances (e.g. polycyclic aromatic hydrocarbons). We found that benzene, methylbenzene, ethenylbenzene and ethylbenzene are always present in fire smoke. The formation of these typical compounds is described by a model. Aside from these compounds which are typically related to the smoke from fires, substances are always observed which are typical for a distinct fuel. Many compounds which are expected to be in the smoke are highly carcinogenic. Therefore, it is necessary for people with a high exposure to the smoke of fires, e.g. firemen, to protect themselves efficiently. In order to obtain more information about the risks to health of fire smoke, toxicological investigations will be necessary.     

Untersuchungen über freie gelöste Aminosäuren in Meerwasser

In the literature concerning the determination of free dissolved amino acids in sea water, the evaluation of the various methods employed varies considerably. During our experiments, a two-stage preparatory method—evaporation of sea water to a small volume and desalination of the solution by ion exchange — which in principle was first used by Palmork (1963a), proved satisfactory. Recovery was about 80%, and reproduction of results sufficiently good. Following this preparatory method, and using the Beckman-Amino acid analyzer “Unichrom” for final analysis, a series of aged seawater samples was submitted to amino acid determination. The water samples always contained very small amounts of amino acids. A larger number of samples was collected in April and May, 1969, near Helgoland (54°11.3′ N, 7°54.0′ E). The samples were immediately filtered through a membrane filter (pore size 0.45 μ) and stored at-20°C until processed. Of the total amino acid content, glycine and serine were present regularly in the largest amounts, followed at some distance by lysine, glutamic acid, proline, and threonine. Quantitative determinations of aspartic acid were not usually possible, as it could not be separated sufficiently from another substance, probably methioninsulfoxide. Particular attention was paid to the danger of contamination of the samples by ninhydrinpositive compounds. The ion exchange resins used proved to be a considerable source of such foreign substances.     

Analysis of insecticide “Toxaphene”; in fish products

The gaschromatographic determination of Toxaphene in the presence of other chlorinated hydrocarbons with similar retention times is often difficult. The practibility of a new method, based on photodehalogenation of the interfering substances, is shown during the analytical determination of Toxaphene residues in selected environmental samples, especially in fish and fish products. Irradiation of the extracts after clean‐up procedures with wavelengths at 254 nm lead directly to photodechlorination products of interfering substances with shorter retention times and makes it possible to determine the Toxaphene components quantitatively, which are mostly stable under the same experimental conditions.     

Erfahrungen des Umweltbundesamtes mit der EU-Biozid-Richtlinie

Biocides are active substances and products which are intended to destroy (…) any harmful organism by chemical or biological means. Typical applications are for instance wood preservatives, antifouling products or disinfectants. In the European Union the use of biocidal products is regulated since 1998 by the Biocidal Product Directive 98/8/EG (BPD). The BPD was transposed into German law in 2001 by the “Biozid-Gesetz”. The Federal Environment Agency is responsible for the environmental risk assessment of biocidal active substances and products under the “Biozid-Gesetz” in Germany. The European Commission has to evaluate the BPD seven years after endorsement and if necessary, has to submit a proposal for the revision of the directive. It is expected that the European Commission will publish soon a review of the enforcement of the BPD together with suggestions for the revision of the directive. In this article the German Federal Environment Agency summarises suggestions for the revision of the BPD based on its ten years experience with the directive: The scope of the BPD needs an exact clarification of borderlines in order to avoid confusion with other legislation. Food and feeding stuff together with natural products like lavender branches and cedar wood, which are used as attracting or repellent agents, have to be excluded from the scope of the BPD. Special data requirements for natural oils and pheromones should be developed to take the complex composition of these substances into account. The advantages of a centralised and decentralised authorisation procedure are discussed for biocidal products in special product types. Furthermore we stipulate that biocidal active substances which are nano particles are treated as separate active substances with own identities. Due to animal welfare reasons it should be obligatory to share data from vertebrate animal studies as it is already mandatory under the REACH regulation. The import of articles treated with biocidal active substances into the European market should only be allowed, if the active substance is approved for their biocidal use within the EU. Finally we suggest to implement an obligation to report the market shares or consumption rates of biocidal active substances and products. Together with procedural simplifications and adaptation in the scope of the directive, changes of the data requirements will be the key issues during the revision of the BPD. Most important, these changes should not reduce but ideally increase the level of protection for human health and the environment.     

Integral approach to industrial effluent quality control in favour of preventing the Rijeka bay pollution

Abstract

INA‐Petrochemical Industry Omi?alj, Yugoslavia is currently producing low density polyethylene, vinyl chloride monomer and ethylene dichloride.

Because of a potentially great hazard for environmental pollution, particularly by low molecular weight chlorinated hydrocarbons, the company has been putting significant effort into its anti‐pollution programme.

Modern technology, polyfunctional organization and proper control of all waste materials has enabled, thus far, no evident or noticable impact on the environment.

Wastewater treatment from the source to final discharged effluent and environmental control results are described.     

Metal Interactions in carcinogenesis†

Mixed exposures to a number of metallic compounds may give rise to a carcinogenic response in humans.

An interaction between occupational exposure to arsenic and cigarette smoking has been documented epidemiologically. A multiplicative effect was indicated concerning the occurrence of lung cancer when both of the exposures were present. Several experimental studies have been reported in the literature concerning interactions between benzo(a)pyrene and Fe₂O₃ as well as some other metallic compounds like Ni₃S₂, PbO, MgO and TiO₂ in relation to respiratory carcinogenicity. There is also limited evidence of a positive interaction between arsenic trioxide and benzo(a)pyrene. Particles containing V and Ni were obtained from the flue gases of power plants burning heavy fuel oil. Such particles were not carcinogenic themselves but enhanced the carcinogenicity of benzo(a)pyrene even more efficiently than Fe₂O₃.

Increased dietary selenium intakes can decrease the carcinogenicity of several organic carcinogens in animals and dietary zinc can effectuate both enhancement and inhibition of carcinogenicity depending on dietary concentration.     

Thermochemical conversion of municipal solid waste into energy and hydrogen: a review

The rising global population is inducing a fast increase in the amount of municipal waste and, in turn, issues of rising cost and environmental pollution. Therefore, alternative treatments such as waste-to-energy should be developed in the context of the circular economy. Here, we review the conversion of municipal solid waste into energy using thermochemical methods such as gasification, combustion, pyrolysis and torrefaction. Energy yield depends on operating conditions and feedstock composition. For instance, torrefaction of municipal waste at 200 °C generates a heating value of 33.01 MJ/kg, while the co-pyrolysis of cereals and peanut waste yields a heating value of 31.44 MJ/kg at 540 °C. Gasification at 800 °C shows higher carbon conversion for plastics, of 94.48%, than for waste wood and grass pellets, of 70–75%. Integrating two or more thermochemical treatments is actually gaining high momentum due to higher energy yield. We also review reforming catalysts to enhance dihydrogen production, such as nickel on support materials such as CaTiO₃, SrTiO₃, BaTiO₃, Al₂O₃, TiO₃, MgO, ZrO₂. Techno-economic analysis, sensitivity analysis and life cycle assessment are discussed.

     

Chlorinated dioxins and furans as trace products of combustion: Some theoretical aspects

Recent advances in combustion theories are reviewed, especially the detailed mechanisms of hydrocarbon oxidation, formation of polynuclear aromatic hydrocarbon from aliphatic fuels, and the behavior of halogens in flames. Experimental observations of polychlorinated dibenzo‐p‐dioxins and dibenzofurans (PCDD/F) formation in combustion of aliphatic fuels such as acetylene, ethylene and methane in the presence of hydrogen chloride are summarized. Then, from combustion chemistry considerations a reaction mechanism for T₄CDD/F formation in the CH₄/ HCl/O₂ system is developed. This mechanism consists of elementary reactions describing the main oxidation steps, formation of chlorinated C₁‐ to C₄‐species, formation of the first aromatic ring, and T₄CDD/F formation. The mechanism may be extended to other hydrocarbon fuels and higher PCDD/F homologues. Possible relevance of the mechanism to the “trace chemistries of fire hypothesis”; is discussed.     

Bioassay zur Bestimmung von TCDD-Toxizitätsäquivalenten (TEQ) von Umweltproben und Reststoffen

Polychlorinated aromatic hydrocarbons (HAH) like 2,3,7,8-tetrachloro-p-dioxin (TCDD) elicit a multitude of toxic and biological effects. A common trait of these substances is their affinity for a cytosolic receptor protein and the subsequent induction of the synthesis of several gene products, including cytochrome P450 1A1 (CYP 1A1). In this publication we present a bioassay to determine the induction of CYP 1A1 as a sum parameter for the total toxic potential of critical halogenated compounds in complex environmental matrices. In order to eliminate compounds like polycyclic aromatic hydrocarbons (PAH) and naturally occurring substances which might interfere with the bioassay we developed a simple cleanup procedure. TEQ values derived from bioassay are in good agreement with those obtained from chemical analysis. This bioassay in combination with the simplified “single column” clean up represents a cost and time effective alternative to chemical analysis for the screening of large numbers of environmental matrices.     

Molecular modeling in environmental science∗

Quantum mechanic computer models are often used in chemistry to predict properties of molecules and to simulate reaction pathways. Such models calculate bond lengths, bond angles, dihedral angles, the energy of the molecular‐orbitals (MO's), the dipole moment, the ionisation potential, and the heat of formation. These results lead to detailed information on electronic structures like bond orders, electronic charges and levels of frontier orbitals (HOMO, LUMO).

It is possible to calculate properties of ground state molecules as well as ionic and radicalic structures, or reaction intermediates and other compounds with very short lifetimes.

From the exact knowledge of electronic structure, frontier orbitals, and reaction intermediates it is possible to predict stability of chemicals in the environment but also of fictive chemicals, which are not yet synthesized. Some authors have shown that there are correlations between electronic structure and toxicity.

The most interesting models for environmental chemistry are semiempirical models, such as MINDO, MNDO or MOPAC. Theses programs are able to handle molecules with 30 and more heavy atoms (all elements without hydrogen), and it is possible to install them on main frame computers (CPU‐time several minutes to hours) and on personal computers, with coprocessors (CPU‐time several hours to a few days).

Normally the molecule is read in from a Z‐matrix (a matrix of polar coordinates of atoms connected in the molecule) and with symmetry data. Furthermore, programs are available which create a Z‐matrix from the molecular structure plotted on the screen with a mouse.     

Photodegradation of the herbicide goal

Photodegradation products of the herbicide Goal active ingredient were obtained with a xenon lamp and analyzed using direct inlet mass spectrometry, MS/MS and GC/MS. A number of products were identified and their generation pathways were established to be mainly Ar—O bond cleavage, dechlorination and photocyclisation. The latter process gives chlorinated and unchlorinated dibenzofurans some of which may be toxic.