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The objectives of this work were to study the PCDD/F emissions during the co-combustion of waste wood/coal co-combustion in an industrial boiler and to determine the relation of the toxic emissions to the fuel properties. Co-combustion experiments were performed in a 13.8 MWthermal industrial moving grate combustor. The fuels which were examined in this study included Greek lignite, natural uncontaminated wood, power poles and medium density fibers (MDFs) which were by-products of the plant production process. Fuel blends were prepared by mixing single components in various concentrations. PCDD/F emissions were collected during experimental runs and were analyzed according to standard methods. Low PCDD/F emissions were obtained during the co-combustion tests, lower than the limit value of 0.1 ng TEQ/Nm3. The lowest values were observed during the combustion of fuel blends containing MDF, possibly due to the inhibitory action of some of the N-containing MDF ingredients, such as urea. No direct correlation was found between the PCDD/F and the copper emissions, while examination of the PCDD/F homologue patterns revealed the predominance of the lower chlorinated isomers over the higher ones.

The present study monitored fish from sites contaminated for many years, and the data reflected the results of actual, long-term environmental exposure. The sum concentrations and TEQs of PCDD/F in the muscle of common carp (Cyprinus carpio (linnaeus)) and big head (Aristichthys nobilis) from the different site of a heavily polluted lake in China are decreased with decrease of PCDD/F concentration in sediment and water. Concentration in fish can be highly variable, but the concentration is comparable in muscle between different species of fish if the concentrations are normalized by lipid content. PCDD/F accumulate in certain tissues with the highest proportions found in the liver of fish. The concentrations and TEQs in livers were also decreased with concentrations of sediments and water. The concentrations of PCDD/F in muscle are significantly correlated with those in liver. BCFs of 2,3,7,8-substituted PCDD/F calculated directly from water were consistent with that calculated indirectly from sediment. PCDD/F concentrations in sediment are much higher than that in water, therefore the measurement is much easier and the results are more accurate. Estimated BCFs for superhydrophobic chemicals derived from sediment may also serve as acceptable surrogates for "true" bioaccumulation potential.

The concentrations of polychlorinaxed dibenzo-p-dioxins and dibenzofurans (PCDD/F) in surface sediment, soil, human hair, and fish muscle from Ya-Er Lake area, China, were analyzed. The results showed that there were very high concentrations of PCDD/F existing in these samples. The results also indicated that Ya-Er Lake, which received a large amount of waste water from a nearby chloroalkali plant, was heavily polluted by PCDD/F. The present study demonstrated that those congeners, which possess at least three chlorine atoms in the lateral position with a fourth chlorine atom in the neighborhood bond of the third single chlorine atom, such as 1,2,7,8-TCDF and 2,3,6,7-TCDF, were very resistant to biodegradation due to the "neighbor effect" of every two chlorine atoms. The present study suggested that human hair may be a suitable alternative bioindicator for detecting PCDD/F exposure.

Bioaccumulation of PCDD/F in the foodweb was investigated in the Ya-Er Lake area, which was heavily polluted by PCDD/F. The high concentrations of PCDD/F in sediment can be transferred and bioaccumulated by aquatic organisms and humans through various pathways. Benthonic invertebrate animals and aquatic plants with a lot of fibers in the root can accumulate PCDD/F from sediment and water. Snail (Bellamya aeruginosa), shrimp (Macrobranchium sp.) and freshwater mussel (Acuticosta chinensis (Lea)) took up PCDD/F from the water and maintained the emission patterns, whereas fish tended to selectively accumulate 2,3,7,8-substituted isomers. The tissues of fish-eating bird and duck (Anas platyrhynchos) were very highly contaminated by PCDD/F due to ingestion of fish and other aquatic organisms from sediment. The residual concentration in breast milk depended on the original concentration of PCDD/F in the food. A resident in Ya-Er Lake area showed a daily intake of PCDD/F of about 9.14 pg TEQ/kg body weight/day. This is higher than the tolerable daily intake (TDI) for PCDD/F (1 pg TEQ/kg body weight/day), which was recommended by the World Health Organization (WHO).

The profiles of different products of incomplete combustion (PIC) in the flue gas of a 1 MW pilot combustion facility were investigated under normal steady-state and disturbed combustion conditions. The behavior of emission profiles after disturbed combustion conditions was investigated in order to obtain a better understanding of emission memory effects. Highly time-resolved, quantitative on-line measurements of several aromatic species down to low ppbv or higher pptv concentrations were performed by a mobile resonance-enhanced multiphoton ionization time-of-flight mass spectrometer. Conventional analytical methods (gas chromatography-mass spectrometry and high-performance liquid chromatography) were also applied for measurement of polycyclic aromatic hydrocarbons (PAH) and polychlorinated dibenzo-p-dioxins and -furans (PCDD/F). The sampling point was located in the high-temperature region of the plant at the outlet of the post-combustion chamber at temperatures between 650 and 880 degrees C, prior to any emission reduction devices. The investigation pointed out that after a short phase of disturbed combustion conditions, e.g., due to process changes, transient puffs, or malfunctions, the composition of combustion byproducts in the flue gas can be changed drastically for a very long time ("memory emission" effect). It is suggested that carbonaceous layers, deposited on the inner walls in the high-temperature zone of the plant, might be responsible for the observed memory emission of some PAH species. Drastic changes in the profiles of the PCDD/F homologues were also observed during memory emission conditions. The PAH memory most likely is due to pyrolytic degradation of the carbonaceous layers, while the altered PCDD/F homologue pattern may be mediated by the high catalytic activity of the freshly formed deposit layers. Finally, it should be emphasized that a rich pattern of aromatic species, including PCDD/F, was found in a temperature regime well above the typical temperature window (approximately 300 degrees C) for de novo PCDD/F formation.

Correlations between products of incomplete combustion (PIC), e.g., chloroaromatic compounds, can be used to characterise the emissions from combustion processes, like municipal or hazardous waste incineration. A possible application of such relationships may be the on-line real-time monitoring of a characteristic surrogate, e.g., with Resonance-Enhanced Multiphoton Ionization-Time-of-Flight Mass Spectrometry (REMPI-TOFMS). In this paper, we report the relationships of homologues and individual congeners of chlorinated benzenes (PCBz), dibenzo-p-dioxins (PCDD), dibenzofurans (PCDF) and phenols (PCPh) to the International Toxicity Equivalent (I-TEQ) of the PCDD/F (I-TEQ value) in the flue gas and stack gas of a 22 MW hazardous waste incinerator (HWI). As the REMPI detection sensitivity is decreasing with the increase of the degree of chlorination, this study focuses on the lower chlorinated species of the compounds mentioned above. Lower chlorinated species, e.g., chlorobenzene (MCBz), 1,4-dichlorobenzene, 2,4,6-trichlorodibenzofuran or 2,4-dichlorophenol, were identified as I-TEQ surrogates in the flue gas. In contrast to the higher chlorinated phenols, the lower chlorinated phenols (degree of chlorination <4) were not reliable as surrogates in the stack gas. The identified surrogates are evaluated in terms of their detectability by REMPI-TOFMS laser mass spectrometry. The outcome is that MCBz is the best suited surrogate for (indirect) on-line measuring of the I-TEQ value in the flue gas by REMPI-TOFMS. The correlation coefficient r of the MCBz concentration to the I-TEQ in the flue gas was 0.85.

The objectives of this work were to study the effect of urea addition to the fuel before the combustion on the suppression of PCDD/F emissions, to examine the influence of urea to PCDD/F isomer patterns by employing statistical analysis techniques and to determine the most effective method of urea addition. Urea in the form of powder and as an aqueous solution was mixed with RDF and the fuel mixtures were incinerated in a lab-scale reactor at 1000 degrees C. PCDD/F emitted during combustion experiments were collected in a quartz wool filter downstream the reactor unit. Analysis and quantification of PCDD/F showed that urea significantly affected PCDD/F emissions. Combustion of RDF containing 10% w/w urea resulted in PCDD/F emissions lower than 8 I-TEQ ng/g RDF, while the corresponding average value from single RDF combustion was 17 I-TEQ ng/g RDF. The PCDD/F prevention capacity of urea was independent from the method of urea addition to the fuel, as similar results were obtained after the addition of urea in the solid and in the aqueous phases. Results assessment by statistical methods showed that isomer patterns remained almost stable and were not affected by the method of urea addition.

Samples from industrial and domestic emissions and materials were investigated by using in vitro assays for dioxin-like-response (DLR) and chemical analysis. The results show a small part of persistent bioaccumulative toxicants (PBT) to be responsive in vitro. Clean-up procedures directed to persistence decrease the amount of inducing toxicants substantially. The comparison of biological in vitro (B) and chemical (A) analysis show ratios between B and A below 10 for DLR of persistent inductors. The consideration of PAH improved the knowledge about unknown less persistent agonists.

By the use of the partial least squares method and 11 fundamental quantum chemical descriptors computed from the PM3 Hamiltonian, a Quantitative Structure-Property Relationship model was obtained for direct photolysis half-lives of selected polycyclic aromatic hydrocarbons (PAHs) under irradiation of sunlight. Direct photolysis half-lives for some other PAHs without reported values were predicted. It was concluded from the model that the main factors affecting photolysis half-lives of PAHs under irradiation of sunlight are PAH absolute hardness and electronegativity, which are related to the energy difference between the lowest unoccupied molecular orbital and the highest occupied molecular orbital, (Elumo - Ehomo) and (Elumo + Ehomo), respectively. Increasing Ehomo and the average molecular polarizability (alpha) values of the PAHs leads to decrease of photolysis half-lives. Increasing (Elumo - Ehomo) and Elumo values of the PAHs leads to an increase of the PAH photolysis half-lives.

Risk assessment of dioxins is currently based on induction of liver tumors in rats. The toxicity of dioxins is characterized by large sensitivity differences among animal species and even strains of the same species, which complicates the risk assessment. The significance of these differences in dioxin-induced carcinogenicity is not known. We therefore studied the liver tumor-promoting activity of 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) in the sensitive Long-Evans (L-E) and the resistant Han/Wistar (H/W) rats differing >1000-fold in their sensitivity to the acute lethaity of TCDD. Female rats were partially hepatectomized, initiated with nitrosodiethylamine, and treated with TCDD for 20 weeks. Altered hepatic foci (AHF) were stereologically quantitated using glutathione S-transferase P as a marker. AHF were significantly (P < 0.001) and dose dependently increased in L-E rats at 10 and 100 ng/kg/day, but in H/W rats only at 1000 ng/kg/day and above, indicating a remarkable (approximately 100-fold) sensitivity difference between L-E and H/W rats. The same sensitivity difference but 10-fold less foci were observed between nonhepatectomized/noninitiated L-E and H/W rats. Induction of AHF was related to hepatotoxicity but not to cytochrome P4501A1 activity in the liver. Liver TCDD concentrations were similar in both strains. H/W rats are exceptionally resistant to induction of AHF by TCDD, and the resistance is associated with an altered transactivation domain of the aryl hydrocarbon receptor. Genetic differences may account for significant interindividual/intraspecies sensitivity differences in dioxin-induced carcinogenesis. Understanding the role of transactivation domain of the aryl hydrocarbon receptor in carcinogenesis is therefore likely to improve dioxin risk assessment.

A new method has been developed to describe the quantitative relationship between molecular structures of PCDFs and their gas chromatographic retention indices on a 30-m fused silica column coated with DB-5 stationary phase. The regression equation is derived with a multiple correlation coefficient greater than 0.9995. The highest residual is 20 index units. The standard deviation is less than 7 index units. Using this regression equation, the retention indices of PCDFs for which data is not available have also been predicted.

The second generation of the European Reference Soil-Set, the so-called EUROSOILS, has been introduced recently. The presence of organic micro-pollutants in this new type of reference materials has already been studied for polycyclic aromatic hydrocarbons, triazines, phenylureas and other pesticides. The already large amount of data concerning the level of different contaminants, the elemental composition and matrix properties is completed by a survey by means of GC/MS on the polychlorinated dibenzodioxins/furans (PCDD/Fs) and other chlorinated hydrocarbons. Higher concentrations for 4,4'-DDT in EUROSOIL 2 (10.57 +/- 0.02 ng/g), for dieldrin in EUROSOIL 3 (8.85 +/- 0.87 ng/g) and for heptachlor-epoxide in EUROSOIL 4 (5.86 +/- 0.16 ng/g) could be detected. Sum concentrations for PCDD/Fs were 15.02 ng/kg (EUROSOIL 1), 214.29 ng/kg (EUROSOIL 2), 873.32 ng/kg (EUROSOIL 3), 54.47 ng/kg (EUROSOIL 4) and 119.61 ng/kg (EUROSOIL 5).

A new approach to study the quantitative relationships between chromatographic retentions and molecular structures of polychlorinated dibenzo-p-dioxins (PCDDs) is described. The retention equations of PCDDs log k' = A + B/T in gas chromatography (GC) are used to evaluate the properties of the regression coefficients A and B, which have been widely accepted as highly reliable chromatographic retentions. The quantitative relationships between the A, B values and the molecular structures are found. The molecular descriptors given for the first time in this article are very effective. As a result, the regression equations are derived with correlation coefficients greater than 0.9995. The A, B values of PCDDs with no standards available have been predicted according to these relationships. They are very useful in chromatographic identification. The retention times of all PCDDs can be conveniently predicted at any temperature program. Compared with the data obtained from the relevant experiments, the results of prediction are very accurate.

The contamination levels of polychlorinated organic compounds (PCOCs) in waters, suspended solids and sediments of the Yangtse River (Nanjing part) were analyzed in this paper. Their concentrations determined by GC/MS were very low in comparison with those in European River. The average concentration of total HCH (alpha-HCH, beta-HCH, gamma-HCH) was much higher than that of other PCOCs in all waters, which made up 65% of total amount of PCOCs. Due to the complete dilution and mixture of pollutants in the mighty Yangtse River, the content of PCOCs at each sampling station demonstrated very similar spatial pattern for waters and suspended solids. Since the small suspended solid (<0.7 microm) passed through the filter was also considered as dissolved part, the dominant parts of HCHs, PCA and PCBs were found in dissolved phase with percentage proportion of 85-94%, 72-85% and 61-78%, respectively. For DDTs, HCB and PeCB, their contents in dissolved phase were slightly higher than in particulate phase. The contents of PCOCs in sediments were also very low and varied with high fluctuation at different sampling points, indicating the heterogeneous deposition. HCB and its metabolite (PeCB) presented the highest contamination levels among PCOCs in sediments.

The retention equations In k' = A + B/T of 49 polychlorinated dibenzo-p-dioxins (PCDDs) and 4 polybrominated dibenzo-p-dioxins (PBDDs) in gas chromatography (GC) have been investigated to evaluate the properties of regression coefficients A and B. The quantitative relationships between A and B values of PCDDs and those of PBDDs are found. The regression equations derived have correlation coefficients greater than 0.997. The A, B values of any PBDD can be predicted by using the A, B values of the PCDD according to these relationships. Using these predicted A and B values, the retention times of all PBDDs can be predicted at any temperature program. It is very useful to identify the peak position of any PBDD because at present there are only a few standards of PBDDs available.

The present study monitored 10-year-old fish and piscivorous birds from sites contaminated for many years. The data reflected the results of actual, long-term environmental exposures. The results demonstrate that different tissues of fish have quite different concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F). The concentration order of PCDD/F within fish is liver congruent with egg congruent with intestine>kidney congruent with heart>gill congruent with bladder>muscle>brain. The concentration order of PCDD/F within piscivorous birds was liver>egg congruent with heart>muscle congruent with stomach>brain. The results obtained also demonstrate that the accumulation patterns of piscivorous birds and fish are quite different. The tissues of fish and piscivorous birds have different capacities for bioaccumulation and biotransformation of PCDD/F; variable proportions of TEQs were also found throughout their bodies. In fish, toxic equivalency quotient (TEQ): PCDD/F ratios in various tissues ranged from 0.01 to 0.07, whereas in birds the ratios ranged from 0.07 to 0.43. If the concentrations are normalized with lipid content, the results vary less. The effect of different lipid properties is obvious in the case of brain tissue, which is richer in phospholipids., (Copyright 2000 Academic Press.)

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.

A sediment reference material (S-37) was prepared as analytical quality control material to be used within an international project on polychlorinated hydrocarbon analysis in two Chinese rivers. The raw material was sampled during a cruise on Yangtse River and transported afterwards to the JRC Ispra for further processing. The material was treated according to the general principles applicable for candidate reference material production. After a thorough homogeneity study of the bulk the material was bottled. A total of 1,080 bottles each containing 50 g of dry sediment powder was obtained. Final homogeneity and stability testing proved the material to be fit for the purpose. Isotope dilution GC/MS was used to establish target values for pentachlorobenzene (1.17 +/- 0.08 ng/g), hexachlorobenzene (3.60 +/- 0.17 ng/g), octachlorostyrene (0.19 +/- 0.01 ng/g), pentachloroanisole (0.52 +/- 0.02 ng/g), alpha-HCH (0.70 +/- 0.05 ng/g), beta-HCH (1.38 +/- 0.18 ng/g), gamma-HCH (0.83 +/- 038 ng/g), 2,4'-DDT (0.36 +/- 0.04 ng/g), 2,4'-DDE (0.29 +/- 0.02 ng/g), 2,4'-DDD (0.49 +/- 0.02), 4,4'-DDT (3.42 +/- 0.47 ng/g), 4,4'-DDD (1.29 +/- 0.17 ng/g), PCB 28 (0.11 +/- 0.01 ng/g), PCB 52 (0.09 +/- 0.003 ng/g), PCB 101 (0.07 +/- 0.003 ng/g), PCB 138 (0.06 +/- 0.003 ng/g) and PCB 153 (0.06 +/- 0.003 ng/g). Furthermore, indicative values for major and minor constituents as well as for polychlorinated dibenzodioxines and -furanes were measured.

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).

A method has been developed for peak recognition of 136 polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) at different temperature programs. Their retention behaviours are predicted on the basis of an identification database of retention values (A, B) of gas chromatography. By the retention times of 13C labelled 2,3,7,8-substituted PCDD/F internal standards, the retentions of all PCDDs and PCDFs can be calculated. After comparison with the retentions of practical environmental samples, the predicted values have been proved to be very accurate.

A bioassay based on genetically modified yeast strains was applied to screen environmental samples for their oestrogen-like activity. The yeast system was selected from the vast number of "oestrogen bioassays" available because it permits rapid and easy handling at low costs. The test protocol developed allowed the examination of dimethyl sulfoxide-dissolved samples within one day, with an EC50 between 1.5 nM and 3.5 nM 17 beta-oestradiol and a detection limit between 0.3 nM and 0.5 nM 17 beta-oestradiol for yeast strain I. Advantages and disadvantages as well as future prospects of this kind of oestrogen bioassay will be considered by discussing selected results.

A multicolumn method for the estimation of the octanol-air partition coefficient (K(OA)) of semivolatile compounds is described. The method is based on the retention time of a compound on gas chromatographic columns of different selectivity and polarity. Log K(OA) values of polychlorinated biphenyls (PCB) were estimated with the novel multicolumn method. The results were in excellent agreement with previously published data using a generator column method. Therefore, we used our multicolumn method to estimate K(OA) for more than 100 PCB congeners.

Polychlorinated bornanes, the main components of Toxaphene, are bioconcentrated in aquatic organisms to a high extent. However, up to this time no bioconcentration tests with individual chlorinated bornanes in aquatic organisms have been performed. Therefore, the bioconcentration factors (BCFs) of seven selected persistent chlorinated bornane congeners which are regularly found in aquatic organisms, were predicted from their n-octanol/water partition coefficients (log Kow). Furthermore, these BCF values were compared with the measured bioaccumulation factors (BAFs) in zooplankton and different fish species from the aquatic environment.

The photolysis of selected pesticides in aqueous solutions has been investigated. The photolysis produced different intermediate substances, which were also found to be soil and microbial degradation products. The phototransformation in the presence of TiO2 and humic substances leads to a disappearance of these compounds. The reaction rate is dependent on the semiconductor oxide and concentration. Photoproducts were isolated and characterized by different spectroscopic methods. Results from this study indicate that degradation products of isoproturon are more toxic on Daphnia magna than on the parent compound.

A new Enzyme ImmunoAssay (EIA) for PCDD/F TEQ measurement in extracts of environmental samples was described. The bioassay TEQ which derived from EIA and EROD were compared with each other and with results from chemical analysis. For all environmental samples, the EROD-TEQ is higher than the value from chemical analysis. However, the EIA-TEQ is much more identical with the value from chemical analysis. Our results indicate that the EIA assay is a complementary method to the EROD assay and should be useful as a rapid and sensitive screening tool for environmental samples in many situations.

A (xeno)oestrogen bioassay was introduced, using a genetically modified yeast strain which produces a fusion protein encompassing the human oestrogen receptor hormone binding domain and the yeast GAL4-DNA binding domain. Upon binding of appropriate substances this fusion protein recognises the respective DNA sequence thereby enhancing the transcription of a beta-galactosidase reporter gene. The bioassay procedure was evaluated by screening 30 compounds, including some known or suspected (xeno)oestrogens and determining EC50-values for 17 beta-oestradiol, 1.5 nM, 4-tert.-octylphenol, 6.7 microM and bisphenol A, 104 microM. Toluene extracts from different environmental matrices were tested for their oestrogenic activity. The positive test results obtained with a sewage sludge extract indicated the applicability of this bioassay for environmental monitoring.

Octa- and heptachlorodibenzo-p-dioxins (OCDD and HpCDD) were formed during semi anaerobic digestion of sewage sludge at low temperature (20 degrees C). A twofold increase of OCDD and HpCDD was found after a digestion period of 192 days even if concentrations were corrected by corresponding accumulation factors caused by the degradation of biomass. Other polychlorinated dibenzo-p-dioxins and furans (PCDD/F) and polychlorinated biphenyls (PCB) were not increased. Under strictly anaerobic and aerobic conditions, however, no OCDD and HpCDD were formed. Semi anaerobic formation of OCDD and HpCDD may explain the prevalence of higher chlorinated PCDD in the homologues pattern typical for sewage sludge.

Several chemicals covering a wide range of octanol-water partition coefficients were assayed for their bioconcentration in Daphnia magna in the presence of an aquatic humic acid. Assuming the properties of the humic acid used were similar to those known for organic matter from soils, the influence of the aquatic humic acid on physicochemical moderation of bioconcentration could not be demonstrated experimentally in a log Kow range of the chemicals between 2 and 6. Thus, the lipophilic character of the aquatic humic acid and the related effect of solubilization of the chemicals in the aqueous phase are much less than expected. This result is confirmed by determining the octanol-water partition coefficient of the aquatic humic acid. Comparing this value with log Kow values of humic acids of terrestrial origin, it can be clearly demonstrated that the lipophilicity of the aquatic humic acid is lower by a factor of 50., (Copyright 1998 Academic Press.)

The study was aimed at establishing a bioassay for the determination of 2,3,7,8-tetrachlorodibenzo-p-dioxin toxicity equivalents (TEQs) in environmental samples. Specifically, development of a rapid cleanup procedure adapted to the needs of the bioassay and simplification of the measurement of its endpoint, the induction of 7-ethoxyresorufin O-deethylase (EROD) in rat H4IIEC3/T hepatoma cells, were desired. The results indicate that a single "sandwich" column suffices to remove substances that may interfere with the bioassay from extracts of various environmental matrices such as sewage sludge, compost, soil, sediment, fly ash, tissue filter dust, and fire residue. The cumbersome conventional in vitro assay for EROD activity on cells exposed to the test material in culture plates could readily be replaced by a simple assay on intact cells grown and treated in 96-well microtiter plates. TEQ values obtained from the bioassays were consistently higher than those derived from chemical analysis of dibenzo-p-dioxins/furans and biphenyls by a factor of 1.5-3.0 depending on the matrix used. The results indicate that this bioassay, which combines a simple cleanup and a rapid procedure for measuring biological effects, offers a cost- and time-effective alternative to chemical analysis when screening large numbers of samples from complex environmental matrices., (Copyright 1998 Academic Press.)

Several biochemical responses were measured in silver crucian carp (Carassius auratus gibelio) after exposure to sediments obtained from contaminated Ya-Er Lake, No. 1 pond, and an unpolluted reference site, Honglian Lake. After 1 week of exposure, a significant induction of the phase I biotransformation enzyme (ethoxylresorufin-o-deethylase, EROD) was found (83-fold of control), whereas the phase II biotransformation enzyme (glutathione S-transferase, GST) exhibited a slight, but significant induction (1.4-fold of control) after 4 weeks of exposure. The level of cellular glutathione in the liver was also slightly elevated after 4 weeks of exposure. The delayed response of GST to the contaminants indicates that the phase I and phase II biotransformation enzymes are regulated differently in fish. The results suggest that EROD is a sensitive bioindicator to assess the toxicity of dioxin-contamined sediment in the laboratory.

Groups of 20 male and 20 female rats were administered five different doses of a mixture of 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD), 1,2,3,7,8-pentaCDD (PCDD), 1,2,3,4,7,8-hexaCDD (HxCDD), and 1,2,3,4,6,7,8-heptaCDD (HpCDD). Doses were selected based on relative potency factors derived from acute toxicity data and a previous subchronic study with HpCDD. The mixture was constituted such that each of the congeners contributed one fourth to total toxic equivalency. Total doses were divided into four daily loading doses and six biweekly maintenance doses. The highest total dose for males was 17.5 microg/kg of TCDD, 87.5 microg/kg of PCDD, 350 microg/kg of HxCDD, and 2500 microg/kg of HpCDD. Positive controls were administered PCDD (350 microg/kg) or HxCDD (1400 microg/kg). Females were given 1.5 times lower doses than males. The dosing period was 13 weeks, after which half of the rats were necropsied and the rest provided with an off-dose period of another 13 weeks. Liver concentrations as determined by GC-MS reflected the doses administered. Body weight gain was dose-dependently reduced throughout the study. Mortality rates at the end of the off-dose period were 80 and 60% for the two highest dosages (mixture) in males and 70 and 10% for females. Clinical signs and necropsy findings suggested that the cause of death was related to wasting, hemorrhage, and anemia. Prothrombin times were prolonged and platelet counts were decreased in some rats receiving high doses. This study provides in vivo support for the validity of the assumption of additive toxicity of CDDs as currently used in the toxicity equivalency factor approach to assess the toxicity of mixtures of CDDs., (Copyright 1998 Academic Press.)

Groups of 20 male and 20 female adult Sprague-Dawley rats were given five different doses of 1,2,3,4,6,7,8-heptachlorodibenzo-p-dioxin (HpCDD). Total doses for males and females (30.9/18.5, 370/222, 2222/1333, 6667/4000, and 10000/6000 microg/kg) were divided into four daily loading doses and six biweekly maintenance doses. Positive controls were administered 2,3,7, 8-tetrachlorodibenzo-p-dioxin (TCDD, total dose 70/41.9 microg/kg). Liver concentrations, as determined by GC/MS, reflected quite accurately the calculated dose ratios. The dosing period was 13 weeks, after which half of the rats were necropsied and the rest provided with an off-dose period of another 13 weeks. Body weight gain was dose-dependently reduced throughout the study. Mortality occurred dose-dependently, starting on Day 22 and continuing until the end of the off-dose period. Mortality rates at the end of the off-dose period were 90 and 40% for males and 60 and 10% for females in the two highest dose groups. Clinical signs and necropsy findings suggested that the cause of death was related to wasting (early deaths), gastrointestinal and nasal hemorrhage (between Days 64 and 126), or anemia (late deaths, after Day 111). Prothrombin times were prolonged intermittently, mainly at the highest dose of HpCDD. Platelet counts were dose-dependently decreased at the two highest doses of HpCDD and in the TCDD-treated group. This study demonstrates that the relative potency derived from acute toxicity studies is the same as that observed in this subchronic/chronic toxicity study of HpCDD and TCDD, confirming the validity of 0.007 as the toxic equivalency factor (TEF) for HpCDD, which is in good agreement with the international TEF of 0.01., (Copyright 1997 Academic Press.)

The levels of chlorinated hydrocarbon (CHC) contaminants in muscle and liver tissues of bream (Abramis brama) along the river Elbe were monitored during 1991, 1993 and 1994. Especially fish from the eastern sampling sites (Prossen, Dresden) has been heavily contaminated by HCB, OCS, DDT-metabolites and PCBs. In 1991, the concentrations of OCS, DDE and PCBs decreased significantly by 65, 65 and 51%, respectively, between Dresden and Vockerode and did not change very much from Vockerode downstream to Cumlosen. Elevated HCH levels were found in Aken, Barby and Heinrichsberg. An increasing temporal pattern during this period was found for HCB, OCS and DDE in Prossen.

Since 1985 the common mussel Mytulis edulis has been collected, characterized and stored within the framework of the German Environmental Specimen Bank program. Selected results about the determination of various pollutants such as heavy metals, polycyclic aromatic hydrocarbons and chlorinated hydrocarbons are presented. Particular emphasis is given to the comparison of seasonal variations with respect to different environmental contaminants and their correlations depending on sampling location and time.

The marked species differences in short-term toxicity (30-day LD50) of ca. 10,000 (LD50: guinea pigs ca. 1 microgram/kg body wt and Han/Wistar Kuopio rats more than 9600 micrograms/kg body wt) of 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) is one of the central issues of the controversies that have developed on the validity of risk assessment strategies for TCDD and related compounds. One of the most challenging issues that toxicologists face today is the identification of genes that contribute to or are responsible for increased resistance or sensitivity to TCDD and related compounds. It is assumed that most, if not all, toxic effects of TCDD are mediated more or less through the binding affinity to the Ah receptor. This hypothesis was extended and tries to explain the differences in sensitivity/resistance of animals including humans to TCDD by their total fat (lipid) content. In this respect the gene or genes which is or are responsible for obesity of mammals including humans are of great interest. An obvious linear positive logarithmic relationship between the oral 30-day LD50 (microgram/kg) of TCDD in different species and strains of mammals and their total body fat content (TBF%) was found: log LD50 = 5.30 x log (TBF)-3.22, or LD50 = 0.000603 x (TBF)5.30. By means of this regression the toxicity of TCDD in mammals including humans of different age and/or body weight can be predicted if their total body fat content is known. Examples of single-gene and polygenic disease models in different mammals, such as nonobese diabetic, diabetic, viable yellow, obese, and fat mice, as well as transgenic mice, and other suitable animal models, such as fatty Zucker rats, Han/Wistar (Kuopio) rats, and minipigs, are discussed, and predicted LD50 values of TCDD in these animals and humans are presented.

Despite their environmental importance, there are still relatively few historical studies of the environmental occurrence of polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), especially in middle Europe. Trends in PCBs and PCDD/Fs were, therefore, assessed in lake sediments of the Grosser Arbersee over the past 130 years (1860-1990). Ballschmiter-PCB concentrations (congeners # 28, 52, 101, 138, 153, 180) increased between 1946 and 1972 from 4.2 to 32.0 microg kg(-1) dry wt, but have since decreased to 25.6 microg kg(-1) dry wt. High chlorinated PCB congeners reached their maxima earlier (1968-1972) than low chlorinated congeners (1985-1991). These trends were consistent with patterns expected from the production and use of PCBs and their precursors. PCDD/F concentrations increased between 1950 from 0.6 microg kg(-1) dry wt to 2.3 microg kg(-1) dry wt in 1977, falling to 1.7 microg kg(-1) dry wt by 1993. PCDF concentrations exceeded those of PCDD until 1968, but afterwards PCDDs (especially OCDD) were predominant. These patterns suggest that domestic heating and waste combustion were the most likely sources, but pollution from local industries, such as metal smelting and glass production, might also have been involved. The data provide a valuable case study from central Europe which confirms the overall declining trends of PCB and PCDD/F contamination shown elsewhere.

The isotope dilution method is characterized by the use of appropiately labelled standard compounds in conjunction with mass spectrometry coupled to chromatographic systems. Although the isotope dilution method seems to be a simple procedure, some quality criteria for sample preparation, measurement and quantification have to be considered. Furthermore, archiving and documentation of analysis data as well as the use of reference materials to validate the analysis method are important with regard to European standard regulations for quality assurance. In view of this background and the increasing application tendency to environmental problems, essential quality critera for the isotope dilution method are presented and discussed, with special respect to sample extraction, separation performance and sensitivity. Also the quantification procedures are summarized.

A software has been developed for the peak recognition of 136 polychlorinated dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF) after high resolution gas chromatography coupled with mass spectrometry (HRGC/HRMS). Based on the retention times of (13)C labelled 2,3,7,8-substituted PCDD/F internal standards, the retention times of all PCDD and PCDF can be calibrated automatically and accurately. Therefore, it is very convenient to identify the peaks by comparing the retention of samples and the calibrated retention times of their chromatograms. Hence, this approach is very significant because it is impossible to obtain always a standard chromatogram and PCDD/F analysis are very expensive and time consuming. The calibration results can be transferred to Excel for calculation. The approach is a first step to store costly and environmentally relevant data for future application.