Ozonation of an azo dye C.I. Remazol Black 5 and toxicological assessment of its oxidation products

The effect of ozonation (20.5 mgl(-1)) on the degradation processes of an azo dye, Remazol Black 5 (RB5; CI) was studied. Conventional parameters such as chemical oxygen demand (COD), total organic carbon (TOC), pH, conductivity, colour removal, biodegradability (BOD(5/28)), and toxic potential of the dye and its degradation products were monitored during the process. The results obtained indicated that ozonation is a highly effective way to remove the colour of a corresponding dye solution. However, a considerable organic load still remained as indicated by high COD and TOC residues. The COD, TOC reductions were about 40% and 25% for 6 h ozonation of 2 gl(-1) RB5 aqueous solution. During the ozonation process the rapid decrease of pH and the sharp increase of conductivity indicated the formation of acidic by-products and small fragments and ions which were identified by high performance ion chromatography. The BOD28 data revealed that first by-products after partial ozonation (10-150 min) of RB5 were more biodegradable than the parent compound and ozonation can enhance the biodegradability of azo dyes. During the first 150 min of total 360 min of oxidation, the formation of first by-products with high toxic potential took place as it could be confirmed by two acute toxicity-screening tests, the bioluminescence test (Vibrio fischerii) and the neutral red cytotoxicity assay (rat hepatoma cells). The significant enhancement of microbial biodegradability after long-term ozonation could also be seen as a decrease of toxic intermediates in correlation with the ozonation time as indicated in BOD28 biological degradation test results.     

Photodegradation of PCDD/Fs adsorbed on spruce (Picea abies (L.) Karst.) needles under sunlight irradiation

Spruce (Picea abies (L.) Karst.) needles were exposed to exhaust gas containing polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) generated by combustion of polyvinyl chloride, wood, high-density polyethylene, and styrene. Photodegradation of PCDD/Fs adsorbed on spruce needles under sunlight irradiation was studied. The photodegradation of PCDD/Fs follows pseudo-first-order reaction kinetics, with photolysis half-lives ranging between 40 and 100 h. The photolysis rates of PCDF congeners are higher than PCDD congeners with the same chlorinated substitutions. Higher chlorinated PCDD/Fs tend to photolyze slowly. The wax components in spruce needles may act as proton donors and accelerate the photolysis rate. C-Cl cleavage through the addition of protons to PCDD/F molecules may be an important route for PCDD/Fs photodegradation.     

Identification of surrogate compounds for the emission of PCdd/F (I-TEQ value) and evaluation of their on-line real-time detectability in flue gases of waste incineration plants by REMPI-TOFMS mass spectrometry

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.     

PCBs and PCDD/Fs in lake sediments of Grosser Arbersee, Bavarian Forest, South Germany

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.     

Reproduction disturbances of Brachionus calyciflorus (rotifer) for the screening of environmental endocrine disrupters

Rotifers and especially the Brachionus calyciflorus species have already shown advantages (e.g. good sensitivity, simplicity, ecological relevance, short generation time) for the chronic toxicity assessment of water pollutants. In this study, the B. calyciflorus three-day test was evaluated on ethinylestradiol, nonylphenol and testosterone for the determination of endocrine disrupting (reproductive) effects. Reproduction (intrinsic rate of population increase) and sex ratio (males/females and mictic females/amictic females) were explored and discussed as suitable endpoints. B. calyciflorus has shown a fair sensitivity to detect reproductive disrupting effects after exposure to ethinylestradiol, nonylphenol and testosterone. Population growth (intrinsic rate of population increase, r) and the ratio ovigerous females/non-ovigerous females are both suitable endpoints, whereas the occurrence of males was not frequent enough to be used as endpoint.     

The suitability of gastropods as biomarkers

The measurement and induction of mixed function oxyigenases (MFOs) of limnetic gastropods were investigated to estimate their suitability as biomarkers. A determination of MFO activities was performed through the measurement of ethoxyresorufin-O-dealkylase (EROD), pentoxy-(PROD) and benzoxyresorufin-O-dealkylase-activity (BROD). Optimal measuring conditions of these activities were investigated in preparations of the digestive gland of 4 species of limnetic gastropods. Results indicate that MFO-activity inhibiting substances are accumulating in the microsomal pellet, the fraction commonly used for the measurement of MFO-activities. Therefore, the fraction used for induction studies was the postmitochondrial supernatant (PMS). EROD, PROD, and BROD activity ofPlanorbis planorbis andPlanorbis carinatus were measured after a treatment with Aroclor 1254 for 1–17 days. Maximal induction of EROD and PROD were 6 and 10 times the value in the control group ofP. carinatus, respectively induction inP. planorbis was lower. BROD-activity could not been measured inP. planorbis. InP. carinatus, BROD-activity increased to a maximum of 2 times after traetment with Aroclor 1254. The level of induction of EROD-activity is comparable to results described in analog studies with fish.     

Toxicity tests with luminescent photobacteria and quantitative structure activity relationships for nitroparaffins

EC₅₀ values of different nitroparaffins were determined by a photobacterium phosphoreum toxicity test. Octanol/water partition coefficients were determined by a reversed phase HPLC method. From these experimental data quantitative structure activity relationships were deduced which point to a dependence of toxicity on a “form factor” that includes the number of methyl and methylene groups in a molecule. The hypothesis will be formulated that the specific effects depend on the number of methylgroups and an equation for specific effects is given.     

Toxic emissions during co-combustion of biomass-waste wood-lignite blends in an industrial boiler

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.