Determination of PCDDs,PCDFs, PCBs and HCB emissions from the metallurgical sector in Poland

Background The aim of the project was to measure the actual emissions of PCDD/F, PCBs and HCB from 20 selected metallurgical installations in Poland, in order to update the national inventory of dioxin emission from metallurgical industry for developing a strategy for dioxins and furans emission abatement from the subject facilities (UNEP 2005). Methods Sampling methodology used in this work was developed at the Cracow University of Technology because of the complexity of simultaneous sampling and determining PCDFs, PCDDs, PCB and HCB. For the determination a GC-MS/MS system was used. Results and Discussion Results from the work indicate that the highest dioxins and PCB concentrations were recorded for iron ore sintering plants at 1.10–1.32 ng total¹ TEQ/Nm³ followed by aluminium scrap melting at 0.03–0.66 ng total TEQ/Nm³. The highest HCB concentrations at 613–1491 ng/Nm³ were also recorded for iron ore sintering plants, whereas at aluminium plants the HCB concentrations were in the range of only 10.1–22.7 ng/Nm³. Conclusions The above investigations indicate that secondary aluminium production is the most significant dioxins source, if calculated as emission factor values. However, iron ore sintering plants are operating at much higher production capacity, causing this process to become the major source of dioxins, PCB and HCB pollution to the atmosphere in Poland. Recommendations and Perspectives Based on the performed tests and the environmental reviews of selected plants several recommendations were formulated for the reduction of generation or of emission of these pollutants from iron ore sintering plants, electric arc furnace steel production processes, hot-blast furnace operations, secondary aluminium smelting and primary zinc production from zinc cathodes.     

Paper fibers as a carbon source for the de novo formation of polychlorinated dioxins and furans

The formation of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDDs/Fs) from carbon that was produced by the pyrolysis of paper fibers and from wood charcoal was investigated experimentally. Fibers obtained from filter paper were pyrolyzed at 300° and 800°C to produce low- and high-temperature carbon samples. The two types of carbon and wood charcoal were mixed with silica (SiO₂) and trace copper oxide to produce three synthetic fly ash samples. Experiments to measure the formation of PCCDs/Fs from the three ash samples were conducted using a bench-scale reactor. The two carbon samples derived from paper fibers generated more PCDDs/Fs than was generated by the wood charcoal. The PCDDs/Fs generated by the low-temperature carbon and by the wood charcoal were dominated by the lower-chlorinated PCDFs. Such unique homologue distribution patterns are very similar to those generated by the open burning of household waste. The high-temperature carbon generated more highly chlorinated PCDDs/Fs. The effect of pyrolysis temperature on the de novo formation of PCDDs/Fs from residual carbon is discussed. Paper and paper products contained in household waste are likely to be the source of unburned carbon that contributes to high PCDD/F emissions in the open burning of household waste.     

Degradation of chlorinated dioxin in denitrifying activated sludge from leachate treatment plant of a landfill

The degradation rate of dioxins added to the activated sludge from a leachate treatment plant of a landfill under denitrification conditions was estimated using six bioreactors. Over 99% of the added dioxins (600ng) were degraded within 7 days. Furthermore, continuous cultivation was carried out for 1 month. The activated sludge degraded 600ng of dioxins (that is, all of the added dioxins) placed in each reactor every 7 days, and this activity was maintained for 35 days. Under aerobic conditions with this sludge, the dioxins were not degraded in 7 days, but 90% of the 600ng of dioxins was degraded in 35 days. The high level of activity observed in the present study may only occur under anaerobic conditions, especially under denitrifying conditions.     

Evaluation of mixture effects in a crude extract of compost using the CALUX bioassay and HPLC fractionation

Potential synergistic interactions between polycyclic aromatic hydrocarbons in a household sewage sludge compost extract were investigated using the Dioxin-Responsive Chemical-Activated Luciferase gene eXpression (DR-CALUX) assay and reverse-phase high-performance liquid chromatography (RP-HPLC) fractionation. The biological activity of the crude extract was measured in vitro using the CALUX assay. The CALUX activity of the extract was as potent as 360-pg CALUX-TEQ (2,3,7,8-TCDD equivalent value) per g sample, this was 70 times above the WHO-TEQ value which was derived from chemical analyses of dioxins/furans and dioxin-like PCBs of the mixture. The CALUX activity pattern of the crude extract and the retention times of 26 polycyclic aromatic compounds (PACs), as determined by RP-HPLC on an octadecylsilica column, suggested that the dioxin-like compounds with the log K(OW) (n-octanol/water partition coefficient) values corresponding to 6.0-7.0 contributed highly to the whole activity. The CALUX activity of the crude extract was three times the sum of the CALUX activities of the RP-HPLC separated fractions. Mixture effects were assessed by co-exposure of each HPLC fraction and 2,3,7,8-TCDD to the cells. The four concentration levels of added 2,3,7,8-TCDD corresponded to the TEQ value in the original compost sample. The experimental CALUX activity was higher than the predicted CALUX activity for some fractions. It was demonstrated that some compounds in the compost sample interacted synergistically with 2,3,7,8-TCDD in terms of dioxin-like activity. This finding points out the necessity for detailed investigation of synergistic effects in environmental samples.     

Potential Long-Term Ecological Impacts Caused by Disturbance of Contaminated Sediments:A Case Study

Several submerged barges were recently removed from the Passaic River, New Jersey, USA, in two areas (areas 1 and 2) where contaminated sediments are known to exist. During removal of the single barge in area 1, elevated turbidity levels and chemical parameters were measured. Greater increases were measured in area 2, where several barges were removed. In both areas, water column concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and several metals exceeded one or more water quality criteria; turbidity levels in area 2 also exceeded regulatory criteria. Potential chemical bioaccumulation from the water column into residential aquatic receptors was estimated using standard models and assumptions. The modeled results predicted that steady-state tissue concentrations of bioaccumulative chemicals would not occur as a result of the brief increase in water column concentrations that occurred during barge removal but that metals and PCDD/Fs could bioaccumulate to levels that exceed regulatory ecological criteria during long-term sediment disturbance activities. In addition, based on some simplistic assumptions regarding settling of suspended sediments, we estimate that chemical bioaccumulation from surface sediments into the food web could result in substantial increases in PCDD/F body burdens in the benthic forage fish, mummichog. Our findings are consistent with the limited number of field studies that have measured increased body burdens of bioaccumulative chemicals following dredging. We suggest that, prior to consideration of extensive dredging as a remedial alternative for any river system, the potential significant and long-term impacts on the food web must be evaluated.     

Brominated dioxins and furans in a cement kiln co-processing municipal solid waste

A field study and theoretical calculations were performed to clarify the levels, profiles, and distributions of polybrominated dibenzo-p-dioxins and dibenzofurans(PBDD/Fs) in a cement kiln co-processing solid waste, with a focus on the PBDF formation mechanism.The raw materials contributed greatly to input of PBDD/Fs into the cement kiln. The PBDD/F concentrations in the raw materials were much higher than those in particle samples from different process stages in the cement kiln. The PBDD/F concentrations in the clinkers were1.40% of the concentrations in the raw materials, which indicated that the high destruction efficiencies for PBDD/Fs by cement kiln. PBDD/F distribution patterns in particle samples collected from different process stages indicated the cement kiln backend was a major site for PBDD/F formation. PBDFs with high levels of halogenation, such as heptabrominated furans(Hp BDF), were the dominant contributors to the total PBDD/F concentrations and accounted for 42%–73% of the total PBDD/F concentrations in the particle samples. Our results showed that co-processing of municipal solid waste in a cement kiln may influence the congener profile of PBDD/Fs, especially for the higher halogenated PBDD fraction. In addition, there were significant correlations between the decabromodiphenyl ether and heptabrominated furan concentrations, which is an indicator of transformation from polybrominated diphenyl ethers to PBDD/Fs. Theoretical calculations were performed and demonstrated that elimination of HBr and Br_2 from polybrominated diphenyl ethers were the dominant formation pathways for PBDD/Fs. These pathways differed from that for polychlorinated dibenzo-p-dioxins and dibenzofurans(PCDD/Fs).     

固体废物焚烧二恶英的生成机制及其控制技术

结合国内外近年来的研究成果,重点介绍了固体废物焚烧过程中二恶英的生成机制及其控制技术,在此基础上,针对我国国情,提出了二恶英的污染控制对策。     

抚顺市二噁英类持久性有机污染物污染现状调查分析

对抚顺市二噁英类持久性有机污染物污染状况进行深入调查,进一步明确污染源和排放情况.     

钢铁行业二噁英减排技术浅析

钢铁行业铁矿石烧结和电弧炉炼钢是我国二噁英减排优先重点控制的行业之一。本文简要介绍了二噁英的危害性和烧结、电炉炼钢工艺二噁英的产生成因,并从清洁生产技术和污染治理技术两方面探讨二噁英的减排途径。     

Emission estimation and congener-specific characterization of polybrominated diphenyl ethers from various stationary and mobile sources

Here we show that combustion sources, including waste incinerators, metallurgical processes, power-heating systems and so on, are also important emitters of polybrominated diphenyl ethers (PBDEs) to the atmosphere. Geometric mean PBDE concentrations in the stack flue gases of the combustion sources ranged from 8.07 to 469 ng/Nm³. The sinter plants (24.7 mg/h), electric arc furnaces (EAFs) (11.3 mg/h) and power plants (50.8 mg/h) possessed the largest PBDE emission rates, which were several orders higher than those of the other reported sources. The occurrences of the PBDEs in the flue gases of the power plants and vehicles, as well as their PBDE concentrations statistically highly correlated with combustion-originated PCDD/Fs, revealing that PBDEs should be the products of combustion. The ranking of major PBDE emission sources in Taiwanese PBDE inventory for combustion sources was power plants (30.85 kg/year), vehicles (14.9 kg/year) and metallurgical processes (5.88 kg/year).