Yuyang Zhao

Field pilot study on emissions, formations and distributions of PCDD/Fs from cement kiln co-processing fly ash from municipal solid waste incinerations

A pilot study was performed to evaluate formation, distribution and emission of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) from cement kilns that co-process fly ash from municipal solid waste incineration (MSWI). Stack gas and particulate samples from multiple stages in the process were collected and analyzed for PCDD/Fs. Stack emissions of PCDD/Fs were below the European Union limit for cement kilns (0.1 ng TEQ m(-3)). PCDD/F concentrations in particulates from the cyclone preheater outlet, suspension preheater boiler, humidifier tower, and back-end bag filter were much higher than in other samples, which suggests that these areas are the major sites of PCDD/F formation. Comparison of PCDD/F homolog and congener profiles from different stages suggested that tetra- and penta-chlorinated furans were mainly formed during cement kiln co-processing of MSWI fly ash. Three lower chlorinated furan congeners, including 2,3,7,8-tetrachlorodibenzofuran, 1,2,3,7,8-pentachlorodibenzo-p-dioxin and 2,3,4,7,8-pentachlorodibenzofuran, were identified as dominant contributors to the toxic equivalents (TEQ) of the PCDD/Fs. The concentration of PCDD/Fs in particulates was correlated with chloride content, which is consistent with its positive effect on PCDD/F formation. This could be mitigated by pretreating the feedstock to remove chloride and metals. Mass balance indicated that cement kilns eliminated about 94% of the PCDD/F TEQ input from the feedstock.

Variations and factors that influence the formation of polychlorinated naphthalenes in cement kilns co-processing solid waste.

Pilot studies of unintentionally produced pollutants should be performed before waste being co-processed in cement kilns. Polychlorinated naphthalene (PCN) formation and emission from cement kilns co-processing sorted municipal solid waste, sewage sludge, and waste acid, however, have not previously been studied. Here, PCNs were analyzed in stack gas samples and solid samples from different stages of three cement production runs. PCN destruction efficiencies were higher when waste was co-processed (93.1% and 88.7% in two tests) than when waste was not co-processed (39.1%), so co-processing waste would not increase PCN outputs. The PCN concentrations were higher in particle samples from the C1 preheater and stages at back end of kiln than in particle samples from other stages, suggesting that cyclone preheater and back end of kiln should be focused for controlling PCN emissions. Besides that, based on the variation of PCN concentrations and corresponding operating conditions in different stages, the temperature, feeding materials, and chlorine content were suggested as the main factors influencing PCN formation. The PCN homologue and congener profiles suggested chlorination and dechlorination were the main PCN formation and decomposition pathways, and congeners CN-23, CN-46, and CN-59 appear to be appropriate indicators of PCNs emitted from coal-burning sources.

Field study and theoretical evidence for the profiles and underlying mechanisms of PCDD/F formation in cement kilns co-incinerating municipal solid waste and sewage sludge

A field study and theoretical calculations on the profile and formation mechanism of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) from two cement kilns co-incinerating municipal solid waste and sewage sludge were performed, and the PCDFs were mainly focused. The back-end areas of the cement kilns were identified to be the major sites of PCDD/F formation according to their distributions in particulate samples from different process stages. The proportions of tetra- to hexa-chlorinated dibenzofurans (∑Cl4-6CDFs) at the kiln back-end areas were in the range of 50-80% of the total PCDD/Fs in mass concentrations and 62-87% in toxic equivalent concentrations. These results indicated that ∑Cl4-6CDFs are the dominant homologs that should be the focus for reducing PCDD/F emissions in cement kilns that co-incinerate municipal solid waste and sewage sludge. It is speculated that the low contents of oxygen and copper compounds, as well as the alkaline conditions, may contribute to the dominance of ∑Cl4-6CDFs in the PCDD/Fs formed. Chlorination was assumed to be the mechanism of formation of PCDFs. The results from model predictions and thermodynamic calculations used to test this assumption were consistent with the PCDF profiles observed from the field study.

Atmospheric occurrence and health risks of PCDD/Fs, polychlorinated biphenyls, and polychlorinated naphthalenes by air inhalation in metallurgical plants

Metallurgical plants are important sources of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs) and polychlorinated naphthalenes (PCNs). It is significant to evaluate the air levels and human risks of PCDD/Fs, PCBs and PCNs in metallurgical plants considering their adverse effects on human health and thousands of metallurgical plants being in operation in China. The estimated inhalation intakes of PCDD/Fs, PCBs, and PCNs together in eight iron ore sintering plants, three secondary copper plants, four secondary aluminum plants, and one secondary lead plant were 4.9-213.4, 21.4-4026.4, 28.7-630, and 11.7fgTEQkg-1day-1, respectively, and the corresponding cancer risks were estimated to be 8.7×10-7 to 3.8×10-5, 5.1×10-6 to 1.1×10-4, 3.8×10-6 to 7.1×10-4, and 2.1×10-6, respectively. The estimated cancer risk were higher than 100 per million people for three secondary aluminum and copper smelters among the sixteen metallurgical plants, indicating high cancer risks. Stack gas samples from metallurgical plants were also collected and analyzed for comparing their emission profiles with that of air samples. The comparison of PCDD/F, PCB and PCN profiles between air samples and stack gas samples by similarity calculation and principal component analysis suggested the influence of stack gas emissions from metallurgical plants on surrounding air. These results are helpful for understanding the exposure risk to PCDD/Fs, PCBs and PCNs in numerous metallurgical plants being operation in China.

Insights into the emission reductions of multiple unintentional persistent organic pollutants from industrial activities.

Industrial activities result in unintentional production of multiple types of persistent organic pollutants (POPs) at various concentrations. Because of the potential adverse effect of these POPs on the environment, biota and human health, methods for controlling emission of POPs are required. Development and application of techniques for controlling emissions of POPs can be a technical and economic burden for the industry involved. Therefore, from the point of view of cost-benefit analysis, reducing emissions of multiple pollutants at the same time is optimal for sustainable industrial development. Although techniques have been developed for reducing the emissions of individual POPs, such as dioxins, further work is required on multi-POP control emissions from industrial activities. This paper discusses three important aspects that need to be taken to achieve multi-POP control. These aspects include the establishment of a comprehensive system for evaluating the risk from emissions of multiple POPs, determination of indicators for total emissions of multiple POPs, and the preparation and application of functional materials to inhibit formation of multiple POPs. These discussion might be helpful for the future research on the multi-POP control in industry.

Formation Pathways of Mono- to Octa-Chlorinated Dibenzo-p-dioxins and Dibenzofurans in Main Organochemical Industries

The concentrations and formation pathways of mono- to octa-chlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) were investigated in main organochemical industries. High levels of PCDDs and PCDFs were detected. The total concentrations of 27 PCDD/F congeners in chloranil, 2,4-D, and 1,4-dichlorobenzene were 5302397 ± 8944449, 20963 ± 15908, and 242 ± 67 pg g(-1), respectively, and the less-chlorinated PCDD/F levels were 12006 ± 20155, 9536 ± 5594, and 195 ± 94 pg g(-1), respectively. The distribution trends of less and more chlorinated PCDD/Fs were similar in different chemical plants because of their similar formation pathways, which may also be related to the degree of chlorination of chemical products and purification processes. 1,2,3,4-TeCDF and 2,4,8-TrCDF were selected as model molecules to calculate the bond dissociation energy, showing that 2-MCDF, 3-MCDF, and 2,8-DCDF are more easily formatted as shown by the analytical results. The formation pathways of less to more chlorinated PCDFs are proposed to explain why 2-MoCDF, 2,8-DiCDF, 2,4,8-TrCDF, and 2,3,4,7,8-PeCDF are the dominant congeners and to explain why 2,3,4,7,8-PeCDF is the largest contributor of I-TEQs in most studies.

Secondary Copper Smelters as Sources of Chlorinated and Brominated Polycyclic Aromatic Hydrocarbons

The generation of and extent to which chlorinated and brominated polycyclic aromatic hydrocarbons (Cl/Br-PAHs) are formed and released from secondary copper smelters remain unknown. This field study, to our knowledge, is the first to identify secondary copper smelters as new sources of Cl/Br-PAHs. Mass concentrations of ∑19Cl-PAHs and ∑19Br-PAHs ranged from 5.8 to 271 ng Nm-3 and 0.59 to 52.4 ng Nm-3, respectively. A comparison of Cl/Br-PAH concentrations in stack gas and fly ash from secondary copper smelters indicated that the use of scrap copper as raw material or the addition of coal or heavy oil as reductant may contribute to the elevated formation and emission of Cl/Br-PAHs. Congener profiles of Cl/Br-PAHs in stack gas and fly ash from secondary copper smelters were different with those of Cl/Br-PAHs from waste incinerations and other previously reported sources, thus could be used as possible fingerprints and source apportionments of environmental Cl/Br-PAHs. Atmospheric levels of Cl/Br-PAHs in the workplace or smelter surroundings were determined and potential exposures were assessed. Although chlorination of PAHs was previously recognized as an important formation pathway of Cl/Br-PAHs, it was not verified to be the major formation pathway for Cl/Br-PAHs from secondary copper smelters in this study.

Molecular Mechanism of Dioxin Formation from Chlorophenol based on Electron Paramagnetic Resonance Spectroscopy

Few studies have investigated the free radical intermediates involved in the formation of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) from chlorophenol. This study clarified the reaction pathways during thermochemical formation of PCDDs from 2,3,6-trichlorophenol (TCP) over a Cu(II)O/silica matrix, which was used to simulate fly ash, at 298-523 K. The reaction was studied using electron paramagnetic resonance (EPR) spectroscopy and theoretical calculations. In situ EPR indicated the TCP radical (TCPR) formed by hydrogen abstraction of TCP. Five elementary processes including dimerization of TCPR, ortho-chloride abstraction, Smiles rearrangement, ring closure, and intra-annular elimination of Cl were proposed to occur during formation of PCDDs. The proposed mechanism was further confirmed by the detection of PCDD products from thermochemical experiments in a tube furnace. Several dominant congeners, including 1,2,6,9-tetrachlorodibenzo-p-dioxin (TeCDD), 1,2,6,7-TeCDD, 1,2,8,9-TeCDD, and 1,4,6,9-TeCDD were detected by gas chromatography/quadrupole time-of-flight mass spectrometry, and further confirmed by gas chromatography/high resolution mass spectrometry. The detected PCDD products agree with the proposed PCDD formation mechanism. Relatively high temperatures were found to lead to dechlorination of TCPR to form phenoxy radicals in addition to PCDD/Fs. These radicals will be attached to particles, which will increase their lifetimes. These reactions were further verified by molecular orbital theory calculations. The discovery of persistent phenoxy radicals is of environmental significance because of their potential toxicity. The details of this mechanism could be used for controlling PCDD/F formation during industrial thermal processes.

Evaluation of dioxins and dioxin-like compounds from a cement plant using carbide slag from chlor-alkali industry as the major raw material

Carbide slag produced from chlor-alkali industry contains high amounts of calcium compounds and can potentially be used as raw material for cement production; however, it contains large amounts of chlorine so it is essential to evaluate the emissions of chlorinated organic pollutants, including polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs), and polychlorinated naphthalenes (PCNs). A field study of the emission profiles of these pollutants in a cement plant using such slag was performed. The average concentrations of PCDD/Fs, PCBs, and PCNs in stack gases collected at the kiln back end were 6.31, 1.07, and 31.89pg TEQ m-3, respectively. PCDFs dominated over PCDDs in particulate samples. Di- to pentachlorinated biphenyls were dominant homologs in the particulate samples. MonoCBs were the dominant homolog in stack gases from the kiln back end, and homolog concentrations decreased with increasing chlorine numbers. Mono- and diCNs accounted for 48-98% of PCNs. The estimated toxic equivalents of stack gas emissions of PCNs, classified as new persistent organic pollutants under Stockholm Convention, were unexpectedly higher than those of PCDD/Fs and PCBs. A mass balance indicated that all of the toxic equivalents were reduced by this cement kiln system. The highest 2,3,7,8-PCDD/F output is with clinker.

Thermal dechlorination of PCB-209 over Ca species-doped Fe₂O₃.

Degradation reaction of decachlorobiphenyl (PCB-209) was investigated over the synthesized Ca species-doped Fe2O3 at 300 °C. The 1%Ca-Fe2O3 exhibited the highest activity among the four catalysts prepared with the pseudo-first order reaction at k(obs) = 0.103 min(-1). PCB-207, PCB-197, PCB-176, PCB-184, PCB-150, PCB-136, PCB-148, PCB-104, PCB-96, PCB-54, PCB-19, PCB-4 and PCB-1 were identified as the dominant isomers in their respective nonachlorobiphenyl (NonaCB) to monochlorobiphenyl (MonoCB) homologue groups. Analysis of the hydrodechlorination products indicated that dechlorination was much more favored on meta- and para-than on ortho-positions. The formation of significantly predominant NonaCB and octachlorobiphenyl (OctaCB) isomers was attributed to lower energy principles and to the 90° dihedral angles of two aromatic rings which prevented the hydrodechlorination at ortho-positions. When the number of chlorine atoms is not more than 7, the steric effect supports the formation of predominant PCB isomers having chlorines at four ortho-positions. During the dechlorination of tetrachlorobiphenyl (TetraCB) formed to generate monochlorobiphenyl (MonoCB) isomers, the chlorine atoms fully substituted at the ortho-positions have to be successively removed, with the first two dechlorinations preferentially occurring at the two different benzene rings. This is dissimilar to that of octachloronaphthalene (PCN-75) in which the hydrodechlorination reaction happened preferentially at ortho-position due to the existence of steric effects. The opposite roles of the steric effect in ortho-position between PCB-209 and PCN-75 might be due to the difference of the π-conjugated plane caused by the dihedral angle of 90° and 0° of the two aromatic rings.