Formation and Inventory of Polychlorinated Dibenzo-p-dioxins and Dibenzofurans and Other Byproducts along Manufacturing Processes of Chlorobenzene and Chloroethylene.

Chlorinated organic chemicals are produced and used extensively worldwide, and their risks to the biology and environment are of increasing concern. However, chlorinated byproducts [e.g., polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs)] formed during the commercial manufacturing processes and present in organochlorine products are rarely reported. The knowledge on the occurrences and fate of unintentional persistent organic chemicals in the manufacturing of organochlorine chemical is necessary for accurate assessment of the risks of commercial chemicals and their production. Here, PCDD/Fs were tracked throughout chlorobenzene and chloroethylene production processes (from raw materials to final products) by target analysis. Other byproducts that can further transform into PCDD/Fs were also identified by performing non-target screening. As a result, the PCDD/F concentrations were mostly the highest in bottom residues, and the octachlorinated congeners were dominant. Alkali/water washing stages may cause the formation of oxygen-containing byproducts including PCDD/Fs and acyl-containing compounds, so more attention should be paid to these stages. PCDD/Fs were of 0.17 and 0.21-1.2 ng/mL in monochlorobenzene and chloroethylene products, respectively. Annual PCDD/F emissions (17 g toxic equivalent in 2018) during chlorobenzene and chloroethylene production were estimated using PCDD/F emission factors. The results can contribute to the improvement of PCDD/F inventories for the analyzed commercial chemicals.

Insight into the formation of polychlorinated dibenzo-p-dioxins and dibenzofurans in hazardous waste incineration and incinerators: Formation process and reduction strategy.

Incineration technology has been widely adopted to safely dispose of hazardous waste (HW). While the incineration process causes the formation of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). Due to its extreme toxicity, many scholars have been committed to determining the PCDD/F formation process and reducing emissions in incinerators. Previous studies ignored the impact of incineration and fluctuation of feeding materials on PCDD/F formation in hazardous waste incinerators (HWIs). In this study, differences in PCDD/F formation between HWIs and municipal solid waste incinerators (MSWIs) were pointed out. The incineration section in HWIs should be carefully considered. Laboratory experiments, conventional analysis and thermogravimetry experiments were conducted. An obvious disparity of PCDD/F formation between 12 kinds of HWs was found. Distillation residue was found with remarkably higher PCDD/F concentrations (11.57 ng/g). Except for the Cl content, aromatic rings and C-O bond organics were also found with high correlation coefficients with PCDD/F concentrations (>0.92). And PCDD/Fs were formed through a chlorination process and structure formation process. All of these are helpful to further understand the PCDD/F formation process during HW incineration, optimize the operation conditions in HWIs and reduce the emission pressure of PCDD/Fs in the future.

TCDD Toxicity Mediated by Epigenetic Mechanisms.

Dioxins are highly toxic and persistent halogenated organic pollutants belonging to two families i.e., Polychlorinated Dibenzo-p-Dioxins (PCDDs) and Polychlorinated Dibenzo Furans (PCDFs). They can cause cancer, reproductive and developmental issues, damage to the immune system, and can deeply interfere with the endocrine system. Dioxins toxicity is mediated by the Aryl-hydrocarbon Receptor (AhR) which mediates the cellular metabolic adaptation to these planar aromatic xenobiotics through the classical transcriptional regulation pathway, including AhR binding of ligand in the cytosol, translocation of the receptor to the nucleus, dimerization with the AhR nuclear translocator, and the binding of this heterodimeric transcription factor to dioxin-responsive elements which regulate the expression of genes involved in xenobiotic metabolism. 2,3,7,8-TCDD is the most toxic among dioxins showing the highest affinity toward the AhR receptor. Beside this classical and well-studied pathway, a number of papers are dealing with the role of epigenetic mechanisms in the response to environmental xenobiotics. In this review, we report on the potential role of epigenetic mechanisms in dioxins-induced cellular response by inspecting recent literature and focusing our attention on epigenetic mechanisms induced by the most toxic 2,3,7,8-TCDD.

A full-scale study on thermal degradation of polychlorinated dibenzo- p-dioxins and dibenzofurans in municipal solid waste incinerator fly ash and its secondary air pollution control in China.

Degradation of polychlorinated dibenzo- p-dioxins and dibenzofurans in municipal solid waste incinerator fly ash is beneficial to its risk control. Fly ash was treated in a full-scale thermal degradation system (capacity 1 t d-1) to remove polychlorinated dibenzo- p-dioxins and dibenzofurans. Apart from the confirmation of the polychlorinated dibenzo- p-dioxin and dibenzofuran decomposition efficiency, we focused on two major issues that are the major obstacles for commercialising this decomposition technology in China, desorption and regeneration of dioxins and control of secondary air pollution. The toxic equivalent quantity values of polychlorinated dibenzo- p-dioxins and dibenzofurans decreased to <6 ng kg-1 and the detoxification rate was ⩾97% after treatment for 1 h at 400 °C under oxygen-deficient conditions. About 8.49% of the polychlorinated dibenzo- p-dioxins and dibenzofurans in toxic equivalent quantity (TEQ) of the original fly ash were desorbed or regenerated. The extreme high polychlorinated dibenzo- p-dioxin and dibenzofuran levels and dibenzo- p-dioxin and dibenzofuran congener profiles in the dust of the flue gas showed that desorption was the main reason, rather than de novo synthesis of polychlorinated dibenzo- p-dioxins and dibenzofurans in the exhaust pipe. Degradation furnace flue gas was introduced to the municipal solid waste incinerator economiser, and then co-processed in the air pollution control system. The degradation furnace released relatively large amounts of cadmium, lead and polychlorinated dibenzo- p-dioxins and dibenzofurans compared with the municipal solid waste incinerator, but the amounts emitted to the atmosphere did not exceed the Chinese national emission limits. Thermal degradation can therefore be used as a polychlorinated dibenzo- p-dioxin and dibenzofuran abatement method for municipal solid waste incinerator source in China.

Identification, Quantification, and Toxicity of PCDDs and PCDFs in Soils from Industrial Areas in the Central and Eastern Regions of Saudi Arabia.

This study was conducted to identify and quantify polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in soil samples collected from selected industrial areas in the central and eastern regions of Saudi Arabia. All the investigated compounds of PCDDs/PCDFs were identified in the studied locations. The average concentrations of PCDDs (sum of seven congeners measured) ranged from 11.5 to 59.6 pg g(-1), with a maximum concentration of 125.7 pg g(-1) at an oil refinery station followed by 100.9 pg g(-1) at a cement factory. The average concentrations of PCDFs (sum of 10 congeners measured) accounted for 11.68-19.35 pg g(-1), with a maximum concentration of 38.67 pg g(-1) at the cement factory. It was generally observed that the soil samples collected from industrial areas have substantially high toxicity equivalence (TEQ) values of PCDDs/PCDFs compared to soils of remote areas. Principal component analysis revealed that the cement factories and oil refineries were the primary sources of PCDDs and PCDFs.

Formation behavior of PCDD/Fs during waste pyrolysis and incineration: Effect of temperature, calcium oxide addition, and redox atmosphere.

The clean and efficient utilization of municipal solid waste (MSW) has attracted increasing concerns in recent years. Pyrolysis of MSW is one of the promising options due to the production of high-value intermediates and the inhibition of pollutants at reducing atmosphere. Herein, the formation behavior of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) during MSW pyrolysis and incineration was experimentally investigated and compared. The influence of reaction temperature, CaO addition, and redox atmosphere on PCDD/Fs formation were compared and discussed. The results showed as the pyrolysis temperature increased, the mass concentration and international toxicity equivalence quantity of PCDD/Fs initially peaked at ∼750 °C before declining. Most of the generated PCDD/Fs were concentrated in the liquid and gaseous products, accounting for ∼90% of the total. Among liquid products, octachlorodibenzo-p-dioxin (O8CDD), 2,3,4,7,8-pentachlorodibenzofuran and 1,2,3,4,6,7,8-heptachlorodibenzofuran (H7CDF) were the most crucial mass concentration contributors, while in gas products, high-chlorinated PCDD/Fs, such as O8CDD, octachlorodibenzofuran (O8CDF) and 1,2,3,4,6,7,8-H7CDF were predominant. Compared to incineration, the formation of PCDD/Fs was 7-20 times greater than that from pyrolysis. This discrepancy can be attributed to the hydrogen-rich and oxygen-deficient atmosphere during pyrolysis, which effectively inhibited the Deacon reaction and the formation of C-Cl bonds, thereby reducing the active chlorine in the system. The addition of in-situ CaO additives also decreased the active chlorine content in the system, bolstering the inhibiting of PCDD/Fs formation during MSW pyrolysis.

Emission reduction of PCDD/Fs by flue gas recirculation and activated carbon in the iron ore sintering.

One of the main sources of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in the environment is the sintering of iron ore. Both flue gas recirculation (FGR) and activated carbon (AC), which have the impact of decreasing both PCDD/Fs and conventional pollutants (NOx, SO2, etc.), are significant technologies for the abatement of PCDD/Fs from the sintering exhaust gas. This work involved the first measurement of PCDD/Fs emissions during FGR and a thorough analysis of the impact of PCDD/Fs reduction following the coupling of FGR and AC technologies. According to the measured data, the ratio of PCDFs to PCDDs in the sintered flue gas was 6.8, indicating that during the sintering process, the PCDD/Fs were primarily produced by de novo synthesis. Further investigation revealed that FGR initially removed 60.7% of PCDD/Fs by returning it to the high temperature bed, and AC further removed 95.2% of the remaining PCDD/Fs through physical adsorption. While AC is better at removing PCDFs and can efficiently remove tetra-to octa-chlorinated homologs, FGR is more effective at removing PCDDs and has higher removal efficiency for hexa-to octa-chlorinated PCDD/Fs. Together, they complement each other with a removal rate of 98.1%. The study's findings are instructional for the process design of combining FGR and AC technologies to reduce PCDD/Fs in the sintered flue gas.

Industrial disposal processes for treatment of polychlorinated dibenzo-p-dioxins and dibenzofurans in municipal solid waste incineration fly ash.

Hazardous waste disposal is a serious environmental concern in China. Therefore, in this study, industrial trials were conducted in a low-temperature thermal degradation facility, a tunnel kiln, and a shaft kiln to effectively treat dioxins in municipal solid waste incineration (MSWI) fly ash. The results indicated that the low-temperature thermal degradation facility efficiently decomposed polychlorinated dibenzo-p-dioxins and dibenzofurans in the MSWI fly ash. Additionally, the concentrations of dioxins in the treated fly ash and exhaust gas were lower than the suggested standard limits and the degradation ratio of dioxins was ∼99%. Therefore, treated fly ash characterized by acceptable dioxin risks could be utilized for the production of non-fired building materials. The results from the tunnel kiln indicated complete decomposition of the dioxins in the firing and insulating sections. However, the addition of fly ash in the tunnel kiln increased the concentration of dioxins in the flue gas. This can be primarily attributed to the heterogeneous catalytic synthesis reaction in the low-temperature section of the tunnel kiln. The results from the shaft kiln indicated degradation of at least 22% of the dioxins in the ash. The dioxin concentration in the flue gas was lower than the national standard while that in the clinker was within a reasonable limit. Furthermore, the environmental risks were significantly reduced at fly ash addition ratios lower than 3%.

Alteration in formation behaviors of chloroaromatic precursors of PCDD/Fs: An experimental study on the effect of extrinsic and intrinsic oxygen on chlorination.

Due to the promotion on Cl radical generation by enhanced oxidation, chlorination of hydrocarbon intermediates becomes a potential formation path for chloroaromatic precursors of PCDD/Fs (polychlorinated dibenzo-p-dioxins and dibenzofurans) in both MSW (municipal solid waste) incineration and gasification-combustion processes, in which intrinsic oxygen might have a significant effect on the competition between oxidation and chlorination. Thus, chlorination of benzene and phenol was experimentally studied on a homogeneous flow reaction system. Effects of temperature and ER (equivalence ratio) were assessed, and comparison was carried out to clarify the alteration in formation behaviors of chloroaromatics by extrinsic and intrinsic oxygen. At 600 °C, chlorobenzenes were already largely formed in benzene chlorination, and the addition of extrinsic oxygen barely affected it. On the contrary, with intrinsic oxygen, phenol tended to decompose to light compounds. With rising temperature, oxidation was promoted and extrinsic oxygen strongly inhibited the formation of chloroaromatics in benzene chlorination at 900 °C and higher temperature. For phenol chlorination, chlorobenzenes were still rarely generated. However, high proportions of octachloronaphthalene and octachlorodibenzofuran were observed, due to the enhancement in polymerization by high temperature. When increasing ER, oxidative decomposition was also promoted in both the chlorination of benzene and phenol. Extra extrinsic oxygen led to a further reduction of chloroaromatics during benzene chlorination, and till ER = 1.0 at 1000 °C, comparable performance to intrinsic oxygen could be achieved in the control of chloroaromatics. Based on these results, formation pathways of the major chloroaromatics from chlorination, oxidation and polymerization were summarized, and the roles of extrinsic and intrinsic oxygen in altering their formation behaviors were revealed.

Inhibition of polychlorinated dibenzo-p-dioxins and dibenzofurans by phosphorus-containing compounds in model fly ash.

Waste incineration is a preferred method in China to dispose the municipal solid waste, but controlling the production of highly toxic polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans effectively during incineration is both challenging and imperative. In this study, the suppression of PCDD/Fs by various phosphorus-containing compounds was explored, and the mechanisms responsible for the inhibition were studied in detail. The experiments took place in a lab-scale vertical tubular reactor at 350 °C under a simulated flue gas (12 vol% O2 in N2 flow), and both the off-gases and residues were collected for PCDD/Fs analysis. The scanning electron microscopy and energy-dispersive X-ray spectroscopy were used to characterize the reaction residues. The experimental results revealed that NH4H2PO4 and (NH4)2·HPO4 showed the highest inhibitory effect (57.2% and 57.3%, respectively) on the PCDD/Fs formation, followed by CaHPO4 with inhibition efficiency of 39.1%. In contrast, KH2PO4 and K2HPO4 barely inhibited the generation of the PCDD/Fs. The inhibitory effect of NH4H2PO4 and (NH4)2·HPO4 was similar to that of nitrogen-based inhibitors. At the same time, it was proven that the inhibitory activity of CaHPO4 might be due to the reaction of it with Cu2+ forming stable compounds.

Thermal oxidation of dieldrin and concomitant formation of toxic products including polychlorinated dibenzo-p-dioxin and dibenzofuran (PCDD/F).

This paper examines the gas phase thermal decomposition of dieldrin and associated formation of toxic combustion products including polychlorinated dibenzo-p-dioxin and dibenzofuran (PCDD/F). Volatile Organic Carbon (VOC) analysis revealed the formation of pentachlorostyrene (PCS), hexachlorostyrene (HCS) and polychlorinated naphthalene as toxic combustion products generated during the combustion of dieldrin. The thermal pyrolysis of dieldrin resulted in the formation of chlorinated benzenes and chlorinated phenols, which are known PCDD/F precursors. The formation of PCDD/F commenced around 823 K @ 5s residence time and results indicate a preference for the formation of PCDF over PCDD under all experimental conditions studied. Subsequent experiments, to examine the yield of PCDD/F as a function of temperature, reveal the progressive chlorination of PCDD/F with temperatures up to 923 K. Octachlorodibenzofuran (OCDF) was the major dioxin congener detected in the oxidation of dieldrin. The highest toxicity factor for dioxin formation was recorded at 923 K with a 6% O2 content in the feed gas and corresponds to 6.24 ng TEQ WHO 2005/mg of dieldrin and total PCDD/F concentration of 96.8 ng/mg of dieldrin.

Emissions of 2,3,7,8-substituted and non-2,3,7,8-substituted polychlorinated dibenzo-p-dioxins and dibenzofurans from secondary aluminum smelters.

The secondary aluminum smelting industry is an important source of polychlorinated dibenzo-p-dioxin and dibenzofurans (PCDD/Fs). However, the formations and emissions of non-2,3,7,8-PCDD/Fs have rarely been studied. Non-2,3,7,8-PCDD/Fs may also be metabolically toxic to mammalians. In this study, four typical secondary aluminum smelters were selected as demonstration smelters and the composition of the raw material they used was adjusted to investigate the influence on PCDD/F emissions and profiles. In addition to 17 congeners of 2,3,7,8-PCDD/Fs, 64 congeners of non-2,3,7,8-PCDD/Fs were firstly reported. Strong, positive correlations were found between non-2,3,7,8-PCDD/Fs and 2,3,7,8-PCDD/Fs. The concentrations of 2,3,7,8-PCDD/Fs in stack gas and fly ash samples were 120.7-870.4 pg/Nm3 and 13.40-292.9 ng/g, respectively. Those of non-2,3,7,8-PCDD/Fs in the stack gas and fly ash samples were 84.03-1183.7 pg/Nm3 and 7.20-344.7 ng/g, respectively. The raw material composition was a key factor affecting PCDD/F emissions and profiles. An analysis of Gibbs free energies (ΔGf) showed that non-2,3,7,8-PCDD/Fs could be transformed into 2,3,7,8-PCDD/Fs, which would increase the PCDD/F environmental risks. The emission inventories of 2,3,7,8-PCDD/Fs, non-2,3,7,8-PCDD/Fs, and International Toxic Equivalents from Chinese secondary aluminum smelters in 2013 were 8247 g, 7253 g, and 608.6 g, respectively. The results of this study could contribute to potential risk evaluations and effective reduction of non-2,3,7,8-PCDD/Fs.

Mechanochemical degradation of PCDD/Fs in fly ash within different milling systems.

Two distinct mechanochemical degradation (MCD) methods are adopted to eliminate the polychlorinated dibenzo-p-dioxins and -furans (PCDD/Fs) from fly ash in municipal solid waste incinerators. First, experiments are conducted in a planetary ball mill for selecting suitable additives, and an additive system of SiO2-Al is chosen for its high-efficiency, low-price, and good practicability. The I-TEQ value of PCDD/Fs in washed fly ash decreases dramatically from 6.75 to 0.64 ng I-TEQ/g, after 14 h of milling with 10 wt % SiO2-Al, and dechlorination is identified as the major degradation pathway. Then, this additive is applied in a horizontal ball mill, and the results indicate that the degradation of PCDD/Fs follows the kinetic model established in planetary ball mills. However, longer milling time is required for the same supplied-energy because of the lower energy density of horizontal ball mills, resulting in partial loss of Al reactivity and a lower degradation efficiency of PCDD/Fs. During MCD, the evolution of PCDD/F-signatures is analogous, indicating a similar acting mechanism of all additives in both the two milling systems. Finally, a major dechlorination pathway of PCDD-congeners is proposed based on the signature analysis of congeners synthesized from chlorophenols.

Bioaccumulation of PCDD/Fs in foodstuffs near Bien Hoa and Da Nang airbases: assessment on sources and distribution.

In this survey, food items were collected from vicinities of Bien Hoa and Da Nang airbase and determined for polychloro-dibenzo-dioxins and polychloro-dibenzo-furans (PCDD/Fs) to assess their accumulation, distribution in the local food items, and risk of PCDD/F exposure through consumption of the local foods. Dioxin compounds were determined using isotope dilution method which is slightly modified from US-EPA method 1613B. The dioxin concentration was the highest in fish followed by eggs, chicken, meat (pork and beef), and vegetables. Particularly, in Bien Hoa airbase, the mean concentrations of dioxin on TEQ and lipid basis (except for vegetables) were 26 pg/g for fish, 13 pg/g for eggs, 20 pg/g for chicken, 4.5 pg/g for meat, and 0.34 pg/g fresh wt for vegetables. In Da Nang airbase, the mean levels of dioxin on TEQ and lipid basis were slightly lower, 12.9 pg/g for fish, 8.7 pg/g for eggs, 5.9 pg/g for chicken, 6.7 pg/g for meat, and 0.17 pg/g for vegetables. It has been interesting to observe that free-range chicken expose to higher level of dioxin than caged chicken. In some free-range chicken, the portion of 2,3,7,8-TCDD was relatively high and implying recent exposure to dioxin.

The fingerprint nature of PCDD in iron ore sinter strand emissions, the effect of suppressants and alternative fuels, and the potential for comparison with the isomer profile of PCDF.

It has been previously shown that the isomer profile of PCDF emissions from iron ore sinter plant only varies within limits even when suppressants or alternative fuels are added, to the extent that it can be said to have a 'fingerprint'. The isomer profiles of PCDD from tetra- to hexacholrodibenzo-p-dioxin from the same samples examined for PCDF emissions have been obtained, and show the same tendency for a 'fingerprint ' isomer distribution to occur. Occasional exceptionally high isomer abundances are observed, but these are uncommon. The potential for comparison of the abundances of PCDF and PCDD isomers with similar chlorination patterns to determine whether the same formation process is involved has been examined. It is found that co-elutions prevent extensive comparisons irrespective of whether the SP2331 or DB5ms column is used in the analyses for separation of isomers to provide the results used for comparisons, although they allow limited results to be obtained. It is suggested that analyses using the two chromatography columns to analyse the same sample in parallel could provide more resolution of the isomer profiles for use in comparisons. A pilot study using samples analysed using each column is limited because of detailed differences in the emissions profiles, but demonstrates that greater resolution is possible if the two columns are used to analyse one sample.

Toxicity of polyhalogenated dibenzo-p-furans in the light of nucleic acid bases interaction.

Quantitative structure-activity relationship (QSAR) investigation utilizing quantum chemical descriptors under density functional theory is performed to predict the toxicity (pEC50) of a series of polyhalogenated dibenzo-p-furans (PHDFs). PHDFs are very important concern to the researchers due to their presence and diverse effects in the environment. A successful two parameter QSAR model is developed with a combination of a global descriptor known as charge transfer (ΔN) between toxins and biosystem and a local descriptor as Fukui function (fmax+) for maximum nucleophilic attack at the toxin site. A systematic analysis is performed to identify the electron donation/acceptance nature of the considered PHDF compounds with the choice of a model biosystems comprising five different nucleic acid bases, namely Adenine, Thymine, Guanine, Cytosine and Uracil to identify proper ΔN descriptor. Accordingly, PHDFs are found to be electron acceptors with maximum charge transfer from Guanine and therefore, ΔNG is utilized as the charge transfer parameter for all the toxins in the present work. The selected combination of global and local descriptors (ΔNG andfmax+) are found to predict 93% of the observed toxicity (pEC50) of the PHDFs. The developed QSAR model is tested for two different test sets: PHDFs and polyhalogenated biphenyls (PHBs) with about 90% of prediction of their toxicity values, which confirms the importance of the selected descriptors.

Low temperature degradation of polychlorinated dibenzo-p-dioxins and dibenzofurans over a VOx-CeOx/TiO2 catalyst with addition of ozone.

In order to find a catalyst to destroy polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) with high efficiency, a homemade VOx-CeOx/TiO2 catalyst was prepared, and then tested in the flue gas of a waste incinerator at temperatures of 180-240 °C. The results shows the best removal efficiency (93.4%) was attained already at 200 °C, yet degradation efficiency further raised with temperature, until 240 °C. Ozone (500 ppm) was also introduced into the system to increase the activity of catalyst, and removal efficiency of PCDD/Fs increased further to 97.4% and 98.8% at 200 and 240 °C, respectively. In addition, a lab-scale reaction system was installed to study the degradation mechanism of PCDD/Fs. Octa-chlorinated dibenzo-p-dioxin (OCDD) was selected as the study object due to the most stable structure and maximum chlorine atom number. The intermediate products resulting from the conversion of OCDD were monitored using gas chromatography/mass spectrometry and Fourier transform infrared spectroscopy and a possible reaction pathway was proposed. Dechlorination persists until the complete conversion of OCDD. Oxidation decomposes OCDD-molecules mainly into organic substances having one, two or more benzene rings, yet also alkanes, cycloalkanes and heterocompounds of sulphur, nitrogen, and halogens appear. However, more work is still needed to fit those trace products into mechanistic schemes.

Removal of PCDD/Fs, PCP and mercury from sediments: Thermal oxidation versus pyrolysis.

A continuous pilot-scale system (CPS) equipped with effective air pollution control devices (APCDs) is used for remediating the sediments contaminated with PCDD/Fs, PCP and Hg simultaneously. The removal efficiencies of these three pollutants in sediments collected from seawater pond and river, respectively, are evaluated via thermal treatment processes. PAHs and CBz formed during thermal oxidation and pyrolysis are also analyzed for better understanding the behaviors of chlorinated organic compounds. Experimental results indicate that low-molecular-weight PAHs are closely related to the formation of CBz, PCDD/Fs, and CPs, while low chlorinated PCDD/Fs and CBz are predominant in flue gas with thermal oxidation. However, the PM concentration is higher in thermal oxidation than pyrolysis due to the higher air flow rate of thermal oxidation. It may bring more particles out of the furnace and have a greater potential to form PCDD/Fs within APCDs. Besides, the high air flow also dilutes the Hg vapor in flue gas and would require more energy to condense and collect Hg with the quench tower. Furthermore, for removal of total amount of PCDD/Fs, pyrolysis is better than thermal oxidation. Thus, pyrolysis is more suitable for remediating the contaminated sediment. The removal efficiencies of PCDD/Fs, PCP and Hg in sediments achieved with pyrolysis increase with increasing operating temperature and retention time in CPS. Overall, the residual concentrations of PCDD/Fs and PCP in river sediment are higher than that in seawater-pond sediment since significant formation of tar is observed due to higher organic matter content in river sediment.

PCDD/PCDF formation in the chlor-alkali process-laboratory study and comparison with patterns from contaminated sites.

Studies on the formation of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) during the electrolysis of sodium chloride solution (brine) using graphite or titanium electrodes were carried out at a laboratory scale. High concentrations of PCDFs but no PCDDs were formed in tests using graphite electrodes. With titanium electrodes, PCDFs were only formed when tar pitch was added and mainly originated from the dibenzofuran present in the tar. For the first time, a detailed assessment of the formation of mono- to octachlorinated PCDD/PCDF from tar pitch was investigated. The assessment included of the chlorination steps proved that PCDFs were formed by successive lateral chlorinated from dibenzofuran to MonoCDFs, DiCDFs, and TriCDFs to form the typical known "chlorine pattern" of TetraCDF to OctaCDF with a dominance of 1,2,7,8- and 2,3,7,8-TetraCDFs, 1,2,3,7,8-PentaCDF, and 1,2,3,4,7,8-HexaCDF as marker congeners. The final homologue distributions depended on reaction time and reaction temperature. In addition, electrolysis with non-chlorinated dibenzo-p-dioxins, dibenzofuran, and biphenyl was carried out. As a result, PCDDs, PCDFs, and PCB were formed at comparable yields. Congener patterns in soil samples from a PCDD/F-contaminated site where chlor-alkali electrolysis had been operated for decades in Japan had identical isomer distribution demonstrating the source and contamination potential and risk of these processes. Therefore, sites where in the past 120 years chlor-alkali electrolysis has been operated or where residues from chlor-alkali production or other chlorine using industries have been disposed should be assessed for their pollution level and exposure relevance. The assessment of total organohalogen content revealed that PCDF is only a small fraction of organohalogens in the contaminated soils. For an appropriate risk assessment, also other chlorinated aromatic compounds such as PCBs or PCNs need to be considered.

Comparative analyses of catalytic degradation of PCDD/Fs in the laboratory vs. industrial conditions.

This study investigates the efficiencies and mechanisms of the catalytic degradation of polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs) first, in simulated laboratory conditions and then, in a commercial municipal solid waste incineration (MSWI) plant. Five commercially available V2O5-WO3/TiO2 (VWTi) catalysts were tested. The degradation efficiency of PCDD/Fs in the simulated flue gas ranged 22.8-91.7% and was generally higher than that in the MSWI flue gas of 8.0-85.4%. The degradation efficiency of PCDD/Fs in the real flue gas of the MSWI plant was largely hindered by the complex composition of the flue gas, which could not be completely reproduced in the simulated laboratory conditions. Furthermore, the degradation of the higher chlorinated PCDD/Fs was easier compared to the lower chlorinated ones in the presence of the VWTi catalysts, which was primarily driven by the tendency of the higher chlorinated PCDD/Fs to be adsorbed on the surface of the catalyst and further destructed due to their lower vapor pressure. In addition, powdered catalysts should be preferred over the honeycomb shaped ones as they exposed higher PCDD/Fs degradation efficiencies under equal reaction conditions. The chemical composition and a range of the relevant to the study properties of the catalysts, such as surface area, crystallinity, oxidation ability, and surface acidity, were analyzed. The study ultimately supports the identification of the preferred characteristics of the VWTi catalysts for the most efficient degradation of toxic PCDD/Fs and elucidates the corresponding deactivation reasons of the catalysts.