Treatment of Sydney N.S. tar pond sludge in a pilot‐scale rotary kiln

Tar pond wastes from Sydney, Nova Scotia, containing 50 ppm or more of polychlorinated biphenyls (PCBs) were treated in a pilot‐scale rotary kiln. In order to use the existing feed system attached to the rotary kiln, the wastes were first oven‐dried. Stack gas sampling was conducted during the test, which included measurement of volatile organic compounds (VOCs), polycyclic aromatic hydrocarbons (PAHs), semi‐volatile organic compounds (SVOCs), HCl, and metals. The purpose of this study was to determine emissions from treatment of the tar pond waste using rotary kiln technology. It was found that the dried sludge could sustain combustion in the kiln without any supporting fuel. The emissions of polychlorinated dibenzodioxins/furans (PCDD/Fs) were higher than the Canadian Council of Ministers of the Environment (CCME) air emissions guidelines, and the reasons for this are discussed. © 2008 Wiley Periodicals, Inc.     

De-novo formation of dioxins and furans and the memory effect in waste incineration flue gases

The formation of dioxin (polychlorinated-rho-dibenzodioxins - PCDD) and furan (polychlorinated dibenzofurans - PCDF) in waste incineration flyash in relation to temperature has been investigated in a bench scale reactor. The PCDD/PCDF released into the exhaust gases of the reactor and trapped in a condensation and vapour phase adsorption system were also determined. The concentrations of PCDD/PCDF in the flyash were analysed in detail for all congeners and isomers including the mono-, di- and tri-PCDD/PCDF. De-novo synthesis of PCDD/PCDF was clearly seen in the flyash with large changes in concentrations of PCDD/PCDF with only small changes in temperature. Exhaust gas PCDD/PCDF were detected at all temperatures, with the maximum emission occurring at a flyash temperature of 350 degrees C, where the equivalent of over 42 times the total dioxin/furan concentration of the original flyash was lost to the vapour phase per unit mass of initial flyash. Although the desorbed species were mainly the lower mono- to tri-congener group of dioxins and furans, the desorbed dioxin/furans had a considerable toxic equivalent value.     

Oxidation catalyst of iron oxide suppressing dioxin formation in polyethylene combustion

A new iron oxide catalyst, which has a superior oxidation activity in carbon monoxide and polyethylene (PE) combustion, was synthesized by an aqueous solution reaction. Catalytic oxidation of carbon monoxide over six kinds of hematite obtained from the goethite was done using a microcatalytic pulse reactor, and the composition of the hematite with the highest oxidation activity was determined. With the aim of suppressing dioxin formation on combustion, incineration tests of solid wastes in PE refuse bags with and without the goethite were carried out using a commercial semibatch-type incinerator with a combustion chamber of 6.2 m³. The result confirmed that the concentration of dioxins in the flue gas decreased considerably when the refuse was incinerated in PE bags manufactured with goethite. Received: July 24, 2000 / Accepted: October 18, 2000     

Sludge as dioxins suppressant in hospital waste incineration

Nitrogen containing compounds such as ammonia, urea and amines can effectively inhibit the formation of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). Sewage sludge accumulates both sulfur and nitrogen during wastewater treatment so it could be used to reduce PCDD/Fs formation. Indeed, it is observed in this study that the gas evolving from the sludge drying process can significantly suppress chlorobenzene (CBz) and PCDD/Fs formation from fly ash collected from a hospital waste incinerator. For instance, the reduction of hexachlorobenzene (HxCBz) and PCDD/Fs amount was 92.1% and 78.7%, respectively, when the drying gas evolving from 2g sludge flew through 2g fly ash. These tests were conducted in the frame of projects devoted to hospital waste incineration. The disposal technology for hospital waste (HW), developed in this institute, features rotary kiln pyrolysis combined with post-combustion followed by flue gas cleaning. Hence, some preliminary tests were devoted to investigate dioxins suppression by co-pyrolysis and co-combustion of polyvinyl chloride (PVC) and sludge in lab scale. More experimental research will be conducted to appropriately assess these effects of sludge on PCDD/Fs emissions during co-pyrolysis/combustion of HW and sludge.     

固硫灰固化焦化废水处理外排污泥

采用机械力化学法活化循环流化床燃煤固硫灰,用于固化焦化废水处理外排污泥(CWT污泥)。探讨了固硫灰活化条件,并通过XRD和FTIR分析了固硫灰固化CWT污泥中重金属的机理。实验结果表明:当m(Ca O)∶m(Ca O+固硫灰)为20%、球磨频率为40 Hz、球磨时间为2 h时,养护28 d固硫灰固化体的平均抗压强度达到72.2 MPa;当污泥掺加量为50%(w)时,养护28 d含污泥固化体的抗压强度达到8.5 MPa,固化体浸出液中Pb2+和As5+的质量浓度分别为0.177 mg/L和0.013 mg/L,均远低于GB 5085.3—2007《危险废物鉴别标准浸出毒性鉴别》的规定限值。XRD和FTIR表征结果表明,在固硫灰活化过程中,混合体系水化生成了C—S—H凝胶、斜方钙沸石和钙矾石,可通过物理包裹、吸附及离子交换的形式实现CWT污泥中Pb2+和As5+的固化/稳定化。     

Winery waste recycling through anaerobic co-digestion with waste activated sludge

In this study biogas and high quality digestate were recovered from winery waste (wine lees) through anaerobic co-digestion with waste activated sludge both in mesophilic and thermophilic conditions. The two conditions studied showed similar yields (0.40 m³/kgCOD_fed) but different biological process stability: in fact the mesophilic process was clearly more stable than the thermophilic one in terms of bioprocess parameters.The resulting digestates showed good characteristics for both the tested conditions: heavy metals, dioxins (PCDD/F), and dioxin like bi-phenyls (PCBs) were concentred in the effluent if compared with the influent because of the important reduction of the solid dry matter, but remained at levels acceptable for agricultural reuse. Pathogens in digestate decreased. Best reductions were observed in thermophilic condition, while at 37 °C the concentration of Escherichia coli was at concentrations level as high as 1000 UFC/g. Dewatering properties of digestates were evaluated by means of the capillary suction time (CST) and specific resistance to filtration (SRF) tests and it was found that a good dewatering level was achievable only when high doses of polymer (more than 25 g per kg dry solids) were added to sludge.     

Emission of dioxins/furans and other U-POPs from test burns of non-POP pesticides in a hazardous waste incinerator

This paper presents the results of test burns for obsolete pesticides (OPs) of the permethrin group in a high temperature incinerator (HTI) in Southeast Asia. Three test burn runs were conducted, a baseline run when no OP was fed to the incinerator, and two test runs with different mixtures of OP compounds (formula 1 and 2, refer to Table 1 for detail) containing chlorine in the feeding wastes. The unintentional formed persistent organic pollutants (U-POPs) including 17 dioxins/furans, 12 dioxin-like PCBs and 12 chlorobenzenes (CBs) were monitored in all input materials and all discharges (flue gas, scrubbing liquid and solid residues). The results show relatively high levels of the U-POPs in the flue gas emission with total dioxins/furans of 4.4, 3.4, and 8.4 ng I-TEQ/m³ in the baseline, test run 1 and test run 2, respectively, which are above international acceptable emission levels. The PCB levels in flue gas were, respectively, 0.01, 0.3 and 0.4 ng I-TEQ/m³. The baseline thus had similar U-POPs levels with the OP test runs.In stack emission, approximately 90% of the U-POPs and 100% of CBs were present in gas phase. The emission factors, mass of pollutants per metric ton (tonne) of input waste, of U-POPs associated with fly ash (from bag house) were the highest, followed by flue gas and bottom ash while those associated with scrubbing liquid were relatively low. Among the waste input material only the black toner power contained U-POPs, but at low levels. The profiles of the dioxins/furans and PCBs in the toner waste were significantly different from that in the discharges. Despite the overall good destruction and removal efficiency of permethrin (better than 90%) the high emission of U-POPs and CBs from the test burn is of another more serious concern. To our best knowledge the findings of this study are the first of this kind for the Southeast Asia. The findings emphasize that if not properly conducted a standard destruction technology of a non-POP chemical can lead to a release of a range of more dangerous U-POPs into the environment.     

Pilot-scale studies on the effect of bromine addition on the emissions of chlorinated organic combustion by-products

The addition of brominated organic compounds to the feed of a pilot-scale incinerator burning chlorinated waste has been found previously, under some circumstances, to enhance emissions of volatile and semivolatile organic chlorinated products of incomplete combustion (PICs) including polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDDs/Fs). This phenomenon appears to be sensitive to temperature and combustion conditions. This paper reports on a study to evaluate the emissions of organic combustion by-products while varying amounts of bromine (Br) and chlorine (Cl) are being fed into a pilot-scale incinerator burning surrogate waste materials. The surrogate waste was fed at a constant molar halogen input rate, with varying Br/Cl molar ratios. In these tests, an approximately 30% decrease in the total PCDD/F concentrations due to the addition of Br was observed. This decrease appears to be a decrease only in the chlorinated dioxin and furan species; other halogenated dioxins and furans were formed instead. PCDD/F homologue distribution shifted towards the higher chlorinated species. Perhalogenated or nearly perhalogenated mixed bromo-chloro furans were also observed in quantities that could potentially account for the observed decrease in PCDDs/Fs. This research illustrates the need for careful trial burn planning if Br will be present in the facility's feed-stock during normal operation.     

Removal of carbon constituents from hospital solid waste incinerator fly ash by column flotation

Hospital solid waste incinerator (HSWI) fly ash contains a large number of carbon constituents including powder activated carbon and unburned carbon, which are the major source of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in fly ash. Therefore, the removal of carbon constituents could reduce PCDD/Fs in fly ash greatly. In this study, the effects of the main flotation parameters on the removal of carbon constituents were investigated, and the characteristics of the final product were evaluated. The results showed that loss on ignition (LOI) of fly ash increased from 11.1% to 31.6% during conditioning process. By optimizing the flotation parameters at slurry concentration 0.05 kg/l, kerosene dosage 12 kg/t, frother dosage 3 kg/t and air flow rate 0.06 m³/h, 92.7% of the carbon constituents were removed from the raw fly ash. Under these conditions, the froth product has LOI of 56.35% and calorific values of 12.5 MJ/kg, LOI in the tailings was below 5%, and the total toxic equivalent (TEQ) of PCDD/Fs decreased from 5.61 ng-TEQ/g in the raw fly ash to 1.47 ng-TEQ/g in the tailings. The results show that column flotation is a potential technology for simultaneous separation of carbon constituents and PCDD/Fs from HSWI fly ash.     

SETTING DIOXIN EMISSION LIMITS FOR MSW INCINERATORS: A MULTIMEDIA EXPOSURE ASSESSMENT FRAMEWORK

Polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) are emitted in trace amounts from municipal solid waste (MSW) incinerators. The exposure to PCDD/Fs experienced by an individual is dominated by the food chain pathway, which accounts for over 98% of the total uptake. Defining a target daily intake (the World Health Organization TDI of 10 pg I-TEQ kg.bw⁻¹day⁻¹) exposure assessment algorithms were then applied to arrive at the corresponding PCDD/F levels in air, soil, plants, food products, etc., which would allow the target intake to be met while retaining the balance of intake between the various exposure pathways. These concentrations were converted to an ambient air concentration of PCDD/Fs and ultimately, by defining criteria for acceptability, to a guide value for PCDD/F concentration in emissions from the MSW incinerator. This strategy was applied to PCDD/F emissions from MSW incinerators of various sizes against two illustrative criteria for acceptability: an “insignificant” release and a threshold above which the release may require further assessment for environmental effects and for control. Using the criteria developed in this paper, the current PCDD/F emission limit of 0.1 ng I-TEQ m⁻³results in an emission that is classed as “insignificant” for all plant sizes. However, higher emission concentrations can also be accommodated below the threshold for further assessment and control.     

PCDD/F in source-sorted waste fractions and emissions from their co-combustion with reed canary-grass

The dry combustible fraction of source-sorted household waste, including material that would otherwise be recycled, was mixed with the energy crop reed canary-grass (Phalaris arundinacea L.), and combusted as briquettes in 150 and 600 kW biofuel-boilers without advanced cleaning systems. The source-sorted waste was further sorted and characterized according to its material and chemical contents. The bulk of the waste's chlorine content came from the non-package plastic fraction, whereas 90-95% of summation operator PCDD/F (74-90% of WHO-TEQ) originated from the textile fraction. The sources of the dioxins in the waste fractions are discussed. The balance of dioxin levels was negative, i.e., the amounts of dioxins output in the flue gas were lower than those input in the fuel, except when there were operational disturbances in the combustion. In one of the combustion trials the total levels of dioxins in the flue-gas and ashes were also lower than the input levels. The use of additional cleaning equipment will be needed to ensure that emissions of dioxins and hydrochloric acid will be below legal limits.     

PHYSICO-CHEMICAL CHARACTERIZATION AND LEACHING OF DESULPHURIZATION COAL FLY ASH

Fly ash produced by coal combustion using two types of desulphurization process were studied: a conventional pulverized coal boiler equipped with lime injection (PCL ash), and a circulating fluidized bed combustion boiler with limestone injection (CFBC ash). The ashes were characterized completely: granulometry, morphology, mineralogy, chemical composition and behaviour to water contact. Both PCL ash and CFBC ash present similar features: fine granulometry, presence of anhydrite phase and sulphate content. However, PCL ash also shows lots of spherical particles, unlike CFBC ash, and a much higher lime content, due to the lower desulphurization rate in PC boilers. Unlike CFBC ash, most of the trace elements in PCL ash show an inverse concentration–particle size dependence. Leachates obtained from both samples are rich in soluble salts [CaSO₄and Ca(OH)₂] and arsenic and selenium are prevented from solubilizing by high lime content. In wetted PCL ash, the formation of ettringite crystals stabilizes calcium and sulphate ions. Simultaneously, arsenate, selenate and chromate anions are trapped in the crystal. CFBC ash does not really harden because the lime content is too low. However, the leached selenium concentration is cut down in wetted CFBC ash samples.     

Removal potential of toxic 2378-substituted PCDD/F from incinerator flue gases by waste-derived activated carbons

The application of activated carbons has become a commonly used emission control protocol for the removal or adsorption of persistent organic pollutants from the flue gas streams of waste incinerators. In this study, the 2378-substituted PCDD/F removal efficiency of three types of activated carbons derived from the pyrolysis of refuse derived fuel, textile waste and scrap tyre was investigated and compared with that of a commercial carbon. Experiments were carried out in a laboratory scale fixed-bed reactor under a simulated flue gas at 275 °C with a reaction period of four days. The PCDD/F in the solid matrices and exhaust gas, were analyzed using gas chromatography coupled with a triple quadrupole mass spectrometer. In the absence of activated carbon adsorbent, there was a significant increase in the concentration of toxic PCDD/F produced in the reacted flyash, reaching up to 6.6 times higher than in the raw flyash. In addition, there was a substantial release of PCDD/F into the gas phase, which was found in the flue gas trapping system. By application of the different commercial, refuse derived fuel, textile and tyre activated carbons the total PCDD/F toxic equivalent removal efficiencies in the exhaust gas stream were 58%, 57%, 64% and 52%, respectively. In general, the removal of the PCDDs was much higher with an average of 85% compared to PCDFs at 41%. Analysis of the reacted activated carbons showed that there was some formation of PCDD/F, for instance, a total of 60.6 μg I-TEQ kg⁻¹ toxic PCDD/F was formed in the refuse derived fuel activated carbon compared to 34 μg I-TEQ kg⁻¹ in the commercial activated carbon. The activated carbons derived from the pyrolysis of waste, therefore, showed good potential as a control material for PCDD/F emissions in waste incinerator flue gases.     

Environmental bioavailability of hydrophobic organochlorines in sediments—A review

A number of hydrophobic organochlorines, such as hexachlorobenzene and polychlorinated dibenzo‐p‐dioxins/dibenzofurans (PCDD/Fs), have been reported to be persistent and bioaccumulative; however, their availability to biota appear to be limited due to strong sorption to soil/sediment and sequestration with age. Studies to date have shown that the bioavailability of hydrophobic organic chemicals (HOCs) in sediments is highly variable, depending not only on a chemical's lipophicity (K_ow), but also molecular steric conformation and sediment characteristics. A subdomain of sediment organic carbon, so‐called black carbon (BC), which has much higher affinity to planar HOCs than amorphous organic carbon, has been found to be the predominant repository of many HOCs. The sediment/soil‐bound HOCs are composed of a rapid and reversible desorbing labile fraction and a slow‐desorbing, or resistant‐to‐desorbing, nonlabile fraction. The latter can account for up to 98 percent of the total. A number of chemical extraction methods have been under development to measure the actual bioavailable concentrations in soil/sediment and have shown some correlation to the results of bioaccumulation and/or biodegradation tests. To date, most of the published studies on this subject have focused on polynuclear aromatic hydrocarbons (PAHs). This review summarizes the governing processes and the testing methodologies relevant to the environmental bioavailability of hydrophobic organochlorines in soils and sediments. © 2004 Wiley Periodicals, Inc.     

Simple removal of dioxins by injecting combustion gas into water

A simple, low-cost method for suppression of dioxins/furans (hereinafter referred to as dioxins) is required because many middle- and, especially, small-scale incinerators have fallen into disuse or have been dismantled because of the high running and system costs of measures for the suppression of dioxins. Therefore, the purpose of the present study was to develop a simple removal method for dioxins from combustion gas and to evaluate the basic removal rate of dioxins. The removal method for suspended matter in a gas mixture (cold model) and dioxins in exhaust gases (hot model) has been investigated by means of gas injection into water, the mechanism of which is that the suspended matter in the gas gathers at the gas–liquid interface. In the cold model, the removal ratio of fine particles (R_P) by gas injection into water was reproduced well by the following equation: R_P (%) = 100 × {1−exp(−0.8 · S_S · t_C)}, where S_S (cm²/cm³) is the specific surface area of bubbles and t_C (s) is the residence time of bubbles in water. The removal ratio of fine particles increased as the product S_s · t_C increased. In a hot model using the exhaust gas from combustion experiments of polyvinyl chloride, the removal ratio of dioxins (R_D) by injecting the exhaust gas into water was estimated by the following equation: R_D (%) = 100 × {1−exp(−0.8 · S_S · t_C · C_D0 ^0.07)}, where C_D0 [ng/cm³ (at standard temperature and pressure)] is the dioxins concentration in the exhaust gas before injection into water. R_D depends greatly on the specific surface area of bubbles and the residence time of the bubbles in water, and only weakly on the dioxins concentration in the exhaust gas. Injection of the exhaust gas into water has been shown to be effective and was evaluated as a simple method for the removal of dioxins from exhaust gas.     

Resource recovery treatment of waste sludge using a solubilizing reagent

The dewatering of waste sludge continues to be a major problem in wastewater treatment. In this study, the solubilization treatment of waste sludge and extracellular polymeric substances using a solubilizing reagent was examined experimentally. For this purpose, a compression test of thickened waste sludge obtained after solubilization treatment was carried out. The total solid content of the dewatered cake was over 30% when using hydrochloric acid or acetic acid as the solubilizing reagent; however, it was about 20% when using sodium hydroxide. The thickened waste sludge was effectively solubilized when the concentration of acetic acid in the sludge, assuming that it was diluted by free water and not bound water in the sludge, was greater than 0.3 kmol/m³. A flocculated sedimentation test using the supernatant water after solubilization treatment was also carried out, revealing that it functions in a similar manner to commercial flocculant in aggregating solid particles under gravity. This result indicates that the supernatant water can act as a bioflocculant. Methane fermentation of the supernatant water was subsequently carried out. The findings showed that by using acetic acid as a solubilizing reagent, solubilized organic substances in the supernatant water could be recovered as a bioenergy resource.     

Environmental Technology Verification (ETV) test of dioxin emission monitors

The performance of four dioxin emission monitors, including two long-term sampling devices, the Dioxin-MonitoringSystem (DMS) and AMESA (the adsorption method for sampling dioxins and furans), and two semireal-time continuous monitors, the resonance ionization with multimirror photon accumulation time-of-flight mass spectrometer (RIMMPA-TOFMS) and the jet resonance-enhanced multiphoton ionization (jet-REMPI) system were tested. A package boiler burning a simulated chlorinated hazardous waste was used for a total of nine tests. Reference samples were collected during each test and analyzed for polychlorinated dibenzodioxins and dibenzofurans (PCDDs/Fs) using gas chromatography mass spectrometry. The PCDD/F concentrations of the reference samples measured by EPA Method 23 ranged from 0.9 to 6.0 ng toxic equivalence (TEQ)/dry standard cubic meter. The relative accuracies achieved by DMS, AMESA, and jet-REMPI varied from 22.6% to 78.2%, with 100% data completeness. The RIMMPA-TOFMS produced no quantifiable results due to various difficulties associated with the instrument during the testing. The two long-term samplers were easy to install and operate and provided a cumulative, averaged emission for the sampling period. The operations of the two semi-real-time continuous monitors were relatively complex, but one of them provided on-site, real-time data for PCDD/F emissions from measurement of a TEQ correlative indicator compound. This article summarizes results from the individual Environmental Technology Verification reports for the four dioxin monitors. This work was presented, in part, at the Fourth International Conference on Combustion, Incineration/Pyrolysis and Emission Control (i-CIPEC)     

Verification results of jet resonance-enhanced multiphoton ionization as a real-time PCDD/F emission monitor

A jet resonance-enhanced multiphoton ionization (REMPI) monitor was tested on a hazardous-waste-fired boiler for its ability to determine concentrations of polychlorinated dibenzodioxins and dibenzofurans (PCDDs/Fs). Jet REMPI is a real-time instrument capable of highly selective and sensitive (from parts per billion to parts per trillion) detection of a broad range of aromatic compounds, including a number of air toxic compounds. The PCDD/F toxic equivalency (TEQ) value was derived from a predetermined correlation (R ² = 0.74) with monochlorobenzene (MClBz). This relationship was applied to nine subsequent jet REMPI on-line measurements of MClBz and parallel, standard extractive sampling for PCDD/F TEQ. For high waste-firing rates, with a range of PCDD/F TEQ values between 3.9 and 6.0 ng TEQ/m³, the TEQ values predicted by jet REMPI had a relative difference of 26% with the standard EPA Method 23 results. At low waste-firing rates (0.9–1.6 ng TEQ/m³), the relative difference increased to 219%. This limited testing shows that jet REMPI has promise as an on-line diagnostic monitor, providing feedback on the effects on PCDD/F emissions of operating parameter changes such as fuel feed interruptions or air pollution control failures.     

Effects of combustion parameters on polychlorinated dibenzodioxin and dibenzofuran homologue profiles from municipal waste and coal co-combustion

Variation in polychlorinated dibenzo-p-dioxin and polychlorinated dibenzofuran (PCDD and PCDF) homologue profiles from a pilot scale (0.6 MW_t, 2×10⁶ Btu/h), co-fired-fuel [densified refuse derived fuel (dRDF) and high-sulfur Illinois coal] combustion system was used to provide insights into effects of combustion parameters on PCDD and PCDF pollutant formation. A 24-run, statistically designed test matrix varied dRDF and/or coal firing rates (at a constant targeted energy release rate) along with a range of process variables including calcium hydroxide injection, hydrogen chloride (HCl) concentration, flue gas temperature, quench, and residence time such that the results would be relatable to a wide variety of combustion conditions. Statistical analysis of the molar homologue profiles enabled interpretation based on non-confounding variables. A multivariate, generalized additive model, based on transformations of the design variables, described 83% of the variation of the profiles characterized by log ratios of the homologue molar concentrations. This method identifies the operating parameters that are most significant in determining the PCDD/F homologue profiles. The model can be exercised to predict homologue profiles through input of these system-specific operating parameters. For example, both higher HCl and sulfur dioxide concentrations favor higher relative formation of the lower chlorinated PCDF homologues.     

Formation of persistent chlorinated aromatic compounds in simulated and real fly ash from iron ore sintering

Effects of carbon concentration and Cu additive in simulated fly ash (SFA) and real fly ash (RFA) on the formation of polychlorinated dibenzofurans (PCDFs), polychlorinated dibenzo-p-dioxins (PCDDs), chlorobenzenes, and polychlorinated biphenyls which were all regarded as persistent chlorinated aromatics in iron ore sintering were investigated. In the annealing process of SFA with various carbon contents, the yield of chlorinated aromatics and the I-TEQ obtained their maximum at 10 wt% carbon content. Active carbon in SFA acted as the carbon source as well as an adsorbent which led to higher production of PCDD/F in solid phase at 10 wt% carbon content. The increase of carbon content will be beneficial on the formation of 2,3,7,8-Chloro-substituted PCDF compared with 2,3,7,8-Chloro-substituted PCDD. In addition, the CuCl₂·2H₂O was a much more powerful catalyst in the formation of chlorinated aromatic compounds compared with elementary Cu, since it served as both a catalyst and a chlorine donor. However, the RFA behaved similarly with SFA with elementary Cu in the formation of chlorinated aromatic compounds. The effect of carbon content and copper additives on formation of 2,3,7,8-chloro-substituted congeners displayed similar characteristics with the tetra- to octa-PCDD/F isomers and even the total PCDD/Fs.