Thermal treatment of polychlorinated dibenzo-p-dioxins and dibenzofurans from contaminated soils

Thermal treatment technology was used to remove polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) from heavily contaminated soil. For a soil with an original PCDD/F content of 35,970ng International Toxic Equivalents (I-TEQ)/kg, >99.99% PCDD/F removal efficiency was obtained with a primary furnace at two different treatment temperatures (750 degrees C and 850 degrees C), while a secondary furnace at 1200 degrees C gave >98% decomposition efficiency. The total PCDD/F I-TEQ contents in treated soils at 750 degrees C and 850 degrees C were 1.56ngI-TEQ/kg and 2.15ngI-TEQ/kg, respectively, which were far below the soil pollution standard of Taiwan (1000ngI-TEQ/kg soil). Although air pollution control devices had significant effects on the removal of PCDD/Fs, the total I-TEQ concentrations in the upstream flue gas of PUF cartridge at 750 degrees C and 850 degrees C (2.61ngI-TEQ/Nm(3) and 2.38ngI-TEQ/Nm(3), respectively) were still higher than the stationary emission limit of the Taiwan EPA (0.5ngI-TEQ/Nm(3)). The above results also suggested that additional APCDs, such as activated carbon injection in front of the filter are needed to enhance PCDD/F removal efficiency.     

Polychlorinated dibenzo-p-dioxin and dibenzofuran emissions from an industrial park clustered with metallurgical industries

Emissions of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) from an industrial park operated as Taiwan's center of metallurgical industries were investigated. The characteristics of mean PCDD/F I-TEQ concentrations, congener profiles and emission factors of each source were studied over samples of stack flue gases of individual sources. Different characteristics of congener profiles and large variations of emission factors of secondary aluminum smelters (ALSs) were observed. The mean emission factors of electric arc furnaces were comparable to those for ALSs and much greater than those of municipal solid waste incinerators and sinter plants, but still less than that of clinical waste incinerators. Annual PCDD/F emission contribution of each source was estimated, raising critical concerns over the overall PCDD/F emissions from metallurgical processes. The metallurgical industries altogether contributed approximately 98.1% of the total annual emissions, while waste incinerators only 1.9%. The contributions by sinter plants and metallurgical industries to the total annual emissions of the Park were much higher than the corresponding national averages of Taiwan. The combined dioxin emissions from the entire metallurgical processes and their controls should be seriously envisaged by industrial parks devoted to metal productions.     

Comparisons of levels of polychlorinated dibenzo-p-dioxins/dibenzofurans in the surrounding environment and workplace of two municipal solid waste incinerators

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in the surrounding environment (outdoor) and workplace air of two municipal solid waste incinerators (MSWIs, T and M) were characterized and compared. T and M represented two typical municipal solid waste incinerators in the north of Taiwan, which have different processes for controlling the PCDD/F emissions. The results of this study are summarized as follows. (1) The total PCDD/F and the total PCDD/F WHO-TEQ concentrations in the workplace air were 5-13 and 5-15 times higher than those in the outdoor air, respectively. Obviously, it is worthwhile to explore more on health risk assessment for exposure of PCDD/Fs emitted from MSWIs, particularly in the workplace air. (2) Mean total PCDD/F I-TEQ concentrations in the outdoor air ranged between 0.0216 and 0.155 pg I-TEQ/Nm(3) and averaged 0.0783 pg I-TEQ/Nm(3) (0.0828 pg WHO-TEQ/Nm(3)) during two seasons for two MSWIs, which were 6.5-fold higher than that of a remote site (0.0119 pg I-TEQ/Nm(3) or 0.0132 pg WHO-TEQ/Nm(3)) in Taiwan. However, the above outdoor air concentration levels in the MSWIs were still much lower than the air quality limitation of PCDD/Fs (0.6 pg I-TEQ/Nm(3)) in Japan []. (3) PCDFs were the primary toxicity distributors for PCDD/Fs in the outdoor air, since the ratios of PCDDs/PCDFs (I-TEQ) at all sampling sites ranged from 0.180 to 0.492 and were less than unity. (4) The OCDD, OCDF, 1,2,3,4,6,7,8-HpCDD and 1,2,3,4,6,7,8-HpCDF were the four dominant species in both workplace and outdoor air near MSWIs. (5) By spraying water on and wetting both the fly and bottom ashes, the mean total PCDD/F I-TEQ concentration in the workplace air was reduced 86.9% in the T MSWI. The above results indicate an appropriate improving action did inhibit the fugitive emission of PCDD/Fs and reduce the health risk of workers during work handling ashes in MSWIs.     

Emissions of polychlorinated dibenzo-p-dioxins and dibenzofurans from a heavy oil-fueled power plant in northern Taiwan

We measured the concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) from the flue gas and the ambient atmosphere of a power plant fueled by heavy oil in northern Taiwan. The mean emission concentration and I-TEQ concentration of total PCDD/Fs were 0.292 ng/Nm(3) and 0.016 ng I-TEQ/Nm(3), respectively. All PCDD/F emission concentrations in the flue gas were supposed to meet the Environmental Protection Administration Executive Yuan, R.O.C. standard (1.0 ng I-TEQ/Nm(3) from 2008). Furthermore, the mean I-TEQ concentration in the ambient atmosphere was 0.011 pg I-TEQ/Nm(3), which was much lower than the environmental quality standards for dioxins in Japan (0.6 pg TEQ/Nm(3)). Also, the PCDD/F emission factor was 0.188 ng I-TEQ/L fuel, which was comparable to the data issued in US EPA [EPA, Locating and estimating air emissions from sources of dioxins and furans, Office of Air Quality Planning and Standards, Research Triangle Park, NC, DCN No. 95-298130-54-01, 1997] (0.2 ng I-TEQ/L of fuel). Also, the result of the correlations of PCDD/Fs and operational parameters illustrated that the positively significant correlation (r=0.502, p=0.048) was found only between PCDD/Fs (I-TEQ) and the flue gas emission temperature (125-157 degrees C). However, PCDD-TEQ/PCDF-TEQ ratios were statistically significantly associated with the decreased flue gas flow (r=-0.659, p=0.006), moisture (r=-0.612, p=0.012) and flue gas temperature (r=-0.503, p=0.047). For proper environmental management of dioxins, it is necessary to establish a complete emission inventory of PCDD/Fs, and, in particular, the government should pay more attention to power plants to address the information shortage.     

Polychlorinated dibenzo-p-dioxins/dibenzofurans distributions in ash from different units in a municipal solid waste incinerator

This study determined the polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs) contents in ash in the super heater (SH), economizer (EC), semi-dryer absorber (SDA), fabric filter (FF), fly ash pit (FAP) and bottom residue (BR) in a municipal solid waste incinerator (MSWI). A high-resolution gas chromatograph/high-resolution mass spectrometer (HRGC/HRMS) was utilized for analyzing 17 PCDD/F species. Experimental results showed that average PCDD/F contents in ash samples from the SH, EC, SDA, FF, FAP and BR were 0.102, 0.788, 0.210, 1.95, 2.04 and 0.0218 ng I-TEQ g(-1), respectively. PCDD/F content was very low in the SH and BR due to high temperatures (around 461 degrees C in the SH and 914 degrees C in combustion chamber). Conversely, total PCDD/F content was significantly high in ash samples from the EC (around 340 degrees C), mainly because the temperature is within the favorable range of 250-400 degrees C for PCDD/F formation due to de nova reformation mechanisms. Although the SDA operated at 245 degrees C, the PCDD/F content decreased very significantly, mainly because the temperature was relatively low and because calcium carbonate was introduced into flue gases to dechlorinate and dilute chlorine-containing species. PCDD/Fs were captured by the active carbon in the FF. Furthermore, the duration that fly ash remained in the FF was longer than that for other incinerator units, and thus causing an increasing trend of PCDD/Fs level downstream (except the SDA). Total PCDD/Fs emission factors (microg tonnes-waste(-1); microg I-TEQ tonnes-waste(-1)) in ash samples from different units were: SH (42.3; 0.846), EC (326; 6.12), SDA (58.1; 1.10), FF (1540; 61.3), FAP (2950; 107) and BR (537; 4.31). Most PCDD/Fs in ash were contributed by the FF (about 56%), and the generation of PCDD/Fs in ash was significant (about 35%) during the transfer process from different units to the FAP. A strong and positive correlation in a logarithmic form existed between PCDD/Fs and chlorine (Cl(-1)) contents in ash. In Taiwan, the government policy for incineration residues advocates their reuse as road sub-bases or secondary building materials provided that total PCDD/Fs content is below the legal limit (1 ng I-TEQ g(-1)). Thus, ash with total PCDD/Fs content below the legal limit, such as that from the SH, EC, SDA and BR, can be collected and transferred to the FAP and reused. Ash with total PCDD/Fs content exceeding the legal limit, such as that from the FF, should be collected separately and be treated properly before being disposal in a landfill.     

Atmospheric dry deposition of polychlorinated dibenzo-p-dioxins and dibenzofurans in the vicinity of municipal solid waste incinerators

This study focuses on the atmospheric dry deposition flux of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in the vicinity of the two municipal solid waste incinerators (MSWIs) located in southern Taiwan. PCDD/Fs in ambient air were taken and analyzed for seventeen 2,3,7,8-substituted PCDD/Fs during November 2004 and July 2005. Results show that the mean concentrations of PCDD/Fs in the ambient air near MSWI-GS and MSWI-RW were 0.090 and 0.097pg I-TEQ/Nm(3), respectively. Dry deposition fluxes of total PCDD/Fs were 18.0 and 23.5pg I-TEQ/(m(2)d) in the ambient air near MSWI-GS and MSWI-RW, respectively, which were considerably higher than that measured in Guangzhou, China. Annual dry deposition fluxes of total PCDD/Fs in the ambient air near MSWI-GS and MSWI-RW were 189 and 217ng/(m(2)year), respectively, which were also much higher than dry deposition of total PCDD/Fs to the Atlantic Ocean. The results of the present study strongly suggest that exposure to PCDD/Fs in this area should be reduced. In addition, parametric sensitivity shows that dry deposition flux of PCDD/Fs is most sensitive to dry deposition velocity of the particle-phase, followed by air temperature and concentration of total suspended particulate but least sensitive to dry deposition velocity of the gas-phase.     

Evaluation of PCDD/Fs emission from fluidized bed incinerators co-firing MSW with coal in China

The levels and homologue profile of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) from stack gas of three typical fluidized bed incinerators co-firing municipal solid waste (MSW) with Chinese coal were measured. The PCDD/Fs emission was in the range of 0.0054-0.1961 ng I-TEQ/N m(3). Comparison of PCDD/Fs detection results by HRGC/HRMS and HRGC/LRMS suggested that it was feasible to detect fly ash with high PCDD/Fs concentration by HRGC/LRMS. Several factors on PCDD/Fs emission were discussed. The primary reason for the lower PCDD/Fs emission was the inhibition mechanism of relatively high sulfur in feeding coal on PCDD/Fs formation. The emission results also showed that there was no directly correlation between PCDD/Fs levels and CO, O(2) and HCl concentration in flue gas. It was estimated that about 0.1034 g I-TEQ was annually emitted to atmosphere from the tested three MSW incinerators (total daily treatment capacity is 800 tonnes MSW).     

Removal characteristics of PCDD/Fs by the dual bag filter system of a fly ash treatment plant

In this study, a dual bag filter system was established to decrease the concentration of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) in the stack flue gases of a fly ash treatment plant, which retained zinc from the fly ash of electric arc furnaces. Compared to the original single bag filter system with activated carbon injection (ACI) of 40 kg h(-1), the PCDD/F concentrations in the stack flue gas after the plant was equipped with the dual bag filter system dropped enormously from 3.38-7.73 ng I-TEQNm(-3) to 0.03 ng I-TEQNm(-3), and the total PCDD/F I-TEQ removal efficiency increased from 97.6% to 99.3% with ACI of 16 kg h(-1), that is, about 40% of the original AC usage. The AC utilization efficiency (0.560 mg I-TEQ absorbed kg ACI(-1)) of the dual bag filter system (AC: 16 kg h(-1)) was estimated about three times higher than that (0.192 mg I-TEQ absorbed kg ACI(-1)) of single bag filter system with ACI (40 kg h(-1)). The reason is that the particulate phase PCDD/Fs and some gas phase PCDD/Fs (captured by the recycled AC/ash mixture) were removed first by the first bag filter, and the rest of the gas phase PCDD/Fs were able to be adsorbed more completely by the AC/ash mixture due to a lower fly ash load, and then were removed by the second bag filter.     

Influence of memory effect caused by aged bag filters on the stack PCDD/F emissions

To our best knowledge, this study is the first research which investigates whether the PCDD/F memory effect could also be caused by bag filters. In this study, the PCDD/F characteristics of the flue gases in front of and behind the bag filters of one municipal solid waste incinerator (MSWI) and two electric arc furnaces (EAFs) were investigated to clarify the memory effect of PCDD/Fs and their influence on emissions. After the bag filters were operated for over four years, the PCDD/F concentrations in the stack flue gases were all higher than those prior to the aged bag filter, rendering a negative PCDD/F removal. This memory effect is because gaseous phase PCDD/Fs are released from the contaminated filters of the aged bag filters. The release of 2,3,7,8-TeCDF, 1,2,3,7,8-PeCDF and 2,3,4,7,8-PeCDF from the contaminated filters of the EAFs increased the PCDD/F concentration and their fractions in the stack flue gases. In contrast, the MSWI exhibited increasing fractions of 1,2,3,4,6,7,8-HpCDD, OCDD after flue gases passed through its aged bag filter. The activated carbon of the MSWI adsorbed more lower chlorinated-substituted PCDD/Fs in the raw flue gases, and the remaining higher chlorinated congeners gradually accumulated on the aged filters, and were released in lower PCDD/F concentration conditions.     

A novel method to enhance polychlorinated dibenzo-p-dioxins and dibenzofurans removal by adding bio-solution in EAF dust treatment plant

In order to understand the effect of different amounts of powder-activated carbon (PAC) injection and bio-solution (NOE-7F) addition on the removal efficiencies of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in a fly ash treatment plant with Waelz rotary kiln process, the PCDD/F concentrations in the stack flue gasses were measured and discussed. In the amount of 20, 40 and 50 kg/h PAC injection, the removal efficiencies of PCDD/Fs in the stack flue gas were 86, 96 and 97%, respectively. While adding more amounts of PAC did enhance the removal efficiencies, the reduction fractions of low chlorinated PCDD/F congeners were much higher than those of highly chlorinated PCDD/F congeners. Particularly, a lower amount of PAC injection (20 kg/h), not only cannot remove highly chlorinated PCDD/Fs, but also the carbon surface of the PAC can act as a precursor for the formation promotion of highly chlorinated PCDD/F congeners. The addition of NOE-7F in the raw materials had the dechlorination effect on the PCDD/F removal and mainly inhibited highly chlorinated PCDD/F formation. The combination of both PAC injection and NOE-7F addition has a high potential for practical application.     

Effect of MSW source-classified collection on the emission of PCDDs/Fs and heavy metals from incineration in China

Municipal solid waste (MSW) source-classified collection represents a change in MSW management in China and other developing countries. Comparative experiments were performed to evaluate the effect of a newly established MSW source-classified collection system on the emission of PCDDs/Fs (polychlorinated dibenzo-p-dioxins and dibenzofurans) and heavy metals (HMs) from a full-scale incinerator in China. As a result of presorting and dewatering, the chlorine level, heavy metal and water content were lower, but heat value was higher in the source-classified MSW (classified MSW) as compared with the conventionally mixed collected MSW (mixed MSW). The generation of PCDDs/Fs in flue gas from the classified MSW incineration was 9.28 ng I-TEQ/Nm(3), only 69.4% of that from the mixed MSW incineration, and the final emission of PCDDs/Fs was only 0.12 ng I-TEQ/Nm(3), although activated carbon injection was reduced by 20%. The level of PCDDs/Fs in fly ash from the bag filter was 0.27 ng I-TEQ/g. These results indicated that the source-classified collection with pretreatment could improve the characteristics of MSW for incineration, and significantly decrease formation of PCDDs/Fs in MSW incineration. Furthermore, distributions of HMs such as Cd, Pb, Cu, Zn, Cr, As, Ni, Hg in bottom ash and fly ash were investigated to assess the need for treatment of residual ash.     

Evaluation of PCDD/F partitioning between vapor and solid phases in MWI flue gases with temperature variation

Partitioning of PCDD/Fs (polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofuran) between vapor and solid phases in flue gas is affected by several factors including temperature variation. In this study, PCDD/F removal efficiencies achieved with activated carbon injection (ACI) and partitioning of vapor/solid phase PCDD/Fs in flue gases with temperature variation in a municipal waste incinerator (MWI) are evaluated via intensive flue gas sampling. Results indicate that most PCDD/Fs in flue gas downstream of the ACI+bag filter (BF) exist in vapor phase (over 90%) while the removal efficiencies of vapor and solid phase PCDD/Fs are 98.5-99.6% and 99.8-99.9%, respectively. The results of flue gas samplings also indicate that there is optimal operating temperature for PCDD/F removal achieved with ACI. Additionally, a pilot-scale adsorption system (PAS) is constructed in this study to evaluate the PCDD/F partitioning affected by temperature. The results of the PAS experimentation indicate that about 55% and 25% vapor phase PCDD/Fs passing through the filter cake (adsorbent) are transferred to solid phase at 150 and 200 degrees C, respectively. As the temperature is increased to 250 degrees C, filter cake (adsorbent) cannot effectively adsorb vapor phase PCDD/Fs and significant PCDD/Fs are formed via de novo synthesis.     

Approaches adopted to assess environmental impacts of PCDD/F emissions from a municipal solid waste incinerator

Different approaches were carried out in this work to assess environmental impacts of a municipal solid waste incinerator. A total of seven sites in the vicinity of the facility were chosen to collect air, banyan leaf and soil samples for analyses of PCDD/Fs by high-resolution gas chromatography/high-resolution mass spectrometry. Based on the PCDD/F concentrations of the three matrices determined at sites upwind, downwind and area of maximum ground concentration, it was found that the environmental impact of the MSWI was not obvious. PCDD/F concentration isopleths of the three environmental compartments coupled with wind rose of the region proved that the influence of the MSWI on the environment was also rather limited. It clarified emission sources by confirming that the PCDD/F concentrations originated mostly from the existing stationary emission sources in the vicinity. Through principal component and cluster analyses on congener profiles, the influence of metallurgical facilities and medical waste incinerators on the ambient air was assessed. Moreover, the modeling of ISCST3 demonstrated also that the contribution of the MSWI to ambient atmospheric PCDD/Fs was minimal. The approaches studied have led to identical conclusions, and thus are useful to cross-evaluate the environmental impact of an MSWI.     

Characteristic of polychlorinated dibenzo-p-dioxins and dibenzofurans in fly ash from incinerators in china

Fly ash from municipal solid waste (MSW), medical waste (MW) and electrical power plant (EPP) incinerators were analyzed for polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). The study showed that the PCDD/F levels in fly ash were EPP < MSW < MW. The homologue profiles of PCDD/Fs in fly ash produced from waste incinerators were similar. However, the homologue profiles of PCDD/Fs in fly ash from electrostatic precipitator (ESP) of electrical power plant were different from that from waste incinerator. The strong correlation was found between the concentration of 2,3,4,7,8-PeCDF and the I-TEQ value of fly ash regardless of the different fly ashes sources.     

Site-specific health risk assessment of dioxins and furans in an industrial region with numerous emission sources

While the sources of releasing dioxins have received much attention, the health risks of incinerators are studied considerably more than those of other sources, such as metallurgical industry. Furthermore, risk assessments focus primarily on the effects of single sources; few have addressed the aggregate risks from multiple sources in a region. When many sources of dioxins exist in an area, such as the Industrial Park located in the densely populated district—Siaogang District in southern Taiwan where 17 primary known PCDD/F stationary emission sources are clustered, is the aggregate exposure to these sources imposing high risks even though individual sources comply with emission standards? The study combined the multimedia and multiple pathway exposure modeling and site-specific exposure scenario to assess dioxin risks contributed by the 17 emission sources in the District, including municipal waste incinerators, medical waste incinerators, sinter plants, electric arc furnace, secondary aluminum smelters, cement kilns, etc. The average cancer risk of a resident living in the District was found to be 3.43E−04 under the site-specific exposure scenario. The top emission source is the sinter plant, followed by the electric arc furnace. The information has driven the local government to conduct more complete assessment and at the same time to consider enforcing a stricter local standard of dioxin emissions in the Siaogang District.     

Patterns and sources of PCDD/Fs and dioxin-like PCBs in surface sediments from the East River, China

The contamination status of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (DL-PCBs) was preliminarily investigated in surface sediments collected from the East River during April 2007. The contamination levels of PCDD/Fs and DL-PCBs ranged from 2.1 to 9.8 with mean concentration of 4.5 pg WHO₉₈-TEQ g⁻¹ and ranged from 0.042 to 0.45 with mean concentration of 0.19 pg WHO₉₈-TEQ g⁻¹, respectively. All sediments were characterized by the elevated levels of PCDDs, especially OCDD. Higher concentrations of PCDD/Fs were found in the sediments from Guangzhou and Dongguan. Source analysis revealed that PCDD/Fs in the sediments from Guangzhou were mainly from the secondary copper smelters and steel-making plants, and PCDD/Fs in the sediment from Dongguan were mainly from MSWIs. PCP and paper mills were unlikely to be the main sources.     

Polychlorinated dibenzo-p-dioxins/dibenzofuran mass distribution in both start-up and normal condition in the whole municipal solid waste incinerator

Although many researches focused on the polychlorinated dibenzo-p-dioxins/dibenzofuran (PCDD/F) emissions from stack, in the bottom ash and in the surrounding environment, researches focused on PCDD/F mass distributions in the whole incineration plant have seldom been addressed. This study determined PCDD/F emissions in the whole plant. A high-resolution gas chromatograph/high-resolution mass spectrometer was utilized for analyzing 17 PCDD/F species. Experimental results displayed that PCDD/Fs were formed during fly ash from super heater (SH), economizer (EC), semi-dryer absorber (SDA) and fabric filter (FF) was transferred to fly ash pit. Mass distribution ratios of PCDD/Fs in g I-TEQ (Toxicity Equivalency Quantity) per week from stack, SH, EC, SDA, FF, generation and bottom residue (BR) in start-up operations were 14.6%, 0.1%, 8.3%, 1.0%, 41.7%, 33.4% and 0.9%, respectively. Above results indicated that main PCDD/F source in the MSWI was from fly ash. However, the fly ash is easily controlled and PCDD/F emitted from stack flue gases will be difficult to be handled. Therefore, we should pay more attention on PCDD/F emission from flue gases especially from start-up procedure. Besides, fly ash should be controlled by sodium hypophosphite before being landfilled. MSWI did require further detoxification treatments for the solid residues and flue gases.     

Removal of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans by three coagulants in simulated coagulation processes for drinking water treatment

Surface water from Guangzhou to which standard polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) were added was treated by coagulation with ferric chloride (FC), polyaluminium chloride (PAC), and aluminium sulfate (AS) at optimum removal dosages for nature organic matter (NOM) to assess the polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) removal efficiencies. PCDD/Fs in suspended particulate matter (SPM) and treated water (TW) after coagulation were analysed. Low residual levels of PCDD/Fs were found in treated water after coagulation: 0.8% for FC, 0.9% for PAC, and 3.1% for AS. The removal efficiency calculated using these results was >99% for FC and PAC and 97-98% for AS. Most PCDD/Fs congeners could be removed by the three coagulation processes; the removal efficiency of FC and PAC was similar, and slightly higher than that of AS. The results also demonstrate that coagulation with FC preferentially removed tetra- and penta-substituted PCDD/Fs from raw water.     

Effects of calcium-based sorbents on PCDD/F formation from pentachlorophenol combustion process

Calcium-based sorbents are widely employed to reduce the acidic gases emission from combustion processes, and also have effects on trace organic pollutants formation and emission. Batch experiments were conducted to investigate the effects of calcium-based sorbents on pentachlorophenol (PCP) forming PCDDs/Fs during high temperature combustion processes. The results indicated that highly chlorinated PCDD/F homologues were the predominant dioxin products from PCP thermo decomposition, and only minor increasing of PCDDs happened when Ca/Cl ratio was lower than 1, while a major jump occurred when Ca/Cl ratio increased from 1 to 2. The CaO addition clearly promoted the production of all chlorinated dibenzo-p-dioxins homologue and 4-7DFs homologue. Comparison of total PCDD/F emission and its I-TEQ for three different calcium-based sorbents addition (CaO, CaCO3, basic fly ash) indicated that CaO and fly ash containing CaO had almost the same promotion effects on PCDDs/Fs originated from PCP, while CaCO3 inhibit PCDD/F formation greatly with inhibition efficiency up to 70%. Such effects may be partly proved by the observed clearly different micro-surface structures of their reaction residues. The mechanism of CaO on condensation and dechlorination reactions for PCP forming PCDDs and acid-base interaction were proposed to speculate the promotion effects of CaO, and the reaction precedence was used to speculate the inhibition effects of CaCO3 on PCDDs/Fs originated from PCP. The results of the present paper might be useful for the industrial application of calcium-based sorbents to control PCDD/F emission.     

Synergistic effect of transition metal oxides and ozone on PCDD/F destruction

Catalytic oxidations of PCDD/Fs (polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans) with ozone on the transition metal oxides (iron oxide or manganese oxide) at the temperature range of 120-180 degrees C were investigated. These two catalysts were prepared by precipitation methods. Iron oxide has a higher surface area (330 m(2)/g) than manganese oxide (53 m(2)/g). In the absence of ozone, the removal efficiencies of PCDD/Fs achieved with iron oxide or manganese oxide were between 83% and 85%, while the destruction efficiencies were only between 20% and 25% at 180 degrees C. It indicates that adsorption was the main removal mechanism of PCDD/Fs over these two catalysts. On the other hand, ozone addition greatly enhanced the catalytic activity of iron oxide or manganese oxide catalysts on the oxidation of gaseous PCDD/Fs. At 180 degrees C, the destruction efficiencies of gaseous PCDD/Fs achieved with iron oxide or manganese oxide with 100 ppm O(3) exceeded 90%. It indicates that catalytic ozonation achieved with iron oxide or manganese oxide is effective in decomposing PCDD/Fs and the application of ozone lowers the reaction temperature of PCDD/F oxidation below 200 degrees C. Furthermore, the synergistic effect of iron oxide and ozone is superior to that of manganese oxide due to the fact that the surface of iron oxide has more hydroxyl groups, which easily form hydrogen bonds with ozone and decompose to form atomic oxygen for the further reaction with dioxin molecules.