Removal of PCDDs/DFs and dl-PCBs in MWI fly ash by heating under vacuum

Temperature dependence of PCDD/DF and dioxin-like polychlorinated biphenyl (dl-PCB) concentrations in fly ash from a municipal waste incinerator (MWI) heated under vacuum has been investigated as a function of sample temperature ranging from T(s)=425 to 800 K to find out if PCDDs/DFs in fly ash evaporate and are trapped in a liquid nitrogen-cooled trap. The results show that more than 99.98% of PCDDs/DFs in TEQ is removed from fly ash by vacuum heat treatment at T(s)>650 K for 4 h. Almost no PCDDs/DFs were detected in the liquid nitrogen-cooled trap. Homologue distributions indicate that dechlorination/hydrogenation (DCH) reactions proceed in fly ash at T(s)>450 K. Arrhenius rate parameters for the DCH reactions have been determined for each homologue assuming that only DCH reactions occur. The fly ash heated under vacuum at 650 or 800 K was reheated at 573 K (300 degrees C) in a stream of dry or humid air to see how much PCDDs/DFs and dl-PCBs are regenerated. We have found that (1) PCDDs/DFs are regenerated in both 650 K and 800 K treated fly ash, whereas dl-PCBs are regenerated in 650 K treated fly ash, (2) formation of PCDFs predominates over that of PCDDs or dl-PCBs, and (3) less chlorinated homologues are abundant for PCDDs/DFs and dl-PCBs.     

Alumina as a model support in the formation and dechlorination of polychlorinated dibenzo-p-dioxins and dibenzofurans

Alumina was studied as a model matrix for formation and dechlorination reactions of PCDDs and PCDFs. Only small differences in PCDD and PCDF formation were found between de-novo synthesis on alumina and on fly ash. The amounts of PCDDs and PCDFs formed on acidic alumina were much larger than on neutral and alkaline alumina. OCDD and OCDF were rapidly dechlorinated on basic alumina.     

Effects of selected metal oxides on the dechlorination and destruction of PCDD and PCDF

OCDD and OCDF spiked silica/graphite based model fly ash containing various copper compounds and metal oxides were thermally treated under oxygen deficient conditions. All copper compounds tested showed a considerable dechlorination/hydrogenation reaction at 260 °C. After 30 min at 340 °C, less than 1% of the spiked OCDD and OCDF was recovered as T₄CDD/F to OCDD/F. Other compounds tested demonstrated a lower rate of dechlorination compared to the copper compounds. However, all other metal oxides showed a small dechlorination effect at 260 °C, which was considerably increased at 340 °C.

The model fly ash containing the different copper compounds or metal oxides showed comparable PCDD and PCDF isomer patterns after thermal treatment. However, small differences were observed among the different tested compounds. The PCDD and PCDF isomer patterns on the model fly ashes were similar to patterns found during dechlorination experiments on fly ashes from waste incineration processes.

Model fly ash containing Ca(OH)₂ exhibited the highest destruction potential, but a low dechlorination potential. In contrast, model fly ash containing any of the remaining compounds tested, was found to predominantly dechlorinate the spiked OCDD and OCDF.     

Dechlorination and destruction of PCDDs/PCDFs in fly ashes from municipal solid waste incinerators by low temperature thermal treatment

Dechlorination and destruction characteristics of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDDs/PCDFs) in fly ashes from commercial-scale municipal solid waste incinerators by low temperature thermal treatment using a laboratory-scale heating system were investigated. Experiments were carried out in reducing atmosphere at temperatures of 300 degrees C, 450 degrees C and 600 degrees C respectively, for the treatment time of 1h and 3h. Concentrations of PCDDs/PCDFs in raw fly ashes ranged from 35.5 to 107.3 microg kg(-1) (1.5-3.4 microg TEQ kg(-1)) and treated fly ashes ranged from 0.34 to 45.3 microg kg(-1) (0.012-1.63 microg TEQ kg(-1)). Concentrations of PCDDs/PCDFs in fly ashes treated at the different temperatures and times were observed to decrease with increase of treatment temperature and time by dechlorination or destruction. The distribution of octa- and hepta-chlorinated congeners were decreased and tetra-, penta- and hexa-chlorinated congeners were increased at 300 degrees C and 450 degrees C, but the distribution of octa- and hepta-chlorinated congeners were increased and tetra-, penta- and hexa-chlorinated congeners were again decreased at 600 degrees C. Total destruction efficiencies of PCDDs/PCDFs in fly ashes showed above 95% at the treatment temperature of 450 degrees C for 3h. However, removal efficiency of each congener in fly ashes varied, especially, 2,3,7,8-TeCDD and 1,2,3,7,8-PeCDD in fly ash A increased. And the dechlorination and destruction characteristics of PCDDs/PCDFs in fly ash A and B was different due to difference in contents of Ca-compounds and metal oxides such as CuO and PbO in fly ashes.     

PCDD/DF in leachates from Korean MSW landfills

We analyzed levels of PCDD/DF in leachate liquid and solid from five Korean municipal solid waste landfills to investigate the relationship between PCDD/DF and dissolved organic carbon and suspended solids in raw leachate. The concentrations of PCDD/DF ranged from 173.2 to 1329.4 pg/l and 4.1 to 46.22 pg-TEQ/l. The range of PCDD/DF was 123.2-1161.3 pg/l in leachate solid and 50.0-383.3 pg/l in leachate liquid. Our results indicated that PCDD/DF in solid play a major role in determining their concentration levels, and the distribution of isomers in solid was almost the same as in liquid leachate. In addition, highly chlorinated PCDD/DF, such as HpCDD/DF and OCDD/DF, accounted for more than 70% of all isomers. Levels of PCDD/DF in liquid were strongly correlated with dissolved organic carbon concentrations, which increase the leachability (R2 = 0.92 in Korean leachate) of PCDD/DF from contaminant sources. Despite this high linearity between dissolved organic carbon and dissolved PCDD/DF, we observed no strong relationship between dissolved organic carbon and solid phase PCDD/DF (R2 = 0.001). Dissolved organic carbon scarcely affects dissolved PCDD/DF to be combined with solids. As a result, it is not appropriate for incinerated ash to be dumped with municipal solid wastes, as they have a large potential to result in high levels of organic matter, and therefore PCDD/DF, in leachate.     

A pilot and field investigation on mobility of PCDDs/PCDFs in landfill site with municipal solid waste incineration residue

A field investigation by boring was carried out in a landfill site primarily with municipal solid waste incineration residue. From the collected core samples, vertical profiles of homologous content of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDDs/PCDFs) in the landfill layer were traced and the behavior of PCDDs/PCDFs was examined. In addition, a pilot-scale study was conducted on the PCDDs/PCDFs leached from incineration fly ash and the treated one using large landfill simulation columns (lysimeters) and the leaching behavior of PCDDs/PCDFs was examined. As a result, it was found that the coexistence of dissolved coloring constituents (DCCs), which might be composed of constituents like dissolved humic matters having strong affinity for hydrophobic organic pollutants, could enhance the leachability of PCDDs/PCDFs, thus contributing to the vertical movement and leaching behavior of PCDDs/PCDFs in the landfill layers of the incineration residue. Moreover, it is highly probable that DCCs derive from the unburned carbon in the bottom ash mixed and buried with the fly ash containing a high content of PCDDs/PCDFs.     

Isomer dependent bioavailability of polychlorinated dibenzo-p-dioxins and dibenzofurans from municipal incinerator fly ash to carp

The isomer dependent bioavailability of PCDDs and PCDFs from municipal incinerator fly ash to freshwater fish was determined. It was observed that carp exposed to fly ash in a continuous flow exposure readily accumulated select isomers of PCDDs and PCDFs. A preference for greater retention of isomers substituted in the 2, 3, 7 and 8 positions was observed. The Bioavailability Index (ratio of contaminant level in fish to level in fly ash) decreased with increasing degree of chlorination.     

Effect of matrix on heterogeneous phase chlorine substitution reactions for dibenzo-p-dioxin and HCl in air

Five materials were used in gas-solid phase reactions between dibenzo-p- dioxin(DD) and HCl in order to determine the role of organic and inorganic components in fly ash on chlorine substitution reactions of chlorinated dioxins. The five solids were: granular activated carbon, silica gel, diatomaceous earth, Tenax-GC, and fly ash. Conditions for reactions were 10 min at 150°C with 5% HCl in air. Extent of chlorination was measured using GC/MS analyses of extracts of fly ash after treatment processes and was expressed as the ratio monochloroDD/original unreacted DD. These ratios were: fly ash, 1.082; silica gel, 0.059; activated carbon, 0.024; and Tenax-GC, 0.001. Measurement of similar behavior on diatomaceous earth was impossible since starting material and possible products were irreversibly adsorbed completely. The major chlorinated dioxin produced under these conditions was 2-chlorodibenzo-p- dioxin which is the isomer favored through an electrophilic substitution mechanism.     

Dioxin contents in fly ash from large-scale MSW incinerators in Taiwan

In this study, fly ash samples were collected from three municipal waste incinerators (MWI) in Taiwan. These MWIs investigated are equipped with different air pollution control devices (APCDs). Preliminary results indicated that 2,3,7,8-PCDD/Fs homologue patterns of various types of fly ash were quite similar for all three MWIs. Concentrations of higher-chlorinated congeners of PCDDs and PCDFs were remarkably higher than those of lower-chlorinated congeners. In the case of MSW-A, the PCDD/PCDF ratios of ashes were found in the decreasing order for cyclone, boiler and baghouse. The PCDD/PCDF ratios in various types of fly ash of MWI-B was boiler-A < boiler-B < ESP < boiler-C. As for MSW-C, no obvious trend has been observed for PCDD/PCDF ratio. However, the ratio in boiler ash was higher than that in baghouse ash of MWI-A. The dioxin contents in fly ash would increase as the fly ash passed through APCD zones. In other words, the environmental conditions of APCD may actually cause the increase of the dioxin contents in fly ash. The trend for dioxin contents in fly ash collected from three MSW incinerators investigated was MSW-C < MSW-A < MSW-B.     

Dechlorination and destruction of PCDD,PCDF and PCB on selected fly ash from municipal waste incineration

The potential of fly ash to dechlorinate and destroy PCDD, PCDF and PCB was tested under oxygen deficient conditions in the laboratory. Specifically, two types of fly ash were compared, originating either from a fluidized bed incinerator using Ca(OH)₂ spray (FA1), or a stoker incinerator without Ca(OH)₂ impact (FA2).

Results from the present study indicate that on FA2 type fly ash, the degradation processes of OCDD, OCDF and D₁₀CB occurred primarily via dechlorination/hydrogenation up to temperature settings of 340 °C. In contrast, FA1 type fly ash was found to effect both dechlorination and destruction of these compounds already at temperature settings of 260 °C.

The dechlorination velocity of PCDD and PCDF did not differ significantly. However, the first dechlorination step of OCDF in the 1,9-position occurred faster compared to the first dechlorination step of OCDD.

The isomer pattern resulting from the dechlorination processes was quite similar on both FA1 and FA2, indicating that differences in alkalinity or elemental composition of the two types of fly ashes do not have a significant influence on the position of dechlorination. PCDD and PCDF dechlorination of the 2,3,7,8-positions was not favoured over dechlorination of the 1,4,6,9-positions on either type of fly ash. In contrast, dechlorination of PCB occurred predominantly on the toxicological relevant 3- and 4-positions.

The dechlorination/destruction processes were completed on both types of fly ash at 380 °C within one hour, which correlates well with results obtained from actual plant operation practices.     

Kinetics of OH radical reactions with dibenzo-p-dioxin and selected chlorinated dibenzo-p-dioxins

The pulsed laser photolysis/pulsed laser-induced fluorescence (PLP/PLIF) technique has been applied to obtain rate coefficients for OH + dioxin (DD) (k1), OH + 2-chlorodibenzo-p-dioxin (2-CDD) (k2), OH + 2,3-dichlorodibenzo-p-dioxin (2,3-DCDD) (k3), OH + 2,7-dichlorodibenzo-p-dioxin (2,7-DCDD) (k4), OH + 2,8-dichlorodibenzo-p-dioxin (2,8-DCDD) (k5), OH + 1,2,3,4-tetrachlorodibenzo-p-dioxin (1,2,3,4-TCDD) (k6), and OH + octachlorodibenzo-p-dioxin (OCDD) (k7) over an extended range of temperature. The atmospheric pressure (740 +/- 10 Torr) rate measurements are characterized by the following Arrhenius parameters (in units of cm3 molecule(-1) s(-1), error limits are 1 omega): k1(326-907 K) = (1.70+/-0.22) x 10(-12)exp(979+/-55)/T, k2(346-905 K) = (2.79+/-0.27) x 10(-12)exp(784+/-54)/T, k3(400-927 K) = 10(-12)exp(742+/-67)/T, k4(390-769 K) = (1.10+/-0.10) x 10(-12)exp(569+/-53)/T, k5(379-931 K) = (1.02+/-0.10) x 10(-12)exp(580+/-68)/T, k6(409-936 K) = (1.66+/-0.38) x 10(-12)exp(713+/-114)/T, k7(514-928 K) = (3.18+/-0.54) x 10(-12)exp(-667+/-115)/T. The overall uncertainty in the measurements, taking into account systematic errors dominated by uncertainty in the substrate reactor concentration, range from a factor of 2 for DD, 2-CDD, 2,3-DCDD, 2,7-DCDD, and 2,8-DCDD to +/- a factor of 4 for 1,2,3,4-TCDD and OCDD. Negative activation energies characteristic of an OH addition mechanism were observed for k1-k6. k7 exhibited a positive activation energy. Cl substitution was found to reduce OH reactivity, as observed in prior studies at lower temperatures. At elevated temperatures (500 K < T < 500 K), there was no experimental evidence for a change in reaction mechanism from OH addition to H abstraction. Theoretical calculations suggest that H abstraction will dominate OH reactivity for most if not all dioxins (excluding OCDD) at combustion temperatures (>1000 K). For OCDD, the dominant reaction mechanism at all temperatures is OH addition followed by Cl elimination.     

Leaching characteristics of PCDDs/DFs and dioxin-like PCBs from landfills containing municipal solid waste and incineration residues

To investigate the leaching characteristic of persistent organic pollutants (POPs), such as non-ortho and mono-ortho substituted chlorobiphebyls (dioxin-like PCBs), polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDDs/DFs), in leachate from municipal solid waste (MSW) landfill sites containing incineration residues, raw leachate samples were collected twice from 12 selected MSW landfill sites. The samples were divided into their liquid and solid phases using GF/B (pore size 1.0 microm), and the concentrations of POPs then determined. The concentrations of PCDDs/DFs ranged from 0.65 to 5.88 pg-TEQ/l (average 2.86 pg-TEQ/l), and those of dioxin-like PCBs from 0.05 to 0.32 pg-TEQ/l (average 0.18 pg-TEQ/l). The major congeners of leached PCDDs/DFs and dioxin-like PCBs in liquid and solid phases were OCDD (about 60%), 2,3',4,4',5-PeCBs (about 30%), and 2,3,4,4',5-PeCBs (about 54%). The relationship between landfill age and the leaching concentration of PCDDs/DFs, and effects of dissolved organic carbon (DOC) on the leaching of PCDDs/DFs are also discussed. Finally, a leaching prediction model of PCDDs/DFs from MSW landfills has been suggested using parameters, such as hydrophobic neutral organic carbons, total dissolved solid, and the ratio of non-biodegradable wastes in landfill sites.     

Novel evidence for natural formation of dioxins in ball clay

Elevated concentrations of dioxins in ancient ball clay from the Mississippi Embayment suggest natural formation of dioxins in the environment. Evidence for such natural formation in ball clay derives from unique congener profiles in undisturbed ancient clay deposits and from the lack of other anthropogenic contaminants. Here we present novel evidence of natural formation of dioxins based on congener-specific carbon isotopic analysis of octachlorodibenzo-p-dioxin (OCDD) in ball clays from the USA and Japan. The analyses were performed using a combination of double-column high performance liquid chromatography clean-up and two-dimensional gas chromatography-isotope ratio mass spectrometry. Elevated concentrations of OCDD found in ball clays from the USA and Japan were isotopically distinguished from the anthropogenic source materials (fly ash and pentachlorophenol) and environmental samples (sediment and soil). The isotopic signatures and the occurrence of OCDD in ancient ball clays deposited in the Tertiary Era provide evidence for the in situ formation of dioxins.     

Clearance of PCDD/Fs via the gastrointestinal tract in occupationally exposed persons.

A digestive tract mass balance was performed on six men with high body burdens of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). Intake via food was measured by analyzing duplicate portions of the food consumed by the volunteers and excretion via feces was determined by quantitative collection and analysis of the feces. Blood samples were taken to determine the current body burden. The results showed that the quantity of non-metabolized chemical excreted in the feces clearly exceeded the uptake via food for all of the 2,3,7,8-substituted PCDDs and some of the PCDFs, indicating a significant clearance across the gastrointestinal tract. The concentrations of these PCDD/F congeners in blood and feces were highly correlated (r > 0.8), demonstrating that the fecal PCDD/F content was determined by the body burden. The half lives in the test persons due to fecal clearance of non-metabolized chemical were estimated from the excretion rate and the current body burden and ranged between 10 years (Cl8DD) and 33 years (2,3,4,7,8-Cl5DF). These were compared with the overall contaminant half-lives due to all clearance processes which were calculated from the body burden and the decrease in blood concentrations measured over several years. The fecal clearance of non-metabolized PCDD/F contributed on average between 37% (2,3,7,8-Cl4DD) and 90% (Cl8DD) to the total elimination. This indicates that the gastrointestinal pathway plays a decisive role in the clearance of most 2,3,7,8-subsituted PCDD/F congeners.     

Changes in PCDD/PCDF formation processes during instationary phases of combustor operation--exemplified by the use of Cl4DD isomer patterns

In this paper results of various measurement campaigns at different municipal waste incineration (MWI) plants concerning the change of the PCDD/PCDF isomer distribution in the crude gas during transiently impaired combustion conditions are presented. The focus is on the Cl4DD isomer distributions exemplarily for all other homologue groups to demonstrate the change in PCDD/PCDF formation mechanism at transient combustion conditions. Additionally to crude gas samples, at one plant filter and boiler ash were investigated simultaneously to determine if there is any difference in the isomer distribution between the matrices. For the ash from an electrostatic precipitator (ESP ash), the boiler ash and the corresponding crude gas sample, nearly identical changes in the Cl4DD isomer distribution under transient combustion conditions in relation to the normal operation process could be detected. By comparing the Cl4DD isomer distributions from different incineration plants (two municipal waste incinerators and one little incinerator burning wood chips for heating domestic household) under transient combustion conditions, in all cases the 1,3,6,8- and 1,3,7,9-Cl4DD were dominating the isomer distribution, whereas under normal operation other isomers were predominant. Obviously PCDD/PCDF formation mechanisms under transient combustion conditions are independent from the type of incinerator and of the burned fuel, respectively. Data sets were analyzed with respect to the possible reaction mechanism via chlorophenols and a good correlation of 2,4,6-trichlorophenol during the second phase of a start-up process and during a CO experiment was found. To get more detailed information about possible formation mechanisms, at one plant the dependence of the PCDD/PCDF isomer distribution on the different matrices was studied. Separate analysis of fly ash collected at the boiler exit, subsequent gas phase, ESP ash and boiler ash under normal operation conditions showed that, apart from the fly ash, the Cl4DD isomer distributions are nearly the same in the different matrices. Surprisingly, the Cl4DD isomer distribution of the fly ash was more similar to the distributions found under transient combustion conditions.     

Investigations into the PCDD contamination of topsoil,river sediments and kaolinite clay in Queensland,Australia

Recent findings of elevated PCDDs from an unknown source in the coastal marine environment of Queensland, Australia has instigated further investigations into the distribution of, and environments associated with the PCDD contamination. This study presents data for OCDD concentrations in the coastal, mountainous and inland environment of Queensland. Additionally, full 2,3,7,8-substituted polychlorinated dibenzo-p-dioxins and dibenzofuran (PCDD/F) profiles from different land-use types and environments in the coastal region were analysed. Distinct east–west gradients were detected in topsoil collected from various bushland regions with elevated OCDD concentrations confined to the coastal region. However, PCDD/F results from topsoil and river sediments collected in the Queensland coastal region suggest that elevated OCDD concentrations cannot be attributed to any of the environments, land-use or industry types investigated. PCDD/F congener profiles from select samples were remarkably similar to those previously described in marine sediments collected along the entire Queensland coastline. In addition, kaolinite clay samples from Queensland exhibited elevated OCDD concentrations, and PCDD/F profiles in these samples were similar to those detected in kaolinite clays elsewhere. Natural formation processes have been hypothesised as the source of elevated PCDDs in Queensland and other locations, where similar PCDD/F profiles and the general lack of anthropogenic sources are evident. This study presents additional data supporting this hypothesis and provides further information that may assist in the identification of the processes involved in the natural formation of PCDDs.     

Release of mercury vapor from coal combustion ash

The long-term stability of Hg in coal combustion by-products (CCBs) was evaluated at ambient and near-ambient temperatures. Six CCB samples with atypically high levels of total Hg were selected for study assuming a greater potential for release of measurable amounts of Hg vapor. The samples selected included two fly ash samples from U.S. eastern bituminous coal, two fly ash samples from South African low-rank coal, one fly ash from Powder River Basin (PRB) subbituminous coal blended with petroleum coke, and one PRB subbituminous coal fly ash incorporated with flue gas desulfurization material. Air scrubbed of Hg was passed through compacted 100-g aliquots of each sample at 1 mL/min and vented to a gold-coated quartz trap to collect released Hg vapor. The samples were maintained at ambient and near-ambient (37 degrees C) temperatures. All samples released low-picogram levels of Hg after 90 days. No pattern was evident to link the total Hg content to the rate of release of Hg vapor. An average of 0.030 pg Hg/g CCB/day was released from the samples, which equates to 2.2 x 10(-8) lb Hg/ton CCB/year. If this were applied to a coal-fired power plant production of 200,000 tons of fly ash per year, there would be a maximum potential release of 0.0044 lb, or 2.00 g, of Hg per year. Experiments are continuing to determine long-term vapor release of Hg from CCBs. All samples have been set up in duplicate at ambient temperature with an improved apparatus to reevaluate results reported in this article.     

The effect of metal catalysts on the formation of polychlorinated dibenzo-p-dioxin and polychlorinated dibenzofuran precursors

The catalytic effects of copper and iron compounds were examined for their behavior in promoting formation of chlorine (Cl₂), the major chlorinating agent of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs), in an environment simulating that of municipal waste fly ash. Formation of Cl₂ occurred as a result of a metal-catalyzed reaction of HCl with O₂. Catalytic activity was greatest at a temperature of approximately 400 °C, supporting a theory of de novo synthesis of PCDDs and PCDFs on fly ash particles downstream of waste combustion.     

Study of PCDD/Fs distribution in fly ash,ash deposits,and bottom ash from a medical waste incinerator in China

Over the past decades in China, the number of medical waste incinerators (MWIs) has been rising rapidly, causing emissions of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). In this study, samples of fly ash, ash deposits, and bottom ash from typical MWIs were analyzed for PCDD/Fs and their distribution characteristics. Results showed international toxic equivalent (I-TEQ) values in the range of 6.9–67 ng I-TEQ/g in fly ash and ash deposits, whereas the concentration in bottom ash was extremely low (only 1.33 pg I-TEQ/g), yet the generation of PCDD/Fs was mostly de novo synthesis in fly ash and ash deposits according to the ratio of PCDFs to PCDDs; the major distribution differences of PCDD/Fs in fly ash was manifested by the content of toxic furan 2,3,7,8-TCDF, but other toxic PCDD/Fs showed similar distribution. Other findings are that 2,3,4,7,8-PeCDF had the most contribution to TEQ concentration, and that the most abundant toxic furan congener is 1,2,3,4,6,7,8-HpCDF. Correlation analysis showed that there was no significant correlation between PCDD/Fs concentration and several other physical and chemical parameters.

Implications: This paper is of interest because it presents the emission performances of PCDD/Fs in ash from medical waste incineration in China. PCDD/F contents in fly ash and ash deposits vary between 6.9 and 67.3 ng I-TEQ/g. However, the concentration in bottom ash was extremely low (only 1.33?×?10^?3 ng I-TEQ/g). The fingerprints of PCDD/Fs in fly ash are almost similar, except for 2,3,7,8-TCDF. There is no marked correlation between PCDD/Fs and other physicochemical properties.

Supplemental Materials: Supplemental materials are available for this paper. Go to the publisher's online edition of the Journal of the Air & Waste Management Association.     

The study on the dechlorination of OCDD with Pd/C catalyst in ethanol-water solution under mild conditions

Dechlorination of octachlorodibenzo-p-dioxin (OCDD) was carried out in ethanol-water (v/v=1:1) solution of NaOH in the presence of Pd/C catalysts with the use of H(2). The substrate was dechlorinated with Pd/C under mild conditions (atmospheric pressure and <100 degrees C) to give a chlorine-free product, dibenzo-p-dioxin (DD), in high yields. After reaction of 3h at 50 degrees C, 95.9% OCDD was degraded to low dechlorinated congeners and the yield of DD was 77.4%. We have also studied the dechlorination selectivity of chlorine atoms on the different substituted positions and postulated the dechlorination pathway of OCDD. For OCDD, the 2-position has higher reactivity than 1-position, but the difference is very small. From the distribution statistics of the intermediates during the reaction, we postulate that the steric effect plays an important role during the reaction and affect the dechlorination pathway of OCDD.