Environ. Sci. Technol.

2009, 43, 368–373

is a very effective oxidizing agent, research on the role of iron
Ferric Oxide Mediated Formation of has focused on the destruction rather than the formation of
PCDD/Fs from 2-Monochlorophenol PCDD/Fs (21-25).
Our recent work on the mechanism of chemisorption of
phenols and other substituted aromatic species on transition-
SHADRACK NGANAI, SLAWO LOMNICKI, metal surfaces suggests that reactions involving iron oxide
AND BARRY DELLINGER† have the potential to be a significant source of PCDD/F
Department of Chemistry, Louisiana State University, emissions (26). Specifically, substituted aromatic species
Baton Rouge, Louisiana 70803 chemisorb to metal oxide or hydroxide surface sites to form
a phenoxyl-type, persistent free radicals (PFRs) (27, 28). These
Received May 9, 2008. Revised manuscript received surface-associated phenoxyl radicals can then react with each
October 6, 2008. Accepted October 27, 2008. other to form PCDD/Fs and other products (29, 30).
Consequently, we have performed a study of the formation
of PCDD/Fs and other reaction products from a 2-monochlo-
rophenol (2-MCP) precursor over a surface of iron oxide
The copper oxide surface-mediated formation of polychlorinated supported on a silica substrate. This study was performed
dibenzo-p-dioxinsanddibenzofurans(PCDD/Fs)fromprecursors using a temperature-controlled packed-bed flow reactor
such as chlorinated phenols is considered to be a major source interfaced to an in-line gas chromatography-mass spec-
of PCDD/F emissions from combustion sources. Even though trometry (GC-MS) instrument for product analysis using
iron oxide is present at 2-50 times higher concentrations than conditions identical to those used in our previously reported
studies of PCDD/F formation from 2-MCP over a copper
copper oxide, virtually no studies of the iron oxide mediated
oxide/silica surface (31). Although a much wider range of
formation of PCDD/Fs have been reported in the literature. We reaction environments and compositions of fly ash exist in
have performed packed-bed, flow-reactor studies of the full-scale combustors, the conditions in this study are
reaction of 50 ppm gas-phase 2-monochlorophenol (2-MCP) comparable to those used in the published literature and
over a surface of 5% iron oxide on silica over a temperature range allow direct comparison of the roles of iron oxide and copper
of 200-500 °C. Dibenzo-p-dioxin (DD), 1-monochlorodibenzo- oxide in the formation of PCDD/Fs under specific, well-
p-dioxin (1-MCDD), 4,6-dichlorodibenzofuran (4,6-DCDF), defined combustion conditions.
and dibenzofuran (DF) were formed in maximum yields of
0.2%, 0.1%, 0.3%, and 0.4%, respectively. The yield of PCDD/Fs Experimental Section
over iron oxide peaked at temperatures 50-100 °C higher in Surface-mediated reactions of 2-chlorophenol over Fe2O3/
temperature than they peak over copper oxide. The maximum SiO2 were studied using the System for Thermal Diagnostic
yields of DD, 1-MCDD were 2 times and for 4,6-DCDF was 5 Studies (STDS), which is described in detail elsewhere (32).
times higher over iron oxide than over copper oxide, whereas Briefly, the system is composed of a thermal reactor located
in a high-temperature furnace housed within a GC oven that
DF was not observed at all for copper oxide. The resulting PCDD/
facilitates precise temperature control as well as reproducible
PCDF ratio was 0.39 for iron oxide versus 1.2 observed copper sample introduction. A computer-interfaced control module
oxide, which is in agreement with PCDD/PCDF ratios in full- is used to set and monitor all experimental parameters. A
scale combustors that are typically ,1. The combination of 2-50 GC-MS system is interfaced in-line with the thermal reactor
times higher concentrations of iron oxide than copper oxide for chemical analysis of the reactor effluent.
in most full-scale combustors and 2.5 times higher yields of PCDD/ We and others have reported multiple studies of the gas-
Fs observed in the laboratory suggests that iron oxide might phase reactions of 2-MCP and other chlorinated phenols.
contribute as much as 5-125 times more than copper oxide to These studies clearly demonstrate that 2-MCP does not
the emissions of PCDD/Fs from full-scale combustors. decompose in the gas phase until above 500 °C and that
gas-phase reactions are unimportant over the 200-500 °C
range of this study (33).
Introduction Catalyst Preparation. The iron oxide catalyst was pre-
Combustion is the dominant source of polychlorinated pared to allow direct comparison with results for copper
dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in the oxide previously published in the literature (31, 34-36).
environment (1-5). It is believed that ∼70% of PCDD/F Accordingly, it was prepared using the same method,
emissions are due to transition-metal-mediated surface materials, and metal oxide concentration. Model fly ashes
reactions in the postflame, cool zone at temperatures between were used for several reasons.
300 and 500 °C (6-8). It is very difficult to discern the effect of a specific metal
Previous research has focused on copper oxide mediated within the complex mixture contained in a typical fly ash
formation from elemental carbon (“de novo” pathway) (9-11) generated in a combustion system, and it is impossible to
and chlorinated phenols (“precursor” pathway) (12-14). The compare the results to those for pure iron or copper oxide.
focus on copper oxide is likely the result of its significant In addition, the combustion-generated fly ashes typically
concentration in municipal waste incinerators, where PCDD/ used in these studies are collected at the end of the
Fs were first discovered in combustion systems, and the well- combustion system after they have been exposed to multiple
known redox activity of copper oxides (15-17). However, organics, and their activities might be altered compared to
iron oxide, which is also redox-active, is almost always the that of fresh, in situ generated fly ashes. Finally, these fly
highest-concentration transition metal in combustion sys- ashes are representative only of the specific system being
tems (18-20), and one might expect iron to mediate or studied under the operating conditions at the time of
catalyze the formation of PCDD/Fs. Probably because iron collection. Thus, to compare their relative reactivities, we
chose to use model systems of pure iron oxide/silica and

Corresponding author e-mail: barryd@lsu.edu. copper oxide/silica.
368 9 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 43, NO. 2, 2009 10.1021/es8022495 CCC: $40.75  2009 American Chemical Society
Published on Web 12/11/2008

The yields of chlorophenols were generally The yield curves presented in the graphs are the results of higher than those of chlorobenzenes and included 2. which was operated in the 2-MCP over an Fe2O3/silica surface. the formed (in moles). The products of reaction were analyzed using an in-line Agilent 6890 GC-MSD system.and mathematical fits generated by Igor. Results and Discussion The yields of the products were calculated using the expression The temperature dependence of the surface-mediated py- rolysis of 2-MCP over Fe2O3/SiO2 and the yields of major yield ) ( [product]A [2-MCP]0 )× 100 organic products are presented in Figures 1-3 (also see Table 1 in the Supporting Information).3.6. NO. The sample was allowed to age for 24 h at room temperature and dried at 120 °C for 12 h before calcination in air for 5 h at 450 °C.) software. it is generally accepted by the scientific community for laboratory studies of PCDD/F formation (39-41). All data organics). yield of 0. Each data point analyzed quantitatively in this study (CO.4.4-DCP + 2. which corresponds to a particle size of 125-150 µm. the catalytic material was oxidized in FIGURE 1. all transfer lines were maintained at a constant temperature of 180 °C. full-scan mode from 15 to 350 amu for the duration of the GC run. resulting in almost complete 2-MCP (in moles) injected into the reactor. Yields of chlorobenzenes from the pyrolysis of Agilent 5973 mass spectrometer.6- VOL. Consequently. This is due to the high temperature and oxygen-rich environment in the flame in which the metals are vaporized or entrained. 2009 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 9 369 . CO2. Above 350 °C. 2-monochlorophenol (2- MCP) (Aldrich).25-m-i.6-DCP) with a maximum were used to calibrate the MS response for all products. All data are for a precursor reaction time of 1 h over the catalytic bed with concomitant collection of the products on the head of capillary column.3-cm-i. and A is the molar degradation of 2-MCP by 500 °C. Silica gel powder (Aldrich. followed by a temperature- programmed ramp from -60 to 300 at 10 °C/min. Product Analysis.. [2-MCP]0 is the initial concentration of reaction rapidly accelerates. iron-rich fly ash. a 30-m-long.4% at 350 °C. was introduced into the flow stream using a digital syringe pump (KD Scientific. Although suboxides of some metals have been reported. 0. 90% of the 2-MCP undergoes surface- where [product] is the concentration of specific product mediated decomposition (cf. 43. not is formed from two 2-MCP molecules). In fact. 2. The sample was then ground and sieved to a mesh size of 100-120. Fifty milligrams of the resulting 5% iron(III) oxide/silica catalyst was placed between quartz wool plugs in a 0. The reactant.d.4. 0. stoichiometric factor (2 in this case.3. The method of incipient wetness was used to prepare the catalytic material that serves as a surrogate for combustion- generated. Prior to each experiment. the principal oxide of copper or iron in a combustor is expected to be the highest oxidation state. For product separation. However. Nitrogen was used as a carrier gas. Detection and quantification of the products were obtained on an FIGURE 2. model-100) through a vaporizer maintained at 180 °C.and 2. Yields of phenols from the pyrolysis of 2-MCP over situ at 450 °C for 1 h at an air flow-rate of 5 cm3/min to an Fe2O3/silica surface. our samples of Fe2(III)O3 and Cu(II)O represent the majority of both metals in most combustion systems (37). C2 and C3 reflects an average result of three experimental runs. robenzenes. and the rate of injection was selected to maintain a constant concentration of 50 ppm of 2-MCP for temper- atures ranging from 200 to 550 °C. activate the surface. as one PCDD/F molecule Apart from the lower-molecular-weight products. The precursor concentration was higher than usually observed in stack measurements at full-scale facilities (38). A water solution of iron(III) nitrate (Aldrich) was used to prepare a catalyst of 5% iron(III) oxide on silica. Figure 1). grade 923 100-200 mesh) was introduced into the solution of iron(III) nitrate in the amount for incipient wetness to occur.0 (Wave Metrics Inc. At the lowest temperature studied (200 °C). the use of the STDS in our studies allowed us to lower the precursor concentration to below that typically reported in the literature. The overall flow rate of the reaction gas stream was maintained at 5 cm3/min.6-dichlorophenol (2. To avoid condensation of the reaction products. because of low reaction yields. the main products were chlorophenols and chlo- were plotted using Igor Pro 6. Reaction Conditions.d. 2. fused silica reactor in the STDS.6-trichlorophenol (2.25-µm-film-thickness column was used (Restek RTS 5MX) with a temperature hold at -60 °C for the reaction period. Quantitative standards 2.

Other chlorobenzenes detected were monochlo.3-TriCBz). This is not the case for benzene.1% yield at 350 °C. Scheme 1). This is reflected in the formation of polychlorinated this temperature should be considered to be undestructed phenols and polychlorinated benzenes (cf. We recently performed EPR 2).1% at 300 and 350 In fact. with a <0. elimination of both H2O and HCl (lower path in Scheme 1) Among chlorobenzene products.2. 4. The maximum yields of compared to CuO/silica. The mechanism of the chlorination reaction increasing temperature. Sub. Table 1).2. 4. and 1.6-DCDF).2. to that of copper oxide. Thus.4-TeCBz + 1. it has 370 9 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. These observations suggest strong detected in trace quantities. respectively. SCHEME 1 Hydroxyl groups are present on almost every terminal plane of metal oxides as a completion of unsatisfied charges and valences of metal ions at terminal positions (26. and biphenyl were also 350 °C (cf. 31.3 mol %).3. with a and metal center (Cu2+ for CuO). magnetic resonance spectroscopy (EPR) (43) and X-ray with a 1.3% maximum yield at 450 °C. The formation of gas-phase chlorinated benzenes can hydrogen bonding of the copper oxide terminal hydroxide result from scission of the carbon-oxygen bond to form a groups and the phenol hydroxide substitutents (28). 1. and Destructive Desorption of a weak or partial metal-oxygen bond of intermediate II on Fe2O3/Silica. indicating the formation of benzene of adsorbed species has never been experimentally dem- as a reaction product (cf. Based on previous experimental results. benzene (1-MCDD). PCDD/F yields from the pyrolysis of 2-MCP over an interaction with gas-phase 2-MCP is expected to be similar Fe2O3/silica surface. even yields of 0. Their formation is probably zofuran (DF) were all detected as the products of 2-MCP related to the stronger oxidative properties of Fe2O3/silica pyrolysis over Fe2O3/Silica surface.4. 1-monochlorodibenzo-p-dioxin Significant quantities of dechlorination products.9% maximum yield at 500 °C) We have previously demonstrated using electron para- and tetrachlorobenzenes (1. Benzene (Bz) was formed associated with the concomitantly formed reduced metal with a constant yield of ∼0. Chlorination.5-TeCBz.3% and 0. 40% more 2-MCP reacted over Fe2O3/ °C. and its concentration bound to the surface and can undergo multiple chlorination declined with increasing temperature.1% from 300-550 °C (cf. onstrated. Figure that are very potent chlorinating agents (26.3.2.6-DCDF and 1-MCDD were 0. though the rapid destruction of 2-MCP was not initiated until Chloronaphthalene. 2.4% maximum yield at 500 °C) were the highest (cf. that are (PCBz). chemisorption have been identified for chlorophenols: (1) and phenol with a maximum yield of 1. are robenzene (MCBz). mechanism is the formation of surface hypochlorite species comparable to the yields of chlorinated benzenes (cf. case of CuO. the yields of hexachlo.6-TCP) with a maximum yield of 7.6-dichlorodibenzofuran (4. at 200 °C. 42). We and others have suggested that the most likely At 200-250 °C. respectively. carbon-oxygen bond seems improbable. the resulting chemisorbed species. whereas DD and DF exhibited maximum silica (90% at 200 °C) than over CuO (50% at 200 °C). were also formed.0% at 250 °C. nevertheless. and phenol. robenzene (HCBz. 43. Iron oxide is no different than other metal oxides.3-trichlorobenzene (1. significant yields PCDD/Fs were observed. reactant. III. 2009 . absorption near-edge spectroscopy (XANES) (42) that. (43). with a 0. However. in the Figure 2). In our previously reported studies.2-DCBz and Bz were detected even at of persistent free radicals as low as 150 °C. Gas-phase chlorinated phenols are formed by the scission Adsorption. resulting in the formation 0. whose measured as was also observed for the CuO/silica system studied concentration increased by 2 orders of magnitude with previously (31).2. Figure 1). its presence at reactions.4-TriCBz + 1.3% at 350 °C (cf. 42). we in Scheme 1 to form a free chlorophenoxyl radical that is demonstrated using FTIR spectroscopy that chlorinated converted to a chlorinated phenol by scavenging a hydrogen phenols chemisorb to the surface of copper oxide by initial atom. Figure 2). 31. Dibenzo-p-dioxin (DD). and its FIGURE 3.2. NO. species II. 3). free chlorophenyl radical that scavenges a hydrogen to form sequent elimination of water and HCl above 150 °C leads to chlorobenzenes. naphthalene.2-DCBz was present in the 2-MCP reagent The chemisorbed chlorophenoxy species are strongly as a minor contaminant (0. analyses of samples of Fe2O3/silica dosed with 2-MCP and Each of these products was formed at temperatures as confirmed behavior similar to that on CuO with the formation low as 250 °C. two pathways of TCP + 2.2 and 0. 1. with yields that increased with adsorption and retention of the adsorbed 2-MCP on the increasing temperature to a maximum at 450-500 °C (cf. elimination of H2O (upper path in Scheme 1) and (2) Figure 1). and pentachlorobenzene of persistent free radicals. 200 °C. and V.4% at 400 and 450 °C.4.1% yield at 250 °C. Figure centers (Cu1+ for CuO) (43. Figures 1 and 2). with a <0. surface of Fe2O3/silica. The scission of the seemingly stronger the formation of a chemisorbed phenoxide (cf. I and IV. 44).and subject to electron transfer between the adsorbed molecule 1. and diben.

2. DF was not observed for copper Formation of unchlorinated phenol or benzene from oxide at all. pathway in Scheme 1 to form 2-chlorophenoxyl radical is The higher yield of phenol again suggests that the cleavage dominant. The formation whereas the bidentate species reacts further at temperatures of DD. PCDFs were the dominant 2-MCP over Fe2O3/silica (s) and CuO/silica ( · · · ) surfaces. various The bidentate intermediate V depicted in Scheme 1 can form a surface-associated phenoxyl radical. with 4. products. 4. 47). VOL. species VIII-XII) by a mechanism similar to that previously proposed for formation the of 4. Such a 2-chlorophenoxyl reactions were DD. Of course. 43. In contrast. 2-MCDD. oxide surfaces can both mediate the formation of PCDD/Fs However. The scission different chemisorption mechanisms. 2009 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 9 371 . which is formed at lower temperatures. and 4. For copper oxide.5 times greater over iron oxide than FIGURE 4.6- reaction occurs when adsorption proceeds through the lower DCDF. yields were comparable. two chemisorption of the weaker partial metal-oxygen bond is preferred. radical is likely by mechanisms previously described by us Implications for Full-Scale Emissions. reactions are evident: (1) the upper pathway in Scheme 1 Surface-associated or gas-phase byproducts of the decom. In the case of iron oxide. the maximum yield of total PCDD/Fs is 2. This back-electron transfer occurs at 400-450 °C. Copper. which then converts to the keto mesomer. VII. such as carbonyls and olefins.vs Iron-Mediated Formation of PCDD/Fs. most combustion Fe2O3/silica surfaces. In the scission of the carbon-oxygen bond needed to form contrast. NO. provide pathway in Scheme 1 where the bidentate species is formed. VI. Surface-Mediated PCDD/F Formation. Our current results indicate that iron is also a mediator of the formation of PCDD/Fs. systems have regions of pyrolysis and oxidation. and the only PCDD/F products detected for 2-MCP requires removal of a chlorine substituent.6-DCDF (formed from 2-chlorophenoxyl the higher yields of chlorinated phenols indicate that scission radical) dominating at temperatures less than 350 °C and DF of the weaker partial metal-oxygen bond is preferred over (formed from phenoxyl radical) dominating above 350 °C.6-DCDF from chlorophenoxyl radical (34-36). and 4.SCHEME 2 been observed experimentally for phenols (45). as evidenced by the maximum in both the phenol and DF formation curves. the of two carbon-oxygen bonds of V followed by scavenging chemisorption at the hydroxyl constituent through the upper of two hydrogen atoms results in the formation of benzene. Comparison of PCDD/F yields from the pyrolysis of over copper oxide. Iron and copper for the reaction of 2-MCP over a CuO/silica surface (31). Figure 4 presents a comparison of the PCDD/F product yields over copper oxide and iron oxide surfaces under otherwise identical conditions. 1-MCDD. Two of the surface-associated keto mesomers then react to form DF (Scheme 2. through back- electron transfer as depicted in the initial step in Scheme 2. for copper oxide. However. The 2-chlorophenoxyl radical proceeds to form 4. The scission of one carbon-oxygen bond These data indicate that the differences in PCDD/F and one metal-oxygen bond in intermediate V followed by formation over copper and iron oxides surfaces result from scavenging of hydrogen atoms forms phenol.6-DCDF in the postcombustion cool zones of combustion systems imply an additional mechanism of formation of PCDFs over under pyrolytic conditions. Over iron oxide. The majority of laboratory studies of the surface-mediated formation of PCDD/Fs have focused on copper and copper oxide (9-11. the source of hydrogen atoms for scavenging. 46.6-DCDF. path of Scheme 1.6-DCDF from 2-chlorophenoxyl above 350 °C to produces phenoxyl radical that forms DF. where 2-chlorophenoxyl radical is formed and (2) the lower position of 2-MCP. Based on a comparison of our data with data generated under comparable conditions for CuO. the PCDD and PCDF product chlorinated benzenes. the formation of DF and higher yields of 4.6-DCDF exhibits a maximum yield at 300 °C and is formed directly from the initially formed chlorophenoxyl radical.

The observation of the formation of PCDD/Fs over iron 1991.. T. E. Technol. N. 81. Response to comment on “Global Pitea. of PCDF formation. 15. Kobayashi. Environ. Takeuchi.. Taylor Chair held by B. Sci. R. Mechanisms of formation and destruction This work was partially supported by the National Institute of polychlorinated dibenzo-p-dioxins and dibenzofurans in of Environmental Health Sciences through Grant RO1 heterogeneous systems. Environ.. Table 3 in the Supporting Information) (12) Hatanaka. resulting in destruction rather than formation of 30. 18.. S. On the de- should still be valid. An initial study of the fine fragmentation fly ash as the current models significantly overpredict PCDD particle mode generated during pulverised coal combustion.5 times higher for iron oxide (7) Ismo. Technol. F. iron (23) Kasai. K. Tsubota. 776–785. iron could result in 5-125 times more PCDD/Fs than copper. McCausland. Addink. (16) Altwicker. Thermal formation of PCDD/PCDF: A survey. 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