Role of Fe2O3 in fly ash surrogate on PCDD/Fs formation from 2-monochlorophenol.
ABSTRACT: The correlation between the content and morphology of Fe2O3 and the yields of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) was studied in this work. Three fly ash surrogates containing 1%, 2.5%, and 4% of Fe2O3 were prepared and their effects on PCDD/Fs formation were investigated and compared to our previously studied 5% iron oxide sample using 2-monochlorophenol precursor model. As the intermediate of PCDD/Fs, environmentally persistent free radical formation propensity was correlated with the PCDD/Fs formation yields for different iron oxide samples. PCDD/Fs yield increases exponentially with the increasing iron content under pyrolytic conditions. On the contrary, low iron oxide content promotes oxidation and lowers yields of PCDD/Fs. Changing iron oxide clusters' morphology (crystallinity and cluster size) affects the mechanism of PCDD/Fs formation - on larger crystallites, a bidentate chemisorption of precursor is preferred leading to lower chlorinated congeners, while smaller clusters promote formation of PCDFs through mixed monodentate-bidentate surface species, resulting in formation of congeners with 1 chlorine more. This study further confirms the propensity of iron oxide to predominantly form PCDFs. The iron content also defines PCDDs:PCDFs ratio.
Project description:Transition metal oxides present in waste incineration systems have the ability to catalyze the formation of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) through surface reactions involving organic dioxin precursors. However, studies have concentrated on the catalytic effects of individual transition metal oxides, while the complex elemental composition of fly ash introduces the possibility of synergistic or inhibiting effects between multiple, catalytically active components. In this study, we have tested fly ash surrogates containing different ratios (by weight) of iron (III) oxide and copper (II) oxide. Such Fe2O3/CuO mixed-oxide surrogates (in the Fe:Cu ratio of 3.5, 0.9 and 0.2 ) were used to study the cooperative effects between two transition metals that are present in high concentrations in most combustion systems and are known to individually catalyze the formation of PCDD/Fs. The presence of both iron and copper oxides increased the oxidative power of the fly ash surrogates in oxygen rich conditions and led to extremely high PCDD/F yields under pyrolytic conditions (up to >5% yield) from 2-monochlorophenol precursor. PCDD/F congener profiles from the mixed oxide samples are similar to results obtained from only CuO, however the total PCDD/F yield increases with increasing Fe2O3 content. Careful analysis of the reaction products and changes to the oxidation states of active metals indicate the CuO surface sites are centers for reaction while the Fe2O3 is affecting the bonds in CuO and increasing the ability of copper centers to form surface-bound radicals that are precursors to PCDD/Fs.
Project description:The copper oxide surface-mediated formation of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs)from precursors such as chlorinated phenols is considered to be a major source of PCDD/F emissions from combustion sources. Even though iron oxide is present at 2-50 times higher concentrations than copper oxide, virtually no studies of the iron oxide mediated formation of PCDD/Fs have been reported in the literature. We have performed packed-bed, flow-reactor studies of the reaction of 50 ppm gas-phase 2-monochlorophenol (2-MCP) over a surface of 5% iron oxide on silica over a temperature range of 200-500 degrees C. Dibenzo-p-dioxin (DD), 1-monochlorodibenzo-p-dioxin (1-MCDD), 4,6-dichlorodibenzofuran (4,6-DCDF), and dibenzofuran (DF) were formed in maximum yields of 0.2%, 0.1%, 0.3%, and 0.4%, respectively. The yield of PCDD/Fs over iron oxide peaked at temperatures 50-100 degrees C higher in temperature than they peak over copper oxide. The maximum yields of DD, 1-MCDD were 2 times and for 4,6-DCDF was 5 times higher over iron oxide than over copper oxide, whereas DF was not observed at all for copper oxide. The resulting PCDD/PCDF ratio was 0.39 for iron oxide versus 1.2 observed copper oxide, which is in agreement with PCDD/PCDF ratios in full-scale combustors that are typically <<1. The combination of 2-50 times higher concentrations of iron oxide than copper oxide in most full-scale combustors and 2.5 times higher yields of PCDD/Fs observed in the laboratory suggests that iron oxide might contribute as much as 5-125 times more than copper oxide to the emissions of PCDD/Fs from full-scale combustors.
Project description:The role of iron in surface-mediated formation of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) from 2-chlorophenol (2-MCP) was investigated over the temperature range of 200-550°C under oxidative conditions. In order to compare and contrast with previous work on copper and ferric oxide-mediated pyrolysis of 2-MCP, identical reaction conditions were maintained (50 ppm 2-MCP, model fly-ash particles containing 5% Fe(2)O(3) on silica). Observed products included dibenzo-p-dioxin (DD), 1-monochlorodibenzo-p-dioxin (1-MCDD), dibenzofuran (DF), 4,6-dichlorodibenzofuran (4,6-DCDF), 2,4- and 2,6-dichlorophenol, 2,4,6-trichlorophenol, quinone, catechol, chloro-o-quinone, chlorocatechol and polychlorinated benzenes. Yields of DD and 1-MCDD were 2 and 5 times higher than under pyolysis conditions, respectively. Although 4,6-DCDF was the major PCDD/F product formed with a yield that was 2.5× greater than under pyrolysis, the yield of non-chlorinated DF, which was the dominant PCDD/F product under pyrolysis, decreased by a factor of 3. Furthermore, the ~2× higher yield of PCDDs under oxidative conditions resulted in a PCDD to PCDF ratio of 0.75 compared to a relatively low ratio of 0.39 previously observed under pyrolytic conditions.
Project description:Sucralose is a widely-used artificial high-intensity sweetener. Although doubts have been raised about the safety of sucralose by several researchers, it can still be found in a broad range of foods and beverages worldwide, including in baked goods. Sucralose may decompose at high temperatures, and participate in chlorination reactions, generating highly toxic compounds. Here, we demonstrate that heating sucralose at high temperatures in stainless steel or other metal utensils in the presence of rust (Al2O3, Fe2O3, and CuO) produces polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). PCDD/Fs were found in smoke generated during the heating of sucralose and in the residues after heating. CuO enhanced the PCDD/F yield in comparison with Al2O3 and Fe2O3.
Project description:Chlorinated aromatics undergo surface-mediated reactions with metal oxides to form Environmentally Persistent Free Radicals (EPFRs) which can further react to produce polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). Previous work using laboratory-made fly ash surrogates composed of transition metal oxides deposited on silica powder has confirmed their ability to mimic fly ash in the production of PCDD/Fs. However, little is known about the propensity of aluminas and aluminosilicates, other components of fly ash, to form PCDD/Fs. A fly ash sample containing both alumina and mullite, an aluminosilicate, was tested for PCDD/F formation ability and compared to PCDD/F yields from the thermal degradation of 2-monochlorophenol (2-MCP) precursor over ?-alumina, ?-alumina, and mullite. A packed-bed flow reactor was used to investigate the thermal degradation of 2-MCP over the various catalysts at 200-600 °C. Fly ash gave similar PCDD/F yields to surrogates made with similar transition metal content. ?-alumina, which is thermodynamically unfavorable, was very catalytically active and gave low PCDD/F yields despite a high destruction of 2-MCP. Mullite and ?-alumina, the thermodynamically favorable form of alumina, yielded higher concentrations of dioxins and products with a higher degree of chlorine substitution than ?-alumina. The data suggest that certain aluminas and aluminosilicates, commonly found in fly ash, are active catalytic surfaces in the formation of PCDD/Fs in the post-flame cool zones of combustion systems and should be considered as additional catalytic surfaces active in the process.
Project description:The discrepancies between polychlorinated dibenzo-p-dioxin to polychlorinated dibenzofuran (PCDD to PCDF) ratios in laboratory and field studies in the exhaust of combustion sources are not fully explained by available formation models. In this paper we present the results of experimental studies of the surface mediated formation of PCDD/F at the conditions mimicking the combustion cool zone from a mixture of 1,2-dichlorobenzene (1,2-DCBz) and 2-monochlorophenol (2-MCP) over a model surface consisting of 5% CuO/Silica. The PCDD to PCDF ratio was found to be strongly dependent on the ratio of chlorinated benzenes to chlorinated phenols and oxygen content. The higher the 1,2-DCBz to 2-MCP ratio, the lower the PCDD to PCDF ratio. PCDFs are formed predominantly from chlorinated benzenes, while chlorinated phenols are responsible for majority of PCDDs. These laboratory results are in general agreement with full-scale measurement and can be used to improve predictive models of PCDD/F formation.
Project description:The occurrence, concentrations, patterns, and loads of 17 2,3,7,8-substituted congeners of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) were determined in treated wastewater collected at the outlets from 14 wastewater treatment plants (WTPs), divided into three size categories. The analysis also considered the effect of wastewater outflow on the final concentrations of PCDDs/Fs, as the samples were collected during flooding and stable hydrological conditions. None of the studied WTPs were found to completely remove toxic congeners of PCDDs/Fs from wastewater: the PCDD concentrations in the outgoing effluent during stable wastewater flow ranged from 2.99 to 177.19 pg/L, PCDFs from 6.05 to 51.30 pg/L, and the Toxic Equivalent (TEQ) was between 0.94 and 4.87 pg/L. The results from high wastewater flow were less diversified, ranging from 5.04 to 8.85 pg/L for PCDDs, from 11.47 to 32.33 pg/L for PCDFs and from 2.00 to 4.65 pg/L for TEQ. The smallest WTPs demonstrated the highest average total and TEQ concentrations due to limited volume, short retention time and outdated technology, and, hence, insufficient treatment efficiency. The largest WTPs have the potential to substantially affect the quality of river water, as despite being associated with the lowest concentrations, they released much greater volumes of treated wastewater and, hence, the greatest amounts of analyzed compounds. Elevated TEQ values were observed at high flow in all WTP size categories indicating the impact of high and stable wastewater flow on the concentrations of the observed PCDDs/Fs.
Project description:The sources of polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs) found in animal feed additive (feed grade cupric sulfate, CuSO4) were investigated and traced back to the formation of chlorinated organic compounds in the chlor-alkali industry. PCDD/Fs could be transported through the supply chain: hydrochloric acid (HCl) by-produced during formation of chlorinated organic compounds in chlor-alkali industry ? spent acid etching solution (acid-SES) generated in printed circuit board production ? industrial cupric salt ? CuSO4 in animal feed, and finally enter the food chain. The concentration ranges in HCl and acid-SES were similar, of which the level in acid-SES was also consistent with that in various cupric salt products including CuSO4 based on Cu element content. PCDD/Fs also showed very similar congener profiles in all the sample types. This indicates a probable direct transport pathway of PCDD/Fs into the food chain, which may eventually be exposed to humans through consumption. To date this is the first study in China that systematically reports on the PCDD/Fs transport from industrial pollution sources to industrial processes and finally enters the human food chain.
Project description:<label>OBJECTIVES</label>The objective of this study was to use ambient polycyclic aromatic hydrocarbon (PAH), polychlorinated dibenzo-p-dioxins (PCDD), and polychlorinated dibenzofurans (PCDF) concentrations measured at Joint Base Balad in Iraq in 2007 to identify the sources of these species and their spatial patterns.<label>METHODS</label>The ratios of the measured species were compared with literature data for likely emission sources. Using the multiple site measurements on specific days, contour maps have been drawn using inverse distance weighting (IDW).<label>RESULTS</label>These analyses suggest multiple sources, including the burn pit (primarily a source of PCDD/PCDFs), the transportation field (primarily as source of PAHs), and other sources of PAHs that include aircraft, space heating, and diesel power generation.<label>CONCLUSIONS</label>The nature and locations of the sources were identified. PCDD/PCDFs were emitted by the burn pit. Multiple PAH sources exist across the base.
Project description:The levels of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and dioxin-like polychlorinated biphenyls (dl-PCBs) in the Pilica River and Sulejów Reservoir were found to be 46% higher during the flood season than during stable flow periods. In addition, PCDD/PCDF and dl-PCB mass loads increased by 5- to 12-fold and by 23- to 60-fold for toxic equivalency (TEQ) during flooding. The Sulejów Reservoir was found to play a positive role in reducing PCDD, PCDF and dl-PCB transport within the study period, with reductions ranging from 17 to 83% for total concentrations, and 33 to 79% for TEQ. Wastewater Treatment Plants (WTPs) were not efficient at mass concentration removal, with small displaying the least efficiency. WTPs discharge pollutants into the aquatic environment, they also produce sludge that requires disposal, similar to reservoir sediments. Sludge- or sediment-born PCDDs, PCDFs and dl-PCBs may be removed using phytoremediation. The cultivation of cucumber and zucchini, two efficient phytoremediators of organic pollutants, on polluted substrate resulted in a mean decrease in PCDD?+?PCDF?+?dl-PCB TEQ concentrations: 64% for cucumber and 69% for zucchini in sludge-amended soil, and by 52% for cucumber and 51% for zucchini in sediment-amended soil.