Investigating environmentally persistent free radicals (EPFRs) emissions of 3D printing process.

In recent years, the emission of particles and gaseous pollutants from 3D printing has attracted much attention due to potential health risks. This study investigated the generation of environmentally persistent free radicals (EPFRs, organic free radicals stabilized on or inside particles) in total particulate matter (TPM) released during the 3D printing process. Commercially available 3D printer filaments, made of acrylonitrile-butadiene-styrene (ABS) in two different colors and metal content, ABS-blue (19.66 µg/g Cu) and ABS-black (3.69 µg/g Fe), were used for printing. We hypothesized that the metal content/composition of the filaments contributes not only to the type and number of EPFRs in TPM emissions, but also impacts the overall yield of TPM emissions. TPM emissions during printing with ABS-blue (11.28 µg/g of printed material) were higher than with ABS-black (7.29 µg/g). Electron paramagnetic resonance (EPR) spectroscopy, employed to measure EPFRs in TPM emissions of both filaments, revealed higher EPFR concentrations in ABS-blue TPM (6.23 × 1017 spins/g) than in ABS-black TPM (9.72 × 1016 spins/g). The presence of copper in the ABS-blue contributed to the formation of mostly oxygen-centered EPFR species with a g-factor of ~2.0041 and a lifetime of 98 days. The ABS-black EPFR signal had a lower g-factor of ~2.0011, reflecting the formation of superoxide radicals during the printing process, which were shown to have an "estimated tentative" lifetime of 26 days. Both radical species (EPFRs and superoxides) translate to a potential health risk through inhalation of emitted particles.

Metal-Free Biomass-Derived Environmentally Persistent Free Radicals (Bio-EPFRs) from Lignin Pyrolysis.

To assess contribution of the radicals formed from biomass burning, our recent findings toward the formation of resonantly stabilized persistent radicals from hydrolytic lignin pyrolysis in a metal-free environment are presented in detail. Such radicals have particularly been identified during fast pyrolysis of lignin dispersed into the gas phase in a flow reactor. The trapped radicals were analyzed by X-band electron paramagnetic resonance (EPR) and high-frequency (HF) EPR spectroscopy. To conceptualize available data, the metal-free biogenic bulky stable radicals with extended conjugated backbones are suggested to categorize as a new type of metal-free environmentally persistent free radicals (EPFRs) (bio-EPFRs). They can be originated not only from lignin/biomass pyrolysis but also during various thermal processes in combustion reactors and media, including tobacco smoke, anthropogenic sources and wildfires (forest/bushfires), and so on. The persistency of bio-EPFRs from lignin gas-phase pyrolysis was outlined with the evaluated lifetime of two groups of radicals being 33 and 143 h, respectively. The experimental results from pyrolysis of coniferyl alcohol as a model compound of lignin in the same fast flow reactor, along with our detailed potential energy surface analyses using high-level DFT and ab initio methods toward decomposition of a few other model compounds reported earlier, provide a mechanistic view on the formation of C- and O-centered radicals during lignin gas-phase pyrolysis. The preliminary measurements using HF-EPR spectroscopy also support the existence of O-centered radicals in the radical mixtures from pyrolysis of lignin possessing a high g value (2.0048).

Influence of polymer additives on gas-phase emissions from 3D printer filaments.

A collection of six commercially available, 3D printer filaments were analyzed with respect to their gas-phase emissions, specifically volatile organic compounds (VOCs), during simulated fused filament fabrication (FFF). Filaments were chosen because they were advertised to contain metal particles or carbon nanotubes. During experimentation, some were found to contain other non-advertised additives that greatly influenced gas-phase emissions. Three polylactic acid (PLA) filaments containing either copper, bronze, or stainless steel particles were studied along in addition to three carbon nanotube (CNT) filaments made from PLA, acrylonitrile-butadiene-styrene (ABS), and polycarbonate (PC). The metal-additive PLA filaments were found to emit primarily lactide, acetaldehyde, and 1-chlorododecane. The presence of metal particles in the PLA is a possible cause of the increased total emissions, which were higher than any other PLA filament reported in the literature. In addition, the filament with stainless steel particles had a threefold increase in total VOCs compared to the copper and bronze particles. Two of three CNT-containing filaments emitted compounds that have not been reported before for PLA and PC. A comparison between certain emitted VOCs and their suggested maximum inhalation limits shows that printing as little as 20 g of certain filaments in a small, unventilated room can subject the user to hazardous concentrations of multiple toxic VOCs with carcinogenic properties (e.g., acetaldehyde, 1,4-dioxane, and bis(2-ethylhexyl) phthalate). The use of certain additives, whether advertised or not, should be reevaluated due to their effects on VOC emissions during 3D printing.

Role of Fe2O3 in fly ash surrogate on PCDD/Fs formation from 2-monochlorophenol.

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.

VOC Emissions and Formation Mechanisms from Carbon Nanotube Composites during 3D Printing.

A commercially available, 3D printer nanocomposite filament of carbon nanotubes (CNTs) and acrylonitrile-butadiene-styrene (ABS) was analyzed with respect to its VOC emissions during simulated fused deposition modeling (FDM) and compared with a regular ABS filament. VOC emissions were quantified and characterized under a variety of conditions to simulate the thermal degradation that takes place during FDM. Increasing the residence time and temperature resulted in significant increases in VOC emissions, and the oxygen content of the reaction gas influenced the VOC profile. In agreement with other studies, the primary emitted VOC was styrene. Multiple compounds are reported in this work for the first time as having formed during FDM, including 4-vinylcyclohexene and 2-phenyl-2-propanol. Our results show that printing 222.0 g of filament is enough to surpass the reference concentration for inhalation exposure of 1 mg/m3 according to the EPA's Integrated Risk Information System (IRIS). The presence of CNTs in the filament influenced VOC yields and product ratios through three types of surface interactions: (1) adsorption of O2 on CNTs lowers the available O2 for oxidation of primary backbone cleavage intermediates, (2) adsorption of styrene and other VOCs to CNTs leads to surface-catalyzed degradation, and (3) CNTs act as a trap for certain VOCs and prevent them from entering vapor emissions. While the presence of CNTs in the filament lowered the total VOC emission under most experimental conditions, they increased the emission of the most hazardous VOCs, such as α-methylstyrene and benzaldehyde. The present study has identified an increased risk associated with the use of CNT nanocomposites in 3D printing.

Polybrominated Diphenylethers (PBDEs) in ambient air samples at the electronic waste (e-waste) reclamation site.

Polybrominated Diphenylethers (PBDEs) were used as flame-retardants in various building materials, plastic and other polymers, airplanes, electronics etc. All or some of their congeners have been already banned in many countries, due to their persistency and adverse health effects. In this study, we are focusing on the e-wastes as a source of emission of PBDEs in ambient air during reclamation processes. The ambient air particulate matter (PM) samples were collected at and near e-waste reclamation site in Bangkok, Thailand. Results showed the presence of various homologues viz: tri, tetra, penta, hexa, and hepta-PBDEs on both PM2.5 and Total Suspended Particle (TSP) samples. The comparison of samples as a function of distance from reclamation site indicated elevated levels of PBDEs in the close proximity to e-waste site. Interestingly, a shift in the congener pattern was observed with lower brominated PBDEs being more prevalent on nearby off-site samples as compared to the PM collected at the e-waste site. The total penta-PBDEs concentration is about double on e-waste site PM2.5 compared to control site samples. For TSP, tetra, penta, and hepta-PBDEs congeners are at higher concentrations at e-waste sites and its vicinity compared to reference sites. Overall, a clear trend can be observed indicating a debromination of PBDEs to more toxic tri and tetra congeners during reclamation process and PBDEs are being translocated from treated materials to ambient air PM. BDE 30 congener is identified as a specific marker of thermal reclamation processes of e-wastes as a most stable degradation product. This work indicates potential hazards related to the reclamation of e-wastes and remediation of sites containing PBDEs. In particular, thermal treatment methods can lead to congener transformation and increased emissions of more toxic lower-brominated congeners.

Synergy of iron and copper oxides in the catalytic formation of PCDD/Fs from 2-monochlorophenol.

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.

A Scalable Field Study Protocol and Rationale for Passive Ambient Air Sampling: A Spatial Phytosampling for Leaf Data Collection.

Stable, bioreactive, radicals known as environmentally persistent free radicals (EPFRs) have been found to exist on the surface of airborne PM2.5. These EPFRs have been found to form during many combustion processes, are present in vehicular exhaust, and persist in the environment for weeks and biological systems for up to 12 h. To measure EPFRs in PM samples, high volume samplers are required and measurements are less representative of community exposure; therefore, we developed a novel spatial phytosampling methodology to study the spatial patterns of EPFR concentrations using plants. Leaf samples for laboratory PM analysis were collected from 188 randomly drawn sampling sites within a 500-m buffer zone of pollution sources across a sampling grid measuring 32.9 × 28.4 km in Memphis, Tennessee. PM was isolated from the intact leaves and size fractionated, and EPFRs on PM quantified by electron paramagnetic resonance spectroscopy. The radical concentration was found to positively correlate with the EPFR g-value, thus indicating cumulative content of oxygen centered radicals in PM with higher EPFR load. Our spatial phytosampling approach reveals spatial variations and potential "hotspots" risk due to EPFR exposure across Memphis and provides valuable insights for identifying exposure and demographic differences for health studies.

Mechanisms and effectivity of sulfate reducing bioreactors using a chitinous substrate in treating mining influenced water.

Mining-influenced water (MIW) is one of the main environmental challenges associated with the mining industry. Passive MIW remediation can be achieved through microbial activity in sulfate-reducing bioreactors (SRBRs), but their actual removal rates depend on different factors, one of which is the substrate composition. Chitinous materials have demonstrated high metal removal rates, particularly for the two recalcitrant MIW contaminants Zn and Mn, but their removal mechanisms need further study. We studied Cd, Fe, Zn, and Mn removal in bioactive and abiotic SRBRs to elucidate the metal removal mechanisms and the differences in metal and sulfate removal rates using a chitinous material as substrate. We found that sulfate-reducing bacteria are effective in increasing metal and sulfate removal rates and the duration of operation in SRBRs, and that the main mechanism involved was metal precipitation as sulfides. The solid residues provided evidence of the presence of sulfides in the bioactive column, more specifically ZnS, according to XPS analysis. The feasibility of passive treatments with a chitinous substrate could be an important option for MIW remediation.

Formation of Environmentally Persistent Free Radicals on α-Al2O3.

Metal oxides exhibit catalytic activity for the formation of environmentally persistent free radicals (EPFRs). Here, we investigate, via first-principles calculations, the activity of alumina α-Al2O3(0001) surface toward formation of phenolic EPFRs, under conditions relevant to cooling down zones of combustion systems. We show that, molecular adsorption of phenol on α-Al2O3(0001) entails binding energies in the range of -202 kJ/mol to -127 kJ/mol. The dehydroxylated alumina catalyzes the conversion of phenol into its phenolate moiety with a modest activation energy of 48 kJ/mol. Kinetic rate parameters, established over the temperature range of 300 to 1000 K, confirm the formation of the phenolate as the preferred pathways for the adsorption of phenol on alumina surfaces, corroborating the role of particulate matter in the cooling down zone of combustion systems in the generation of EFPRs.

Formation of PCDD/Fs in Oxidation of 2-Chlorophenol on Neat Silica Surface.

This contribution studies partial oxidation of 2-chlorophenol on surfaces of neat silica at temperatures of 250, 350, and 400 °C; i.e., temperatures that frequently lead to catalytic formation of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) from their precursors. We have identified 2,6-dichlorophenol (2,6-DCPh), 2,4-dichlorophenol (2,4-DCPh), and 2,4,6-trichlorophenol (2,4,6-TriCPh), but have detected no chlorinated benzenes (CBzs). The detected chlorinated and nonchlorinated DD/Fs comprise dibenzo-p-dioxin (DD), 1- and 2-monochlorodibenzo-p-dioxin (1-, 2-MCDD), 1,6-, 1,9-, 1,3-dichlorodibenzo-p-dioxin (1,6-, 1,9-, 1,3-DCDD), 4-monochlorodibenzofuran (4-MCDF), and 4,6-dichlorodibenzofuran (4,6-DCDF) at the reaction temperatures of 350 and 400 °C. However, at a lower reaction temperature, 250 °C, we have detected no PCDD/Fs. We have demonstrated that neat silica surfaces catalyze the generation of PCDD/Fs from chlorophenols at the upper range of the catalytic formation temperature of PCDD/F. The present finding proves the generation of PCDD/Fs on particles of fly ash, even in the absence of transition metals.

Contribution of aluminas and aluminosilicates to the formation of PCDD/Fs on fly ashes.

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 γ-alumina, α-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. γ-alumina, which is thermodynamically unfavorable, was very catalytically active and gave low PCDD/F yields despite a high destruction of 2-MCP. Mullite and α-alumina, the thermodynamically favorable form of alumina, yielded higher concentrations of dioxins and products with a higher degree of chlorine substitution than γ-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.

Exposure to Deepwater Horizon Crude Oil Burnoff Particulate Matter Induces Pulmonary Inflammation and Alters Adaptive Immune Response.

The ″in situ burning" of trapped crude oil on the surface of Gulf waters during the 2010 Deepwater Horizon (DWH) oil spill released numerous pollutants, including combustion-generated particulate matter (PM). Limited information is available on the respiratory impact of inhaled in situ burned oil sail particulate matter (OSPM). Here we utilized PM collected from in situ burn plumes of the DWH oil spill to study the acute effects of exposure to OSPM on pulmonary health. OSPM caused dose-and time-dependent cytotoxicity and generated reactive oxygen species and superoxide radicals in vitro. Additionally, mice exposed to OSPM exhibited significant decreases in body weight gain, systemic oxidative stress in the form of increased serum 8-isoprostane (8-IP) levels, and airway inflammation in the form of increased macrophages and eosinophils in bronchoalveolar lavage fluid. Further, in a mouse model of allergic asthma, OSPM caused increased T helper 2 cells (Th2), peribronchiolar inflammation, and increased airway mucus production. These findings demonstrate that acute exposure to OSPM results in pulmonary inflammation and alteration of innate/adaptive immune responses in mice and highlight potential respiratory effects associated with cleaning up an oil spill.

Environmentally persistent free radicals inhibit cytochrome P450 activity in rat liver microsomes.

Combustion processes generate particulate matter that affects human health. When incineration fuels include components that are highly enriched in aromatic hydrocarbons (especially halogenated varieties) and redox-active metals, ultrafine particulate matter containing air-stable, environmentally persistent free radicals (EPFRs) is generated. The exposure to fine EPFRs (less than 2.5 µm in diameter) has been shown to negatively influence pulmonary and cardiovascular functions in living organisms. The goal of this study was to determine if these EPFRs have a direct effect on cytochrome P450 function. This was accomplished by direct addition of the EPFRs to rat liver microsomal preparations and measurement of several P450 activities using form-selective substrates. The EPFRs used in this study were formed by heating vapors from an organic compound (either monochlorophenol (MCP230) or 1,2-dichlorobenzene (DCB230)) and 5% copper oxide supported on silica (approximately 0.2 µm in diameter) to 230°C under vacuum. Both types of EPFRs (but not silica, physisorbed silica, or silica impregnated with copper oxide) dramatically inhibited the activities of CYP1A, CYP2B, CYP2E1, CYP2D2 and CYP3A when incubated at concentrations less than 0.1 mg/ml with microsomes and NADPH. Interestingly, at the same concentrations, the EPFRs did not inhibit HO-1 activity or the reduction of cytochrome c by NADPH-cytochrome P450 reductase. CYP2D2-selective metabolism by rat liver microsomes was examined in more detail. The inhibition of CYP2D2-selective metabolism by both DCB230- and MCP230-EPFRs appeared to be largely noncompetitive and was attenuated in the presence of catalase suggesting that reactive oxygen species may be involved in the mechanism of inhibition.

Assessment of environmentally persistent free radicals in soils and sediments from three Superfund sites.

We previously reported the presence of environmentally persistent free radicals (EPFRs) in pentachlorophenol (PCP) contaminated soils at a closed wood treatment facility site in Georgia. The reported EPFRs were pentachlorophenoxyl radicals formed on soils under ambient conditions via electron transfer from PCP to electron acceptors in the soil. In this study, we present results for soil and sediment samples from additional Superfund sites in Montana and Washington. Paramagnetic centers associated with different chemical environments were characterized by distinct g-factors and line widths (ΔHp-p). EPFR concentrations in contaminated samples were ~30×, ~12×, and ~2× higher than background samples at the Georgia, Montana, and Washington sites, respectively. EPR signals in the Montana contaminated soils were very similar to those previously observed for pentachlorophenol contaminated soils at the Georgia site, i.e., g = 2.00300 and ΔHp-p = 6.0 G, whereas signals in the Washington sediment samples were similar to those previously observed for other PAH contaminated soils, i.e., g = 2.00270 and ΔHp-p = 9.0 G. Total carbon content measurements exhibited direct correlation with EPFR concentration. The presence of radicals in sites contaminated a decade to a century ago suggests continuous formation of EPFRs from molecular contaminants in the soil and sediment.

Model combustion-generated particulate matter containing persistent free radicals redox cycle to produce reactive oxygen species.

Particulate matter (PM) is emitted during thermal decomposition of waste. During this process, aromatic compounds chemisorb to the surface of metal-oxide-containing PM, forming a surface-stabilized environmentally persistent free radical (EPFR). We hypothesized that EPFR-containing PM redox cycle to produce ROS and that this redox cycle is maintained in biological environments. To test our hypothesis, we incubated model EPFRs with the fluorescent probe dihydrorhodamine (DHR). Marked increases in DHR fluorescence were observed. Using a more specific assay, hydroxyl radicals ((•)OH) were also detected, and their level was further increased by cotreatment with thiols or ascorbic acid (AA), known components of epithelial lining fluid. Next, we incubated our model EPFR in bronchoalveolar lavage fluid (BALF) or serum. Detection of EPFRs and (•)OH verified that PM generate ROS in biological fluids. Moreover, incubation of pulmonary epithelial cells with EPFR-containing PM increased (•)OH levels compared to those in PM lacking EPFRs. Finally, measurements of oxidant injury in neonatal rats exposed to EPFRs by inhalation suggested that EPFRs induce an oxidant injury within the lung lining fluid and that the lung responds by increasing antioxidant levels. In summary, our EPFR-containing PM redox cycle to produce ROS, and these ROS are maintained in biological fluids and environments. Moreover, these ROS may modulate toxic responses of PM in biological tissues such as the lung.

Formation and stabilization of combustion-generated, environmentally persistent radicals on Ni(II)O supported on a silica surface.

Previous studies have indicated environmentally persistent free radicals (EPFRs) are formed when hydroxyl- and chlorine-substituted aromatics chemisorbed on Cu(II)O and Fe(III)(2)O(3) surfaces and were stabilized through their interactions with the surface metal cation. The current study reports our laboratory investigation on the formation and stabilization of EPFRs on a Ni(II)O surface. The EPFRs were produced by the chemisorption of adsorbates on the supported metal oxide surface and transfer of an electron from the adsorbate to the metal center, resulting in reduction of the metal cation. Depending on the temperature and the nature of the adsorbate, more than one type of organic radical was formed. A phenoxyl-type radical, with g-value between 2.0029 and 2.0044, and a semiquinone-type radical, with g-value from 2.0050 to as high as 2.0081, were observed. The half-lives on Ni(II)O were long and ranged from 1.5 to 5.2 days, which were similar to what were observed on Fe(III)(2)O(3). The yields of the EPFRs formed on Ni(II)O were ~8× higher than on Cu(II)O and ~50× higher than on Fe(III)(2)O(3).

Effect of low temperature thermal treatment on soils contaminated with pentachlorophenol and environmentally persistent free radicals.

The effect of low temperature thermal treatment on soils from a former Superfund wood-treating site contaminated with pentachlorophenol (PCP) and the environmentally persistent free radical (EPFR), pentachlorophenoxyl, was determined. The pentachlorophenoxyl EPFRs' and the PCP molecules' chemical behavior were simultaneously monitored at temperatures ranging from 25 to 300 °C via electron paramagnetic resonance (EPR) spectroscopy and GC-MS analysis, respectively. Two types of thermal treatment were employed: a closed heating (oxygen-starved condition) where the soil was heated under vacuum and an open heating system (oxygen-rich conditions), where the soil was heated in ambient air. EPR analyses for closed heating indicated the EPFR concentration was 2-12 × 10(18) spins/g of soil, with a g-factor and line width (ΔHp-p) of 2.00311-2.00323 and 4.190-5.472 G, respectively. EPR analyses for the open heating soils revealed a slightly broader and weaker radical signal, with a concentration of 1-10 × 10(18) spins/g of soil, g-factor of 2.00327-2.00341, and ΔHp-p of 5.209-6.721 G. This suggested the open heating resulted in the formation of a more oxygen-centered structure of the pentachlorophenoxyl radical or additional, similar radicals. The EPFR concentration peaked at 10 × 10(18) spins/g of soil at 100 °C for open heating and 12 × 10(18) spins/g at 75 °C for closed heating. The half-lives of the EPFRs were 2-24 days at room temperature in ambient air. These results suggest low temperature treatment of soils contaminated with PCP can convert the PCP to potentially more toxic pentachlorophenoxyl EPFRs, which may persist in the environment long enough for human exposure.

Formation of PCDD/Fs from the copper oxide-mediated pyrolysis and oxidation of 1,2-dichlorobenzene.

Formation of polychorinated dibenzo-p-dioxins (PCDDs) has been demonstrated to occur via surface-mediated reactions of chlorinated phenols. However, polychlorinated dibenzofurans (PCDFs) are observed in much lower yields in laboratory studies than in full-scale combustors where PCDFs are in higher concentrations than PCDDs. This has led to the suggestion that at least PCDFs are formed from elemental carbon in the de novo process. However, the potential for PCDF formation from reactions of chlorinated benzenes has been largely overlooked. In this study, we investigated the potential contribution of chlorinated benzenes to formation of PCDD/Fs using 1,2-dichlorobenzene as a surrogate for reactions of other chlorinated benzenes and CuO/silica (3 wt % Cu) as a surrogate for fly ash. Results were similar for oxidative and pyrolytic conditions with a slight increase in more chlorinated products under oxidative conditions. Reaction products included chlorobenzene, polychlorinated benzenes, phenol, 2-monochlorophenol (2-MCP), dichlorophenols, and trichlorophenols with yields ranging from 0.01 to 2% for the phenols and from 0.01 to 10% for chlorinated benzenes. 4,6-Dichlorodibenzo furan (4,6-DCDF) and dibenzofuran (DF) were observed in maximum yields of 0.2% and 0.5%, respectively, under pyrolytic conditions and 0.1% and 0.3%, respectively, under oxidative conditions. In previous studies of the pyrolysis of 2-MCP under identical conditions, 4,6-DCDF and dibenzo-p-dioxin (DD) were observed with maximum yields of ∼0.2% and ∼0.1%, respectively, along with trace quantities of 1-monochlorodibenzo-p-dioxin (1-MCDD). Under oxidative conditions, 1-MCDD, DD, and 4,6-DCDF were observed with maximum yields of 0.3%, 0.07% and 0.1%, respectively. When combined with the fact that measured concentrations of chlorinated benzenes are 10-100× that of chlorinated phenols in full-scale combustion systems, the data suggest surface-mediated reactions of chlorinated benzenes can be a significant source of PCDD/F emissions.