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.

Oxidation 1-methyl naphthalene based on the synergy of environmentally persistent free radicals (EPFRs) and PAHs in particulate matter (PM) surface.

Studies of the environmental fate through the interactions of particle-associated polycyclic aromatic hydrocarbons (PAHs) with environmentally persistent free radicals (EPFRs) are presented. The formation of PAHs and EPFRs typically occurs side by side during combustion-processes. The laboratory simulation studies of the model PAH molecule 1-Methylnaphthalene (1-MN) interaction with model EPFRs indicate a transformational synergy between these two pollutants due to mutual and matrix interactions. EPFRs, thorough its redox cycle result in the oxidation of PAHs into oxy-/hydroxy-PAHs. EPFRs have been shown before to produce OH radical during its redox cycle in aqueous media and this study has shown that produced OH radical can transform other PM constituents resulting in alteration of PM chemistry. In model PM, EPFRs driven oxidation process of 1-MN produced 1,4-naphthoquinone, 1-naphthaldehyde, 4-hydroxy-4-methylnaphthalen-1-one, and various isomers of (hydroxymethyl) naphthalene. Differences were observed in oxidation product yields, depending on whether EPFRs and PAHs were cohabiting the same PM or present on separate PM. This effect is attributed to the OH radical concentration gradient as a factor in the oxidation process, further strengthening the hypothesis of EPFRs' role in the PAH oxidation process. This finding is revealing new environmental role of EPFRs in a natural degradation process of PAHs. Additionally, it points to implications of such PM surface chemistry in the changing mobility of PAHs into an aqueous medium, thus increasing their bioavailability.

The elemental fingerprint as a potential tool for tracking the fate of real-life model nanoplastics generated from plastic consumer products in environmental systems.

Metals and metalloids are widely used in producing plastic materials as fillers and pigments, which can be used to track the environmental fate of real-life nanoplastics in environmental and biological systems. Therefore, this study investigated the metal and metalloids concentrations and fingerprint in real-life model nanoplastics generated from new plastic products (NPP) and from environmentally aged ocean plastic fragments (NPO) using single particle-inductively coupled plasma-mass spectrometry (SP-ICP-TOF-MS) and transmission electron microscopy coupled with energy dispersive X-ray spectroscopy (TEM-EDX). The new plastic products include polypropylene straws (PPS), polyethylene terephthalate bottles (PETEB), white low-density polyethylene bags (LDPEB), and polystyrene foam shipping material (PSF). All real-life model nanoplastics contained metal and metalloids, including Si, Al, Sr, Ti, Fe, Ba, Cu, Pb, Zn, Cd, and Cr, and were depleted in rare earth elements. Nanoplastics generated from the white LDPEB were rich in Ti-bearing particles, whereas those generated from PSF were rich in Cr, Ti, and Pb. The Ti/Fe in the LDPEB nanoplastics and the Cr/Fe in the PSF nanoplastics were higher than the corresponding ratios in natural soil nanoparticles (NNPs). The Si/Al ratio in the PSF nanoplastics was higher than in the NNPs, possibly due to silica-based fillers. The elemental ratio of Si/Al, Fe/Cr, and Fe/Ni in the nanoplastics derived from ocean plastic fragments was intermediate between the nanoplastics derived from real-life plastic products and NNPs, indicating a combined contribution from pigments and fillers used in plastics and from natural sources. This study provides a method to track real-life nanoplastics in controlled laboratory studies based on nanoplastic elemental fingerprints. It expands the realm of nanoplastics that can be followed based on their metallic signatures to all kinds of nanoplastics. Additionally, this study illustrates the importance of nanoplastics as a source of metals and metal-containing nanoparticles in the environment.

A high-throughput, automated technique for microplastics detection, quantification, and characterization in surface waters using laser direct infrared spectroscopy.

A high-throughput approach to detecting, quantifying, and characterizing microplastics (MPs) by shape, size, and polymer type using laser direct infrared (LDIR) spectroscopy in surface water samples is demonstrated. Three urban creeks were sampled for their MP content near Cincinnati, OH. A simple Fenton reaction was used to oxidize the surface water samples, and the water samples were filtered onto a gold-coated polyester membrane. Infrared (IR) analysis for polymer identification was conducted, with recoveries of 88.3% ± 1.2%. This method was able to quantify MPs down to a diameter of 20 µm, a size comparable to that of MPs quantified by other techniques such as Fourier transform infrared spectroscopy (FTIR) and Raman spectroscopy. A shape-classifying algorithm was designed using the aspect ratio values of particles to categorize MPs as fibers, fibrous fragments, fragments, spherical fragments, or spheres. Cut-off values were identified from measurements of known sphere, fragment, and fibrous particles. About half of all environmental samples were classified as fragments while the other shapes accounted for the other half. A cut-off hit quality index (HQI) value of 0.7 was used to classify known and unidentified particles based on spectral matches to a reference library. Center for Marine Debris Research Polymer Kit 1.0 standards were analyzed by LDIR and compared to the given FTIR spectra by HQI, showing that LDIR obtains similar identifications as FTIR analysis. The simplicity and automation of the LDIR allows for quick, reproducible particle analysis, making LDIR attractive for high-throughput analysis of MPs.

Zinc transport and partitioning of a mine-impacted watershed: An evaluation of water and sediment quality.

Watershed systems influenced by mining waste products can persist for many years after operations are ceased, leading to negative impacts on the health of the surrounding environment. While geochemical behaviors of these trace metals have been studied extensively at the benchtop-scale, much fewer studies have looked at controls on their distributions at the watershed-level. In this study, trace metals (As, Cd, Cr, Cu, Ni, and Zn) were reported from water and stream bed sediments at eight sites between the years 2014-2018 along a watershed undergoing active remediation efforts. Zn was determined to be the only trace metal analyzed with concentrations above EPA and Kansas Department of Health guidelines for both water and sediment in the watershed, and thus was the primary focus for determining the health of the watershed system. Controls on trace metal pollution distribution over the watershed were investigated to determine where remediation efforts should be focused. Surface cover seemed to have the highest effectivity with pasture lands having a strong positive correlation to Zn concentrations. Initial remediation efforts were assessed by calculating the geoaccumulation index (Igeo) and the contamination factor (Cf-sediment) from sediments and contamination factor from water (Cf-water) after decades of chat pile removal efforts. Most of the sites showed significant reduction in metal concentration values compared to previous studies in the watershed for water and sediment, with four sites still reporting concentrations that reveal potential health risks. Results from this study will inform management and policy makers for areas to focus their remediation efforts on the Spring River Watershed as well as providing a framework for assessing pollution at a watershed scale.

Silver Nanoparticle Interactions with Surfactant-Based Household Surface Cleaners.

Silver nanoparticles (AgNPs) are the most widely used engineered nanomaterials in consumer products, primarily due to their antimicrobial properties. This widespread usage has resulted in concerns regarding potential adverse environmental impacts and increased probability of human exposure. As the number of AgNP consumer products grows, the likelihood of interactions with other household materials increases. AgNP products have the potential to interact with household cleaning products in laundry, dishwashers, or during general use of all-purpose surface cleaners. This study has investigated the interaction between surfactant-based surface cleaning products and AgNPs of different sizes and with different capping agents. One AgNP consumer product, two laboratory-synthesized AgNPs, and ionic silver were selected for interaction with one cationic, one anionic, and one nonionic surfactant product to simulate AgNP transformations during consumer product usage before disposal and subsequent environmental release. Changes in size, morphology, and chemical composition were detected during a 60 min exposure to surfactant-based surface cleaning products using ultraviolet-visible (UV/Vis) spectroscopy, transmission electron microscopy-energy dispersive X-ray spectroscopy (TEM-EDX), and dynamic light scattering (DLS). Generally, once AgNP suspensions were exposed to surfactant-based surface cleaning products, all the particles showed an initial aggregation, likely due to disruption of their capping agents. Over the 60 min exposure, cleaning agent-1 (cationic) showed more significant particle aggregates than cleaning agent-2 (anionic) and cleaning agent-3 (nonionic). In addition, UV/Vis, TEM-EDX, and DLS confirmed formation of incidental AgNPs from interaction of ionic silver with all surfactant types.

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.

Isotope ratio mass spectrometry and spectroscopic techniques for microplastics characterization.

Micro- and nano-scale plastic particles in the environment result from their direct release and degradation of larger plastic debris. Relative to macro-sized plastics, these small particles are of special concern due to their potential impact on marine, freshwater, and terrestrial systems. While microplastic (MP) pollution has been widely studied in geographic regions globally, many questions remain about its origins. It is assumed that urban environments are the main contributors but systematic studies are lacking. The absence of standard methods to characterize and quantify MPs and smaller particles in environmental and biological matrices has hindered progress in understanding their geographic origins and sources, distribution, and impact. Hence, the development and standardization of methods is needed to establish the potential environmental and human health risks. In this study, we investigated stable carbon isotope ratio mass spectrometry (IRMS), attenuated total reflectance - Fourier transform infrared (ATR-FTIR) spectroscopy, and micro-Raman spectroscopy (µ-Raman) as complementary techniques for characterization of common plastics. Plastic items selected for comparative analysis included food packaging, containers, straws, and polymer pellets. The ability of IRMS to distinguish weathered samples was also investigated using the simulated weathering conditions of ultraviolet (UV) light and heat. Our IRMS results show a difference between the δ13C values for plant-derived and petroleum-based polymers. We also found differences between plastic items composed of the same polymer but from different countries, and between some recycled and nonrecycled plastics. Furthermore, increasing δ13C values were observed after exposure to UV light. The results of the three techniques, and their advantages and limitations, are discussed.

Sources, transport, measurement and impact of nano and microplastics in urban watersheds.

The growing and pervasive presence of plastic pollution has attracted considerable interest in recent years, especially small (< 5 mm) plastic particles known as 'microplastics' (MPs). Their widespread presence may pose a threat to marine organisms globally. Most of the nano and microplastic (N&MP) pollution in marine environments is assumed to originate from land-based sources, but their sources, transport routes, and transformations are uncertain. Information on freshwater and terrestrial systems is lacking, and data on nanoplastic pollution are particularly sparse. The shortage of systematic studies of freshwater and terrestrial systems is a critical research gap because estimates of plastic release into these systems are much higher than those for oceans. As most plastic pollution originates in urban environments, studies of urban watersheds, particularly those with high population densities and industrial activities, are especially relevant with respect to source apportionment. Released plastic debris is transported in water, soil, and air. It can be exchanged between environmental compartments, adsorb toxic compounds, and ultimately be carried long distances, with potential to cause both physical and chemical harm to a multitude of species. Measurement challenges and a lack of standardized methods has slowed progress in determining the environmental prevalence and impacts of N&MPs. An overall aim of this review is to report the sources and abundances of N&MPs in urban watersheds. We focus on urban watersheds, and summarize monitoring methods and their limitations, knowing that identifying N&MPs and their urban/industrial sources is necessary to reduce their presence in all environments.

Transformation of Silver Nanoparticle Consumer Products during Simulated Usage and Disposal.

Twenty-two silver nanoparticle (AgNP) consumer products (CPs) were analyzed with respect to their silver speciation. Three CPs and three lab-synthesized particles were selected to simulate environmental fate and transport by simulating their intended usage and disposal methods. Since many of these products are meant for ingestion, we simulated their usage by exposing them to human synthetic stomach fluid followed by exposure to wastewater sludge. We found that during the products individual exposure to wastewater sludge, the conversion rate of silver to AgCl and Ag2S was affected by both the amount of silver ion present and the properties of the AgNP. The rates of conversion of metallic silver to silver sulfide was heavily dependent on the particle size for the lab-synthesized particles, with 90 nm PVP-capped particles reacting to a much lesser extent than the 15 nm PVP-capped or the citrate-capped particles. We observed similar sulfidation rates on two of the tested CPs with the 15 nm lab-synthesized particles despite containing silver nanoparticles >5 times larger, indicating the presence of other influencing factors. Pre-treatment with synthetic stomach fluid modified the rates of Ag2S formation. Due to the variable composition of CPs and the conditions they are exposed to between manufacture, sale, use, and disposal, their final composition may be somewhat unpredictable in the environment. In the present study, we have achieved a more accurate approximation of the expected interactions between silver nanoparticle-containing CPs and environmental media by utilizing real CPs and evaluating them with solid phase and aqueous phase analytical techniques.

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.

Correction to: Rapid and versatile pre-treatment for quantification of multi-walled carbon nanotubes in the environment using microwave-induced heating.

The original publication of this paper contains a mistake.

Distribution and Speciation of Copper and Arsenic in Rice Plants ( Oryza sativa japonica 'Koshihikari') Treated with Copper Oxide Nanoparticles and Arsenic during a Life Cycle.

A 6 × 2 factorial study was conducted to investigate the effects of copper oxide nanoparticles (nCuO, 0-100 mg/L), arsenic (As, 0-10 mg/kg), and their interaction on uptake, distribution, and speciation of Cu and As in rice plants ( Oryza sativa japonica 'Koshihikari'). Arsenic (in As-addition treatments) and Cu in seedling roots (SRs) were 1.45 and 1.58 times those in soil, respectively. Arsenic and Cu concentrations further increased in mature plant roots (MRs), which were 2.06 and 2.35 times those in soil, respectively. Arsenic and Cu concentrations in seedling shoots (SSs) were 79% and 54% lower than those in SRs, respectively. The mature stems, however, contained only 3% and 44% of As and Cu in SSs. Copper in flag leaves did not vary much compared to that in stems, whereas As was 14.5 times that in stems. Species transformations of Cu and As were observed in rice including reductions of Cu(II) to Cu(I) and As(V) to As(III). Arsenic in dehusked grains was negatively correlated with Cu and was lowered by nCuO below the WHO (World Health Organization) maximum safe concentration for white rice (200 ng/g). This may alleviate As adverse effects on humans from rice consumption.

Rapid and versatile pre-treatment for quantification of multi-walled carbon nanotubes in the environment using microwave-induced heating.

The concerns regarding potential environmental release and ecological risks of multi-walled carbon nanotubes (MWCNTs) rise with their increased production and use. As a result, there is the need for an analytical method to determine the environmental concentration of MWCNTs. Although several methods have been demonstrated for the quantification of well-characterized MWCNTs, applying these methods to field samples is still a challenge due to interferences from unknown characteristics of MWCNTs and environmental media. To bridge this gap, a recently developed microwave-induced heating method was investigated for the quantification of MWCNTs in field samples. Our results indicated that the microwave response of MWCNTs was independent of the sources, length, and diameter of MWCNTs; however, the aggregated MWCNTs were not able to convert the microwave energy to heat, making the method inapplicable. Thus, a pre-treatment process for dispersing bundled MWCNTs in field samples was crucial for the use of the microwave method. In the present paper, a two-step pre-treatment procedure was proposed: the aggregated MWCNTs loaded environmental samples were first exposed to high temperature (500 °C) and then dispersed by using an acetone-surfactant solution. A validation study was performed to evaluate the effectiveness of the pre-treatment process, showing that an 80-120% recovery range of true MWCNT loading successfully covered the microwave-measured MWCNT mass.

Dissolution of Silver Nanoparticles in Colloidal Consumer Products: Effects of Particle Size and Capping Agent.

The utilization of silver nanoparticles (AgNPs) in consumer products has significantly increased in recent years, primarily due to their antimicrobial properties. Increased use of AgNPs has raised ecological concerns. Once released into an aquatic environment, AgNPs may undergo oxidative dissolution leading to the generation of toxic Ag+. Therefore, it is critical to investigate the ecotoxicological potential of AgNPs and determine the physicochemical parameters that control their dissolution in aquatic environments. We have investigated the dissolution trends of aqueous colloidal AgNPs in five products, marketed as dietary supplements and surface sanitizers. The dissolution trends of AgNPs in studied products were compared to the dissolution trends of AgNPs in well-characterized laboratory-synthesized nanomaterials: citrate-coated AgNPs, polyvinylpyrrolidone-coated AgNPs, and branched polyethyleneimine-coated AgNPs. The characterization of the studied AgNPs included: particle size, anion content, metal content, silver speciation, and capping agent identification. There were small differences in the dissolved masses of Ag+ between products, but we did not observe any significant differences in the dissolution trends obtained for deionized water and tap water. The decrease of the dissolved mass of Ag+ in tap water could be due to the reaction between Ag+ and Cl-, forming AgCl and affecting their dissolution. We observed a rapid initial Ag+ release and particle size decrease for all AgNP suspensions due to the desorption of Ag+ from the nanoparticles surfaces. The observed differences in dissolution trends between AgNPs in products and laboratory-synthesized AgNPs could be caused by variances in capping agent, particle size, and total AgNP surface area in suspensions.

Characterization of engineered nanoparticles in commercially available spray disinfectant products advertised to contain colloidal silver.

Given the potential for human exposure to silver nanoparticles from spray disinfectants and dietary supplements, we characterized the silver-containing nanoparticles in 22 commercial products that advertised the use of silver or colloidal silver as the active ingredient. Characterization parameters included: total silver, fractionated silver (particulate and dissolved), primary particle size distribution, hydrodynamic diameter, particle number, and plasmon resonance absorbance. A high degree of variability between claimed and measured values for total silver was observed. Only 7 of the products showed total silver concentrations within 20% of their nominally reported values. In addition, significant variations in the relative percentages of particulate vs. soluble silver were also measured in many of these products reporting to be colloidal. Primary silver particle size distributions by transmission electron microscopy (TEM) showed two populations of particles - smaller particles (<5nm) and larger particles between 20 and 40nm. Hydrodynamic diameter measurements using nanoparticle tracking analysis (NTA) correlated well with TEM analysis for the larger particles. Z-average (Z-Avg) values measured using dynamic light scattering (DLS); however, were typically larger than both NTA or TEM particle diameters. Plasmon resonance absorbance signatures (peak absorbance at around 400nm indicative of metallic silver nanoparticles) were only noted in 4 of the 9 yellow-brown colored suspensions. Although the total silver concentrations were variable among products, ranging from 0.54mg/L to 960mg/L, silver containing nanoparticles were identified in all of the product suspensions by TEM.

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.

Low-Temperature Catalytic Decomposition of 130 Tetra- to Octa-PCDD/Fs Congeners over CuOX and MnOX Modified V2O5/TiO2-CNTs with the Assistance of O3.

In this study, a reliable and steady PCDD/F generation system was utilized to investigate the performance of catalysts, in which 130 congeners of tetra- to octapolychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) vapors were studied under simulated flue gas with/without O3. TiO2 and carbon nanotubes (CNTs) supported vanadium oxides (VOX/TiO2-CNTs) modified with MnOX and CuOX, which were reported to be beneficial to the decomposition of model molecules, were found to have a negative effect on the removal of real PCDD/Fs in the simulated flue gas without O3. Moreover, the addition of MnOX presented different effects depending on whether CuOX existed in catalysts or not, which was also contrary to its effects on the degradation of model molecules. In an O3-containing atmosphere, low chlorination level PCDD/Fs congeners were removed well over VOX-MnOX/TiO2-CNTs, while high chlorination level PCDD/Fs congeners were removed well over VOX-CuOX/TiO2-CNTs. Fortunately, all PCDD/Fs congeners decomposed well over VOX-MnOX-CuOX/TiO2-CNTs. Finally, the effects of tetra- to octachlorination level for the adsorption and degradation behaviors of PCDD/Fs congeners were also investigated.

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.