Combustion by-products and their health effects: Summary of the 16th international congress.

The 16th International Congress on Combustion By-Products and their Health Effects (PIC2019) was held in Ann Arbor, Michigan, from July 10 to 12, 2019. For the last 28 years, this conference has served as an interdisciplinary platform for the discussion of the formation, environmental fate, health effects, policy, and remediation of combustion by-products. The technical areas for PIC2019 included mobile and stationary sources in urban environments, open fires, indoor air pollution, and halogenated pollutants. The congress was sponsored by the National Institute of Environmental Health Sciences (NIEHS), the U.S. EPA, the School of Public Health at the University of Michigan, the Civil and Environmental Engineering Department at the University of Michigan, the Mechanical Engineering Department at the University of Michigan, the Aerospace Engineering Department at the University of Michigan, and the Climate and Space Sciences and Engineering Department at the University of Michigan. Special features of the conference included a career path and round table discussion on translating research and engaging communities.

Comparative Studies of Environmentally Persistent Free Radicals on Total Particulate Matter Collected from Electronic and Tobacco Cigarettes.

In the current study, electron paramagnetic resonance (EPR) spectroscopy was employed to measure environmentally persistent free radicals (EPFRs) in the total particulate matter (TPM) of mainstream and sidestream TPM of conventional cigarettes and the TPM of e-cigarettes. Comparable concentrations of EPFRs were detected in both sidestream (8.05 ± 1.32) × 104 pmol/g and mainstream TPM (7.41 ± 0.85) × 104 pmol/g of conventional cigarettes. TPM exposure to air resulted in long-lived oxygen centered, secondary radicals with EPR g values of 2.0041 for mainstream and 2.0044 for sidestream. Surprisingly, despite no combustion process, the TPM from e-cigarettes (menthol flavor of NJOY and V2 brands) also contain EPFRs with g values of 2.0031-2.0033, characteristic of carbon centered radicals, while the radical signal in the vanilla flavor of V2 brand was remarkably similar to semiquinones in cigarette smoke with a higher g value (2.0063). The radical concentration in e-cigarettes was much lower as compared to tobacco TPM. Although the production of ROS generated by e-cigarettes is comparatively lower than ROS generated by conventional cigarettes, EPFRs in e-cigarettes appear to be more potent than those in tobacco TPM with respect to hydroxyl radical generation yield per unit EPFR. EPFRs in e-cigarette TPM may be a potential source of health impacts.

Environmentally Persistent Free Radicals: Insights on a New Class of Pollutants.

Environmentally persistent free radicals, EPFRs, exist in significant concentration in atmospheric particulate matter (PM). EPFRs are primarily emitted from combustion and thermal processing of organic materials, in which the organic combustion byproducts interact with transition metal-containing particles to form a free radical-particle pollutant. While the existence of persistent free radicals in combustion has been known for over half-a-century, only recently that their presence in environmental matrices and health effects have started significant research, but still in its infancy. Most of the experimental studies conducted to understand the origin and nature of EPFRs have focused primarily on nanoparticles that are supported on a larger micrometer-sized particle that mimics incidental nanoparticles formed during combustion. Less is known on the extent by which EPFRs may form on engineered nanomaterials (ENMs) during combustion or thermal treatment. In this critical and timely review, we summarize important findings on EPFRs and discuss their potential to form on pristine ENMs as a new research direction. ENMs may form EPFRs that may differ in type and concentration compared to nanoparticles that are supported on larger particles. The lack of basic data and fundamental knowledge about the interaction of combustion byproducts with ENMs under high-temperature and oxidative conditions present an unknown environmental and health burden. Studying the extent of ENMs on catalyzing EPFRs is important to address the hazards of atmospheric PM fully from these emerging environmental contaminants.

Effect of Particulate Matter Mineral Composition on Environmentally Persistent Free Radical (EPFR) Formation.

Environmentally Persistent Free Radicals (EPFRs) are newly discovered, long-lived surface bound radicals that form on particulate matter and combustion borne particulates, such as fly ash. Human exposure to such particulates lead to translocation into the lungs and heart resulting in cardio-vascular and respiratory disease through the production of reactive oxygen species. Analysis of some waste incinerator fly ashes revealed a significant difference between their EPFR contents. Although EPFR formation occurs on the metal domains, these differences were correlated with the altering concentration of calcium and sulfur. To analyze these phenomena, surrogate fly ashes were synthesized to mimic the presence of their major mineral components, including metal oxides, calcium, and sulfur. The results of this study led to the conclusion that the presence of sulfates limits formation of EPFRs due to inhibition or poisoning of the transition metal active sites necessary for their formation. These findings provide a pathway toward understanding differences in EPFR presence on particulate matter and uncover the possibility of remediating EPFRs from incineration and hazardous waste sites.

Spatiotemporal patterns of childhood asthma hospitalization and utilization in Memphis Metropolitan Area from 2005 to 2015.

OBJECTIVE: To identify the key risk factors and explain the spatiotemporal patterns of childhood asthma in the Memphis metropolitan area (MMA) over an 11-year period (2005-2015). We hypothesize that in the MMA region this burden is more prevalent among urban children living south, downtown, and north of Memphis than in other areas. METHODS: We used a large-scale longitudinal electronic health record database from an integrated healthcare system, Geographic information systems (GIS), and statistical and space-time models to study the spatiotemporal distributions of childhood asthma at census tract level. RESULTS: We found statistically significant spatiotemporal clusters of childhood asthma in the south, west, and north of Memphis city after adjusting for key covariates. The results further show a significant increase in temporal gradient in frequency of emergency department (ED) visits and inpatient hospitalizations from 2009 to 2013, and an upward trajectory from 4 per 1,000 children in 2005 to 16 per 1,000 children in 2015. The multivariate logistic regression identified age, race, insurance, admit source, encounter type, and frequency of visits as significant risk factors for childhood asthma (p < 0.05). We observed a greater asthma burden and healthcare utilization for African American (AA) patients living in a high-risk area than those living in a low-risk area in comparison to the white patients: AA vs. white [odds ratio (OR) = 3.03, 95% confidence interval (CI): 2.75-3.34]; and Hispanic vs. white (OR = 1.62, 95% CI: 1.21-2.17). CONCLUSIONS: These findings provide a strong basis for developing geographically tailored population health strategies at the neighborhood level for young children with chronic respiratory conditions.

Environmentally persistent free radical-containing particulate matter competitively inhibits metabolism by cytochrome P450 1A2.

Combustion processes generate different types of particulate matter (PM) that can have deleterious effects on the pulmonary and cardiovascular systems. Environmentally persistent free radicals (EPFRs) represent a type of particulate matter that is generated after combustion of environmental wastes in the presence of redox-active metals and aromatic hydrocarbons. Cytochromes P450 (P450/CYP) are membrane-bound enzymes that are essential for the phase I metabolism of most lipophilic xenobiotics. The EPFR formed by chemisorption of 2-monochlorophenol to silica containing 5% copper oxide (MCP230) has been shown to generally inhibit the activities of different forms of P450s without affecting those of cytochrome P450 reductase and heme oxygenase-1. The mechanism of inhibition of rat liver microsomal CYP2D2 and purified rabbit CYP2B4 by MCP230 has been shown previously to be noncompetitive with respect to substrate. In this study, MCP230 was shown to competitively inhibit metabolism of 7-benzyl-4-trifluoromethylcoumarin and 7-ethoxyresorufin by the purified, reconstituted rabbit CYP1A2. MCP230 is at least 5- and 50-fold more potent as an inhibitor of CYP1A2 than silica containing 5% copper oxide and silica, respectively. Thus, even though PM generally inhibit multiple forms of P450, PM interacts differently with the forms of P450 resulting in different mechanisms of inhibition. P450s function as oligomeric complexes within the membrane. We also determined the mechanism by which PM inhibited metabolism by the mixed CYP1A2-CYP2B4 complex and found that the mechanism was purely competitive suggesting that the CYP2B4 is dramatically inhibited when bound to CYP1A2.

PCDD/PCDF ratio in the precursor formation model over CuO surface.

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.

Effect of copper oxide concentration on the formation and persistency of environmentally persistent free radicals (EPFRs) in particulates.

Environmentally persistent free radicals (EPFRs) are formed by the chemisorption of substituted aromatics on metal oxide surfaces in both combustion sources and superfund sites. The current study reports the dependency of EPFR yields and their persistency on metal loading in particles (0.25, 0.5, 0.75, 1, 2, and 5% CuO/silica). The EPFRs were generated through exposure of particles to three adsorbate vapors at 230 °C: phenol, 2-monochlorophenol (2-MCP), and dichlorobenzene (DCBz). Adsorption resulted in the formation of surface-bound phenoxyl- and semiquinoine-type radicals with characteristic EPR spectra displaying a g value ranging from ∼ 2.0037 to 2.006. The highest EPFR yield was observed for CuO concentrations between 1 and 3% in relation to MCP and phenol adsorption. However, radical density, which is expressed as the number of radicals per copper atom, was highest at 0.75-1% CuO loading. For 1,2-dichlorobenzene adsorption, radical concentration increased linearly with decreasing copper content. At the same time, a qualitative change in the radicals formed was observed--from semiquinone to chlorophenoxyl radicals. The two longest lifetimes, 25 and 23 h, were observed for phenoxyl-type radicals on 0.5% CuO and chlorophenoxyl-type radicals on 0.75% CuO, respectively.

Combustion By-Products and their Health Effects--combustion engineering and global health in the 21st century: issues and challenges.

The 13th International Congress on Combustion By-Products and their Health Effects was held in New Orleans, Louisiana from May 15 to 18, 2013. The congress, sponsored by the Superfund Research Program, National Institute of Environmental Health Sciences, and National Science Foundation, brought together international academic and government researchers, engineers, scientists, and policymakers. With industrial growth, increased power needs and generation and coal consumption and their concomitant emissions, pernicious health effects associated with exposures to these emissions are on the rise. This congress provides a unique platform for interdisciplinary exchange and discussion of these topics. The formation, conversion, control, and health effects of combustion by-products, including particulate matter and associated heavy metals, persistent organic pollutants, and environmentally persistent free radicals, were discussed during the congress. This review will summarize and discuss the implications of the data presented.

Tar balls from Deep Water Horizon oil spill: environmentally persistent free radicals (EPFR) formation during crude weathering.

Tar balls collected from the Gulf of Mexico shores of Louisiana and Florida after the BP oil spill have shown the presence of electron paramagnetic resonance (EPR) spectra characteristic of organic free radicals as well as transition metal ions, predominantly iron(III) and manganese(II). Two types of organic radicals were distinguished: an asphaltene radical species typically found in crude oil (g = 2.0035) and a new type of radical resulting from the environmental transformations of crude (g = 2.0041-47). Pure asphaltene radicals are resonance stabilized over a polyaromatic structure and are stable in air and unreactive. The new radicals were identified as products of partial oxidation of crude components and result from the interaction of the oxidized aromatics with metal ion centers. These radicals are similar to semiquinone-type, environmentally persistent free radicals (EPFRs) previously observed in combustion-generated particulate and contaminated soils.

Particulate matter containing environmentally persistent free radicals and adverse infant respiratory health effects: a review.

The health impacts of airborne particulate matter (PM) are of global concern, and the direct implications to the development/exacerbation of lung disease are immediately obvious. Most studies to date have sought to understand mechanisms associated with PM exposure in adults/adult animal models; however, infants are also at significant risk for exposure. Infants are affected differently than adults due to drastic immaturities, both physiologically and immunologically, and it is becoming apparent that they represent a critically understudied population. Highlighting our work funded by the ONES award, in this review we argue the understated importance of utilizing infant models to truly understand the etiology of PM-induced predisposition to severe, persistent lung disease. We also touch upon various mechanisms of PM-mediated respiratory damage, with a focus on the emerging importance of environmentally persistent free radicals (EPFRs) ubiquitously present in combustion-derived PM. In conclusion, we briefly comment on strengths/challenges facing current PM research, while giving perspective on how we may address these challenges in the future.

EPFR Formation from Phenol adsorption on Al2O3 and TiO2: EPR and EELS studies.

We have examined the formation of environmentally persistent free radicals (EPFRs) from phenol over alumina and titania using both powder and single-crystal samples. Electron paramagnetic resonance (EPR) studies of phenol adsorbed on metal oxide powders indicates radical formation on both titania and alumina, with both oxides forming one faster-decaying species (lifetime on the order of 50-100 hours) and one slower-decayng species (lifetimes on the order of 1000 hours or more). Electron energy loss spectroscopy (EELS) measurements comparing physisorbed phenol on single-crystal TiO2(110) to phenoxyl radicals on the same substrate indicate distinct changes in the π-π* transitions from phenol after radical formation. The identical shifts are observed from EELS studies of phenoxyl radicals on ultrathin alumina grown on NiAl(110), indicating that this shift in the π-π* transition may be taken as a general hallmark of phenoxyl radical formation.

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.

Household characteristics associated with environmentally persistent free radicals in house dust in two Australian locations.

The association between air pollution and adverse health outcomes has been extensively studied, and while oxidative stress in likely to be involved, the underlying mechanism(s) remain unclear. Recent studies propose environmentally persistent free radicals (EPFRs) as the missing connection between air pollution and detrimental health impacts. However, the indoor environment is rarely considered in EPFR research. We measured EPFRs in household dust from two locations in Australia and investigated household characteristics associated with EPFRs. Random forest models were built to identify important household characteristics through variable importance plots and the associations were analysed using Spearman's rho test. We found that age of house, type of garage, house outer wall material, heating method used in home, frequency of extractor fan use when cooking, traffic related air pollution, frequency of cleaning and major house renovation were important household characteristics associated with EPFRs in Australian homes. The direction of association between household characteristics and EPFRs differ between the locations. Hence, further research is warranted to determine the generalisability of our results.

Lifetime of combustion-generated environmentally persistent free radicals on Zn(II)O and other transition metal oxides.

Previous studies indicated that Environmentally Persistent Free Radicals (EPFRs) are formed in the post-flame, cool zone of combustion. They result from the chemisorption of gas-phase products of incomplete combustion (particularly hydroxyl- and chlorine-substituted aromatics) on Cu(II)O, Fe(III)(2)O(3), and Ni(II)O domains of particulate matter (fly ash or soot particles). This study reports our detailed laboratory investigation on the lifetime of EPFRs on Zn(II)O/silica surface. Similarly, as in the case of other transition metals, chemisorption of the adsorbate on the Zn(II)O surface and subsequent transfer of electron from the adsorbate to the metal forms a surface-bound EPFR and a reduced metal ion center. The EPFRs are stabilized by their interaction with the metal oxide domain surface. The half-lives of EPFRs formed on Zn(II)O domains were the longest observed among the transition metal oxides studied and ranged from 3 to 73 days. These half-lives were an order of magnitude longer than those formed on nickel and iron oxides, and were 2 orders of magnitude longer compared to the EPFRs on copper oxide which have half-lives only on the order of hours. The longest-lived radicals on Zn(II)O correspond to the persistency in ambient air particles of almost a year. The half-life of EPFRs was found to correlate with the standard reduction potential of the associated metal.

Environmentally persistent free radicals decrease cardiac function before and after ischemia/reperfusion injury in vivo.

Exposure to airborne particles is associated with increased cardiovascular morbidity and mortality. During the combustion of chlorine-containing hazardous materials and fuels, chlorinated hydrocarbons chemisorb to the surface of transition metal-oxide-containing particles, reduce the metal, and form an organic free radical. These radical-particle systems can survive in the environment for days and are called environmentally persistent free radicals (EPFRs). This study determined whether EPFRs could decrease left ventricular function before and after ischemia and reperfusion (I/R) in vivo. Male Brown-Norway rats were dosed (8 mg/kg, intratracheal) 24 h prior to testing with particles containing the EPFR of 1, 2-dichlorobenzene (DCB230). DCB230 treatment decreased systolic and diastolic function. DCB230 also produced pulmonary and cardiac inflammation. After ischemia, systolic, but not diastolic function was significantly decreased in DCB230-treated rats. Ventricular function was not affected by I/R in control rats. There was greater oxidative stress in the heart and increased 8-isoprostane (biomarker of oxidative stress) in the plasma of treated vs. control rats after I/R. These data demonstrate for the first time that DCB230 can produce inflammation and significantly decrease cardiac function at baseline and after I/R in vivo. Furthermore, these data suggest that EPFRs may be a risk factor for cardiac toxicity in healthy individuals and individuals with ischemic heart disease. Potential mechanisms involving cytokines/chemokines and/or oxidative stress are discussed.

Environmentally persistent free radicals (EPFRs). 1. Generation of reactive oxygen species in aqueous solutions.

Reactive oxygen species (ROS) generated by environmentally persistent free radicals (EPFRs) of 2-monochlorophenol, associated with CuO/silica particles, were detected using the chemical spin trap, 5,5-dimethyl-1-pyrroline-N-oxide (DMPO), in conjunction with electron paramagnetic resonance (EPR) spectroscopy. Yields of hydroxyl radical ((•)OH), superoxide anion radical (O(2)(•-)), and hydrogen peroxide (H(2)O(2)) generated by EPFR-particle systems were reported. Failure to trap superoxide radicals in aqueous solvent, formed from reaction of EPFRs with molecular oxygen, results from fast transformation of the superoxide to hydrogen peroxide. However, formation of superoxide as an intermediate product in hydroxyl radical formation in aprotic solutions of dimethyl sulfoxide (DMSO) and acetonitrile (AcN) was observed. Experiments with superoxide dismutase (SOD) and catalase (CAT) confirmed formation of superoxide and hydrogen peroxide, respectively, in the presence of EPFRs. The large number of hydroxyl radicals formed per EPFR and monotonic increase of the DMPO-OH spin adduct concentration with incubation time suggest a catalytic cycle of ROS formation.

Phytosampling-a supplementary tool for particulate matter (PM) speciation characterization.

Ambient air particulate matter (PM) and PM-associated environmentally persistent free radicals (EPFRs) have been documented to contribute to pollution-related health effects. Studies of ambient air PM potentially bear artifacts stemming from the collection methods. We have investigated the applicability of PM phytosampling (PHS) as a supplementary tool to a classic PM sampler in respect of achieving better PM chemical composition assessment (primarily organic fraction). Phytosampling is a static PM collection method relying on the particle entrapment by the plant's leaf through electrostatic forces and surface trichomes. We have investigated the differences in the EPFR and polycyclic aromatic hydrocarbon (PAH) speciation and concentration on ambient air PM for PHS and high-volume PM sampler (HVS). The advantages of PHS are easy particle recovery from the matrix, collection under natural environmental conditions, and the ability to apply a dense collection network to accurately represent spatial pollutant distribution. The experimental results show that the PHS can provide valuable speciation information, sometimes different from that observed for HVS. For PM collected by PHS, we detected the larger contribution of oxygen-centered EPFRs, different decay behavior, and more consistent PAH distribution between different PM sizes compared to the PM from HVS. These results indicate that the isolation of samples from the ambient during HVS sampling and exposure to high-volume airflow may alter the chemical composition of the samples, while the PHS method could provide details on the original speciation and concentration and be more representative of the PM surface. However, PHS cannot evaluate an absolute air concentration of PM, so it serves as an excellent supplementary tool to work in conjunction with the standard PM collection method.

Size-selective synthesis of immobilized copper oxide nanoclusters on silica.

We report a straightforward route for preparing bulk quantities of size-controlled and low size dispersity copper oxide nanoclusters on amorphous silica. Adsorption of the copper-dendrimer complex on the silica surface minimizes aggregation, which results in previously unachieved low size dispersity of the nanoclusters. Copper oxide nanoclusters with mean diameters of 1-5 nm with size dispersities of only 8-15% were prepared by calcination of silica impregnated with Cu(II)-poly(propylene imine) dendrimer complexes of varying stoichiometry. The size and size distribution of the copper oxide nanoparticles are tunably controlled by the ratio of the Cu(II) to the terminal primary amines in the copper-dendrimer complex, DAB-Am n -Cu(II) x , the surface coverage of the DAB-Am n -Cu(II) x , and the impregnation procedure. This method is anticipated to be useful in the preparation of other metal oxide nanoparticles, e.g., Ni and Fe, and with other oxide substrates.

Formation of DF, PCDD/Fs and EPFRs from 1,2,3-trichlorobenzene over metal oxide/silica surface.

The formation of dibenzofuran (DF), polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and environmentally persistent free radicals (EPFRs) from 1,2,3-trichlorobenzene (1,2,3-TrCBz) over metal oxide / silica surface were investigated using a tubular furnace. PCDD/Fs increased exponentially from 250 to 550 °C over copper oxide / silica surface and PCDD/Fs had the maximum growth from 400 to 450 °C. The ratio of PCDD / PCDF was much less than 1, especially when the temperature raised from 450 to 550 °C. Pentachlorianated dibenzo-p-furan (PeCDF) dominated among the homologues, which contributed 45-61% to the total PCDD/Fs. Two peaks of the yield of DF occurred at 400 °C and 500 °C respectively. Furthermore, the oxygen contents have different effects for PCDD and PCDF formation, and low oxygen could promote PCDD production, especially for tetrachlorinated dibenzo-p-dioxin (TCDD). More PCDF were formed on the oxygen rich condition, indicating that the oxygen promoted the chlorination of DF. Iron oxides are better than copper oxides to catalyze the formation of PCDD/Fs from 1,2,3-TrCBzs at 350 °C, especially for PCDF. The major EPFRs on the catalysts were formed with g values in the range of 2.0040 to 2.0049, which were phenoxy radicals and semiquinone occurred with higher g value of 2.0075 when the temperature increased to 550 °C, and more EPFRs were produced with the temperature increasing. The addition of iron oxides reduced the spins concentrations of oxygen-centered radicals but increase the spins concentrations of signals with lower g values. The different possible formation pathways of PCDD and PCDF from 1,2,3-TrCBz over metal oxide surface were also proposed.