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.

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.

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.

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.