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.

A Community-Integrated Geographic Information System Study of Air Pollution Exposure Impacts in Colfax, LA.

A community-integrated geographic information systems (CIGIS) study assimilating qualitative and quantitative information about human exposures and health was conducted in Colfax, Louisiana, which hosts a commercial open burn/open detonation thermal treatment (TT) facility that destroys waste from Superfund sites, explosives, military ordnances, and propellants. Fifty-eight percent of residents identified as Black, and median annual income was $16,318, with 90% of the population living below the poverty line. We conducted oral history interviews of twenty-nine residents and mined public records to document the community's experiences. Interviews focused on themes of Colfax's history, changing community fabric, resident health, and air pollution. The oral histories and public comments by community members provided information about lived experiences, including several health conditions, toleration of noise and vibration, property damage, and resulting changes to activity levels. These statements provided insight into the extent of suffering experienced by the local community. We also ran dispersion models for dates in 2020 when the waste stream composition, mass, and burn/smoldering times were provided in the facility's public records. The dispersion models placed the air pollution at the homes of residents during some of the time, and waste stream records from the TT facility agree with community testimony about health effects based on the known health effects of those compounds. CIGIS integration of our community-based qualitative data and maps with quantitative air pollution dispersion model output illustrated alignment between community complaints of impacts to health and property, known toxicological information about waste stream compounds, and dispersion model output.

Increased alveolar epithelial TRAF6 via autophagy-dependent TRIM37 degradation mediates particulate matter-induced lung metastasis.

Epidemiological and clinical studies have shown that exposure to particulate matter (PM) is associated with an increased incidence of lung cancer and metastasis. However, the underlying mechanism remains unclear. Here, we demonstrated the central role of PM-induced neutrophil recruitment in promoting lung cancer metastasis. We found that reactive oxygen species (ROS)-mediated alveolar epithelial macroautophagy/autophagy was essential for initiating neutrophil chemotaxis and pre-metastatic niche formation in the lungs in response to PM exposure. During PM-induced autophagy, the E3 ubiquitin ligase TRIM37 was degraded and protected TRAF6 from proteasomal degradation in lung epithelial cells, which promoted the NFKB-dependent production of chemokines to recruit neutrophils. Importantly, ROS blockade, autophagy inhibition or TRAF6 knockdown abolished PM-induced neutrophil recruitment and lung metastasis enhancement. Our study indicates that host lung epithelial cells and neutrophils coordinate to promote cancer metastasis to the lungs in response to PM exposure and provides ideal therapeutic targets for metastatic progression.Abbreviations: ACTA2/α-SMA: actin alpha 2, smooth muscle, aorta; ATII: alveolar type II; Cho-Traf6 siRNA: 5'-cholesterol-Traf6 siRNA; EMT: epithelial-mesenchymal transition; HBE: human bronchial epithelial; HCQ: hydroxychloroquine; MAPK: mitogen-activated protein kinase; NAC: N-acetyl-L-cysteine; NFKB: nuclear factor of kappa light polypeptide gene enhancer in B cells; NS: normal saline; PM: particulate matter; ROS: reactive oxygen species; TRAF6: TNF receptor-associated factor 6; TRIM37: tripartite motif-containing 37.

Impact of biochar, fertilizers and cultivation type on environmentally persistent free radicals in agricultural soil.

Environmentally persistent free radicals (EPFRs) have been considered as emerging contaminants due to their detrimental effects on human health. The adverse health impacts are attributed to oxidative stress induced by EPFRs through the formation of reactive oxygen species (ROS). In soils, it may also increase the degradation process of polymeric organic matter and/or undesired organic pollutants through hydroxyl radical activity. The biochar pyrolysis process entails the thermal decomposition of organic compounds in the biomass, with the carbonization conditions and feedstock type facilitating the formation of EPFRs. When biochar is used to amend soil, these radicals may promote the formation of ROS, and thus influence the transformation of organic and inorganic contaminants in soil and impact the rhizosphere. Agricultural soils are being amended with biochar to mainly increase carbon content and facilitate the plant growing conditions. Therefore, agricultural soils may become a source of EPFRs. However, the fate and transformations of EPFRs in soils after biochar amendment are not well understood or studied. This paper presents the first (to our knowledge) studies of EPFRs behaviour in agricultural soil with different input of biochar, cultivation types and residence time period. Different cultivation types, addition of fertilisers and variation in biochar input, on the one hand, and presence of metals in soil, biochar and fertilizers, on the other hand, provide different conditions for EPFRs formation, accumulation and fate in agricultural soils. Two significant factors have been found to determine the fate of EPFRs in soil: transition metal content (particularly those in reaction available form) and cultivation level of soil. Cultivation significantly decreased presence of EPFRs, both carbon-centered and oxygen-centered, in relatively short periods of time, while metal presence (and particularly through fertilizer supplementation) increases the half-life of radicals and transforms organic matter to more oxygen-centered EPFRs. The amount of biochar addition plays a secondary role as the EPFRs content in the soils is in a longer term primarily controlled by the other two factors.

A critical review of environmentally persistent free radical (EPFR) solvent extraction methodology and retrieval efficiency.

Long-lived environmentally persistent free radical (EPFR) exposures have been shown in toxicology studies to lead to respiratory and cardiovascular effects, which were thought to be due to the persistence of EPFR and their ability to produce reactive oxygen species. To characterize EPFR exposure and resulting health impacts, it is necessary to identify and systematize analysis protocols. Both direct measurement and solvent extraction methods have been applied to analyze environmental samples containing EPFR. The use of different protocols and solvents in EPFR analyses makes it difficult to compare results among studies. In this work, we reviewed EPFR studies that involved solvent extraction and carefully reported the details of the extraction methodology and retrieval recovery. EPFR recovery depends on the structure of the radical species and the solvent. For the limited number of studies available for review, the polar solvents had superior recovery in more studies. Radicals appeared to be more oxygen-centered following extraction for fly ash and particulate matter (PM) samples. Different solvent extraction methods to retrieve EPFR may produce molecular products during the extraction, thus potentially changing the sample toxicity. The number of studies reporting detailed methodologies is limited, and data in these studies were not consistently reported. Thus, inference about the solvent and protocol that leads to the highest EPFR extraction efficiency for certain types of radicals is not currently possible. Based on our review, we proposed reporting criteria to be included for future EPFR studies.

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.

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.