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It has been demonstrated that propylene glycol (PG), vegetable glycerin (VG), and flavoring chemicals can thermally degrade to form carbonyls during vaping, but less is known about carbonyl emissions produced by transformation of flavoring chemicals and the interactive effects among e-liquid constituents. This study characterized carbonyl composition and levels in vaping emissions of PG-VG (e-liquid base solvents) and four e-liquid formulations flavored with trans-2-hexenol, benzyl alcohol, l-(-)-menthol, or linalool. Utilizing gas chromatography (GC)- and liquid chromatography (LC)-mass spectrometry (MS) methods, 14 carbonyls were identified and quantified. PG-VG emitted highest levels of formaldehyde, acetaldehyde, and acrolein. However, flavored e-liquids contributed to the production of a wider variety of carbonyls, with some carbonyls directly corresponding to the oxidation of alcohol moieties in flavoring compounds (e.g., trans-2-hexenol and benzyl alcohol transformed into trans-2-hexenal and benzaldehyde, respectively). Detections of formaldehyde-GSH and trans-2-hexenal-GSH adducts signify interactions of carbonyls with biological nucleophiles. The global reactivity descriptors (I, A, μ, η, and ω) and condensed Fukui parameters ( f k 0 , f k − , f k + , and dual-descriptor) were computed to elucidate site reactivities of selected simple and α,β-unsaturated carbonyls found in vaping emissions. Overall, this study highlights carbonyl emissions and reactivities and their potential health risk effects associated with vaping. [ABSTRACT FROM AUTHOR]

Oxidative potential (OP) has been proposed as a useful descriptor for the ability of particulate matter (PM) to generate reactive oxygen species (ROS) and consequently induce oxidative stress in biological systems, which has been recognized as one of the most important mechanisms responsible for PM toxicity. The dithiothreitol (DTT) assay is one of the most frequently used techniques to quantify OP because it is low-cost, easy-to-operate, and has high repeatability. With two thiol groups, DTT has been used as a surrogate of biological sulfurs that can be oxidized when exposed to ROS. Within the DTT measurement matrix, OP is defined as the DTT consumption rate. Often, the DTT consumption can be attributed to the presence of transition metals and quinones in PM as they can catalyze the oxidation of DTT through catalytic redox reactions. However, the DTT consumption by non-catalytic PM components has not been fully investigated. In addition, weak correlations between DTT consumption, ROS generation, and cellular responses have been observed in several studies, which also reveal the knowledge gaps between DTT-based OP measurements and their implication on health effects. In this review, we critically assessed the current challenges and limitations of DTT measurement, highlighted the understudied DTT consumption mechanisms, elaborated the necessity to understand both PM-bound and PM-induced ROS, and concluded with research needs to bridge the existing knowledge gaps. [ABSTRACT FROM AUTHOR]

Exposure to diesel exhaust particles (DEP) has been linked to a variety of adverse health effects, including increased morbidity and mortality from cardiovascular diseases, chronic obstructive pulmonary disease (COPD), metabolic syndrome, and lung cancer. The epigenetic changes caused by air pollution have been associated with increased health risks. However, the exact molecular mechanisms underlying the lncRNA-mediated pathogenesis induced by DEP exposure have not been revealed. Through RNA-sequencing and integrative analysis of both mRNA and lncRNA profiles, this study investigated the role of lncRNAs in altered gene expression in healthy and diseased human primary epithelial cells (NHBE and DHBE-COPD) exposed to DEP at a dose of 30 μg/cm2. We identified 503 and 563 differentially expressed (DE) mRNAs and a total of 10 and 14 DE lncRNAs in NHBE and DHBE-COPD cells exposed to DEP, respectively. In both NHBE and DHBE-COPD cells, enriched cancer-related pathways were identified at mRNA level, and 3 common lncRNAs OLMALINC, AC069234.2, and LINC00665 were found to be associated with cancer initiation and progression. In addition, we identified two cis-acting (TMEM51-AS1 and TTN-AS1) and several trans-acting lncRNAs (e.g. LINC01278, SNHG29, AC006064.4, TMEM51-AS1) only differentially expressed in COPD cells, which could potentially play a role in carcinogenesis and determine their susceptibility to DEP exposure. Overall, our work highlights the potential importance of lncRNAs in regulating DEP-induced gene expression changes associated with carcinogenesis, and individuals suffering from COPD are likely to be more vulnerable to these environmental triggers. [ABSTRACT FROM AUTHOR]

Thermal treatment is effective for the removal of perfluorooctanoic acid (PFOA). However, how temperatures, heating methods, and granular activated carbon (GAC) influence pyrolysis of PFOA, and emission risks are not fully understood. We studied thermal behaviors of PFOA at various conditions and analyzed gaseous products using real-time detection technologies and gas chromatography-mass spectrometry (GC-MS). The thermal decomposition of PFOA is surface-mediated. On the surface of quartz, PFOA decomposed into perfluoro-1-heptene and perfluoro-2-heptene, while on GAC, it tended to decompose into 1 H-perfluoroheptane (C 7 HF 15). Neutral PFOA started evaporating around 100 ℃ without decomposition in ramp heating. During pyrolysis, when PFOA was pre-adsorbed onto GAC, it was mineralized into SiF 4 and produced more than 45 volatile organic fluorine (VOF) byproducts, including perfluorocarbons (PFCs) and hydrofluorocarbons (HFCs). The VOF products were longer-chain (hydro)fluorocarbons (C4-C7) at low temperatures (< 500 ℃) and became shorter-chain (C1-C4) at higher temperatures (> 600 ℃). PFOA transformations include decarboxylation, VOF desorption, further organofluorine decomposition and mineralization in ramp heating of PFOA-laden GAC. Decarboxylation initiates at 120 ℃, but other processes require higher temperatures (>200 ℃). These results offer valuable information regarding the thermal regeneration of PFAS-laden GAC and further VOF control with the afterburner or thermal oxidizer. [Display omitted] • Neutral PFOA has strong emission potential at lower temperatures (< 100 °C). • Surface-mediated thermal decomposition determines the fate of PFOA degradation products. • PFOA decomposes into 1-C7F14 on the surface of quartz but C7HF15 on the GAC. • Pyrolysis of PFOA-laden GAC yielded SiF4 and 45 VOF by-products. • PFOA has three thermal transformation stages during ramp heating. [ABSTRACT FROM AUTHOR]

Thermal treatment is a widely used remediation strategy for PFAS-contaminated materials such as soil, spent sorbents, and domestic waste. To better understand the effectiveness and environmental impact of thermal treatments for PFAS-contaminated materials, a fundamental understanding of PFAS thermal degradation mechanisms is required. This work aims to study the pyrolysis of six representative PFAS compounds, all of which have an eight-carbon length but with different functional groups. To assess the thermal stability and pyrolysis products of these six PFAS compounds, evolved gas analysis (EGA) was performed using thermogravimetric analysis/differential scanning calorimetry (TGA/DSC) coupled with an infrared spectrometer (IR) and a mass spectrometer (MS), as well as pyrolysis-GCMS (Pyr-GCMS). The EGA data demonstrates that compounds with lower estimated vapor pressures were generally found to be more thermally labile, and the presence of an ionic bond necessitates higher temperatures for pyrolysis. Pyrolysis at 900 °C yielded a variety of fluorinated organic compounds at significant signals. Tetrafluoroethene constituted the majority of the Pyr-GCMS signal for all the compounds. Moreover, a significant fraction of detected products was unable to be identified, underscoring a need for better tools to help with the identification of unknowns. Pyrolysis can occur through random chain scission, scission of the functional group, scission of the terminal CF 3 group, and HF elimination. Some compounds may undergo more complete beta-scission to produce smaller pyrolysis products compared to others. The presence of acidic protons within the functional group can help facilitate HF elimination, whereas the salt form of a PFAS compound is less likely to undergo HF elimination. Termination of radical intermediates can either be recombination with a CF 3 radical or hydrogen abstraction (H-abstraction). Observed hydrogen-substituted products indicate that functional groups with higher hydrocarbon character may lead to more H-abstraction terminated products. Overall findings show that the functional group of a PFAS may decrease or increase its thermal stability and lead to different profiles of pyrolysis products. [Display omitted] • PFAS functional groups affect thermal stability and pyrolysis product distribution. • Incomplete destruction remains from high temperature pyrolysis. • Pyrolysis products have been characterized with a significant fraction of unknowns. • Functional groups with more hydrocarbons yield more hydrogen-substituted products. • Functional groups influence the initiation and termination pathways. [ABSTRACT FROM AUTHOR]

222 nm UV indoor disinfection using KrCl* excimer lamps has been gaining popularity due to claims of minimal ocular and skin damage from direct irradiation. However, the secondary aerosol formation under irradiation of KrCl* excimer lamps, which could be an inhalation hazard, is less explored. SO 2 , a well-known precursor of outdoor sulfate aerosol, is also ubiquitous in indoor environments in urban cities in northern China where coal is used for domestic heating and cooking. In this work, we studied secondary aerosol formation by 222 nm irradiation on SO 2 , using a Go: PAM flow reactor, a scanning mobility particle sizer (SMPS), and a time-of-flight aerosol chemical composition monitor (ToF-ACSM). The formation of sulfate nanoparticles was found much more effective at 222 nm than at 254 nm and under fluorescent lamp (FL) irradiation at the same UV doses and RH, likely due to different SO 2 oxidation mechanisms. We have also found that NH 3 and cooking volatile organic compounds (CVOC), as other indoor-relevant gases, promoted the formation of secondary aerosols by 222 nm radiation on SO 2. Overall, 222 nm disinfection can generate secondary pollutants in indoor environments. Caution should be taken during its indoor applications, especially in areas with high SO 2 concentrations such as coal-fueled households. • 222 nm UV irradiation drives more rapid SO 2 oxidation to sulfate, compared to 254 nm and fluorescence lamps. • Sulfate formation under 222 nm irradiation is more prominent at higher RHs. • Indoor-relevant gases such as NH 3 promote secondary aerosol formation initiated by 222 nm SO 2 photochemistry. • 222 nm SO 2 photochemistry has great potential to elevate the indoor particulate level. [ABSTRACT FROM AUTHOR]

Nearly two years after vitamin E acetate (VEA) was identified as the potential cause of the 2019–2020 outbreak of e-cigarette, or vaping product-associated lung injuries (EVALI), the toxicity mechanisms of VEA vaping are still yet to be fully understood. Studies since the outbreak have found that e-liquids such as VEA undergo thermal degradation during the vaping process to produce various degradation products, which may pose a greater risk of toxicity than exposure to unvaped VEA. Additionally, a wide range of customizable parameters–including the model of e-cigarette used, puffing topography, or the applied power/temperature used to generate aerosols–have been found to influence the physical properties and chemical compositions of vaping emissions. However, the impact of heating coil temperature on the chemical composition of VEA vaping emissions has not been fully assessed. In this study, we investigated the emission product distribution of VEA vaping emissions produced at temperatures ranging from 176 to 356°C, corresponding to a variable voltage vape pen set at 3.3 to 4.8V. VEA degradation was found to be greatly enhanced with increasing temperature, resulting in a shift towards the production of lower molecular weight compounds, such as the redox active duroquinone (DQ) and short-chain alkenes. Low temperature vaping of VEA resulted in the production of long-chain molecules, such as phytol, exposure to which has been suggested to induce lung damage in previous studies. Furthermore, differential product distribution was observed in VEA degradation products generated from vaping and from pyrolysis using a tube furnace in the absence of the heating coil at equivalent temperatures, suggesting the presence of external factors such as metals or oxidation that may enhance VEA degradation during vaping. Overall, our findings indicate that vaping behavior may significantly impact the risk of exposure to toxic vaping products and potential for vaping-related health concerns. [ABSTRACT FROM AUTHOR]

• C in soils across a single furrow irrigated orchard were assessed in soils with contrasting wet-dry cycling frequencies. • CO 2 efflux in repeated wet-dry soils from furrow irrigation is diffusion controlled. • SOC in furrow that have undergone wet-dry cycling is more stable than SOC in berms. • Oxidation state of furrow porewater DOC is strongly suggestive of selective substrate use. • Anaerobic microbes dominate in furrow; aerobic bacteria dominate in berm. Drying-rewetting cycles are ubiquitous across natural and managed ecosystems. These cycles are known to mobilize carbon (C) in soils producing dramatic pulses in microbial respiration. While many factors contribute to these pulses, the drying-rewetting history of soils affecting carbon emissions remains unclear, especially in irrigated soils where soil moisture fluctuations are more repetitive and/or frequent than natural, seasonally influenced soils. To understand the controls of repeated wet-up and dry down effects on agricultural soils, we used a systems approach to examine the cross section of a furrow irrigated orchard to delineate soil C dynamics. Specifically, we compared two contrasting water regimes, (1) soils temporarily but repeatedly inundated during water delivery (i.e., furrows) and (2) soils at the base of trees (i.e., berms) that only receive water during precipitation events in a semi-arid Mediterranean climate. Overall, our findings show that the heterogeneous landscape of a furrow irrigated field results in two separate systems within the field scale in gaseous release of C as CO 2 , microbial selectivity of substrates, and mechanisms for C stabilization. By monitoring soil moisture as a function of depth for over two years, our results reveal that furrow soils undergo dramatic wet-dry cycles, while moisture within the berm is relatively constant. We were able to capture the distinct heterogeneity of soil moisture changes within the furrow and berm soils by continuously monitoring CO 2 flux throughout water input events in both the wet and dry season. Soil CO 2 efflux is suppressed upon irrigation within furrows, while carbon oxidation in berm soils exhibits pore-connectivity limitations that result in lower fluxes when dry. Solid phase soil C speciation determined by C 1s NEXAFS demonstrated C of higher aromaticity remained in furrow soil compared to berm soils. Microbial community analysis shows significantly different communities reside within berm and furrow soils, where furrow soils support more anaerobic metabolisms and spore-formers while berm soils have relatively higher abundance of aerobic microbes capable of degrading larger, more complex C compounds. Our findings show that water regime (periodic inundation vs episodic rainfall) controlling rewetting history can greatly differentiate C respiration within managed soils. [ABSTRACT FROM AUTHOR]

In this study, we assessed the toxicological potencies of particulate matter (PM) emissions from a modern vehicle equipped with a gasoline direct injection (GDI) engine when operated on eight different fuels with varying aromatic hydrocarbon and ethanol contents. Testing was conducted over the LA92 driving cycle using a chassis dynamometer with a constant volume sampling system, where particles were collected onto Teflon filters. The extracted PM constituents were analyzed for their oxidative potential using the dithiothreitol (DTT) chemical assay and exposure-induced gene expression in human airway epithelial cells (BEAS-2B). Different trends of DTT activities were seen when testing PM samples in 100% aqueous buffer solutions versus elevated fraction of methanol in aqueous buffers (50:50), indicating the effect of solubility of organic PM constituents on the measured oxidative potential. Higher aromatics content in fuels corresponded to higher DTT activities in PM. Exposure to PM exhaust upregulated the expression of HMOX-1 , but downregulated the expression of IL-6 , TNF-α , CCL5 and NOS2 in BEAS-2B cells. The principal component regression analysis revealed different patterns of correlations. Aromatics content contributed to more significant PAH-mediated IL-6 downregulation, whereas ethanol content was associated with decreased downregulation of IL-6. Our findings highlighted the key role of fuel composition in modulating the toxicological responses to GDI PM emissions. Unlabelled Image • Solubility of reactive PM components affects measured aerosol oxidative potential. • Higher aromatic content in fuels corresponded to higher DTT activities in PM. • PM upregulated HMOX-1 , and downregulated IL-6 , TNF-α , CCL5 and NOS2 in BEAS-2B. • Different correlation patterns identified for aromatic and ethanol content in fuels • Higher ethanol fuel was associated with decreased downregulation of IL-6. [ABSTRACT FROM AUTHOR]

Thermal treatment of perfluoroalkyl and polyfluoroalkyl substances (PFASs) presents a promising opportunity to halt the PFAS cycle. However, how co-occurring materials such as granular activated carbon (GAC) influence thermal decomposition products of PFASs, and underlying mechanisms remain unclear. We studied the pyrolysis of two potassium salts of perfluoroalkanesulfonates (PFSAs, C n F 2n+1 SO 3 K), perfluorobutanesulfonate (PFBS-K), and perfluorooctanesulfonate (PFOS-K), with or without GAC. PFBS-K is more stable than PFOS-K for pure standards, but when it is adsorbed onto GAC, its thermal stabilities and decomposition behaviors are similar. Temperatures and heating rates can significantly influence the decomposition mechanisms and products for pure standards, while these effects are less pronounced when PFSAs are adsorbed onto GAC. We further studied the underlying decomposition mechanisms. Pure standards of C n F 2n+1 SO 3 K can decompose directly in their condense phase by reactions: F(CF 2 ) n SO 3 K → F(CF 2 ) n-2 CF═CF 2 + KFSO 3 or F(CF 2 ) n SO 3 K → F(CF 2 ) n - + K + + SO 3 . GAC appears to facilitate breakage of the C-S bond to release SO 2 at temperatures as low as 280 °C. GAC promotes fluorine mineralization through functional reactive sites. SiO 2 is particularly important for the surface-mediated mineralization of PFASs into SiF 4 . These findings offer valuable insights into optimizing thermal treatment strategies for PFAS-contaminated waste.

The molybdenum- and tungsten-containing formate dehydrogenases from a variety of microorganisms catalyze the reversible interconversion of formate and CO 2 ; several, in fact, function as CO 2 reductases in the reverse direction under physiological conditions. CO 2 reduction catalyzed by these enzymes occurs under mild temperature and pressure rather than the elevated conditions required for current industrial processes. Given the contemporary importance of remediation of atmospheric CO 2 to address global warming, there has been considerable interest in the application of these enzymes in bioreactors. Equally important, understanding the detailed means by which these biological catalysts convert CO 2 to formate, a useful and easily transported feedstock chemical, might also inspire the development of a new generation of highly efficient, biomimetic synthetic catalysts. Here we have examined the ability of the FdsDABG formate dehydrogenase from Cupriavidus necator to catalyze the exchange of solvent oxygen into product CO 2 during the course of formate oxidation under single-turnover conditions. Negligible incorporation of 18 O is observed when the experiment is performed in H 2 18 O, indicating that bicarbonate cannot be the immediate product of the enzyme-catalyzed reaction, as previously concluded. These results, in conjunction with the observation that the reductive half-reaction exhibits mildly acid-catalyzed rather than base-catalyzed chemistry, are consistent with a reaction mechanism involving direct hydride transfer from formate to the enzyme's molybdenum center, directly yielding CO 2 . Our results are inconsistent with any mechanism in which the initial product formed on oxidation of formate is bicarbonate.

The light absorption properties of brown carbon (BrC), which are linked to molecular chromophores, may play a significant role in the Earth's energy budget. While nitroaromatic compounds have been identified as strong chromophores in wildfire-driven BrC, other types of chromophores remain to be investigated. Given the electron-withdrawing nature of carbonyls ubiquitous in the atmosphere, we characterized carbonyl chromophores in BrC samples from the nighttime oxidation of furan and pyrrole derivatives, which are important but understudied precursors of secondary organic aerosols primarily found in wildfire emissions. Various carbonyl chromophores were characterized and quantified in BrC samples, and their ultraviolet-visible spectra were simulated by using time-dependent density functional theory. Our findings suggest that chromophores with carbonyls bonded to nitrogen (i.e., imides and amides) derived from N-containing heterocyclic precursors substantially contribute to BrC light absorption. The quantified N-containing carbonyl chromophores contributed to over 40% of the total light absorption at wavelengths below 350 nm and above 430 nm in pyrrole BrC. The contributions of chromophores to total light absorption differed significantly by wavelength, highlighting their divergent importance in different wavelength ranges. Overall, our findings highlight the significance of carbonyl chromophores in secondary BrC and underscore the need for further investigation.

Fluoroalkylether substances (ether PFAS) constitute a large group of emerging PFAS with uncertain environmental fate. Among them, GenX is the well-known alternative to perfluorooctanoic acid and one of the six proposed PFAS to be regulated by the U.S. Environmental Protection Agency. This study investigated the structure-biodegradability relationship for 12 different ether PFAS with a carboxylic acid headgroup in activated sludge communities. Only polyfluorinated ethers with at least one -CH 2 - moiety adjacent to or a C=C bond in the proximity of the ether bond underwent active biotransformation via oxidative and hydrolytic O-dealkylation. The bioreactions at ether bonds led to the formation of unstable fluoroalcohol intermediates subject to spontaneous defluorination. We further demonstrated that this aerobic biotransformation/defluorination could complement the advanced reduction process in a treatment train system to achieve more cost-effective treatment for GenX and other recalcitrant perfluorinated ether PFAS. These findings provide essential insights into the environmental fate of ether PFAS, the design of biodegradable alternative PFAS, and the development of cost-effective ether PFAS treatment strategies., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

Despite previous studies indicating the thermal stability of vitamin E acetate (VEA) at low temperatures, VEA has been shown to readily decompose into various degradation products such as alkenes, long-chain alcohols, and carbonyls such as duroquinone (DQ) at vaping temperatures of <200 °C. While most models simulate the thermal decomposition of e-liquids under pyrolysis conditions, numerous factors, including vaping behavior, device construction, and the surrounding environment, may impact the thermal degradation process. In this study, we investigated the role of the presence of molecular oxygen (O 2 ) and transition metals in promoting thermal oxidation of e-liquids, resulting in greater degradation than predicted by pure pyrolysis. Thermal degradation of VEA was performed in inert (N 2 ) and oxidizing atmospheres (clean air) in the absence and presence of Ni-Cr and Cu-Ni alloy nanopowders, metals commonly found in the heating coil and body of e-cigarettes. VEA degradation was analyzed using thermogravimetric analysis (TGA) and gas chromatography/mass spectrometry (GC/MS). While the presence of O 2 was found to significantly enhance the degradation of VEA at both high (356 °C) and low (176 °C) temperatures, the addition of Cu-Ni to oxidizing atmospheres was found to greatly enhance VEA degradation, resulting in the formation of numerous degradation products previously identified in VEA vaping emissions. O 2 and Cu-Ni nanopowder together were also found to significantly increase the production of OH radicals, which has implications for e-liquid degradation pathways as well as the potential risk of oxidative damage to biological systems in real-world vaping scenarios. Ultimately, the results presented in this study highlight the importance of oxidation pathways in VEA thermal degradation and may aid in the prediction of thermal degradation products from e-liquids.

Background: Existing studies on the health effects of e-cigarettes focused on e-cigarette users themselves. To study the corresponding effects on passive vapers, it is crucial to quantify e-cigarette chemicals deposited in their airways., Objective: This study proposed an innovative approach to estimate the deposited dose of e-cigarette chemicals in the passive vapers' airways. The effect of the distance between active and passive vapers on the deposited dose was also examined., Methods: The chemical constituent analysis was conducted to detect Nicotine and flavoring agents in e-cigarette aerosol. The Mobile Aerosol Lung Deposition Apparatus (MALDA) was employed to conduct aerosol respiratory deposition experiments in real-life settings to generate real-time data., Results: For e-cigarette aerosol in the ultrafine particle regime, the deposited doses in the alveolar region were on average 3.2 times higher than those in the head-to-TB airways, and the deposited dose in the passive vaper's airways increased when being closer to the active vaper., Significance: With prolonged exposure and close proximity to active vapers, passive vapers may be at risk for potential health effects of harmful e-cigarette chemicals. The methodology developed in this study has laid the groundwork for future research on exposure assessment and health risk analysis for passive vaping., (© 2021. The Author(s), under exclusive licence to Springer Nature America, Inc.)

The C-F bond is one of the strongest single bonds in nature. Although microbial reductive dehalogenation is well known for the other organohalides, no microbial reductive defluorination has been documented for perfluorinated compounds except for a single, nonreproducible study on trifluoroacetate. Here, we report on C-F bond cleavage in two C 6 per- and polyfluorinated compounds via reductive defluorination by an organohalide-respiring microbial community. The reductive defluorination was demonstrated by the release of F - and the formation of the corresponding product when lactate was the electron donor, and the fluorinated compound was the sole electron acceptor. The major dechlorinating species in the seed culture, Dehalococcoides , were not responsible for the defluorination as no growth of Dehalococcoides or active expression of Dehalococcoides- reductive dehalogenases was observed. It suggests that minor phylogenetic groups in the community might be responsible for the reductive defluorination. These findings expand our fundamental knowledge of microbial reductive dehalogenation and warrant further studies on the enrichment, identification, and isolation of responsible microorganisms and enzymes. Given the wide use and emerging concerns of fluorinated organics (e.g., per- and polyfluoroalkyl substances), particularly the perfluorinated ones, the discovery of microbial defluorination under common anaerobic conditions may provide valuable insights into the environmental fate and potential bioremediation strategies of these notorious contaminants.

Exposure to fine particulate matter (PM 2.5 ), of which secondary organic aerosol (SOA) is a major constituent, is linked to adverse health outcomes, including cardiovascular disease, lung cancer, and preterm birth. Atmospheric oxidation of isoprene, the most abundant nonmethane hydrocarbon emitted into Earth's atmosphere primarily from vegetation, contributes to SOA formation. Isoprene-derived SOA has previously been found to alter inflammatory/oxidative stress genes. MicroRNAs (miRNAs) are epigenetic regulators that serve as post-transcriptional modifiers and key mediators of gene expression. To assess whether isoprene-derived SOA alters miRNA expression, BEAS-2B lung cells were exposed to laboratory-generated isoprene-derived SOA constituents derived from the acid-driven multiphase chemistry of authentic methacrylic acid epoxide (MAE) or isomeric isoprene epoxydiols (IEPOX) with acidic sulfate aerosol particles. These IEPOX- and MAE-derived SOA constituents have been shown to be measured in large quantities within PM 2.5 collected from isoprene-rich areas affected by acidic sulfate aerosol particles derived from human activities. A total of 29 miRNAs were identified as differentially expressed when exposed to IEPOX-derived SOA and 2 when exposed to MAE-derived SOA, a number of which are inflammatory/oxidative stress associated. These results suggest that miRNAs may modulate the inflammatory/oxidative stress response to SOA exposure, thereby advancing the understanding of airway cell epigenetic response to SOA.

Twelve undescribed sesquiterpenoids, fomitopins A-L (1-12), were isolated via bioassay-guided purification from the bracket fungus Fomitopsis pinicola (Sw.) P. Karst, and this fungus have been reported to exhibit anti-microbial and anti-inflammatory activities. The structures of 1-12 were elucidated by spectroscopic and spectrometric analyses and their absolute configurations were further confirmed by ECD simulations. Ten isolated compounds were evaluated for their anti-inflammatory potential and compound 11 exhibited the most significant inhibition of superoxide anion generation and elastase release with IC 50 values of 0.81 ± 0.15 and 0.74 ± 0.12 μM. These newly purified sesquiterpenoids could be potential candidates for further anti-inflammatory studies., Competing Interests: The authors declare no competing financial interest., (This journal is © The Royal Society of Chemistry.)

In the southeastern US, substantial emissions of isoprene from deciduous trees undergo atmospheric oxidation to form secondary organic aerosol (SOA) that contributes to fine particulate matter (PM 2.5 ). Laboratory studies have revealed that anthropogenic pollutants, such as sulfur dioxide (SO 2 ), oxides of nitrogen (NO x ), and aerosol acidity, can enhance SOA formation from the hydroxyl radical (OH)-initiated oxidation of isoprene; however, the mechanisms by which specific pollutants enhance isoprene SOA in ambient PM 2.5 remain unclear. As one aspect of an investigation to examine how anthropogenic pollutants influence isoprene-derived SOA formation, high-volume PM 2.5 filter samples were collected at the Birmingham, Alabama (BHM), ground site during the 2013 Southern Oxidant and Aerosol Study (SOAS). Sample extracts were analyzed by gas chromatography-electron ionization-mass spectrometry (GC/EI-MS) with prior trimethylsilylation and ultra performance liquid chromatography coupled to electrospray ionization high-resolution quadrupole time-of-flight mass spectrometry (UPLC/ESI-HR-QTOFMS) to identify known isoprene SOA tracers. Tracers quantified using both surrogate and authentic standards were compared with collocated gas- and particle-phase data as well as meteorological data provided by the Southeastern Aerosol Research and Characterization (SEARCH) network to assess the impact of anthropogenic pollution on isoprene-derived SOA formation. Results of this study reveal that isoprene-derived SOA tracers contribute a substantial mass fraction of organic matter (OM) (~ 7 to ~ 20 %). Isoprene-derived SOA tracers correlated with sulfate ( SO 4 2 - ) ( r 2 = 0.34, n = 117) but not with NO x . Moderate correlations between methacrylic acid epoxide and hydroxymethyl-methyl-α-lactone (together abbreviated MAE/HMML)-derived SOA tracers with nitrate radical production (P[NO 3 ]) ( r 2 = 0.57, n = 40) were observed during nighttime, suggesting a potential role of the NO 3 radical in forming this SOA type. However, the nighttime correlation of these tracers with nitrogen dioxide (NO 2 ) ( r 2 = 0.26, n = 40) was weaker. Ozone (O 3 ) correlated strongly with MAE/HMML-derived tracers ( r 2 = 0.72, n = 30) and moderately with 2-methyltetrols ( r 2 = 0.34, n = 15) during daytime only, suggesting that a fraction of SOA formation could occur from isoprene ozonolysis in urban areas. No correlation was observed between aerosol pH and isoprene-derived SOA. Lack of correlation between aerosol acidity and isoprene-derived SOA is consistent with the observation that acidity is not a limiting factor for isoprene SOA formation at the BHM site as aerosols were acidic enough to promote multiphase chemistry of isoprene-derived epoxides throughout the duration of the study. All in all, these results confirm previous studies suggesting that anthropogenic pollutants enhance isoprene-derived SOA formation.

Exposure to volatile organic compounds from outdoor air pollution is a major public health concern; however, there is scant information about the health effects induced by inhalation exposure to photochemical transformed products of primary emissions. In this study, we present a stable and reproducible exposure method to deliver ppm-ppb levels of gaseous standards in a humidified air stream for in vitro cell exposure through a direct air-liquid interface. Gaseous species were generated from a diffusion vial, and coupled to a gas-phase in vitro exposure system. Acrolein and methacrolein, which are major first-generation photochemical transformation products of 1,3-butadiene and isoprene, respectively, were selected as model compounds. A series of vapor concentrations (0.23-2.37 ppmv for acrolein and 0.68-10.7 ppmv for methacrolein) were investigated to characterize the exposure dose-response relationships. Temperature and the inner diameter of the diffusion vials are key parameters to control the evaporation rates and diffusion rates for the delivery of target vapor concentrations. Our findings suggest that this exposure method can be used for testing a wide range of atmospheric volatile organic compounds, and permits both single compound and multiple compound sources to generate mixtures in air. The relative standard deviations (%RSD) of output concentrations were within 10% during the 4-hour exposure time. The comparative exposure-response data allow us to prioritize numerous hazardous gas phase air pollutants. These identified pollutants can be further incorporated into air quality simulation models to better characterize the environmental health risks arising from inhalation of the photochemical transformed products.

Urban streetscapes are outdoor areas in which the general public can appreciate green landscapes and engage in outdoor activities along the street. This study tested the extent to which the degree of awareness of urban street trees impacts attention restoration and perceived restorativeness. We manipulated the degree of awareness of street trees. Participants were placed into four groups and shown different images: (a) streetscapes with absolutely no trees; (b) streetscapes with flashes of trees in which participants had minimal awareness of the content; (c) streetscapes with trees; and (d) streetscapes with trees to which participants were told to pay attention. We compared the performance of 138 individuals on measures of attention and their evaluations of perceived restorativeness. Two main findings emerged. First, streetscapes with trees improved the performance of participants on attentional tests even without their awareness of the trees. Second, participants who had raised awareness of street trees performed best on the attentional test and rated the streetscapes as being more restorative. These findings enhance our knowledge about the role of an individual's awareness of restorative elements and have implications for designers and individuals who are at risk of attentional fatigue.

Isoprene epoxydiols (IEPOX), formed from the photooxidation of isoprene under low-NO(x) conditions, have recently been proposed as precursors of secondary organic aerosol (SOA) on the basis of mass spectrometric evidence. In the present study, IEPOX isomers were synthesized in high purity (>99%) to investigate their potential to form SOA via reactive uptake in a series of controlled dark chamber studies followed by reaction product analyses. IEPOX-derived SOA was substantially observed only in the presence of acidic aerosols, with conservative lower-bound yields of 4.7-6.4% for β-IEPOX and 3.4-5.5% for δ-IEPOX, providing direct evidence for IEPOX isomers as precursors to isoprene SOA. These chamber studies demonstrate that IEPOX uptake explains the formation of known isoprene SOA tracers found in ambient aerosols, including 2-methyltetrols, C(5)-alkene triols, dimers, and IEPOX-derived organosulfates. Additionally, we show reactive uptake on the acidified sulfate aerosols supports a previously unreported acid-catalyzed intramolecular rearrangement of IEPOX to cis- and trans-3-methyltetrahydrofuran-3,4-diols (3-MeTHF-3,4-diols) in the particle phase. Analysis of these novel tracer compounds by aerosol mass spectrometry (AMS) suggests that they contribute to a unique factor resolved from positive matrix factorization (PMF) of AMS organic aerosol spectra collected from low-NO(x), isoprene-dominated regions influenced by the presence of acidic aerosols.