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E-cigarette emissions, which contain a variety of hazardous compounds, contribute significantly to indoor air pollution and raise concerns about secondhand exposure to vaping byproducts. Compared to fresh vape emissions, our understanding of chemically aged products in indoor environments remains incomplete. Terpenes are commonly used as flavoring agents in e-liquids, which have the ability to react with the dominant indoor oxidant ozone (O 3 ) to produce reactive oxygenated byproducts and result in new particle formation. In this study, mixtures of propylene glycol (PG), vegetable glycerin (VG), and terpenes as e-liquids were injected into a 2 m 3 FEP chamber to simulate the indoor aging process. 100 ppbv O 3 was introduced into the chamber and allowed to react with the fresh vape emissions for 1 h. Complementary online and offline analytical techniques were used to characterize the changes in the aerosol size distribution and chemical composition during the aging processes. We observed more ultrafine particles and a greater abundance of highly oxygenated species, such as carbonyls, in aged e-cigarette aerosols. Compared with their fresh counterparts, the aged emissions exhibited greater cytotoxic potential, which can be attributed to the formation of these highly oxygenated compounds that are not present in the fresh emissions. This work highlights the dynamic chemistry and toxicity of e-cigarette aerosols in the indoor environment as well as the indirect risks of secondhand exposure.

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.

Sulfur-containing volatile organic compounds emitted during wildfire events, such as dimethyl sulfide, are known to form secondary aerosols containing inorganic sulfate (SO 4 2- ) and surfactant-like organic compounds; however, little is known about the fate of sulfur in other emitted reduced organosulfur species. This study aimed to determine the sulfurous product distribution resulting from the nighttime oxidation of thiophene as a model system. Ion chromatography (IC) and aerosol mass spectrometry (a mini aerosol mass spectrometer, mAMS) were used to constrain the proportions of sulfurous compounds produced under wildfire-relevant conditions ([NO 2 ]/[O 3 ] = 0.1). With constraints from IC, results indicated that the sulfurous particle mass consisted of 30.3 ± 6.6% SO 4 2- , while mAMS fractionation attributed 24.5 ± 1.6% of total sulfate signal to SO 4 2- , 15.4 ± 1.9% to organosulfates, and 60.1 ± 0.9% to sulfonates. Empirical formulas of organosulfur products were identified as C1-C8 organosulfates and sulfonates using complementary mass spectrometry techniques. This study highlights the nighttime oxidation of thiophene and its derivatives as a source of SO 4 2- and particulate organosulfur compounds, which have important implications for the atmospheric sulfur budget and aerosol/droplet physical and chemical properties., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

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., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

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 production of e-cigarette aerosols through vaping processes is known to cause the formation of various free radicals and reactive oxygen species (ROS). Despite the well-known oxidative potential and cytotoxicity of fresh vaping emissions, the effects of chemical aging on exhaled vaping aerosols by indoor atmospheric oxidants are yet to be elucidated. Terpenes are commonly found in e-liquids as flavor additives. In the presence of indoor ozone (O 3 ), e-cigarette aerosols that contain terpene flavorings can undergo chemical transformations, further producing ROS and reactive carbonyl species. Here, we simulated the aging process of the e-cigarette emissions in a 2 m 3 FEP film chamber with 100 ppbv of O 3 exposure for an hour. The aged vaping aerosols, along with fresh aerosols, were collected to detect the presence of ROS. The aged particles exhibited 2- to 11-fold greater oxidative potential, and further analysis showed that these particles formed a greater number of radicals in aqueous conditions. The aging process induced the formation of various alkyl hydroperoxides (ROOH), and through iodometric quantification, we saw that our aged vaping particles contained significantly greater amounts of these hydroperoxides than their fresh counterparts. Bronchial epithelial cells exposed to aged vaping aerosols exhibited an upregulation of the oxidative stress genes, HMOX-1 and GSTP1 , indicating the potential for inhalation toxicity. This work highlights the indirect danger of vaping in environments with high ground-level O 3 , which can chemically transform e-cigarette aerosols into new particles that can induce greater oxidative damage than fresh e-cigarette aerosols. Given that the toxicological characteristics of e-cigarettes are mainly associated with the inhalation of fresh aerosols in current studies, our work may provide a perspective that characterizes vaping exposure under secondhand or thirdhand conditions as a significant health risk.

Light-absorbing secondary organic aerosols (SOAs), also known as secondary brown carbon (BrC), are major components of wildfire smoke that can have a significant impact on the climate system; however, how environmental factors such as relative humidity (RH) influence their formation is not fully understood, especially for heterocyclic precursors. We conducted chamber experiments to investigate secondary BrC formation from the nighttime oxidation of furan and pyrrole, two primary heterocyclic precursors in wildfires, in the presence of pre-existing particles at RH < 20% and ∼ 50%. Our findings revealed that increasing RH significantly affected the size distribution dynamics of both SOAs, with pyrrole SOA showing a stronger potential to generate ultrafine particles via intensive nucleation processes. Higher RH led to increased mass fractions of oxygenated compounds in both SOAs, suggesting enhanced gas-phase and/or multiphase oxidation under humid conditions. Moreover, higher RH reduced the mass absorption coefficients of both BrC, contrasting with those from homocyclic precursors, due to the formation of non-absorbing high-molecular-weight oxygenated compounds and the decreasing mass fractions of molecular chromophores. Overall, our findings demonstrate the unique RH dependence of secondary BrC formation from heterocyclic precursors, which may critically modulate the radiative effects of wildfire smoke on climate change., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

The chemical and optical properties of secondary organic aerosols (SOA) have been widely studied through environmental chamber experiments, and some of the results have been parametrized in atmospheric models to help understand their radiative effects and climate influence. While most chamber studies investigate the aerosol formed from a single volatile organic compound (VOC), the potential interactions between reactive intermediates derived from VOC mixtures are not well understood. In this study, we investigated the SOA formed from pure and mixtures of anthropogenic (phenol and 1-methylnaphthalene) and/or biogenic (longifolene) VOCs using continuous-flow, high-NO x photooxidation chamber experiments to better mimic ambient conditions. SOA optical properties, including single scattering albedo (SSA), mass absorption coefficient (MAC), and refractive index (RI) at 375 nm, and chemical composition, including the formation of oxygenated organic compounds, organic-nitrogen compounds (including organonitrates and nitro-organics), and the molecular structure of the major chromophores, were explored. Additionally, the imaginary refractive index values of SOA in the multi-VOC system were predicted using a linear-combination assumption and compared with the measured values. When two VOCs were oxidized simultaneously, we found evidence for changes in SOA chemical composition compared to SOA formed from single-VOC systems, and this change led to nonlinear effects on SOA optical properties. The nonlinear effects were found to vary between different systems., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

E-cigarette aerosols contain a complex mixture of harmful and potentially harmful chemicals. Once released into the environment, they evolve and become new sources of indoor air pollutants that could pose a significant threat to both users and non-users. However, current understanding of the physicochemical properties of e-cigarette aerosol constituents that govern gas-particle partitioning in the atmosphere is limited, making it difficult to estimate the health risks associated with exposure. Here, we used correlation gas chromatography (C-GC) and two-dimensional volatility basis set (2D-VBS) methods to determine the vapor pressures and volatility for commonly reported toxic and irritating e-cigarette aerosol constituents. The vapor pressures of target compounds at 298 K were estimated from the Antoine-type linear relationship between the vapor pressure of reference standards and their retention times. Our C-GC results showed an overall positive correlation (R = 0.84) with estimates using the EPI (Estimation Programs Interface) Suite. The volatility calculated by 2D-VBS correlates well with the calculated vapor pressure from both C-GC (R = 0.82) and EPI Suite (R = 0.85). The volatility distribution also indicated fresh e-cigarette aerosol constituents are mainly more volatile organic compounds. Our case study revealed that low-vapor-pressure compounds (e.g., σ-dodecalactone, γ-decalactone, and maltol) become enriched in the e-cigarette aerosols within 2 hours following vaping emissions. Overall, these findings demonstrate the applicability of the C-GC and 2D-VBS methods for determining the physiochemical properties of e-cigarette aerosol constituents, which can aid in assessing the dynamic chemical composition of e-cigarette aerosols and exposures to vaping emissions in indoor environments.

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.

Hydroxyl radical ( · OH)-initiated oxidation of isoprene, the most abundant nonmethane hydrocarbon in the atmosphere, is responsible for substantial amounts of secondary organic aerosol (SOA) within ambient fine particles. Fine particulate 2-methyltetrol sulfate diastereoisomers (2-MTSs) are abundant SOA products formed via acid-catalyzed multiphase chemistry of isoprene-derived epoxydiols with inorganic sulfate aerosols under low-nitric oxide conditions. We recently demonstrated that heterogeneous · OH oxidation of particulate 2-MTSs leads to the particle-phase formation of multifunctional organosulfates (OSs). However, it remains uncertain if atmospheric chemical aging of particulate 2-MTSs induces toxic effects within human lung cells. We show that inhibitory concentration-50 (IC 50 ) values decreased from exposure to fine particulate 2-MTSs that were heterogeneously aged for 0 to 22 days by · OH, indicating increased particulate toxicity in BEAS-2B lung cells. Lung cells further exhibited concentration-dependent modulation of oxidative stress- and inflammatory-related gene expression. Principal component analysis was carried out on the chemical mixtures and revealed positive correlations between exposure to aged multifunctional OSs and altered expression of targeted genes. Exposure to particulate 2-MTSs alone was associated with an altered expression of antireactive oxygen species (ROS)-related genes ( NQO-1, SOD-2, and CAT ) indicative of a response to ROS in the cells. Increased aging of particulate 2-MTSs by · OH exposure was associated with an increased expression of glutathione pathway-related genes ( GCLM and GCLC ) and an anti-inflammatory gene ( IL-10 ).

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.)

Background: 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., Methods: 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/cm 2 ., Results: 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., Conclusions: 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.

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.

In this study, the regulated emissions, gaseous toxics, and the physical, chemical, and toxicological properties of particulate matter (PM) emissions from a legacy off-road diesel engine operated on hydrogenated vegetable oil (HVO) and HVO blends with biodiesel were investigated. This is one of the very few studies currently available examining the emissions and potential health effects of HVO and its blends with biodiesel from diesel engines. Extended testing was conducted over the nonroad transient cycle (NRTC) and the 5-mode D2 ISO 8718 cycle. Nitrogen oxide (NOx) emissions showed statistically significant reductions for HVO compared to diesel, whereas the biodiesel blends statistically significant increases in NOx emissions. PM and solid particle number reductions with pure HVO and the biodiesel blends were also observed. Low-molecular weight polycyclic aromatic hydrocarbons (PAHs) were the dominant species in the exhaust for all fuels, with pure HVO and the biodiesel blends showing lower concentrations of these pollutants compared to diesel fuel. Our results showed that the oxidative stress and cytotoxicity in PM emissions decreased with the use of biofuels. Notable correlations were observed between PM emissions and oxidative stress and cytotoxicity, especially elemental carbon and particle-phase PAH emissions.

Nitrogen-containing heterocyclic volatile organic compounds (VOCs) are important components of wildfire emissions that are readily reactive toward nitrate radicals (NO 3 ) during nighttime, but the oxidation mechanism and the potential formation of secondary organic aerosol (SOA) and brown carbon (BrC) are unclear. Here, NO 3 oxidation of three nitrogen-containing heterocyclic VOCs, pyrrole, 1-methylyrrole (1-MP), and 2-methylpyrrole (2-MP), was investigated in chamber experiments to determine the effect of precursor structures on SOA and BrC formation. The SOA chemical compositions and the optical properties were analyzed using a suite of online and offline instrumentation. Dinitro- and trinitro-products were found to be the dominant SOA constituents from pyrrole and 2-MP, but not observed from 1-MP. Furthermore, the SOA from 2-MP and pyrrole showed strong light absorption, while that from 1-MP were mostly scattering. From these results, we propose that NO 3 -initiated hydrogen abstraction from the 1-position in pyrrole and 2-MP followed by radical shift and NO 2 addition leads to light-absorbing nitroaromatic products. In the absence of a 1-position hydrogen, NO 3 addition likely dominates the 1-MP chemistry. We also estimate that the total SOA mass and light absorption from pyrrole and 2-MP are comparable to those from phenolic VOCs and toluene in biomass burning, underscoring the importance of considering nighttime oxidation of pyrrole and methylpyrroles in air quality and climate models.

We numerically study an anyon chain based on the Haagerup fusion category and find evidence that it leads in the long-distance limit to a conformal field theory whose central charge is ∼2. Fusion categories generalize the concept of finite group symmetries to noninvertible symmetry operations, and the Haagerup fusion category is the simplest one which comes from neither finite groups nor affine Lie algebras. As such, ours is the first example of conformal field theories which have truly exotic generalized symmetries. Basically the same result was independently obtained in the preceding Letter [Phys. Rev. Lett. 128, 231602 (2022)PRLTAO0031-900710.1103/PhysRevLett.128.231602].

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., Competing Interests: The authors have declared that no competing interests exist.

In late 2019, the outbreak of e-cigarette or vaping-associated lung injuries (EVALIs) in the United States demonstrated to the public the potential health risks of vaping. While studies since the outbreak have identified vitamin E acetate (VEA), a diluent of tetrahydrocannabinol (THC) in vape cartridges, as a potential contributor to lung injuries, the molecular mechanisms through which VEA may cause damage are still unclear. Recent studies have found that the thermal degradation of e-liquids during vaping can result in the formation of products that are more toxic than the parent compounds. In this study, we assessed the role of duroquinone (DQ) in VEA vaping emissions that may act as a mechanism through which VEA vaping causes lung damage. VEA vaping emissions were collected and analyzed for their potential to generate reactive oxygen species (ROS) and induce oxidative stress-associated gene expression in human bronchial epithelial cells (BEAS-2B). Significant ROS generation by VEA vaping emissions was observed in both acellular and cellular systems. Furthermore, exposure to vaping emissions resulted in significant upregulation of NQO1 and HMOX-1 genes in BEAS-2B cells, indicating a strong potential for vaped VEA to cause oxidative damage and acute lung injury; the effects are more profound than exposure to equivalent concentrations of DQ alone. Our findings suggest that there may be synergistic interactions between thermal decomposition products of VEA, highlighting the multifaceted nature of vaping toxicity.

Organic hydroperoxides (ROOHs) play key roles in the atmosphere as a reactive intermediate species. Due to the low volatility and high hydrophilicity, ROOHs are expected to reside in atmospheric condensed phases such as aerosols, fogs, and cloud droplets. The decomposition mechanisms of ROOHs in the liquid phase are, however, still poorly understood. Here we report a temperature-dependent kinetics and theoretical calculation study of the aqueous-phase decompositions of C 12 or C 13 α-alkoxyalkyl-hydroperoxides (α-AHs) derived from ozonolysis of α-terpineol in the presence of 1-propanol, 2-propanol, and ethanol. We found that the temporal profiles of α-AH signals, detected as chloride-adducts by negative ion electrospray mass spectrometry, showed single-exponential decay, and the derived first-order rate coefficient k for α-AH decomposition increased as temperature increased, e.g. , k (288 K) = (5.3 ± 0.2) × 10 -4 s -1 , k (298 K) = (1.2 ± 0.3) × 10 -3 s -1 , k (308 K) = (2.1 ± 1.4) × 10 -3 s -1 for C 13 α-AHs derived from the reaction of α-terpineol Criegee intermediates with 1-propanol in the solution at pH 4.5. Arrhenius plot analysis yielded an activation energy ( E a ) of 12.3 ± 0.6 kcal mol -1 . E a of 18.7 ± 0.3 and 13.8 ± 0.9 kcal mol -1 were also obtained for the decomposition of α-AHs (at pH 4.5) derived from the reaction of α-terpineol Criegee intermediates with 2-propanol and with ethanol, respectively. Based on the theoretical kinetic and thermodynamic calculations, we propose that a proton-catalyzed mechanism plays a central role in the decomposition of these α-AHs in acidic aqueous organic media, while water molecules may also participate in the decomposition pathways and affect the kinetics. The decomposition of α-AHs could act as a source of H 2 O 2 and multifunctionalized species in atmospheric condensed phases., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Helicobacter pylori infection is associated with the development of several gastric diseases including gastric cancer. To reach a long-term colonization in the host stomach, H. pylori employs multiple outer membrane adhesins for binding to the gastric mucosa. However, due to the redundancy of adhesins that complement the adhesive function of bacteria, targeting each individual adhesin alone usually achieves nonideal outcomes for preventing bacterial adhesion. Here, we report that key adhesins AlpA/B and BabA/B in H. pylori are modified by glycans and display a two-step molecular weight upshift pattern from the cytoplasm to the inner membrane and from the inner membrane to the outer membrane. Nevertheless, this upshift pattern is missing when the expression of some enzymes related to lipopolysaccharide (LPS) biosynthesis, including the LPS O-antigen assembly and ligation enzymes WecA, Wzk, and WaaL, is disrupted, indicating that the underlying mechanisms and the involved enzymes for the adhesin glycosylation are partially shared with the LPS biosynthesis. Loss of the adhesin glycosylation not only reduces the protease resistance and the stability of the tested adhesins but also changes the adhesin-binding ability. In addition, mutations in the LPS biosynthesis cause a significant reduction in bacterial adhesion in the in vitro cell-line model. The current findings reveal that H. pylori employs a general protein glycosylation system related to LPS biosynthesis for adhesin modification and its biological significance. The enzymes required for adhesin glycosylation rather than the adhesins themselves are potentially better drug targets for preventing or treating H. pylori infection.

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 (fk0, fk-, fk+, 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.

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.)

We report the first synthesis of aluminum hexafluorophosphate (Al(PF 6 ) 3 ) and its electrochemical properties in dimethyl sulfoxide (DMSO). The single crystal structure of the synthesized Al(PF 6 ) 3 is revealed as [Al(DMSO) 6 ](PF 6 ) 3 , and 0.25 M Al(PF 6 ) 3 in DMSO with high ionic conductivity is obtained. The purity of this electrolyte was further confirmed with nuclear magnetic resonance spectroscopy and electrospray ionization mass spectrometry. We then demonstrated the reversibility of Al deposition-stripping in this electrolyte using scanning electron microscopy and an X-ray photoelectron spectroscopy depth profiling study. The parasitic reaction involving DMSO decomposition during Al deposition is also identified via gas chromatography/electron ionization mass spectrometry.

Dimethyl selenide (DMSe) is one of the major volatile organoselenium compounds released into the atmosphere through plant metabolism and microbial methylation. DMSe has been recently revealed as a precursor of secondary organic aerosol (SOA), and its resultant SOA possesses strong oxidizing capability toward thiol groups that can perturb several major biological pathways in human airway epithelial cells and is linked to genotoxicity, DNA damage, and p53-mediated stress responses. Mounting evidence has suggested that long noncoding RNAs (lncRNAs) are involved in stress responses to internal and environmental stimuli. However, the underlying molecular interactions remain to be elucidated. In this study, we performed integrative analyses of lncRNA-mRNA coexpression in the transformed human bronchial epithelial BEAS-2B cell line exposed to DMSe-derived SOA. We identified a total of 971 differentially expressed lncRNAs in BEAS-2B cells exposed to SOA derived from O 3 and OH oxidation of DMSe. Gene ontology (GO) network analysis of cis -targeted genes showed significant enrichment of DNA damage, apoptosis, and p53-mediated stress response pathways. trans -Acting lncRNAs, including PINCR , PICART1 , DLGAP1-AS2 , and LINC01629 , known to be associated with human carcinogenesis, also showed altered expression in cell treated with DMSe-SOA. Overall, this study highlights the regulatory role of lncRNAs in altered gene expression induced by DMSe-SOA exposure.

Ozonolysis of unsaturated organic species with water produces α-hydroxyalkyl-hydroperoxides (α-HHs), which are reactive intermediates that lead to the formation of H 2 O 2 and multifunctionalized species in atmospheric condensed phases. Here, we report temperature-dependent rate coefficients ( k ) for the aqueous-phase decomposition of α-terpineol α-HHs at 283-318 K and terpinen-4-ol α-HHs at 313-328 K. The temporal profiles of α-HH signals, detected as chloride adducts by negative-ion electrospray mass spectrometry, showed single-exponential decay, and the derived first-order k for α-HH decomposition increased as temperature increased, e.g., k (288 K) = (4.7 ± 0.2) × 10 -5 , k (298 K) = (1.5 ± 0.4) × 10 -4 , k (308 K) = (3.4 ± 0.9) × 10 -4 , k (318 K) = (1.0 ± 0.2) × 10 -3 s -1 for α-terpineol α-HHs at pH 6.1. Arrhenius plot analysis yielded activation energies of 17.9 ± 0.7 (pH 6.1) and 17.1 ± 0.2 kcal mol -1 (pH 6.2) for the decomposition of α-terpineol and terpinen-4-ol α-HHs, respectively. Activation energies of 18.6 ± 0.2 and 19.2 ± 0.5 kcal mol -1 were also obtained for the decomposition of α-terpineol α-HHs in acidified water at pH 5.3 and 4.5, respectively. Theoretical kinetic and thermodynamic calculations confirmed that both water-catalyzed and proton-catalyzed mechanisms play important roles in the decomposition of these α-HHs. The relatively strong temperature dependence of k suggests that the lifetime of these α-HHs in aqueous phases (e.g., aqueous aerosols, fog, cloud droplets, wet films) is controlled not only by the water content and pH but also by the temperature of these media.

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.

Recent reports have linked severe lung injuries and deaths to the use of e-cigarettes and vaping products. Nevertheless, the causal relationship between exposure to vaping emissions and the observed health outcomes remains to be elucidated. Through chemical and toxicological characterization of vaping emission products, this study demonstrates that during vaping processes, changes in chemical composition of several commonly used vape juice diluents (also known as cutting agents) lead to the formation of toxic byproducts, including quinones, carbonyls, esters, and alkyl alcohols. The resulting vaping emission condensates cause inhibited cell proliferation and enhanced cytotoxicity in human airway epithelial cells. Notably, substantial formation of the duroquinone and durohydroquinone redox couple was observed in the vaping emissions from vitamin E acetate, which may be linked to acute oxidative stress and lung injuries reported by previous studies. These findings provide an improved molecular understanding and highlight the significant role of toxic byproducts in vaping-associated health effects.

The toxicity of organic aerosols has been largely ascribed to the generation of reactive oxygen species, which could subsequently induce oxidative stress in biological systems. The reaction of DTT with redox-active species in PM has been generally assumed to be pseudo-first order, with the oxidative potential of PM being represented by the DTT consumption per minute of reaction time per μg of PM. Although catalytic reactive species such as transition metals and quinones are long believed to be the main contributors of DTT responses, the role of non-catalytic DTT reactive species such as organic hydroperoxides (ROOH) and electron-deficient alkenes (e.g., conjugated carbonyls) in DTT consumption has been recently highlighted. Thus, understanding the reaction kinetics and mechanisms of DTT consumption by various PM components is required to interpret the oxidative potential measured by DTT assays more accurately. In this study, we measured the DTT consumptions over time and characterized the reaction products using model compounds and secondary organic aerosols (SOA) with varying initial concentrations. We observed that the DTT consumption rates linearly increased with both initial DTT and sample concentrations. The overall reaction order of DTT with non-catalytic reactive species and SOA in this study is second order. The reactions of DTT with different functional groups have significantly different rate constants. The reaction rate constant of isoprene SOA with DTT is mainly determined by the concentration of ROOH. For toluene SOA, both ROOH and electron-deficient alkenes may dominate its DTT reaction rates. These results provide some insights into the interpretation of DTT-based aerosol oxidative potential and highlight the need to study the toxicity mechanism of ROOH and electron-deficient alkenes in PM for future work., Competing Interests: Declaration of competing interest The authors declare no conflict of interest., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

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., (Copyright © 2019 Elsevier B.V. All rights reserved.)

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.

Isoprene (C 5 H 8 ) is the main non-methane hydrocarbon emitted into the global atmosphere. Despite intense research, atmospheric transformations of isoprene leading to secondary organic aerosol (SOA) are still not fully understood, including its multiphase chemical reactions. Herein, we report on the detailed structural characterization of atmospherically relevant isoprene-derived organosulfates (OSs) with a molecular weight (MW) of 212 (C 5 H 8 SO 7 ), which are abundantly present in both ambient fine aerosol (PM 2.5 ) and laboratory-generated isoprene SOA. The results obtained from smog chamber-generated isoprene SOA and aqueous-phase laboratory experiments coupled to the S(IV)-autooxidation chemistry of isoprene, 3-methyl-2(5 H )-furanone, and 4-methyl-2(5 H )-furanone, allowed us for the first time to fully elucidate the isomeric structures of the MW 212 OSs. By applying liquid chromatography interfaced to electrospray ionization high-resolution mass spectrometry, we firmly confirmed six positional isomers of the MW 212 OSs in PM 2.5 collected from different sites in Europe and the United States. Our results also show that despite the low solubility of isoprene in water, aqueous-phase or multiphase chemistry can play an important role in the formation of OSs from isoprene. Possible formation mechanisms for the MW 212 OSs are also tentatively proposed.

Dimethyl selenide (DMSe) is one of the major volatile organoselenium compounds released from aquatic and terrestrial environments through microbial transformation and plant metabolism. The detailed processes of DMSe leading to secondary organic aerosol (SOA) formation and the pulmonary health effects induced by inhalation of DMSe-derived SOA remain largely unknown. In this study, we characterized the chemical composition and formation yields of SOA produced from the oxidation of DMSe with OH radicals and O 3 in controlled chamber experiments. Further, we profiled the transcriptome-wide gene expression changes in human airway epithelial cells (BEAS-2B) after exposure to DMSe-derived SOA. Our analyses indicated a significantly higher SOA yield resulting from the OH-initiated oxidation of DMSe. The oxidative potential of DMSe-derived SOA, as measured by the dithiothreitol (DTT) assay, suggested the presence of oxidizing moieties in DMSe-derived SOA at levels higher than typical ambient aerosols. Utilizing RNA sequencing (RNA-Seq) techniques, gene expression profiling followed by pathway enrichment analysis revealed several major biological pathways perturbed by DMSe-derived SOA, including elevated genotoxicity, DNA damage, and p53-mediated stress responses, as well as downregulated cholesterol biosynthesis, glycolysis, and interleukin IL-4/IL-13 signaling. This study highlights the significance of DMSe-derived SOA as a stressor in human airway epithelial cells.

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.)

Carbonyls are reactive and electrophilic compounds found ubiquitously in the atmosphere. The interactions between atmospheric carbonyls and biological nucleophiles (e.g., thiol-containing compounds) have important implications on their toxicity, but the underlying mechanisms have not been fully understood. In this study, we used combined computational and experimental approaches to assess the reactivities of atmospheric carbonyls in respect to their electrophilic properties. Global electrophilicity indexes (ω) were calculated based on density functional theory. The reactivities of carbonyls with thiols were assessed using the dithiothreitol (DTT) assay as a surrogate of biological nucleophilic antioxidants. The computational results indicated that the ω of a given carbonyl compound is largely influenced by its molecular structure and adjacent functional groups. The calculated ω values showed a strong linear correlation with the logarithm of measured carbonyl mass-normalized DTT consumption rates (r 2 = 0.8378 and 0.9899 for simple and α,β-unsaturated carbonyls, respectively). The removal of DTT through the nucleophilic addition pathway was confirmed by the detection of carbonyl-DTT adducts using the gas chromatography/electron ionization-mass spectrometry (GC/EI-MS) technique. Our results demonstrated that electrophilicity index can be potentially used as a molecular descriptor to predict toxicity of atmospheric carbonyls towards thiol-containing biomolecules. This work also highlights the significance of carbonyls in interpreting DTT-based aerosol oxidative potential.

Isoprene-derived secondary organic aerosol (SOA), which comprise a large portion of atmospheric fine particulate matter (PM 2.5 ), can be formed through various gaseous precursors, including isoprene epoxydiols (IEPOX), methacrylic acid epoxide (MAE), and isoprene hydroxyhydroperoxides (ISOPOOH). The composition of the isoprene-derived SOA affects its reactive oxygen species (ROS) generation potential and its ability to alter oxidative stress-related gene expression. In this study we assess effects of isoprene SOA derived solely from ISOPOOH oxidation on human bronchial epithelial cells by measuring the gene expression changes in 84 oxidative stress-related genes. In addition, the thiol reactivity of ISOPOOH-derived SOA was measured through the dithiothreitol (DTT) assay. Our findings show that ISOPOOH-derived SOA alter more oxidative-stress related genes than IEPOX-derived SOA but not as many as MAE-derived SOA on a mass basis exposure. More importantly, we found that the different types of SOA derived from the various gaseous precursors (MAE, IEPOX, and ISOPOOH) have unique contributions to changes in oxidative stress-related genes that do not total all gene expression changes seen in exposures to atmospherically relevant compositions of total isoprene-derived SOA mixtures. This study suggests that amongst the different types of known isoprene-derived SOA, MAE-derived SOA are the most potent inducer of oxidative stress-related gene changes but highlights the importance of considering isoprene-derived SOA as a total mixture for pollution controls and exposure studies.

Secondary organic aerosol (SOA) derived from the photochemical oxidation of isoprene contributes a substantial mass fraction to atmospheric fine particulate matter (PM 2.5 ). The formation of isoprene SOA is influenced largely by anthropogenic emissions through multiphase chemistry of its multigenerational oxidation products. Considering the abundance of isoprene SOA in the troposphere, understanding mechanisms of adverse health effects through inhalation exposure is critical to mitigating its potential impact on public health. In this study, we assessed the effects of isoprene SOA on gene expression in human airway epithelial cells (BEAS-2B) through an air-liquid interface exposure. Gene expression profiling of 84 oxidative stress and 249 inflammation-associated human genes was performed. Our results show that the expression levels of 29 genes were significantly altered upon isoprene SOA exposure under noncytotoxic conditions (p < 0.05), with the majority (22/29) of genes passing a false discovery rate threshold of 0.3. The most significantly affected genes belong to the nuclear factor (erythroid-derived 2)-like 2 (Nrf2) transcription factor network. The Nrf2 function is confirmed through a reporter cell line. Together with detailed characterization of SOA constituents, this study reveals the impact of isoprene SOA exposure on lung responses and highlights the importance of further understanding its potential health outcomes.

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.

In the present study, formation of aromatic organosulfates (OSs) from the photo-oxidation of polycyclic aromatic hydrocarbons (PAHs) was investigated. Naphthalene (NAP) and 2-methylnaphthalene (2-MeNAP), two of the most abundant gas-phase PAHs and thought to represent "missing" sources of urban SOA, were photochemically oxidized in an outdoor smog chamber facility in the presence of nonacidified and acidified sulfate seed aerosol. Effects of seed aerosol composition, acidity and relative humidity on OS formation were examined. Chemical characterization of SOA extracts by ultra performance liquid chromatography coupled to electrospray ionization high-resolution quadrupole time-of-flight mass spectrometry revealed the formation of OSs and sulfonates from photo-oxidation in the presence of sulfate seed aerosol. Many of the organosulfur compounds identified in the smog chamber extracts were also measured in urban fine aerosol collected at Lahore, Pakistan, and Pasadena, USA, demonstrating that PAH photo-oxidation in the presence of sulfate aerosol is a hitherto unrecognized source of anthropogenic secondary organosulfur compounds, and providing new PAH SOA tracers.

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.

Secondary organic aerosol (SOA) produced from reactive uptake and multiphase chemistry of isoprene epoxydiols (IEPOX) has been found to contribute substantially (upward of 33%) to the fine organic aerosol mass over the Southeastern U.S. Brown carbon (BrC) in rural areas of this region has been linked to secondary sources in the summer when the influence of biomass burning is low. We demonstrate the formation of light-absorbing (290 < λ < 700 nm) SOA constituents from reactive uptake of trans-β-IEPOX onto preexisting sulfate aerosols as a potential source of secondary BrC. IEPOX-derived BrC generated in controlled chamber experiments under dry, acidic conditions has an average mass absorption coefficient of ∼ 300 cm(2) g(-1). Chemical analyses of SOA constituents using UV-visible spectroscopy and high-resolution mass spectrometry indicate the presence of highly unsaturated oligomeric species with molecular weights separated by mass units of 100 (C5H8O2) and 82 (C5H6O) coincident with the observations of enhanced light absorption, suggesting such oligomers as chromophores, and potentially explaining one source of humic-like substances (HULIS) ubiquitously present in atmospheric aerosol. Similar light-absorbing oligomers were identified in fine aerosol collected in the rural Southeastern U.S., supporting their atmospheric relevance and revealing a previously unrecognized source of oligomers derived from isoprene that contributes to ambient fine aerosol mass.

Aromatic organosulfates are identified and quantified in fine particulate matter (PM 2.5 ) from Lahore, Pakistan, Godavari, Nepal, and Pasadena, California. To support detection and quantification, authentic standards of phenyl sulfate, benzyl sulfate, 3-and 4-methylphenyl sulfate and 2-, 3-, and 4-methylbenzyl sulfate were synthesized. Authentic standards and aerosol samples were analyzed by ultra-performance liquid chromatography (UPLC) coupled to negative electrospray ionization (ESI) quadrupole time-of-flight (ToF) mass spectrometry. Benzyl sulfate was present in all three locations at concentrations ranging from 4 - 90 pg m -3 . Phenyl sulfate, methylphenyl sulfates and methylbenzyl sulfates were observed intermittently with abundances of 4 pg m -3 , 2-31 pg m -3 , 109 pg m -3 , respectively. Characteristic fragment ions of aromatic organosulfates include the sulfite radical ( • SO 3 - , m/z 80) and the sulfate radical ( • SO 4 - , m/z 96). Instrumental response factors of phenyl and benzyl sulfates varied by a factor of 4.3, indicating that structurally-similar organosulfates may have significantly different instrumental responses and highlighting the need to develop authentic standards for absolute quantitation organosulfates. In an effort to better understand the sources of aromatic organosulfates to the atmosphere, chamber experiments with the precursor toluene were conducted under conditions that form biogenic organosulfates. Aromatic organosulfates were not detected in the chamber samples, suggesting that they form through different pathways, have different precursors (e.g. naphthalene or methylnaphthalene), or are emitted from primary sources.

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.

Objective: To evaluate the outcomes associated with fetal ventriculomegaly., Materials and Methods: Reports of women who underwent ultrasound scanning between 18 and 36 weeks of gestation during the period from January 1, 2000, to December 31, 2010, were reviewed. According to the defined severity of ventriculomegaly of affected fetuses, the women were divided into the following groups: (1) mild ventriculomegaly (Group A); (2) moderate ventriculomegaly (Group B); and (3) severe ventriculomegaly (Group C). The women were classified into the "gray zone" group if the fetal lateral ventricle measured between 7 mm and <10 mm. All cases were followed up with additional ultrasound scans. Postnatal information was obtained from the computer database or the medical charts., Results: A total of 41 cases were recruited for this analysis. Four (9.8%) cases had an abnormal karyotype. Twelve women (29.3%) opted for termination of pregnancy. Of the 29 women who delivered, 56.1% (N = 23) were from Group A, 14.6% (N = 6) were from Group B, and none was from Group C. All children in Group A had normal neurological development. Three children in Group B had normal neurological development, whereas the other three had neurologic deficits. A total of 432 cases were classified into the "gray zone" group. Of these cases, 2.8% (N = 12) progressed to ventriculomegaly., Conclusion: Cases of isolated and mild ventriculomegaly without additional structural anomalies or chromosomal aberrations had good prognoses. However, the parents of fetuses with moderate or severe ventriculomegaly should be counseled regarding related risks. If the ventricular size of the fetus falls within the "gray zone", at least one additional exam in the third trimester should be performed, for early detection of ventriculomegaly and other related abnormalities. It is important to make the parents of these fetuses aware of these risks, from a medico-legal point of view., (Copyright © 2014. Published by Elsevier B.V.)

Secondary organic aerosol (SOA) formation from 2-methyl-3-buten-2-ol (MBO) photooxidation has recently been observed in both field and laboratory studies. Similar to the level of isoprene, the level of MBO-derived SOA increases with elevated aerosol acidity in the absence of nitric oxide; therefore, an epoxide intermediate, (3,3-dimethyloxiran-2-yl)methanol (MBO epoxide), was synthesized and tentatively proposed to explain this enhancement. In this study, the potential of the synthetic MBO epoxide to form SOA via reactive uptake was systematically examined. SOA was observed only in the presence of acidic aerosol. Major SOA constituents, 2,3-dihydroxyisopentanol and MBO-derived organosulfate isomers, were chemically characterized in both laboratory-generated SOA and in ambient fine aerosol collected from the BEACHON-RoMBAS field campaign during the summer of 2011, where MBO emissions are substantial. Our results support the idea that epoxides are potential products of MBO photooxidation leading to the formation of atmospheric SOA and suggest that reactive uptake of epoxides may explain acid enhancement of SOA observed from other biogenic hydrocarbons.

Isoprene significantly contributes to organic aerosol in the southeastern United States where biogenic hydrocarbons mix with anthropogenic emissions. In this work, the Community Multiscale Air Quality model is updated to predict isoprene aerosol from epoxides produced under both high- and low-NOx conditions. The new aqueous aerosol pathways allow for explicit predictions of two key isoprene-derived species, 2-methyltetrols and 2-methylglyceric acid, that are more consistent with observations than estimates based on semivolatile partitioning. The new mechanism represents a significant source of organic carbon in the lower 2 km of the atmosphere and captures the abundance of 2-methyltetrols relative to organosulfates during the simulation period. For the parametrization considered here, a 25% reduction in SOx emissions effectively reduces isoprene aerosol, while a similar reduction in NOx leads to small increases in isoprene aerosol.

Objective: To investigate the perinatal outcomes of women who suffered from thrombocytopenia at delivery but did not have other diseases during pregnancy., Materials and Methods: We considered all singleton deliveries after 24 weeks of gestation at Chang Gung Memorial Hospital, Taipei, Taiwan between 2001 and 2010. Women were excluded from this study if they suffered from any of the following conditions: chronic hypertension, hepatitis, acute fatty liver, liver cirrhosis, nephropathy, overt diabetes mellitus, connective tissue disease, systemic lupus erythematosus, or immune thrombocytopenia. Pregnancies complicated by gestational hypertension, preeclampsia, or fetal anomalies during gestation were also excluded. A total of 18,384 deliveries were included for analysis. Women were divided into three groups according to platelet count at admission., Results: A total of 787 pregnancies (4.3%) were complicated by thrombocytopenia. Thrombocytopenic women had a significantly higher rate of cesarean delivery compared to women who did not have this condition. No other differences were observed among these three groups regarding the rates of adverse pregnancy outcomes., Conclusions: The results indicate that women who suffered from incidental thrombocytopenia at delivery but did not have other diseases during pregnancy were not at increased risk for adverse pregnancy outcomes., (Copyright © 2013. Published by Elsevier B.V.)

To investigate the toxicological effects of biogenic- versus anthropogenic-source secondary organic aerosol (SOA) on the cardiovascular system, the Secondary Particulate Health Effects Research program irradiation chamber was used to expose atherosclerotic apolipoprotein E null (Apo E-/-) mice to SOA from the oxidation of either α-pinene or toluene for 7 days. SOA atmospheres were produced to yield 250-300 μg/m(3) of particulate matter and ratios of 10:1:1 α-pinene:nitrogen oxide (NOx):ammonia (NH3); 10:1:1:1 α-pinene:NOx:NH3:sulfur dioxide (SO2) or 10:1:1 toluene:NOx:NH3; and 10:1:1:1 toluene:NOx:NH3:SO2. Resulting effects on the cardiovascular system were assessed by measurement of vascular lipid peroxidation (thiobarbituric acid reactive substance (TBARS)), as well as quantification of heme-oxygenase (HO)-1, endothelin (ET)-1, and matrix metalloproteinase (MMP)-9 mRNA expression for comparison to previous program exposure results. Consistent with similar previous studies, vascular TBARS were not increased significantly with any acute SOA exposure. However, vascular HO-1, MMP-9, and ET-1 observed in Apo E-/- mice exposed to α-pinene + NOx + NH3 + SO2 increased statistically, while α-pinene + NOx + NH3 exposure to either toluene + NOx + NH3 or toluene +NOx + NH3 + SO2 resulted in a decreased expression of these vascular factors. Such findings suggest that the specific chemistry created by the presence or absence of acidic components may be important in SOA-mediated toxicity in the cardiovascular system and/or progression of cardiovascular disease.

Isoprene is a substantial contributor to the global secondary organic aerosol (SOA) burden, with implications for public health and the climate system. The mechanism by which isoprene-derived SOA is formed and the influence of environmental conditions, however, remain unclear. We present evidence from controlled smog chamber experiments and field measurements that in the presence of high levels of nitrogen oxides (NO(x) = NO + NO2) typical of urban atmospheres, 2-methyloxirane-2-carboxylic acid (methacrylic acid epoxide, MAE) is a precursor to known isoprene-derived SOA tracers, and ultimately to SOA. We propose that MAE arises from decomposition of the OH adduct of methacryloylperoxynitrate (MPAN). This hypothesis is supported by the similarity of SOA constituents derived from MAE to those from photooxidation of isoprene, methacrolein, and MPAN under high-NOx conditions. Strong support is further derived from computational chemistry calculations and Community Multiscale Air Quality model simulations, yielding predictions consistent with field observations. Field measurements taken in Chapel Hill, North Carolina, considered along with the modeling results indicate the atmospheric significance and relevance of MAE chemistry across the United States, especially in urban areas heavily impacted by isoprene emissions. Identification of MAE implies a major role of atmospheric epoxides in forming SOA from isoprene photooxidation. Updating current atmospheric modeling frameworks with MAE chemistry could improve the way that SOA has been attributed to isoprene based on ambient tracer measurements, and lead to SOA parameterizations that better capture the dependency of yield on NO(x).

We investigate the sources, chemical composition, and spectral properties of light-absorbing organic aerosol extracts (i.e., brown carbon, or BrC) in the Los Angeles (LA) Basin during the CalNex-2010 field campaign. Light absorption of PM2.5 water-soluble components at 365 nm (Abs365), used as a proxy for water-soluble BrC, was well correlated with water-soluble organic carbon (WSOC) (r(2) = 0.55-0.65), indicating secondary organic aerosol (SOA) formation from anthropogenic emissions was the major source of water-soluble BrC in this region. Normalizing Abs365 to WSOC mass yielded an average solution mass absorption efficiency (MAE365) of 0.71 m(2) g(-1) C. Detailed chemical speciation of filter extracts identified eight nitro-aromatic compounds that were correlated with Abs365. These compounds accounted for ∼4% of the overall water-soluble BrC absorption. Methanol-extracted BrC in LA was approximately 3 and 21 times higher than water-soluble BrC at 365 and 532 nm, respectively, and had a MAE365 of 1.58 m(2) g(-1) C (Abs365 normalized to organic carbon mass). The water-insoluble BrC was strongly correlated with ambient elemental carbon concentration, suggesting similar sources. Absorption Ångström exponent (Å(a)) (fitted between 300 and 600 nm wavelengths) was 3.2 (±1.2) for the PILS water-soluble BrC measurement, compared to 4.8 (±0.5) and 7.6 (±0.5) for methanol- and water-soluble BrC from filter extracts, respectively. These results show that fine particle BrC was prevalent in the LA basin during CalNex, yet many of its properties and potential impacts remain unknown.