48 Search Results

Biomass burning is one of the most significant sources of organic aerosol in the atmosphere. Biomass burning organic aerosol (BBOA) has been observed to undergo liquid– liquid phase separation (LLPS) to give core–shell morphology with the hydrophobic phase encapsulating the hydrophilic phase, potentially impacting the evolution of light-absorbing components, i.e., brown carbon (BrC), through multiphase processes. Here, we demonstrate how multiphase processing differs between the watersoluble (i.e., hydrophilic) and insoluble (i.e., hydrophobic) phases of BBOA in terms of reactive uptake of ozone in a coated-wall flow tube. Effects of relative humidity (RH) and ultraviolet (UV) irradiation were investigated. Experimental timeseriesmore » were used to inform simulations using multilayer kinetic modeling. Among non-irradiated thin films, the uptake coefficient was greatest for the water-soluble phase at 75% RH (3 × 10^–5, corresponding to a diffusion coefficient of BrC, D_BrC, of 3 × 10^–9 cm² s^–1) and least for the same phase at 0% RH (1 × 10^–5, corresponding to D_BrC of 1 × 10^–10 cm² s^–1). The uptake coefficient for the water-insoluble phase fell between these two (about 1.5 × 10^–5), regardless of RH, and the corresponding D_BrC increased only slightly (8 × 10^–10 cm² s^–1 at 0% RH to 9 × 10^–10 cm² s^–1 at 75% RH). The uptake coefficients of both phases at 0% RH decreased significantly after UV irradiation, consistent with a transition from viscous liquid to solid and supported by qualitative microscopy observations. Modeling multiphase ozone oxidation of primary BrC components in the atmosphere demonstrated, first, that LLPS may extend the lifetime of water-soluble BBOA encapsulated by water-insoluble species by a factor of 1.5 at moderate to high RH and, also, that UV irradiation may extend the lifetime of both phases by more than a factor of 2.5.« less

Oxygen electrochemistry goes beyond O₂, as the formation of reactive oxygen species (ROS) such as H₂O₂ and O₃ during water oxidation is key in the destruction of persistent pollutants in water remediation technologies as well as in the degradation of fuel cell and electrolyzer components. In this study, we developed an in situ method utilizing the rotating ring-disk electrode technique to quantify the formation of O₂, O₃, and H₂O₂ species across a broad pH range (1–8.3). Oxygen selectivity trends over Pt, IrO₂, and PbO₂ surfaces reveal that even O₂ evolution catalysts may produce small yet measurable amounts of ROS, furthermore » modulated by pH and electrode potential. In conclusion, these findings emphasize the need to probe the selectivity of oxygen electrochemistry for a more complete picture of advanced materials for electrochemical technologies.« less

Vibrational kinetics of O₂ is studied during the O atom recombination in an O₂–Ar mixture, partially dissociated by a burst of ns discharge pulses in a heated plasma flow reactor. The time-resolved temperature in the discharge afterglow is determined by Rayleigh scattering. Time-resolved O atom number density is measured by ps Two-Photon absorption Laser Induced Fluorescence, calibrated in xenon. Time-resolved vibrational level populations of molecular oxygen, O₂(v= 8–20), are measured by ps Laser Induced Fluorescence (LIF), with the absolute calibration by NO LIF. Time-resolved ozone number density is monitored by broadband UV absorption. The results are compared with the predictionsmore » of a state-specific kinetic model. The experimental data indicate a rapid initial decay of O₂(v) populations generated by electron impact in the discharge, due to the vibration-translation (V–T) relaxation by O atoms. This is followed by a slower population reduction, on the time scale much longer compared to that for V–T relaxation or vibration-vibration (V–V) exchange. Both O atoms and the O₂(v) populations decay on the same time scale, indicating that chemical reactions initiated by the O atom recombination result in the generation of vibrationally excited O₂ molecules. These trends are reproduced by the kinetic model, which shows that the reaction of O atoms with ozone is the dominant pathway of O₂(v) generation at the present conditions. The predicted relative O₂(v) populations are close to the experimental results, but absolute number densities differ from the experimental data. This is likely due to uncertainties in the absolute calibration of LIF measurements and in the spectroscopic model used in the data reduction. The present work demonstrates the capability for the absolute, time-resolved measurements of vibrationally excited O₂ in recombining gas flows, to quantify the energy partition in the recombination reactions.« less

As a subtropical anticyclonic high-pressure system that typically forms over the northwestern Pacific Ocean in summer, the Western Pacific subtropical high (WPSH) affects meteorological conditions and ozone pollution in China. The relationship between maximum daily 8-h average ozone (MDA8 O₃) concentrations and the extremely strong and westward-extended WPSH occurred in 2022 is investigated using observations, reanalysis data and GEOS-Chem model simulations. The intensity of WPSH has a significant positive correlation with MDA8 O3 over southern China during July-August in 2022, with a correlation coefficient of +0.44, but the correlation is negative (–0.40) in northern China. During the strong WPSH days,more » MDA8 O₃ increased by 16.5µgm^-3 (16.4% relative to July-August average) over southern China and decreased by 19.0µgm^-3 (14.5%) in northern China compared to the weak WPSH days. The unique dipole pattern in the relationship between ozone levels and the WPSH in 2022 exhibited a contrast to that during 2015–2021. The difference is primarily due to the extremely strong WPSH intensity and its unusual westward expansion in 2022. In this case, an anomalous anticyclone at 500 hPa dominates over southern China, which creates conditions conducive for ozone formation and accumulation. The anticyclone weakened horizontal winds and reduced the dispersion of ozone, alongside a high temperature and low relative humidity, which favored the chemical production of ozone. In contrast, abnormal northerly winds enhanced ozone diffusion in northern China and the low temperature reduced ozone chemical production. Here, this study reveals the mechanism for the significant impact of strong and westward-extended WPSH on ozone concentrations over China, emphasizing the role of the WPSH location in modulating meteorology and ozone levels.« less

In this study, electrochemical ozone production (EOP), a six-electron water oxidation reaction, offers promising avenues for creating value-added oxidants and disinfectants. However, progress in this field is slowed by a dearth of understanding of fundamental reaction mechanisms. In this work, we combine experimental electrochemistry, spectroscopic detection of reactive oxygen species (ROS), oxygen-anion chemical ionization mass spectrometry, and computational quantum chemistry calculations to determine a plausible reaction mechanism on nickel- and antimony-doped tin oxide (Ni/Sb–SnO₂, NATO), one of the most selective EOP catalysts. Antimony doping is shown to increase the conductivity of the catalyst, leading to improved electrochemical performance. Spectroscopic analysismore » and electrochemical experiments combined with quantum chemistry predictions reveal that hydrogen peroxide (H₂O₂) is a critical reaction intermediate. We propose that leached Ni⁴⁺ cations catalyze hydrogen peroxide into solution phase hydroperoxyl radicals (^•OOH); these radicals are subsequently oxidized to ozone. Isotopic product analysis shows that ozone is generated catalytically from water and corrosively from the catalyst oxide lattice without regeneration of lattice oxygens. Further quantum chemistry calculations and thermodynamic analysis suggest that the electrochemical corrosion of tin oxide itself might generate hydrogen peroxide, which is then catalyzed to ozone. The proposed pathways explain both the roles of dopants in NATO and its lack of stability. Our study interrogates the possibility that instability and electrochemical activity are intrinsically linked through the formation of ROS. In doing so, we provide the first mechanism for EOP that is consistent with computational and experimental results and highlight the central challenge of instability as a target for future research efforts.« less

Photochemical modeling outputs showing high ozone concentrations over the Gulf of Mexico and Galveston Bay during ozone episodes in the Houston–Galveston–Brazoria (HGB) region have not been previously verified using in situ observations. Such data were collected systematically, for the first time, from July to October 2021 from three boats deployed for the Galveston Offshore Ozone Observations (GO3) and Tracking Aerosol Convection Interactions Experiment—Air Quality (TRACER-AQ) field campaigns. A pontoon boat and a commercial vessel operated in Galveston Bay, while another commercial vessel operated in the Gulf of Mexico offshore of Galveston. All three boats had continuously operating sampling systems thatmore » included ozone analyzers and weather stations, and the two boats operating in Galveston Bay had a ceilometer. The sampling systems operated autonomously on the two commercial boats as they traveled their daily routes. Thirty-seven ozonesondes were launched over water on forecast high ozone days in Galveston Bay and the Gulf of Mexico. During the campaigns, multiple periods of ozone exceeding 100 ppbv were observed over water in Galveston Bay and the Gulf of Mexico. These events included previously identified conditions for high ozone events in the HGB region, such as the bay/sea-breeze recirculation and postfrontal environments, as well as a localized coastal high ozone event after the passing of a tropical system (Hurricane Nicholas) that was not well forecast.« less

Abstract Simulating whole atmosphere dynamics, chemistry, and physics is computationally expensive. It can require high vertical resolution throughout the middle and upper atmosphere, as well as a comprehensive chemistry and aerosol scheme coupled to radiation physics. An unintentional outcome of the development of one of the most sophisticated and hence computationally expensive model configurations is that it often excludes a broad community of users with limited computational resources. Here, we analyze two configurations of the Community Earth System Model Version 2, Whole Atmosphere Community Climate Model Version 6 (CESM2(WACCM6)) with simplified “middle atmosphere” chemistry at nominal 1 and 2° horizontalmore » resolutions. Using observations, a reanalysis, and direct model comparisons, we find that these configurations generally reproduce the climate, variability, and climate sensitivity of the 1° nominal horizontal resolution configuration with comprehensive chemistry. While the background stratospheric aerosol optical depth is elevated in the middle atmosphere configurations as compared to the comprehensive chemistry configuration, it is comparable among all configurations during volcanic eruptions. For any purposes other than those needing an accurate representation of tropospheric organic chemistry and secondary organic aerosols, these simplified chemistry configurations deliver reliable simulations of the whole atmosphere that require 35% and 86% fewer computational resources at nominal 1 and 2° horizontal resolution, respectively.« less

Individuals with psychosocial stress often experience an exaggerated response to air pollutants. Ozone (O₃) exposure has been associated with the activation of the neuroendocrine stress-response system. We hypothesized that preexistent mild chronic stress plus social isolation (CS), or social isolation (SI) alone, would exacerbate the acute effects of O₃ exposure on the circulating adrenal-derived stress hormones, and the expression of the genes regulating glucocorticoid stress signaling via an altered stress adaptation in a brain-region-specific manner. Male Wistar–Kyoto rats (5 weeks old) were socially isolated, plus were subjected to either CS (noise, confinement, fear, uncomfortable living, hectic activity, and single housing),more » SI (single housing only, restricted handling and no enrichment) or no stress (NS; double housing, frequent handling and enrichment provided) for 8 weeks. The rats were then exposed to either air or O₃ (0.8 ppm for 4 h), and the samples were collected immediately after. The indicators of sympathetic and hypothalamic–pituitary axis (HPA) activation (i.e., epinephrine, corticosterone, and lymphopenia) increased with O₃ exposure, but there were no effects from CS or SI, except for the depletion of serum BDNF. CS and SI revealed small changes in brain-region-specific glucocorticoid-signaling-associated markers of gene expression in the air-exposed rats (hypothalamic Nr3c1, Nr3c2 Hsp90aa1, Hspa4 and Cnr1 inhibition in SI; hippocampal HSP90aa1 increase in SI; and inhibition of the bed nucleus of the stria terminalis (BNST) Cnr1 in CS). Gene expression across all brain regions was altered by O₃, reflective of glucocorticoid signaling effects, such as Fkbp5 in NS, CS and SI. The SI effects on Fkbp5 were greatest for SI in BNST. O₃ increased Cnr2 expression in the hypothalamus and olfactory bulbs of the NS and SI groups. O₃, in all stress conditions, generally inhibited the expression of Nr3c1 in all brain regions, Nr3c2 in the hippocampus and hypothalamus and Bdnf in the hippocampus. SI, in general, showed slightly greater O₃-induced changes when compared to NS and CS. Serum metabolomics revealed increased sphingomyelins in the air-exposed SI and O₃-exposed NS, with underlying SI dampening some of the O₃-induced changes. These results suggest a potential link between preexistent SI and acute O₃-induced increases in the circulating adrenal-derived stress hormones and brain-region-specific gene expression changes in glucocorticoid signaling, which may partly underlie the stress dynamic in those with long-term SI.« less

Tree growth and survival are dependent on their ability to perceive signals, integrate them, and trigger timely and fitted molecular and growth responses. While ectomycorrhizal symbiosis is a predominant tree-microbe interaction in forest ecosystems, little is known about how and to what extent it helps trees cope with environmental changes. We hypothesized that the presence of Laccaria bicolor influences abiotic cue perception by Populus trichocarpa and the ensuing signaling cascade. We submitted ectomycorrhizal or non-ectomycorrhizal P. trichocarpa cuttings to short-term cessation of watering or ozone fumigation to focus on signaling networks before the onset of any physiological damage. Poplar genemore » expression, metabolite levels, and hormone levels were measured in several organs (roots, leaves, mycorrhizas) and integrated into networks. We discriminated the signal responses modified or maintained by ectomycorrhization. Ectomycorrhizas buffered hormonal changes in response to short-term environmental variations systemically prepared the root system for further fungal colonization and alleviated part of the root abscisic acid (ABA) signaling. Furthermore, the presence of ectomycorrhizas in the roots also modified the leaf multi-omics landscape and ozone responses, most likely through rewiring of the molecular drivers of photosynthesis and the calcium signaling pathway. In conclusion, P. trichocarpa-L. bicolor symbiosis results in a systemic remodeling of the host's signaling networks in response to abiotic changes. In addition, ectomycorrhizal, hormonal, metabolic, and transcriptomic blueprints are maintained in response to abiotic cues, suggesting that ectomycorrhizas are less responsive than non-mycorrhizal roots to abiotic challenges.« less

Abstract The dry deposition of ozone from the atmosphere to ecosystems is an important coupling mechanism between atmospheric chemistry and terrestrial biogeochemical processes. In most Earth system models, dry deposition is simulated using a resistor‐in‐series approach that aims to parameterize the governing biological, chemical, and physical processes through a series of functional approximations. Here, we evaluate the influence of carbon cycle‐climate responses on this parameterization using the results of the Energy Exascale Earth System Model v1.1 Biogeochemistry simulation campaign. This simulation campaign was designed in part to explore the biophysical and radiative effects of rising historical CO ₂ concentrations onmore » the Earth system. We find that while the global annual ozone dry deposition is relatively insensitive to these effects, regionally the influence can be up to 10%. The strongest regional sensitivities in ozone dry deposition are predominantly in higher latitudes over land in the northern hemisphere and are dominated by the radiative effect of CO ₂ , with little net influence of biophysical responses. Of all the impacts of the radiative effect of CO ₂ , we point to the potential importance of accurately representing ozone deposition to snow in Earth System Models and provide recommendations for future simulation campaigns.« less