The frequency and intensity of forest fires are amplified by climate change. Substantial quantities of PM1 emitted from forest fires can undergo gradual atmospheric dispersion and long-range transport, thus impacting air quality far from the source. However, the chemical composition and physical properties of PM emitted from forest fires and its changes during atmospheric transport remain uncertain. In this study, the evolution of organic carbon (OC), elemental carbon (EC), water-soluble ions, and water-soluble metals in the particulate phase of smoke emitted from the typical forest vegetation combustion in Southwest China before and after photo-oxidation was investigated in the laboratory. Two aging periods of 5 and 9 days were selected. The OC and TC mass concentrations tended to decrease after 9-days aged compared to fresh emissions. OP, OC2, and OC3 in PM1 are expected to be potential indicators of fresh smoke, while OC3 and OC4 may serve as suitable markers for identifying aged carbon sources from the typical forest vegetation combustion in Southwest China. K+ exhibited the highest abundant water-soluble ion in fresh PM1, whereas NO3- became the most abundant water-soluble ion in aged PM1. NH4NO3 emerged as the primary secondary inorganic aerosol emitted from typical forest vegetation combustion in Southwest China. Notably, a 5-day aging period proved insufficient for the complete formation of the secondary inorganic aerosols NH4NO3 and (NH4)2SO4. After aging, the mass concentration of the water-soluble metal Ni in PM1 from typical forest vegetation combustion in Southwest China decreased, while the mean mass concentrations of all other water-soluble metals increased in varying degrees. These findings provide valuable data support and theoretical guidance for studying the atmospheric evolution of forest fire aerosols, as well as contribute to policy formulation and management of atmospheric environment safety and human health.

Pyruvic acid (PA) is a ubiquitous 2-oxocarboxylic acid in the atmosphere. Its photochemical process at the air-liquid (a-l) interface has been suggested as an important source of aqueous secondary organic aerosols. We investigated the photochemical reaction pathways of PA at the a-l interface using synchrotron-based vacuum ultraviolet single-photon ionization mass spectrometry (VUV SPI-MS) coupled with the System for Analysis at the Liquid Vacuum Interface (SALVI) microreactor. Results from mass spectral analysis and the determination of appearance energies (AEs) indicate that photolysis of PA can generate radicals, then they recombine with carboxylic acids and simple molecular oligomers. Furthermore, the preliminary products could form larger oligomers via radical reaction or esterification in the presence of hydroxyl and carboxyl functional groups. Mass spectral comparison shows that most photochemical reactions would complete within 4 h. The expanded photochemistry-driven reaction flowchart of PA is proposed based on the newly discovered products. Our results reveal that the interfacial PA photochemical reactions have different mechanisms from the bulk liquid due to the interfacial properties, such as molecular density, composition, and ion concentration. Our findings show that in situ mass spectral analysis with bright photon ionization is useful to elucidate the contribution of a-l interfacial reactions leading to aqSOA formation.

The mechanism and kinetics of reactive oxygen species (ROS) formation when atmospheric secondary organic aerosol (SOA) is exposed to solar radiation are poorly understood. In this study, we combined an in situ UV-vis irradiation system with electron paramagnetic resonance (EPR) spectroscopy to characterize the photolytic formation of ROS in aqueous extracts of SOA formed by the oxidation of isoprene, α-pinene, α-terpineol, and toluene. We observed substantial formation of free radicals, including •OH, superoxide (HO2•), and organic radicals (R•/RO•) upon irradiation. Compared to dark conditions, the radical yield was enhanced by a factor of ∼30 for •OH and by a factor of 2-10 for superoxide radicals, and we observed the emergence of organic radicals. Total peroxide measurements showed substantial decreases of peroxide contents after photoirradiation, indicating that organic peroxides can be an important source of the observed radicals. A liquid chromatography interfaced with high-resolution mass spectrometry was used to detect a number of organic radicals in the form of adducts with a spin trap, BMPO. The types of detected radicals and aqueous photolysis of model compounds indicated that photolysis of carbonyls by Norrish type I mechanisms plays an important role in the organic radical formation. The photolytic ROS formation serves as the driving force for cloud and fog processing of SOA.

Particulate organic matter (POM), as an important component of organic matter, can act as a redox mediator and thus intervene in the environmental behavior of microplastics (MPs). However, quantitative information on the role of POM in the photoaging of MPs under ultraviolet (UV) light is still lacking. To raise the knowledge gap, through environmental simulation experiments and qualitative/quantitative experiments of active substances, we found that POM from peat soil has stronger oxidation capacity than POM from sediment, and the involvement of POM at high water content makes the aging of MPs more obvious. This is because the persistent radicals and electron-absorbing groups on the surface of POM indirectly generate reactive oxygen species (ROS) by promoting electron transfer, and the dissolved organic matter (DOM) released from POM under UV light (POM-DOM) is further excited to generate triplet-state photochemistry of DOM (3DOM*) to promote the aging of MPs. Theoretical calculations revealed that the benzene ring, mainly C = C, and C = O in the main chain in the plastic macromolecule structure are more susceptible to ROS attack, and the differences in the vulnerable sites contained in different plastic structures as well as the differences in the energy band gaps lead to differences in their aging processes. This study firstly elucidates the key role and intrinsic mechanism of POM in the photoaging of MPs, providing a theoretical basis for a comprehensive assessment of the effect of POM on MPs in the environment.

Secondary organic aerosol (SOA) is a significant component of atmospheric fine particulate matter (PM2.5), and their physicochemical properties can be significantly changed in the aging process. In this study, we used a combination consisting of a smog chamber (SC) and oxidation flow reactor (OFR) to investigate the continuous aging process of gas-phase organic intermediates and SOA formed from the photooxidation of toluene, a typical aromatic hydrocarbon. Our results showed that as the OH exposure increased from 2.6 × 1011 to 6.3 × 1011 molecules cm-3 s (equivalent aging time of 2.01-4.85 days), the SOA mass concentration (2.9 ± 0.05-28.7 ± 0.6 μg cm-3) and corrected SOA yield (0.073-0.26) were significantly enhanced. As the aging process proceeds, organic acids and multiple oxygen-containing oxidation products are continuously produced from the photochemical aging process of gas-phase organic intermediates (mainly semi-volatile and intermediate volatility species, S/IVOCs). The multigeneration oxidation products then partition to the aerosol phase, while functionalization of SOA rather than fragmentation dominated in the photochemical aging process, resulting in much higher SOA yield after aging compared to that in the SC. Our study indicates that SOA yields as a function of OH exposure should be considered in air quality models to improve SOA simulation, and thus accurately assess the impact on SOA properties and regional air quality.

Effective density (ρeff) is an important property describing particle transportation in the atmosphere and in the human respiratory tract. In this study, the particle size dependency of ρeff was determined for fresh and photochemically aged particles from residential combustion of wood logs and brown coal, as well as from an aerosol standard (CAST) burner. ρeff increased considerably due to photochemical aging, especially for soot agglomerates larger than 100 nm in mobility diameter. The increase depends on the presence of condensable vapors and agglomerate size and can be explained by collapsing of chain-like agglomerates and filling of their voids and formation of secondary coating. The measured and modeled particle optical properties suggest that while light absorption, scattering, and the single-scattering albedo of soot particle increase during photochemical processing, their radiative forcing remains positive until the amount of nonabsorbing coating exceeds approximately 90% of the particle mass.

Black carbon (BC) exerts profound impacts on air quality, human health, and climate. Here, we investigated concentrations and size distributions of refractory BC (rBC) and mixing state and morphology of rBC-containing particles in urban Seoul for 2019 summer. Mass concentrations of rBC ranged from 0.02 μgm-3 to 2.89 μgm-3, and daily maximums of rBC mass, daily minimums of rBC mass median diameter (MMD) (110-130 nm), and shell-to-core ratio (Rshell/core) occurred with NO2 maximums during morning rush hour. As the first report of ground observations on rBC mixing state, these results indicate that vehicle emissions are a major local source of rBC in Seoul. MMDs of 127-146 nm and the greatest mass loadings of ≥1 μg m-3 were accompanied by high O3 and PM2.5, in contrast to the largest MMDs (135-165 nm) associated with transport from upstream regions. The average Rshell/core was 1.25 for the mass-equivalent diameter (DrBC) of 140-220 nm. Rshell/core increased gradually through the day and was positively correlated with Ox concentration, indicating photochemical aging of rBC particles. Co-emissions of rBC and volatile organic compounds from vehicles facilitated internal mixing during the daytime. However, Rshell/core tended to be low at temperature >~30 °C and 58 % of rBC with Rshell/core exceeding 1.25 were found at nighttime under relative humidity >75 %. These results demonstrate that the mixing state of freshly-emitted rBC particles was altered through coating by photochemically oxidized vapors during the day and hygroscopic growth at night. Additionally, the delay-time approach revealed rBC morphological characteristics, the most common being the bare type (74 %), and the attached type (6 %) was relatively large in numbers during morning rush hour. Therefore, it is suggested that during summer, rBC particles from traffic emissions should be considered in parallel to winter pollution mitigation strategies in urban atmosphere of northeast Asia.

Residential solid fuel combustion (RSFC) is an important source of PM2.5. Here we investigate the cytotoxicity of primarily emitted and photochemically aged PM2.5 to A549 cells. Owing to the formation of water-soluble ions and organics (e.g., oPAHs and nPAHs), emission factors of PM2.5 were increased by 44.4% on average after 7-day equivalent photochemical aging, which greatly altered chemical profiles of freshly emitted PM2.5. Consequently, the cytotoxicity varied with aging duration that 2-day and 7-day aged PM2.5 induced 22.5% and 35.1%, respectively, higher levels of reactive oxygen species than primary emissions. Similar increases were also observed for multi-cytotoxicity. Correlation analysis and western blot results collectively confirmed HO-1/Nrf-2 signaling pathway dominated the cytotoxicity of aged PM2.5 from RSFC, which was regulated by the enhanced o-PAHs and n-PAHs during photochemical aging. Thus, aged and secondary aerosol exposure needs to be paid more attention due to the enhanced cytotoxicity and the vast crowd involved.

Microplastics (MPs) interact frequently with dissolved organic matter (DOM) commonly found in the environment, but information on the aging behavior of MPs under the participation of DOM is still lacking. Thus, the polystyrene microplastic (PSMP) aging process with DOM participation was systematically studied by electron paramagnetic resonance spectroscopy, high-performance liquid chromatography, Fourier transform infrared (FTIR) spectroscopy, and two-dimensional correlation spectroscopy analyses under dark and ultraviolet (UV) light conditions. DOM was found to promote electron transfer to generate reactive oxygen species (ROS) under dark conditions and the aging of PSMPs, while the process of DOM generating ROS under UV light was more susceptible to photoelectrons and accelerated the aging process of PSMPs. However, among the four DOM types, fulvic acid (FA) has a more significant promoting effect on the aging process of PSMPs than humic acid, which can be attributed to the stronger conversion ability of FA to semiquinone radicals. Density functional theory calculations are used to describe the difference in the aging process of different structures of plastics with the participation of DOM. This study provides a necessary theoretical basis for the study of the migration of MPs in groundwater and deep surface water.

Light-absorbing organic aerosols, also known as brown carbon (BrC), enhance the warming effect of the Earth\'s atmosphere. The seasonal and spatial variability of BrC absorption properties is poorly constrained and accounted for in the climate models resulting in a substantial underestimation of their radiative forcing estimates. This study reports seasonal and spatial variability of absorption properties and simple forcing efficiency of light-absorbing water-soluble organic carbon (WSOC, SFEWSOC) by utilizing current and previous field-based measurements reported mostly from Asia along with a few observations from Europe, the USA, and the Amazon rainforest. The absorption coefficient of WSOC at 365 nm (babs-365) and the concentrations of carbonaceous species at Kanpur were about an order of magnitude higher during winter than in the monsoon season owing to differences in the boundary layer height, active sources and their strengths, and amount of seasonal wet precipitation. The WSOC aerosols during winter exhibited ∼1.6 times higher light absorption capacity than in the monsoon season at Kanpur site. The assessment of spatial variability of the imaginary component of the refractive index spectrum (kλ) across South Asia has revealed that it varies from ∼1 to 2 orders of magnitude and light absorption capacity of WSOC ranges from 3 to 21 W/g. The light absorption capacity of WSOC aerosols exhibited less spatial variability across East Asia (5-13 W/g) when compared to that in the South Asia. The photochemical aging of WSOC aerosols, indicated by the enhancement in WSOC/OC ratio, was linked to degradation in their light absorption capacity, whereas the absorption Ångström exponent (AAE) remained unaffected. This study recommends the adoption of refined climate models where sampling regime specific absorption properties are calculated separately, such that these inputs can better constrain the model estimates of the global effects of BrC.