Effects Of Photochemical Aging Research Articles

The effects of photochemical aging and interactions with secondary organic aerosols on cellular toxicity of combustion particles

Fine particulate matter (PM2.5) is associated with numerous adverse health effects, including pulmonary and cardiovascular diseases and premature death. Significant contributors to ambient PM2.5 include combustion particles and secondary organic aerosols (SOA). Combustion particles enter the atmosphere and undergo an aging process that changes their shape and composition, but there is limited study on the health effects of combustion particle aging and interactions with SOA. This study aimed to understand how biological responses to combustion particles would be affected by atmospheric aging and interaction with anthropogenic SOA. Fresh combustion particles underwent photochemical aging in a potential aerosol mass (PAM) oxidation flow reactor and interacted with SOA produced by the oxidation of toluene vapor in the PAM reactor. Photochemical aging and SOA interactions lead to significant changes in the PAH content and oxidative potential of the particle. Photochemical aging and SOA interactions also affected the biological responses, such as the inflammatory response and CYP1A1 induction of the particles in monoculture and coculture cells. These findings highlight the significance of photochemical aging and SOA interactions on the composition and cellular responses of combustion particles.

Effects of photochemical aging on the molecular composition of organic aerosols derived from agricultural biomass burning in whole combustion process

Biomass burning organic aerosols (BBOA) are key components of atmospheric particulate matter, yet the effects of aging process on their chemical composition and related properties remain poorly understood. In this study, fresh smoke emissions from the combustion of three types of agricultural biomass residues (rice, maize, and wheat straws) were photochemically aged in an oxidation flow reactor. The changes in BBOA composition were characterized by offline analysis using ultrahigh performance liquid chromatography coupled with Orbitrap mass spectrometry. The BBOA molecular composition varied dramatically with biomass type and aging process. Fresh and aged BBOA were predominated by CHO and nitrogen-containing CHON, CHN, and CHONS species, while with very few CHOS and other non‑oxygen species. The signal peak area variations revealed that individual molecular species underwent dynamic changes, with 77–81 % of fresh species decreased or even disappeared and 33–46 % of aged species being newly formed. A notable increase was observed in the number and peak area of CxHyO≥6 compounds in aged BBOA, suggesting that photochemical process served as an important source of highly oxygenated species. Heterocyclic CxHyN2 compounds mostly dominated in fresh CHN species, whereas CxHyN1 were more abundant in aged ones. Fragmentation and homologs oxidation by addition of oxygen-containing functional groups were important pathways for the BBOA aging. The changes in BBOA composition with aging would have large impacts on particle optical properties and toxicity. This study highlights the significance of photochemical aging process in altering chemical composition and related properties of BBOA.

Effects of driving conditions on secondary aerosol formation from a GDI vehicle using an oxidation flow reactor

A comprehensive study on the effects of photochemical aging on exhaust emissions from a vehicle equipped with a gasoline direct injection engine when operated over seven different driving cycles was assessed using an oxidation flow reactor. Both primary emissions and secondary aerosol production were measured over the Federal Test Procedure (FTP), LA92, New European Driving Cycle (NEDC), US06, and the Highway Fuel Economy Test (HWFET), as well as over two real-world cycles developed by the California Department of Transportation (Caltrans) mimicking typical highway driving conditions. We showed that the emissions of primary particles were largely depended on cold-start conditions and acceleration events. Secondary organic aerosol (SOA) formation also exhibited strong dependence on the cold-start cycles and correlated well with SOA precursor emissions (i.e., non-methane hydrocarbons, NMHC) during both cold-start and hot-start cycles (correlation coefficients 0.95–0.99), with overall emissions of ∼68–94 mg SOA per g NMHC. SOA formation significantly dropped during the hot-running phases of the cycles, with simultaneous increases in nitrate and ammonium formation as a result of the higher nitrogen oxide (NOx) and ammonia emissions. Our findings suggest that more SOA will be produced during congested, slow speed, and braking events in highways.

Measurement report: Effects of photochemical aging on the formation and evolution of summertime secondary aerosol in Beijing

Abstract. Atmospheric submicrometer aerosols have a great effect on air quality and human health, while their formation and evolution processes are still not fully understood. Herein, the crucial role of atmospheric oxidation capacity, as characterized by OH exposure dose in the formation and evolution of secondary submicrometer aerosols, was systematically investigated based on a highly time-resolved chemical characterization of PM1 in a southern suburb of Beijing in summertime from 25 July to 21 August 2019. The averaged concentration of PM1 was 19.3 ± 11.3 µg m−3, and nearly half (48.3 %) of the mass was organic aerosols (OAs) during the observation period. The equivalent photochemical age (ta) estimated from the ratios of toluene to benzene was applied to characterize the OH exposure dose of the air mass, in which an observation period with the similar sources and minimal influence of fresh emission was adopted. The relationships of non-refractory PM1 species, OA factors (i.e., one hydrocarbon-like and three oxygenated organic aerosol factors) and elemental compositions (e.g., H∕C, O∕C, N∕C, S∕C, OM∕OC, and OSc) to ta were analyzed in detail. It was found that higher PM1 concentration accompanied longer ta, with an average increase rate of 0.8 µgm-3h-1. Meanwhile, the formation of sulfate and more oxidized oxygenated OA were most sensitive to the increase in ta, and their contributions to PM1 were enhanced from 22 % to 28 % and from 29 % to 48 %, respectively, as ta increased. In addition, OSc and the ratios of O∕C and OM∕OC increased with the increase in ta. These results indicated that photochemical aging is a key factor leading to the evolution of OA and the increase in PM1 in summertime.

Biomass-burning-derived particles from a wide variety of fuels – Part 2: Effects of photochemical aging on particle optical and chemical properties

Abstract. Particles in smoke emitted from biomass combustion have a large impact on global climate and urban air quality. There is limited understanding of how particle optical properties – especially the contributions of black carbon (BC) and brown carbon (BrC) – evolve with photochemical aging of smoke. We analyze the evolution of the optical properties and chemical composition of particles produced from combustion of a wide variety of biomass fuels, largely from the western United States. The smoke is photochemically aged in a reaction chamber over atmospheric-equivalent timescales ranging from 0.25 to 8 d. Various aerosol optical properties (e.g., the single-scatter albedo, the wavelength dependence of absorption, and the BC mass absorption coefficient, MACBC) evolved with photochemical aging, with the specific evolution dependent on the initial particle properties and conditions. The impact of coatings on BC absorption (the so-called lensing effect) was small, even after photochemical aging. The initial evolution of the BrC absorptivity (MACBrC) varied between individual burns but decreased consistently at longer aging times; the wavelength dependence of the BrC absorption generally increased with aging. The observed changes to BrC properties result from a combination of secondary organic aerosol (SOA) production and heterogeneous oxidation of primary and secondary OA mass, with SOA production being the major driver of the changes. The SOA properties varied with time, reflecting both formation from precursors having a range of lifetimes with respect to OH and the evolving photochemical environment within the chamber. Although the absorptivity of BrC generally decreases with aging, the dilution-corrected absorption may actually increase from the production of SOA. These experimental results provide context for the interpretation of ambient observations of the evolution of particle optical properties in biomass-combustion-derived smoke plumes.

Catalyzed Gasoline Particulate Filters Reduce Secondary Organic Aerosol Production from Gasoline Direct Injection Vehicles.

The effects of photochemical aging on exhaust emissions from two light-duty vehicles with gasoline direct injection (GDI) engines equipped with and without catalyzed gasoline particle filters (GPFs) were investigated using a mobile environmental chamber. Both vehicles with and without the GPFs were exercised over the LA92 drive cycle using a chassis dynamometer. Diluted exhaust emissions from the entire LA92 cycle were introduced to the mobile chamber and subsequently photochemically reacted. It was found that the addition of catalyzed GPFs will significantly reduce tailpipe particulate emissions and also provide benefits in gaseous emissions, including nonmethane hydrocarbons (NMHC). Tailpipe emissions composition showed important changes with the use of GPFs by practically eliminating black carbon and increasing the fractional contribution of organic mass. Production of secondary organic aerosol (SOA) was reduced with GPF addition, but was also dependent on engine design which determined the amount of SOA precursors at the tailpipe. Our findings indicate that SOA production from GDI vehicles will be reduced with the application of catalyzed GPFs through the mitigation of reactive hydrocarbon precursors.

Secondary organic aerosol formation exceeds primary particulate matter emissions for light-duty gasoline vehicles

Abstract. The effects of photochemical aging on emissions from 15 light-duty gasoline vehicles were investigated using a smog chamber to probe the critical link between the tailpipe and ambient atmosphere. The vehicles were recruited from the California in-use fleet; they represent a wide range of model years (1987 to 2011), vehicle types and emission control technologies. Each vehicle was tested on a chassis dynamometer using the unified cycle. Dilute emissions were sampled into a portable smog chamber and then photochemically aged under urban-like conditions. For every vehicle, substantial secondary organic aerosol (SOA) formation occurred during cold-start tests, with the emissions from some vehicles generating as much as 6 times the amount of SOA as primary particulate matter (PM) after 3 h of oxidation inside the chamber at typical atmospheric oxidant levels (and 5 times the amount of SOA as primary PM after 5 × 106 molecules cm−3 h of OH exposure). Therefore, the contribution of light-duty gasoline vehicle exhaust to ambient PM levels is likely dominated by secondary PM production (SOA and nitrate). Emissions from hot-start tests formed about a factor of 3–7 less SOA than cold-start tests. Therefore, catalyst warm-up appears to be an important factor in controlling SOA precursor emissions. The mass of SOA generated by photooxidizing exhaust from newer (LEV2) vehicles was a factor of 3 lower than that formed from exhaust emitted by older (pre-LEV) vehicles, despite much larger reductions (a factor of 11–15) in nonmethane organic gas emissions. These data suggest that a complex and nonlinear relationship exists between organic gas emissions and SOA formation, which is not surprising since SOA precursors are only one component of the exhaust. Except for the oldest (pre-LEV) vehicles, the SOA production could not be fully explained by the measured oxidation of speciated (traditional) SOA precursors. Over the timescale of these experiments, the mixture of organic vapors emitted by newer vehicles appears to be more efficient (higher yielding) in producing SOA than the emissions from older vehicles. About 30% of the nonmethane organic gas emissions from the newer (LEV1 and LEV2) vehicles could not be speciated, and the majority of the SOA formed from these vehicles appears to be associated with these unspeciated organics. By comparing this study with a companion study of diesel trucks, we conclude that both primary PM emissions and SOA production for light-duty gasoline vehicles are much greater than for late-model (2007 and later) on-road heavy-duty diesel trucks.