Photochemical Aging Research Articles

Photooxidation of Nonanoic Acid by Molecular and Complex Environmental Photosensitizers.

Photochemical aging and photooxidation of atmospheric particles play a crucial role in both the chemical and physical processes occurring in the troposphere. In particular, the presence of organic chromophores within atmospheric aerosols can trigger photosensitized oxidation that drives the atmospheric processes in these interfaces. However, the light-induced oxidation of the surface of atmospheric aerosols, especially those enriched with organic components, remains poorly understood. Herein, we present a gravimetric and vibrational spectroscopy study aimed to investigate the photosensitized oxidation of nonanoic acid (NA), a model system of fatty acids within organic aerosols, in the presence of complex organic photosensitizers and molecular proxies. Specifically, this study shows a comparative analysis of the photosensitized reactions of thin films containing nonanoic acid and four different organic photosensitizers, namely marine dissolved organic matter (m-DOM) and humic acids (HA) as environmental photosensitizers, and 4-imidazolecarboxaldehyde (4IC) and 4-benzoylbenzoic acid (4BBA) as molecular proxies. All reactions show predominant photooxidation of nonanoic acid, with important differences in the rate and yield of product formation depending on the photosensitizer. Limited changes were observed in the organic photosensitizer itself. Results show that, among the photosensitizers examined, 4BBA is the most effective in photooxidizing nonanoic acid. Overall, this work underscores the role of chromophores in the photooxidation of organic thin films and the relevance of such reactions on the surface of aerosols in the marine environment.

Significant Biogenic Source of Oxygenated Volatile Organic Compounds and the Impacts on Photochemistry at a Regional Background Site in South China.

Oxygenated volatile organic compounds (OVOCs) significantly modulate atmospheric chemistry, but the sources and air quality impacts of OVOCs in aged urban outflows remain to be elucidated. At a background site in South China, the ozone formation potential of six nonformaldehyde OVOCs studied was equivalent to that of 3.56 ppbv of formaldehyde, more than half of which was contributed by acetaldehyde. Source apportionment incorporating photochemical age revealed that considerable fractions (52.7%-62.6%) of the OVOCs were of biogenic origin, except for ethanol, which was primarily derived from anthropogenic emissions. The oxidation of cis-/trans-2-butene explained 71.1% of the in situ acetaldehyde formation. In contrast, α/β-pinenes and isoprene contributed 73.8% and 28.4% to acetone and methylglyoxal formation, respectively. An average of 12.4% of net in situ ozone (O3) production rate was attributed to the OVOCs studied, where the biogenic fractions accounted for 59%. The changes in the O3 production rate and hydroxyl radical (OH) concentration caused by OVOCs were mainly affected by ozone formation sensitivity. The effects of primary acetaldehyde and acetaldehyde-led O3 on secondary acetaldehyde formation were weak at this background site; however, they cannot be ignored in polluted areas. This study provides a scientific basis for mitigating O3 pollution driven by biogenic emissions and OVOCs.

Deciphering the role of nonylphenol adsorption in soil by microplastics with different polarities and ageing processes.

In the soil environment, microplastics (MPs) commonly coexist with organic pollutants such as nonylphenol (NP), affecting the migration of NP through adsorption/desorption. However, few studies have focused on the interaction between NP and MPs in soil, especially for MPs of different types and ageing characteristics. In this study, non-polar polypropylene (PP) and polar polyamide (PA) MPs were aged either photochemically (144 h) or within soil (60 days), then used to determine the effect of 5 % MPs on the adsorption behaviour of NP (0.1-4.0 mg/L) in soil. Results showed that both ageing processes significantly promoted the conversion of -CH3 groups to C-O and CO on the surface of PPMPs, while PAMPs exhibited amide groups changes and a reduction in average particle size due to ageing. Additionally, both ageing processes promoted the adsorption of NP by soil containing PPMPs, due to an increase in oxygen-containing functional groups and specific surface area. In contrast, the NP adsorption capacity of soil containing PAMPs decreased by 15.4 % following photochemical ageing due to hydrolysis of amide groups, but increased by 21.15 % after soil ageing due to reorganization of amide groups, respectively. The soil-PAMPs systems exhibited a stronger affinity for NP compared to the soil-PPMPs systems, which was primarily attributed to the dominant role of hydrogen bonding. NP was found to be distributed mainly on soil particles in the soil-PPMPs systems, while it tended to be adsorbed by MPs in the soil-PAMPs systems, especially in the soil aged MPs system. This study provides a comprehensive analysis of the complex effects of MPs on coexisting pollutants in soil environments, highlighting the effect of MP characteristics on the adsorption of organic pollutants, which is essential for understanding the transport behaviour of organic pollutants.

Chemical Characterization of Organic Aerosol Tracers Derived from Burning Biomass Indigenous to Sub-Saharan Africa: Fresh Emissions versus Photochemical Aging

Chemical Characterization of Organic Aerosol Tracers Derived from Burning Biomass Indigenous to Sub-Saharan Africa: Fresh Emissions versus Photochemical Aging

Coupling Effect of Elemental Carbon and Organic Carbon on the Changes of Optical Properties and Oxidative Potential of Soot Particles under Visible Light.

Soot particles, coming from the incomplete combustion of fossil or biomass fuels, feature a core-shell structure with inner elemental carbon (EC) and outer organic carbon (OC). Both EC and OC are known to be photoactive under solar radiation. However, research on their coupling effect during photochemical aging remains limited. This study examines how the optical properties and oxidative potential (OP) of wood, coal, and diesel soot particles with varying EC and OC levels are affected by exposure to visible light. Wood soot, which has the highest OC content, showed the most significant changes in both optical properties and OP, indicating its highest sensitivity to visible light aging. Molecular composition analysis revealed that the reduction of polycyclic aromatic hydrocarbons (PAHs) and methyl-PAHs primarily affects the optical properties, while oxygenated PAHs play a major role in OP. Combined with the results from reactive oxygen species detection, it is suggested that EC initiates photoreactions by generating superoxide anions, while OC undergoes compositional changes that result in subsequent atmospheric effects. These findings enhance our understanding of the photochemical aging process of soot particles and their implications for climate and health.

Characterization of polyethylene films drawn by machine direction orientation and consequences on their photooxidation

The effect of uniaxial drawing by Machine Direction Orientation (MDO) on polyethylene films was first studied by complementary analytical methods. XRD and polarized FTIR spectroscopy revealed the transformation of the initial spherulitic structure of PE into microfibrils composed of small crystalline blocks connected by amorphous chains oriented along the drawing direction. No stress-induced crystallization was observed upon MDO processing, but the permeability to oxygen was reduced by 30 % owing to this morphology change. In a second time, the effect of photooxidation on undrawn and MDO-drawn films was studied. There was no difference in the photooxidation kinetics and stoichiometry between them. A slight reorganization of the polymer structure due to physical ageing was observed before any photooxidation, but no change in orientation occurred upon photochemical ageing. Finally, the oxygen permeability of undrawn and MDO-drawn films decreased owing to the changes brought by photooxidation, especially the formation of polar functions within the initially apolar polyethylene and the occurrence of chemicrystallization.

Global Influence of Organic Aerosol Volatility on Aerosol Microphysical Processes: Composition and Number

AbstractWe present MATRIX‐VBS, a new aerosol scheme that simulates organic partitioning in an aerosol microphysics model, as part of the NASA GISS ModelE Earth System Model. MATRIX‐VBS builds on its predecessor aerosol microphysics model MATRIX (Bauer et al., 2008, https://doi.org/10.5194/acp‐8‐6003‐2008) and was developed in the box model framework (Gao et al., 2017, https://doi.org/10.5194/gmd‐10‐751‐2017). The scheme features the inclusion of organic partitioning between the gas and particle phases and the photochemical aging process using the volatility‐basis set (Donahue et al., 2006, https://doi.org/10.1021/es052297c). To assess the performance of the new model, we compared its mass concentration, number concentration, and activated number concentration to the original scheme MATRIX, and evaluated its mass concentrations in four seasons against data from the NASA Atmospheric Tomography Mission (ATom) aircraft campaign. Results from MATRIX‐VBS show that organics are transported further away from their source, and their mass concentration increases aloft and decreases at the surface compared to those in MATRIX. The mass concentration of organics at the surface agrees well with measurements, and there are discrepancies for vertical profiles aloft. In the new scheme, the global mass load of organic aerosols increased by 50%, there is also an increased number of particles at the surface and fewer activated ones in most regions. The new scheme presents advanced and more comprehensive capability in simulating aerosol processes.

Stable isotopic, bulk, and molecular compositions of post-monsoon biomass-burning aerosols in Delhi suggest photochemical ageing during regional transport is more pronounced than local processing

Stable isotopic, bulk, and molecular compositions of post-monsoon biomass-burning aerosols in Delhi suggest photochemical ageing during regional transport is more pronounced than local processing

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.

Comparative analysis of winter composite-PM2.5 in Central Indo Gangetic Plain cities: Combined organic and inorganic source apportionment and characterization, with a focus on the photochemical age effect on secondary organic aerosol formation

To gain insights into air quality dynamics, a high-end instrument such as High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS) alongside an Aethalometer was used to measure the Composite PM2.5 (C-PM2.5) in Lucknow and Kanpur during winter. It encompasses non-refractive PM2.5 (NR-PM2.5) and Black Carbon (BC) mass concentrations. Significant variation was noted in average C-PM2.5 concentrations at both sites, as 168.8 ± 61.3 μg m−3 in Lucknow and 90.7 ± 25.7 μg m−3 in Kanpur. Organics emerged as the predominant component, constituting ∼55%–65% of the C-PM2.5 mass, followed by inorganics (24% and 30%) and BC (20% and 8%). The present study employs Positive Matrix Factorization (PMF) on combined organic and inorganic source apportionment, resolving eight and seven source factors at Lucknow and Kanpur, respectively. Both sites exhibit significant contributions from solid-fuel combustion organic aerosol (SFC-OA), with ∼11% in Lucknow and 8% in Kanpur. However, SFC-OA mass concentration in Lucknow, at 24.67 μg m-³, is nearly double that in Kanpur (12.05 μg m-³). This was likely due to domestic coal burning in the nearby households, unregulated open burning, and burning of garbage on roadsides. The study shows that both sites were affected by oxidized biomass burning OA (O-BBOA) emissions, with increased concentration during the night due to dark oxidation by NO3 radicals. The diurnal variation of secondary organic aerosols (SOA), such as O-BBOA and semi-volatile oxygenated OA (SVOOA), shows increasing concentration during daytime hours. Therefore, the photochemical aging (ta) role in SOA formation was analyzed, and it was revealed that the formation might primarily be driven by photochemical oxidation. Additionally, two inorganic-rich factors, sulfate and nitrate-related OA (SO4-OA and NO3-OA) at both sites and additional ammonium chloride-related OA (NH4Cl-OA) resolved at Lucknow. Our study shows that NO3-OA and SO4-OA formation was dominated by aqueous phase processes due to high relative humidity and decline in concentration with increasing ta (ta > 30 h) during winter.

Photoinduced Evolutions of Permafrost-Derived Carbon in Subarctic Thermokarst Pond Surface Waters.

In subarctic regions, rising temperature and permafrost thaw lead to the formation of thermokarst ponds, where organics from eroding permafrost accumulate. Despite its environmental significance, limited knowledge exists regarding the photosensitivity of permafrost-derived carbon in these ponds. In this study, laboratory experiments were conducted to explore the photochemical transformations of organic matter in surface water samples from thermokarst ponds from different environments in northern Quebec, Canada. One pond near Kuujjuarapik is characterized by the presence of a collapsing palsa and is therefore organically rich, while the other pond near Umiujaq is adjacent to a collapsing lithalsa and thus contains fewer organic matters. Photobleaching occurred in the Umiujaq sample upon irradiation, whereas the Kuujjuarapik sample exhibited an increase in light absorbance at wavelength related to aromatic functionalities, indicating different photochemical aging processes. Ultrahigh-resolution mass spectrometry analysis reveals that the Kuujjuarapik sample preferentially photoproduced highly unsaturated CHO compounds with great aromaticity, while the irradiated Umiujaq sample produced a higher proportion of CHON aromatics with reduced nitrogen functionalities. Overall, this study illustrates that the photochemical reactivity of thermokarst pond water varies with the source of organic matter. The observed differences in reactivity contribute to an improved understanding of the photochemical emission of volatile organic compounds discovered earlier. Further insights into the photoinduced evolutions in thermokarst ponds may require the classification of permafrost-derived carbon therein.

Aging of microplastics and its photo-catalytic degradation of coexisting tetracycline

Photodegradation processes play a crucial role in the transforming of antibiotics in aqueous environments, while photochemical aging influences the properties of microplastics (MPs). In this study, the efficacy of ultraviolet (UV) irradiation in eliminating tetracycline (TC) was examined. Especially, TC degradation was mediated by polyethylene microplastics (PE-MPs) was subjected to aging through UV exposure and a combination of UV and thermal-activated persulfate treatments. The effects of MPs concentration, salinity, and pH on TC degradation were investigated. The characteristics of aging PE-MPs and the corresponding active free radicals were analyzed to understand the mechanism of TC degradation. The results showed that the existence of PE-MPs significantly influenced TC degradation under photosensitized conditions. However, as the concentration of PE-MPs increased, the degradation rate initially increased and subsequently declined. TC degradation increased from approximately 35 % to 85 % when pH increased from 3 to 11 mediated by aged PE-MPs. Moreover, the TC degradation ability increased with increasing salinity, and a higher aging degree facilitated the photodegradation of TC, achieving a removal rate of 62 %. At the same time, free radical quenching confirmed that the singlet oxygen (1O2), hydroxyl radical (OH), and superoxide radical (O2·−) produced all involved in the photolysis process of TC mediated by PE-MPs, especially 1O2. The analysis of the degradation products of TC and prediction of its toxicity revealed that the ecological risk associated with the degradation solution diminished compared with that of the TC mother solution.

Effects of Ammonia Mitigation on Secondary Organic Aerosol and Ammonium Nitrate Particle Formation in Photochemical Reacted Gasoline Vehicle Exhausts

Gaseous air pollutants emitted primarily by anthropogenic sources form secondary products through photochemical reactions, complicating the regulatory analysis of anthropogenic emissions in the atmosphere. We used an environmental chassis dynamometer and a photochemical smog chamber to conduct a parameter sensitivity experiment to investigate the formation of secondary products from a gasoline passenger car. To simulate the mitigation of ammonia emissions from gasoline vehicle exhausts assuming future emission controls and to allow photochemical oxidation and aging of the vehicle exhaust, ammonia was selectively removed by a series of five denuders installed between the vehicle and photochemical smog chamber. Overall, there were no differences in the formation of secondary organic aerosols and ozone with or without ammonia mitigation. However, the potential for ammonium nitrate particle formation was significantly reduced with ammonia mitigation. In addition, ammonia mitigation resulted in increased aerosol acidity due to nitric acid in the gas phase not being neutralized by ammonia and condensing onto the liquid particle phase, indicating a potentially important secondary effect associated with ammonia mitigation. Thus, we provide new insights into the effects of ammonia mitigation on secondary emissions from gasoline vehicle exhaust and into a potentially useful experimental approach for determining primary and secondary emissions.

Black carbon and particle lung-deposited surface area in residential wood combustion emissions: Effects of an electrostatic precipitator and photochemical aging

Residential wood combustion (RWC) remains a significant global source of particulate matter (PM) emissions with adverse impacts on regional air quality, climate, and human health. The lung-deposited surface area (LDSA) and equivalent black carbon (eBC) concentrations have emerged as important metrics to assess particulate pollution. In this study we estimated combustion phase-dependent emission factors of LDSA for alveolar, tracheobronchial, and head-airway regions of human lungs and explored the relationships between eBC and LDSA in fresh and photochemically aged RWC emissions. Photochemical aging was simulated in an oxidative flow reactor at OH• exposures equivalent to 1.4 or 3.4 days in the atmosphere. Further, the efficiency of a small-scale electrostatic precipitator (ESP) for reducing LDSA and eBC from the wood stove was determined. For fresh emission eBC correlated extremely well with LDSA, but the correlation decreased after aging. Soot-dominated flaming phase showed the highest eBC dependency of LDSA whereas for ignition and char burning phases non-BC particles contributed strongly the LDSA. Deposition to the alveolar region contributed around 60 % of the total lung-deposition. The ESP was found as an effective method to mitigate particulate mass, LDSA, as well as eBC emissions from wood stoves, as they were reduced on average by 72%, 71%, and 69%, respectively. The reduction efficiencies, however, consistently dropped over the span of an experiment, especially for eBC. Further, the ESP was found to increase the sub-30 nm ultrafine particle number emissions, with implications for LDSA. The results of this study can be used for assessing the contribution of RWC to LDSA concentrations in ambient air.

Stable isotope compositions, source apportionment and transformation processes of carbonaceous aerosols in PM10 in the urban city of Hyderabad, India

This study apportions sources of carbonaceous aerosols using isotopic characteristics of total carbon (TC) and elemental carbon (EC) in PM10 aerosols using filter-based CTO-375 method for pre-monsoon (summer), post-monsoon, and winter (2019–2021) over Hyderabad, India. Highest secondary organic carbon, SOC (primary organic carbon, POC) of 13.78 ± 10.25 (7.87 ± 2.48) μg/m3 was during post-monsoon 2020 (2019), while lowest was 8.90 ± 5.55 (4.18 ± 0.92) μg/m3 during pre-monsoon 2021 (post-monsoon 2020), respectively. Average effective carbon ratio (ECR) > 1 indicates dominance of light scattering aerosols during pre-monsoon and post-monsoon. δ13CTC and δ13CEC varied from – 28.1 to – 24.7 ‰ (avg. – 26.5 ± 0.7) and - 32.5 to – 24.6 ‰ (avg. – 27.4 ± 1.1), indicating contribution from C3 plant burning and liquid fuel combustion. Positive value of δ13COC – δ13CEC and heavier δ13CTC, along with gradual enrichment in δ13CTC and δ13CEC from December 2020 to March 2021, suggested photochemical aging of carbonaceous aerosols. Lighter δ13CTC and OC/EC > 4 for all seasons indicates dominance of biomass burning (wood and crop residue burning), photochemical oxidation and secondary organic aerosol (SOA) formation. The tropical study experiences dominance of lighter δ13CEC compared to subtropical, high latitude regions.

Evolution of Light Absorption Enhancement of Black Carbon Aerosols From Biomass Burning in Atmospheric Photochemical Aging

AbstractThe light absorption enhancement (Eabs) of black carbon (BC) coated with non‐BC materials is crucial in the assessment of radiative forcing, yet its evolution during photochemical aging of plumes from biomass burning, the globe's largest source of BC, remains poorly understood. In this study, plumes from open burning of corn straw were introduced into a smog chamber to explore the evolution of Eabs during photochemical aging. The light absorption of BC was measured with and without coating materials by using a thermodenuder, while the size distributions of aerosols and composition of BC coating materials were also monitored. Eabs was found to increase initially, and then decrease with an overall downward trend. The lensing effect dominated in Eabs at 520 nm, with an estimated contribution percentages of 47.5%–94.5%, which is far greater than light absorption of coated brown carbon (BrC). The effects of thickening and chemical composition changes of the coating materials on Eabs were evaluated through comparing measured Eabs with that calculated by the Mie theory. After OH exposure of 1 × 1010 molecules cm−3 s, the thickening of coating materials led to an Eabs increase by 3.2% ± 1.6%, while the chemical composition changes or photobleaching induced an Eabs decrease by 4.7% ± 0.6%. Simple forcing estimates indicate that coated BC aerosols exhibit warming effects that were reduced after aging. The oxidation of light‐absorbing CxHy compounds, such as polycyclic aromatic hydrocarbons (PAHs), to CxHyO and CxHyO>1 compounds in coating materials may be responsible for the photobleaching of coated BrC.

The Condition of Contemporary Murals in Sun-Exposed Urban Environments: A Model Study Based on Spray-Painted Mock-Ups and Simulated Light Ageing

The present work investigates the physicochemical stability of spray paints when irradiated with artificial solar light (at spectral range 300–800 nm). This research highlights the importance of understanding the materials used in street art and public murals, recognising them as a significant component of contemporary cultural heritage. By examining the stability and degradation of spray paints toward solar light exposure, the study aims to contribute to the preservation of contemporary murals, which reflect current social and cultural narratives. A physicochemical approach was employed for the study of spray paints’ physical and thermal properties, as well as the effect of specific photochemical ageing reactions/processes. The photochemical ageing results were compared with reference (unaged) samples. Specifically, a multi-technique approach was applied using stereo microscopy, scanning electron microscopy (SEM), atomic force microscopy (AFM), contact angle measurement, colorimetry, glossimetry, differential scanning calorimetry (DSC), UV-Vis spectroscopy, attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR), and pyrolysis-GC/MS (Py-GC/MS). The photodegradation of the spray paints occurred from the first 144 h of solar light irradiation, resulting in changes in morphology, colour, gloss, roughness, and wettability. Regarding photochemical stability, ageing seems to affect the binders more than the synthetic organic pigments and the inorganic fillers. In particular, acrylic binders showed small chemical changes, whereas the alkyd, nitrocellulose, and styrene binders underwent severe chemical modification. The results suggest that simulated daylight irradiation prompts the migration of additives toward the surface of the spray paint films. In addition, the results of the analyses on the white spray paints in comparison with the coloured paints (from the same manufacturer) showed that there seems to be an active distinct photoageing mechanism involving titanium dioxide, but the whole issue needs further investigation.

Photo-induced ageing processes in bitumen

Asphalt roads and waterproofing membranes on roofs are exposed to sunlight, which induces irreversible changes in those materials. The underlying chemical processes initially affect the surface but later on impact the bulk chemistry and the mechanical properties. Bitumen, the binding and sealing material, is particularly susceptible to such influences. However, the molecular processes that initiate material deterioration are still poorly explored. Here, we show that ultraviolet and visible light cause the formation of a unique set of oxidation products and alter aromatic structures on the bituminous surface. Qualitative and quantitative information is obtained using infrared, fluorescence and NMR spectroscopy. Bulk ageing studies have shown a shift of molecules from the aromatics to the resins and asphaltenes fractions, potentially influencing colloidal stability. The evaluation of surface processes was facilitated in ageing studies with thin sub-µm specimens. We find that gaseous oxygen is essential for molecular changes to occur. The formation of carboxylic acids, esters and aliphatic alcohols, coupled with the degradation and restructuring of aromatic systems, demonstrates the unique nature of light ageing. This is due to a nuanced interplay between oxidation, degradation, condensation and aromatisation reactions. The ageing rates depend on the origin of the binder and increase as the wavelength of the light source decreases. Ageing follows an asymptotic growth with time. All results considered, this study enabled us to decipher critical molecular processes during photochemical ageing. In this regard, we hope to develop more effective strategies for mitigating and preventing the adverse impact of solar radiation on bituminous infrastructure in the future.

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.

Evolution of refractory black carbon mixing state in an urban environment

The size distribution and hygroscopicity of the refractory black carbon (rBC) aerosol are critical properties for understanding its impact on human health, the extent to which the particles disperse through the atmosphere, and the effect that the particles have on clouds and the climate system. The hygroscopicity of black carbon is primarily controlled by the degree to which the black carbon cores are coated with other compounds. Here we show new measurements of rBC obtained from a single particle soot photometer at an urban location in Houston, TX, USA during the Department of Energy TRacking Aerosol Convection Interactions ExpeRiment (TRACER) campaign. We classified rBC particles into uncoated, thinly coated and thickly coated, where the latter is defined as the optical coating thickness exceeding 10 nm. To understand how aerosol aging and the prevailing winds interact to affect rBC coatings, a slice of the size distribution with rBC core diameter 143–166 nm is considered. For this slice, the average coating thickness of thickly coated particles was 29 ± 8 nm. The rBC number concentration, the fraction of thinly and thickly coated particles, and the average coating thickness strongly vary with the wind direction. We found that onshore flows are associated with lower number concentrations, more thinly coated particles, and thinner coatings when compared to offshore flows. Diurnal profiles show that the fraction of coated particles increases during daytime, likely due to photochemical aging. The estimated fraction of rBC particles that may activate into cloud droplets at 0.1% and 1% water supersaturation was generally ∼0.6% and ∼9%, respectively. This suggests that substantial further aging is needed to precondition the majority of rBC particles for incorporation into cloud droplets.