Secondary Organic Aerosol Formation from Volatile Chemical Product Emissions: Model Parameters and Contributions to Anthropogenic Aerosol.

Volatile chemical products (VCP) are an increasingly important source of hydrocarbon and oxygenated volatile organic compound (OVOC) emissions to the atmosphere, and these emissions are likely to play an important role as anthropogenic precursors for secondary organic aerosol (SOA). While the SOA from VCP hydrocarbons is often accounted for in models, the formation, evolution, and properties of SOA from VCP OVOCs remain uncertain. We use environmental chamber data and a kinetic model to develop SOA parameters for 10 OVOCs representing glycols, glycol ethers, esters, oxygenated aromatics, and amines. Model simulations suggest that the SOA mass yields for these OVOCs are of the same magnitude as widely studied SOA precursors (e.g., long-chain alkanes, monoterpenes, and single-ring aromatics), and these yields exhibit a linear correlation with the carbon number of the precursor. When combined with emissions inventories for two megacities in the United States (US) and a US-wide inventory, we find that VCP VOCs react with OH to form 0.8-2.5× as much SOA, by mass, as mobile sources. Hydrocarbons (terpenes, branched and cyclic alkanes) and OVOCs (terpenoids, glycols, glycol ethers) make up 60-75 and 25-40% of the SOA arising from VCP use, respectively. This work contributes to the growing body of knowledge focused on studying VCP VOC contributions to urban air pollution.

Development and Application of a Chemical Ionization Focusing Integrated Ionization Source TOFMS for Online Detection of OVOCs in the Atmosphere.

Single photon ionization (SPI) based on vacuum ultraviolet (VUV) lamps has been extensively investigated and applied due to its clean mass spectra as a soft ionization method. However, the photon energy of 10.6 eV and photon flux of 1011 photons s-1 of a commercial VUV lamp limits its range of ionizable analytes as well as its sensitivity. This work designs a chemical ionization focusing integrated (CIFI) ionization source time-of-flight mass spectrometry (TOFMS) based on a VUV lamp for the detection of volatile organic compounds (VOCs) and oxygenated volatile organic compounds (OVOCs). The photoelectrons obtained from the VUV lamp via the photoelectric effect ionized the oxygen and water in the air to obtain the reagent ions. The ion-molecule-reaction region (IMR) is constituted by a segmented quadrupole that radially focuses the ions using a radio-frequency electric field. This significantly enhances the yield and transport efficiency of the product ions leading to a great improvement in sensitivity. As a result, a 44-fold and 1154-fold increase in the signal response for benzene and pentanal were achieved, respectively. To verify the reliability of the ionization source, the linear correspondence and repeatability of benzene and pentanal were investigated. Satisfactory dynamic linearity was obtained in the mixing ratio range of 5-50 ppbv, and the relative standard deviation (RSD) of inter-day reached 3.91% and 6.26%, respectively. Finally, the CIFI-TOFMS was applied to the determination of OVOCs, and the LOD of 12 types of OVOCs reached the pptv level, indicating that the ionization source has the potential for accurate and sensitive online monitoring of atmospheric OVOCs.

Fate of Oxygenated Volatile Organic Compounds in the Yangtze River Delta Region: Source Contributions and Impacts on the Atmospheric Oxidation Capacity.

The Community Multiscale Air Quality model (CMAQv5.2) was implemented to investigate the sources and sinks of oxygenated volatile organic compounds (OVOCs) during a high O3 and high PM2.5 season in the Yangtze River Delta (YRD) region, based on constraints from observations. The model tends to overpredict non-oxygenated VOCs and underpredict OVOCs, which has been improved with adjusted emissions of all VOCs. The OVOCs in the YRD are dominated by ketones, aldehydes, and alcohols. Ketones and aldehydes mainly originate from direct emissions and secondary formation in the northern YRD, and primarily originate from secondary formation in the southern part influenced by biogenic emissions. The concentration of secondary organic aerosols (SOA) produced by OVOCs is 0.5-1.5 µg/m3, with 40-80% originated from organic nitrates, 20-70% originated from dicarbonyls, and 0-20% originated from isoprene epoxydiols. The influences of OVOCs on the atmospheric oxidation capacity are dominated by the OH• pathway during the day (∼350%) and by the NO3• pathway at night (∼150%). Consequently, O3 is enhanced by 30-70% in the YRD. Aerosols are also enhanced by 50-140%, 20-80%, and ∼20% for SOA, nitrate, and sulfate, respectively.

Wall losses of oxygenated volatile organic compounds from oxidation of toluene: Effects of chamber volume and relative humidity.

Vapor wall losses can affect the yields of secondary organic aerosol. The effects of surface-to-volume (S/V) ratio and relative humidity (RH) on the vapor-wall interactions were investigated in this study. The oxygenated volatile organic compounds (OVOCs) were generated from toluene-H2O2 irradiations. The average gas to wall loss rate constant (kgw) of OVOCs in a 400 L reactor (S/V = 7.5 m-1) is 2.47 (2.41 under humid conditions) times higher than that in a 5000 L reactor (S/V = 3.6 m-1) under dry conditions. In contrast, the average desorption rate constant (kwg) of OVOCs in 400 L reactor is only 1.37 (1.20 under humid conditions) times higher than that in 5000 L reactor under dry conditions. It shows that increasing the S/V ratio can promote the wall losses of OVOCs. By contrast, the RH effect on kgw is not prominent. The average kgw value under humid conditions is almost the same as under dry conditions in the 400 L (5000 L) reactor. However, increasing RH can decrease the desorption rates. The average kwg value under dry conditions is 1.45 (1.27) times higher than that under humid conditions in the 400 L (5000 L) reactor. The high RH can increase the partitioning equilibrium timescales and enhance the wall losses of OVOCs.

Chemical Production of Oxygenated Volatile Organic Compounds Strongly Enhances Boundary-Layer Oxidation Chemistry and Ozone Production.

Photolysis of oxygenated volatile organic compounds (OVOCs) produces a primary source of free radicals, including OH and inorganic and organic peroxy radicals (HO2 and RO2), consequently increasing photochemical ozone production. The amplification of radical cycling through OVOC photolysis provides an important positive feedback mechanism to accelerate ozone production. The large production of OVOCs near the surface helps promote photochemistry in the whole boundary layer. This amplifier effect is most significant in regions with high nitrogen oxides (NOx) and VOC concentrations such as Wangdu, China. Using a 1-D model with comprehensive observations at Wangdu and the Master Chemical Mechanism (MCM), we find that OVOC photolysis is the largest free-radical source in the boundary layer (46%). The condensed chemistry mechanism we used severely underestimates the OVOC amplifier effect in the boundary layer, resulting in a lower ozone production rate sensitivity to NOx emissions. Due to this underestimation, the model-simulated threshold NOx emission value, below which ozone production decreases with NOx emission decrease, is biased low by 24%. The underestimated OVOC amplifier effect in a condensed mechanism implies a low bias in the current 3-D model-estimated efficacy of NOx emission reduction on controlling ozone in polluted urban and suburban regions of China.

Microlayer source of oxygenated volatile organic compounds in the summertime marine Arctic boundary layer.

Summertime Arctic shipboard observations of oxygenated volatile organic compounds (OVOCs) such as organic acids, key precursors of climatically active secondary organic aerosol (SOA), are consistent with a novel source of OVOCs to the marine boundary layer via chemistry at the sea surface microlayer. Although this source has been studied in a laboratory setting, organic acid emissions from the sea surface microlayer have not previously been observed in ambient marine environments. Correlations between measurements of OVOCs, including high levels of formic acid, in the atmosphere (measured by an online high-resolution time-of-flight mass spectrometer) and dissolved organic matter in the ocean point to a marine source for the measured OVOCs. That this source is photomediated is indicated by correlations between the diurnal cycles of the OVOC measurements and solar radiation. In contrast, the OVOCs do not correlate with levels of isoprene, monoterpenes, or dimethyl sulfide. Results from box model calculations are consistent with heterogeneous chemistry as the source of the measured OVOCs. As sea ice retreats and dissolved organic carbon inputs to the Arctic increase, the impact of this source on the summer Arctic atmosphere is likely to increase. Globally, this source should be assessed in other marine environments to quantify its impact on OVOC and SOA burdens in the atmosphere, and ultimately on climate.

Indoor ozone/human chemistry and ventilation strategies.

This study aimed to better understand and quantify the influence of ventilation strategies on occupant-related indoor air chemistry. The oxidation of human skin oil constituents was studied in a continuously ventilated climate chamber at two air exchange rates (1 h-1 and 3 h-1 ) and two initial ozone mixing ratios (30 and 60 ppb). Additional measurements were performed to investigate the effect of intermittent ventilation ("off" followed by "on"). Soiled t-shirts were used to simulate the presence of occupants. A time-of-flight-chemical ionization mass spectrometer (ToF-CIMS) in positive mode using protonated water clusters was used to measure the oxygenated reaction products geranyl acetone, 6-methyl-5-hepten-2-one (6-MHO) and 4-oxopentanal (4-OPA). The measurement data were used in a series of mass balance models accounting for formation and removal processes. Reactions of ozone with squalene occurring on the surface of the t-shirts are mass transport limited; ventilation rate has only a small effect on this surface chemistry. Ozone-squalene reactions on the t-shirts produced gas-phase geranyl acetone, which was subsequently removed almost equally by ventilation and further reaction with ozone. About 70% of gas-phase 6-MHO was produced in surface reactions on the t-shirts, the remainder in secondary gas-phase reactions of ozone with geranyl acetone. 6-MHO was primarily removed by ventilation, while further reaction with ozone was responsible for about a third of its removal. 4-OPA was formed primarily on the surfaces of the shirts (~60%); gas-phase reactions of ozone with geranyl acetone and 6-MHO accounted for ~30% and ~10%, respectively. 4-OPA was removed entirely by ventilation. The results from the intermittent ventilation scenarios showed delayed formation of the reaction products and lower product concentrations compared to continuous ventilation.

Emission of oxygenated volatile organic compounds (OVOCs) during the aerobic decomposition of orange wastes.

Oxygenated volatile organic compounds (OVOCs) emitted from orange wastes during aerobic decomposition were investigated in a laboratory-controlled incubator for a period of two months. Emission of total OVOCs (TOVOCs) from orange wastes reached 1714 mg/dry kg (330 mg/wet kg). Ethanol, methanol, ethyl acetate, methyl acetate, 2-butanone and acetaldehyde were the most abundant OVOC species with shares of 26.9%, 24.8%, 20.3%, 13.9%, 2.8% and 2.5%, respectively, in the TOVOCs released. The emission fluxes of the above top five OVOCs were quite trivial in the beginning but increased sharply to form one "peak emission window" with maximums at days 1-8 until leveling off after 10 days. This type of "peak emission window" was synchronized with the CO2 fluxes and incubation temperature of the orange wastes, indicating that released OVOCs were mainly derived from secondary metabolites of orange substrates through biotic processes rather than abiotic processes or primary volatilization of the inherent pool in oranges. Acetaldehyde instead had emission fluxes decreasing sharply from its initial maximum to nearly zero in about four days, suggesting that it was inherent rather than secondarily formed. For TOVOCs or all OVOC species except 2-butanone and acetone, over 80% of their emissions occurred during the first week, implying that organic wastes might give off a considerable amount of OVOCs during the early disposal period under aerobic conditions.

Characteristics and sources of oxygenated VOCs in Hong Kong: Implications for ozone formation.

To investigate the characteristics of oxygenated volatile organic compounds (OVOCs) and their potential contribution to ozone (O3) generation, we conducted 3-h high-resolution observations during the summertime of 2022 and the wintertime of 2021. This study focused on a total of 28 OVOCs in five different chemical classes, which were encompassed at two representative sites in Hong Kong, including a roadside and an urban area. During the summertime, the total concentrations of quantified OVOCs (∑OVOCs) were 45 ± 12 and 63 ± 20 µg m-3 at the roadside and urban sites, respectively, whereas the ∑OVOCs decreased by 31 ± 11 % and 38 ± 13 %, respectively, during the wintertime. Among the classes of OVOCs, carbonyls and alcohols were the two predominant at both sites, with relatively higher concentration levels of acetone, methanol, butanaldehyde, and acrolein. The sources of OVOCs have significant spatial and temporal characteristics. Spatially, OVOCs were predominately attributed to primary emission and background at the roadside site, whereas they were a combination of primary emission, secondary formation, and background at the urban site. Temporally, background sources dominated the summertime OVOCs, while the contribution of primary emissions increased for the wintertime OVOCs. The O3 formation potential (OFP) for the OVOCs was calculated. The OFPs were 67 ± 16 and 119 ± 31 µg m-3 at the roadside and urban sites during the summertime, whereas the winter OFPs declined 30 % at the roadside and 38 % at the urban site. The background sources of carbonyls and alcohols at the roadside and of carbonyls and acrylates in the urban area were the major contributors to the summer OFP. Controlling the OVOC sources from local non-combustion sources such as gasoline-fuel evaporation and volatile chemical-containing products could lead to a reduction of OVOCs in the background and subsequently mitigate the OFP. This is beneficial for local O3 reduction in Hong Kong and surrounding regions.

Characteristics of Volatile Organic Compounds Emitted from Airport Sources and Their Effects on Ozone Production.

In recent years, commercial air transport has increased considerably. However, the compositions and source profiles of volatile organic compounds (VOCs) emitted from aircraft are still not clear. In this study, the characteristics of VOCs (including oxygenated VOCs (OVOCs)) emitted from airport sources were measured at Shenzhen Bao'an International Airport. The results showed that the compositions and proportions of VOC species showed significant differences as the aircraft operating state changed. OVOCs were the dominant species and accounted for 63.17%, 58.44%, and 51.60% of the total VOC mass concentration during the taxiing, approach, and take-off stages. Propionaldehyde and acetone were the main OVOCs, and dichloromethane and 1,2-dichloroethane were the main halohydrocarbons. Propane had the highest proportion among all alkanes, while toluene and benzene were the predominant aromatic hydrocarbons. Compared with the source profiles of VOCs from construction machinery, the proportions of halogenated hydrocarbons and alkanes emitted from aircraft were significantly higher, as were those of propionaldehyde and acetone. OVOCs were still the dominant VOC species in aircraft emissions, and their calculated ozone formation potential (OFP) was much higher than that of other VOC species at all stages of aircraft operations. Acetone, propionaldehyde, formaldehyde, acetaldehyde, and ethylene were the greatest contributors to ozone production. This study comprehensively measured the distribution characteristics of VOCs, and its results will aid in the construction of a source profile inventory of VOCs emitted from aircraft sources in real atmospheric environments.

Comprehensive measurement of carbonyls in Lhasa, Tibetan Plateau: Implications for strong atmospheric oxidation capacity.

Carbonyls are ubiquitous in the troposphere and play a crucial role in atmospheric oxidation capacity (AOC), particularly in photochemistry-active regions such as the Tibetan Plateau (TP). However, the composition and evolution of carbonyls over the TP is still poorly understood due to a lack of comprehensive observations and modelling. Here, we conducted an intensive field measurement of 37 carbonyls and their precursors at a suburban site in Lhasa during summer 2022. Markedly higher levels of carbonyls (7.24 ± 3.83 ppbv) were found during ozone pollution episodes, with 36 % higher than those during non-episodes. Formaldehyde was the most abundant carbonyl (38 %), which primarily originating from photochemical secondary formations. Simulations using the Rapid adaptive Optimization Model for Atmospheric Chemistry (ROMAC) indicated strong AOC in Lhasa, with the daytime maximum of ·OH and ·HO2 of 9.8 × 106 and 4.2 × 108 molecules cm-3, respectively, which were even higher than that in most of the megacities in China. Notably, AOC significantly enhanced with the increasing carbonyls during the episodes, with the concentrations of ·OH and ·HO2 were boosted 21 % and 67 % than those during non-episodes, respectively. Budget analysis revealed that the ·HO2 + NO (88 %) and ·OH + VOC (74 %) pathways dominated the generation and loss of ·OH, respectively. And for ·HO2, they were ·RO2 + NO (67 %) and ·HO2 + NO (83 %). This study provides valuable insights into the strong AOC in the ecologically-fragile and climate-sensitive TP region, and highlighted the crucial role of anthropogenic-biogenic interactions in the active photochemistry of TP.

[Compositional Characteristics of Volatile Organic Compounds in Typical Industrial Areas of the Pearl River Delta: Importance of Oxygenated Volatile Organic Compounds].

Volatile organic compounds (VOCs) are key components of tropospheric chemistry, of which industrial emissions are an important source of atmospheric VOCs. In this study, online measurements of 74 VOCs were made in a typical industrial area of the Pearl River Delta in southern China during the early summer of 2021. The mean volume mixing ratio of total volatile organic compounds (TVOC) was (81.9±45.4)×10-9 during the campaign. Among them, oxygenated volatile organic compounds (OVOCs) accounted for the largest fraction of TVOC, with an average of 51.5%, followed by aromatics, accounting for 19.4% of TVOC. The proportion of OVOCs in TVOC gradually increased with the increase in TVOC concentration. Industry-related emissions were the main contributors to aromatics and OVOCs in this region. Aromatics and OVOCs were the two major contributors to the ozone formation potential (OFP), accounting for 56.4% and 26.7%, respectively. Furthermore, OVOCs also contributed 40.0% of the total ·OH reactivity from VOCs. Xylenes, toluene, acrolein, and ethyl acetate had a greater contribution to the formation of secondary pollution; thus, these species should be given priority for controlling secondary pollution. Our results underscore the severity of OVOCs pollution in industrial areas and the important roles of OVOCs in secondary pollution.

Ambient volatile organic compounds in urban and industrial regions in Beijing: Characteristics, source apportionment, secondary transformation and health risk assessment.

Field measurements of volatile organic compounds (VOCs) were conducted simultaneously at an urban site and one industrial park site in Beijing in summer. The VOCs concentrations were 94.3 ± 157.8 ppbv and 20.7 ± 8.9 ppbv for industrial and urban sites, respectively. Alkanes and aromatics were the major contributors to VOCs in industrial site, while oxygenated volatile organic compounds (OVOCs) contributed most in urban site. The most abundant VOC species were n-pentane and formaldehyde for industrial site and urban site, respectively. The calculated ozone formation potential (OFP) and OH loss rates (LOH) were 621.1 ± 1491.9 ppbv (industrial site), 102.9 ± 37.3 ppbv (urban site), 22.0 ± 39.0 s-1 (industrial site) and 5.3 ± 2.2 s-1 (urban site), respectively. Based on the positive matrix factorization (PMF) model, solvent utilization I (34.1 %), solvent utilization II (27.9 %), mixture combustion source (19.3 %), OVOCs related source (9.6 %) and biogenic source (9.1 %) were identified in the industrial site, while OVOCs related source (27.8 %), vehicle exhaust (22.1 %), solvent utilization (19.3 %), coal combustion (16.0 %) and biogenic source (14.8 %) were identified in the urban site. The results of O3-VOCs-NOx sensitivity indicated that O3 formation were respectively under the VOC-limited and NOx-limited conditions in Beijing urban and industrial regions. Additionally, aromatics accounted remarkable SOA formation ability both in the two sites, and SOA potentials of xylene, toluene and ethylbenzene as the indicator species for the solvent utilization in industrial site were remarkable higher than those obtained in urban regions. The hazard index values in the industrial and urban sites were 1.72 and 3.39, respectively, suggesting a high non-carcinogenic risks to the exposed population. Formaldehyde had the highest carcinogenic risks in the two sites, and the cumulative carcinogenic risks in the industrial site and urban site were 1.95 × 10-5 and 1.21 × 10-5, respectively.

Volatile organic compounds at a roadside site in Hong Kong: Characteristics, chemical reactivity, and health risk assessment.

Volatile organic compounds (VOCs) and oxygenated VOCs (OVOCs) play important roles in atmospheric chemistry and are recognized as the major pollutants in roadside microenvironments of metropolitan Hong Kong, China. In this study, the ambient VOCs and OVOCs were intensively monitored at a roadside site in Hong Kong for one month during morning and evening rush hours. The emission characterizations, as well as ozone formation potentials (OFP) and hydroxyl radical (OH) loss rates (LOH) were determined. Results from the campaign showed that the average concentrations of detected VOCs/OVOCs ranged from 0.21 to 9.67 ppb, and higher toluene to benzene (T/B) ratio was observed during evening sections due to the variation of fuel types in vehicle fleets and mix of additional emission sources in this site. On average, OVOCs had much higher concentrations than the targeted VOC species. Acetone, formaldehyde, and acetaldehyde were the three most abundant species, while formaldehyde showed the highest contributions to both OFP (32.20 %) and LOH (16.80 %). Furthermore, potential health hazards with inhalation exposure to formaldehyde, acetaldehyde, propionaldehyde, methyl ethyl ketone (MEK), 1,3-butadiene, toluene, benzene, and acrylonitrile were found. These results reveal that it is imperative to implement efficient control measures to reduce vehicle emissions for both primary and secondary pollutants and to protect both roadside workers and pedestrians.

Development of an enhanced method for atmospheric carbonyls and characterizing their roles in photochemistry in subtropical Hong Kong.

Carbonyl compounds are ubiquitous and play vital roles in tropospheric photochemistry and oxidation capacity, particularly affecting radical cycling and ozone formation. An enhanced method based on ultra-high-performance liquid chromatography and electrospray ionization tandem mass spectrometry was developed to simultaneously quantify 47 carbonyl compounds with carbon (C) numbers from 1 to 13. Applying this new method to samples collected at ground and ship-borne field campaigns, we investigated the abundance, characteristic distribution, and photochemical activity of carbonyl species in the coastal atmosphere of Hong Kong. The total concentration of detected carbonyls ranged from 9.1 to 32.7 ppbv and exhibited distinct spatial variability. In addition to the usual abundant carbonyl species (formaldehyde, acetaldehyde, and acetone), aliphatic saturated aldehydes with C ≥ 5 (particularly hexaldehyde and nonanaldehyde), and di­carbonyls, exhibit significant abundance and photochemical reactivity in the coastal site and on the sea. The measured carbonyls could contribute to an estimated peroxyl radical formation rate of 1.88-8.43 ppb/h via OH oxidation and photolysis, greatly enhancing oxidation capacity and radical cycling. The ozone formation potential (OFP) estimated from the maximum incremental reactivity (MIR) was dominated (69 %-82 %) by formaldehyde and acetaldehyde, with significant contribution (4 %-13 %) from di­carbonyls. Furthermore, another dozens of long-chain carbonyls without MIR values, which were typically below detection or not included in the conventional analytical method, would increase the ozone formation rate by an additional 2 %-33 %. Additionally, the glyoxal, methylglyoxal, benzaldehyde and other α, ß-unsaturated aldehydes also exhibited considerable contribution to secondary organic aerosol (SOA) formation potential. This study highlights the importance of various reactive carbonyls in the atmospheric chemistry of urban and coastal regions. The newly developed method can effectively characterize more carbonyl compounds and advance our understanding of their roles in photochemical air pollution.

Biomass-burning emissions could significantly enhance the atmospheric oxidizing capacity in continental air pollution.

Volatile organic compounds (VOCs) are important precursors of photochemical pollution. However, a substantial fraction of VOCs, namely, oxygenated VOCs (OVOCs), have not been sufficiently characterized to evaluate their sources in air pollution in China. In this study, a total of 119 VOCs, including 60 OVOCs in particular, were monitored to provide a more comprehensive picture based on different online measurement techniques, proton-transfer-reaction time-of-flight mass spectrometry (PTR-ToF-MS) and online gas chromatography/mass spectrometry (GC/MS), at a receptor site in southeastern China during a photochemically active period. Positive matrix factorization (PMF) and photochemical age-based parameterization were combined to identify and quantify different sources of major VOCs during daytime hours, with the advantage of including VOC decay processes. The results revealed the unexpected role of biomass burning (21%) in terms of ozone (O3) formation potential (OFP) when including the contributions of OVOCs and large contributions (30-32%) of biomass burning to aldehydes, as more OVOCs were measured in this study. We argue that biomass burning could significantly enhance the continental atmospheric oxidizing capacity, in addition to the well-recognized contributions of primary pollutants, which should be seriously considered in photochemical models and air pollution control strategies.

[Sources Apportionment of Oxygenated Volatile Organic Compounds (OVOCs) in a Typical Southwestern Region in China During Summer].

Oxygenated volatile organic compounds (OVOCs) are important intermediates in the troposphere and the most important sources of ozone. Proton-transfer-reaction time-of-flight mass spectrometry (PTR-TOF-MS) was used to measure VOCs in the Chengdu Plain, Southwestern China. The diurnal variations, photochemical reactivity, O3 formation potential, and sources were also investigated. The mixing ratios of ten kinds of VOCs (acetaldehyde, acetone, isoprene, Methyl ethyl ketone, Methyl vinyl ketone and Methacrolein, benzene, toluene, styrene, C8 aromatics, and C9 aromatics) were (10.97±4.69)×10-9. The concentrations of OVOCs, aromatic hydrocarbons, and biogenic VOCs were (8.54±3.44)×10-9, (1.53±0.93)×10-9, and (0.90±0.32)×10-9, respectively. Isoprene, acetaldehyde, and m-xylene were the top three photochemically active species with the greatest O3 formation potentials. The dominant three OVOCs species (acetaldehyde, acetone, and MEK) were mainly derived from local biogenic sources and anthropogenic secondary sources, and acetone had a strong regional background level, indicating that pollution in this area is significantly affected by regional transmission. This study deepens the understanding of regional O3 formation mechanisms in southwest China and provides a basis for the scientifically informed control of O3 pollution.

Photochemical aging of Beijing urban PM2.5: Production of oxygenated volatile organic compounds.

PM2.5 has become the dominant atmospheric pollutant in many countries. Many components of PM2.5 are highly photoactive. However, the photochemical aging of PM2.5 remains poorly understood. In this study, the photoaging of real PM2.5 samples collected from 2017 to 2018 in Beijing under simulated solar radiation (λ ~ 340-850 nm) was investigated. Our study showed that large amounts of oxygenated volatile organic compounds (OVOCs), such as acetaldehyde, formic acid, acetone and acetic acid, were released during the photochemical aging of PM2.5. Furthermore, although a positive correlation between the OVOCs yield and the organic matter (OM) in PM2.5 was observed, the product distribution from the photoaging of PM2.5 was different from that in the direct photolysis of artificially synthesized SOA. Because of the release of OVOCs, the PM2.5 mass loss was evaluated to be ~1.80% per day under typical atmospheric conditions. The OVOCs released during the photoaging of PM2.5 may contribute substantially to the OVOCs sources omitted from troposphere chemistry models and may have a significant effect on the OVOCs distribution and oxidation capacity of the atmosphere.

Outburst of senescence-related VOC emissions from a bioenergy poplar plantation.

Leaf senescence is a catabolic process that emits volatile organic compounds (VOCs). In densely planted monocultures these VOC emissions occur in outbursts that might be relevant for the local air quality since these VOCs are typically oxygenated. The VOC emissions of a high-density poplar (Populus) bioenergy plantation were monitored along with meteorological parameters, CO2 and H2O exchanges, canopy greenness, and leaf area index during the second half of the year 2015. The emissions of 25 VOCs peaked at the beginning of September, coinciding with the onset of senescence. Together these VOC emissions amounted to a total of 2.85 mmol m-2, translated into 98.3 mg C m-2. The emission peak was mainly composed of oxygenated VOCs as methanol, acetic acid, and lipoxygenase products that are all typical for catabolic processes. So, the senescence process of the poplar plantation was very well reflected in the peak of VOC emissions.

Characterization of organic aerosols and their precursors in southern China during a severe haze episode in January 2017.

The rapid industrialization and economic development in the Pearl River Delta (PRD) region of southern China have led to a substantial increase in anthropogenic emissions and hence frequent haze pollution over the past two decades. In early January 2017, a severe regional haze pollution episode was captured in the PRD region, with a peak PM2.5 concentration of around 400µgm-3, the highest value ever reported at this site. During the haze episode, elevated concentrations of oxygenated volatile organic compounds (OVOCs, 33±16 ppbv) and organic matter (41±15µg m-3) were observed, indicating the enhanced roles of secondary organic aerosols (SOAs) in the formation of haze pollution. Water-soluble organic carbon (WSOC, 12.8±5.5µg C m-3) dominated the organic aerosols, with a WSOC/OC ratio of 0.63±0.12 and high correlation (R=0.85) with estimated secondary organic carbon (SOC), suggesting the predominance of a secondary origin of the measured organic aerosols during the haze episode. Four carboxylic acids (oxalic, acetic, formic, and pyruvic acids) were characterized in the aerosols (1.30±0.38µgm-3) and accounted for 3.6±1.2% of WSOC in carbon mass, with oxalic acid as the most abundant species. The simultaneous measurements of volatile organic compounds (VOCs), OVOCs, and organic acids in aerosols at this site provided an opportunity to investigate the relationship between the precursors and the products, as well as the potential formation pathways. Water-soluble aldehydes and ketones, predominantly produced via the oxidation of anthropogenic VOCs (mainly propane, toluene, n-butane, and m, p-xylene), were the main contributors of the organic acids. The formation of OVOCs is largely attributed to gas-phase photochemical oxidation, whereas the WSOC and dicarboxylic acids were produced from both photochemistry and nocturnal heterogeneous reactions. These findings provided further insights into the oxidation and evolution of organic compounds during the haze pollution episode.