VOC Precursors Research Articles

Source Assessment of PM-2.5 in Yeongam and Hampyeong

The Daebul National Industrial Complex in Yeongam emits less VOC, SOX, and NOx precursors of PM2.5 than Gwangyang Bay. However, Yeongam had the highest PM-2.5 concentrations, at 21 µg/m3, in Jeollanam-do as of 2021. Therefore, evaluating source contributions is necessary. In this study, component analysis was performed for Hampyeong and Yeongam. Based on the results, pollution sources were analyzed using the PMF, CPF, and CWT models. The average PM-2.5 concentration was found to be similar in both regions. In addition, the modeling results revealed that PM-2.5 concentrations in both regions were largely influenced by factors originating from foreign countries. Specifically, the concentrations were presumably largely due to foreign sources, and in the case of Yeongam, secondary nitrates generated domestically also had an influence. Yeongam is a domestic source and was found to be mainly influenced by industrial activities; therefore, it is necessary to manage its emission sources. Because Hampyeong is largely influenced by biological combustion and traffic emissions, managing crop burning and traffic in this town is crucial.

Sources of elevated organic acids in the mountainous background atmosphere of southern China

Formic acid (FA) and acetic acid (AA) are pivotal organic acids in the troposphere, significantly influencing atmospheric chemistry. However, their abundance and sources in the mountainous background atmosphere remain underexplored. We undertook continuous measurements of FA and AA in Nanling mountains, southern China, during autumn 2020 using a high-resolution time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS). Both acids registered higher concentrations than in other global high-altitude or forested locations, averaging at 0.89 (max: 3.91) and 0.95 (max: 3.52) ppbv for FA and AA, respectively. High concentrations of FA and AA in this forested background area arose from secondary formation and biomass burning, collectively contributing 71 % to 89 %. During episodes, FA and AA concentrations surged 2–3 times, owing to the enhanced atmospheric oxidation capacity. The secondary FA production was predominantly due to isoprene oxidation among the VOC precursors studied. However, observed inconsistencies between calculated and actual FA concentrations suggest overlooked precursors or mechanisms warranting further investigation. Our findings can enhance the understanding of organic acid characteristics and the interplay of biogenic and anthropogenic sources in the background atmosphere.

Ozone generation and chemistry from 222 nm germicidal ultraviolet light in a fragrant restroom.

Devices using 222 nm germicidal ultraviolet light (GUV222) have been marketed to reduce virus transmission indoors with low risk of occupant harm from direct UV exposure. GUV222 generates ozone, an indoor air pollutant and oxidant, under constrained laboratory conditions, but the chemistry byproducts of GUV222-generated ozone in real indoor spaces is uncharacterized. We deployed GUV222 in a public restroom, with an air change rate of 1 h-1 one weekend and 2 h-1 the next, to measure ozone formation and byproducts generated from ozone chemistry indoors. Ozone from GUV222 increased background concentrations by 5 ppb on average for both weekends and reacted rapidly (e.g., at rates of 3.7 h-1 for the first weekend and 2.0 h-1 for the second) with gas-phase precursors emitted by urinal screens and on surfaces. These ozone reactions generated volatile organic compound and aerosol byproducts (e.g., up to 2.6 μg m-3 of aerosol mass). We find that GUV222 is enhancing indoor chemistry by at least a factor of two for this restroom. The extent of this enhanced chemistry will likely be different for different indoor spaces and is dependent upon ventilation rates, species and concentrations of precursor VOCs, and surface reactivity. Informed by our measurements of ozone reactivity and background aerosol concentrations, we present a framework for predicting aerosol byproduct formation from GUV222 that can be extended to other indoor spaces. Further research is needed to understand how typical uses of GUV222 could impact air quality in chemically diverse indoor spaces and generate indoor air chemistry byproducts that can affect human health.

Time-Resolved Molecular Characterization of Secondary Organic Aerosol Formed from OH and NO3 Radical Initiated Oxidation of a Mixture of Aromatic Precursors.

Aromatic hydrocarbons (ArHCs) and oxygenated aromatic hydrocarbons (ArHC-OHs) are emitted from a variety of anthropogenic activities and are important precursors of secondary organic aerosol (SOA) in urban areas. Here, we analyzed and compared the composition of SOA formed from the oxidation of a mixture of aromatic VOCs by OH and NO3 radicals. The VOC mixture was composed of toluene (C7H8), p-xylene + ethylbenzene (C8H10), 1,3,5-trimethylbenzene (C9H12), phenol (C6H6O), cresol (C7H8O), 2,6-dimethylphenol (C8H10O), and 2,4,6-trimethylphenol (C9H12O) in a proportion where the aromatic VOCs were chosen to approximate day-time traffic-related emissions in Delhi, and the aromatic alcohols make up 20% of the mixture. These VOCs are prominent in other cities as well, including those influenced by biomass combustion. In the NO3 experiments, large contributions from CxHyOzN dimers (C15-C18) were observed, corresponding to fast SOA formation within 15-20 min after the start of chemistry. Additionally, the dimers were a mixture of different combinations of the initial VOCs, highlighting the importance of exploring SOAs from mixed VOC systems. In contrast, the experiments with OH radicals yielded gradual SOA mass formation, with CxHyOz monomers (C6-C9) being the dominant constituents. The evolution of SOA composition with time was tracked and a fast degradation of dimers was observed in the NO3 experiments, with concurrent formation of monomer species. The rates of dimer decomposition in NO3 SOA were ∼2-3 times higher compared to those previously determined for α-pinene + O3 SOA, highlighting the dependence of particle-phase reactions on VOC precursors and oxidants. In contrast, the SOA produced in the OH experiments did not dramatically change over the same time frame. No measurable effects of humidity were observed on the composition and evolution of SOA.

基于VOCs在线观测的六安市一次典型臭氧污染过程及其前体物VOCs排放特征分析

基于VOCs在线观测的六安市一次典型臭氧污染过程及其前体物VOCs排放特征分析

Secondary organic aerosol formation from mixed volatile organic compounds: Effect of RO2 chemistry and precursor concentration

Secondary organic aerosol (SOA) plays a significant role in contributing to atmospheric fine particles, as well as in global air quality and climate. However, the current understanding of the atmospheric formation of SOA and its simulation is still highly uncertain due to the complexity of its precursor VOCs. In our study, SOA formation in different mixed VOC scenarios was investigated using a 30 m3 indoor smog chamber. By comparing SOA formation in individual VOC scenarios, it was found that SOA yield from anthropogenic VOCs (AVOCs) can be positively (+83.9%) affected by coexisting AVOCs, while inhibited (−51.4%) by the presence of isoprene, via the OH scavenging effect. The cross-reactions of peroxyl radical (RO2) generated from different AVOCs were proved to be the main contributor (up to 39.0%) to SOA formation, highlighting the importance of RO2 + RʹO2 reactions in mixed VOC scenarios. Meanwhile, the formation of gas-phase organic intermediates of different volatility categories from the RO2 reactions was also affected by the precursor concentration, and a higher SOA yield was found at lower precursor concentrations due to the larger contribution of intermediates with lower volatility. Our study provides new insights into SOA formation by considering the interactions between intermediate products from mixed VOCs.

Secondary Organic Aerosol Mass Yields from NO3 Oxidation of α-Pinene and Δ-Carene: Effect of RO2 Radical Fate.

Dark chamber experiments were conducted to study the SOA formed from the oxidation of α-pinene and Δ-carene under different peroxy radical (RO2) fate regimes: RO2 + NO3, RO2 + RO2, and RO2 + HO2. SOA mass yields from α-pinene oxidation were <1 to ∼25% and strongly dependent on available OA mass up to ∼100 μg m-3. The strong yield dependence of α-pinene oxidation is driven by absorptive partitioning to OA and not by available surface area for condensation. Yields from Δ-carene + NO3 were consistently higher, ranging from ∼10-50% with some dependence on OA for <25 μg m-3. Explicit kinetic modeling including vapor wall losses was conducted to enable comparisons across VOC precursors and RO2 fate regimes and to determine atmospherically relevant yields. Furthermore, SOA yields were similar for each monoterpene across the nominal RO2 + NO3, RO2 + RO2, or RO2 + HO2 regimes; thus, the volatility basis sets (VBS) constructed were independent of the chemical regime. Elemental O/C ratios of ∼0.4-0.6 and nitrate/organic mass ratios of ∼0.15 were observed in the particle phase for both monoterpenes in all regimes, using aerosol mass spectrometer (AMS) measurements. An empirical relationship for estimating particle density using AMS-derived elemental ratios, previously reported in the literature for non-nitrate containing OA, was successfully adapted to organic nitrate-rich SOA. Observations from an NO3- chemical ionization mass spectrometer (NO3-CIMS) suggest that Δ-carene more readily forms low-volatility gas-phase highly oxygenated molecules (HOMs) than α-pinene, which primarily forms volatile and semivolatile species, when reacted with NO3, regardless of RO2 regime. The similar Δ-carene SOA yields across regimes, high O/C ratios, and presence of HOMs, suggest that unimolecular and multistep processes such as alkoxy radical isomerization and decomposition may play a role in the formation of SOA from Δ-carene + NO3. The scarcity of peroxide functional groups (on average, 14% of C10 groups carried a peroxide functional group in one test experiment in the RO2 + RO2 regime) appears to rule out a major role for autoxidation and organic peroxide (ROOH, ROOR) formation. The consistently substantially lower SOA yields observed for α-pinene + NO3 suggest such pathways are less available for this precursor. The marked and robust regime-independent difference in SOA yield from two different precursor monoterpenes suggests that in order to accurately model SOA production in forested regions the chemical mechanism must feature some distinction among different monoterpenes.

Monoterpene Photooxidation in a Continuous-Flow Chamber: SOA Yields and Impacts of Oxidants, NOx, and VOC Precursors.

Monoterpene photooxidation plays an important role in secondary organic aerosol (SOA) formation in the atmosphere. The low-volatility products can enhance new particle formation and particle growth and thus influence climate feedback. Here, we present the results of α-pinene and Δ-3-carene photooxidation experiments conducted in continuous-flow mode in an environmental chamber under several reaction conditions. The roles of oxidants, addition of NO, and VOC molecular structure in influencing SOA yield are illustrated. SOA yield from α-pinene photooxidation shows a weak dependence on H2O2 concentration, which is a proxy for HO2 concentration. The high O/C ratios observed in the α-pinene photooxidation products suggest the production of highly oxygenated organic molecules (HOM). Addition of ozone to the chamber during low-NOx photooxidation experiments leads to higher SOA yield. With the addition of NO, the production of N-containing HOMs is enhanced and the SOA yield shows a modest, nonlinear dependence on the input NO concentration. Carene photooxidation leads to higher SOA yield than α-pinene under similar reaction conditions, which agrees with the lower volatility retrieved from evaporation kinetics experiments. These results improve the understanding of SOA formation from monoterpene photooxidation and could be applied to refine the representation of biogenic SOA formation in models.

Influence of thermal decomposition and regional transport on atmospheric peroxyacetyl nitrate (PAN) observed in a megacity in southern China

Peroxyacetyl nitrate (PAN) is a typical secondary product of photochemical smog and is widely considered an indicator when evaluating the severity of photochemical pollution, but there have been few quantitative studies on the thermal decomposition of ambient PAN in southern China. In this study, online sampling of PAN and ozone (O3) was conducted from August to November 2020, which is the most severe photochemical pollution period of the year, in Shenzhen, a megacity in southern China. During the sampling period, two photochemical pollution periods occurred in August (EP1) and October (EP2). The mean O3 concentrations during EP1 and EP2 were very close, 36.3 and 36.9 ppb, respectively, while PAN concentrations were very different (0.66 and 1.06 ppb, respectively). The diurnal variation showed that the PAN formation rate in the initial stage of photochemical reactions (9:00–11:00) during EP1 was significantly faster than that during EP2, while there was significant consumption at noon and almost complete decomposition at night in EP1. Calculating the thermal decomposition of PAN (TPAN), we found that the average concentration of TPAN in EP1 was 8.47 ppb, approximately 9 times that in EP2 (0.94 ppb), which significantly reduced the concentration of PAN in EP1. This indicates that when using PAN as an indicator of photochemical reaction activity, the consumption of PAN due to thermal decomposition must be considered. In addition, we found that regional transport may significantly contribute to the formation of PAN by increasing the concentration of precursor VOCs, although the lifetime of PAN was only a few hours due to a large amount of thermal decomposition.

Pollution Characteristic and Control Factor Analysis of Atmospheric Ozone During Summer Typical Periods in Linyi, Shandong

In June 2020, an observation experiment of O3 and its precursors was carried out in Linyi City, Shandong Province. Based on the observation data and MCM photochemical model simulation, the formation mechanism and control mechanism of an ozone pollution case in mid-June were analyzed. The study found that, despite the high precipitation during the observation period, ozone concentrations rapidly accumulated and exceeded the limits once the weather cleared, with the 1-h average and 8-h φ (O3) exceeding the national ambient air quality standards on 10 days (32% in frequency)and 14 days (45%), respectively. The diurnal variation in O3 concentration was unimodal and accompanied by the afternoon peak at 16:00. MCM simulation results showed that the daily net reaction rate of O3 was 20×10-9 h-1, and HO2·+NO and RO2·(except CH3O2·)+NO contributed 49.0%-51.1% and 37.3%-40.2% of O3 generation, respectively. The contribution of the·OH+NO2 reaction to the total consumption of O3 was 35.1%-57.4%. The results of VOCs reactivity, relative incremental reactivity (RIR), and the EKMA curve method showed that the generation of O3 was more sensitive to alkenes (mainly trans-2-pentene and trans-2-butene)and aromatics (mainly m/p-xylene and toluene)but was negatively sensitive to NOx. In other words, the reduction in VOCs concentration would lead to the decrease in O3 concentration, whereas the reduction in NOx concentration would lead to the increase in O3 concentration. PMF source analysis results showed that volatile sources used by solvents and vehicle exhaust emissions contributed significantly to the above key precursor VOC species. Considering the titration effect of NO from vehicle exhaust emissions on ozone, controlling the use of volatile sources of solvents can realize the control of O3 pollution accurately and efficiently.

Aerosol number concentrations and new particle formation events over a polluted megacity during the COVID-19 lockdown

The present study investigates the particle number concentrations and size distributions in the ultrafine and fine-sized regimes over a polluted megacity, New Delhi (28.75° N, 77.12° E), India. The experiments were conducted during the periods (April–May 2020) of strict social and travel restrictions (lockdown) imposed by the Government of India aiming to contain the spread of Coronavirus Disease 19 (COVID-19) pandemic. The different phases of the COVID-19 lockdown witnessed restrictions of varying magnitudes with the significant cessation of anthropogenic sources, viz., industrial, road, railways, and air traffic emissions. Using this unique opportunity, the impact of varying urban emissions on particle number size distributions and new particle formation events were examined. The mean total number concentrations were in the range of ~ (2–3.5) x 104 cm−3 and depicted a gradual increase (~26%) with progressive unlock of the anthropogenic activities. At the same time, accumulation particle concentrations were doubled. However, ultrafine particles (UFP) (diameter < 100 nm) dominated (50–88%) the total number concentrations during most of the days and several new particle formation (NPF) events resulting in elevated (2–5 fold) UFP concentrations were observed. Subsequently, the particles grew to larger sizes with rates ~3.31–8.37 nm h−1. The NPF events occurred during the daytime, and during the events, a clear enhancement in the concentrations of [H2SO4] proxy (2–3.5 × 107 molecules cm−3; 2–3 orders higher than the non-event values) suggesting the role of strong gas-phase photochemistry. Also, some of the NPF events were associated with increased odd oxygen concentrations [Ox = O3+NO2], indicating the regional nature of the precursors and participation of VOC precursors in nucleation/growth. Interestingly, different classes of NPF events were seen during the strictest lockdown period, whereas more frequent and well-defined NPF events were witnessed when anthropogenic activities were opened up with conditional relaxations. These events demonstrated the competition between source strengths of precursor vapors from anthropogenic activities and primary particles acting as condensation sink restricting NPF. This study highlighted that urban pollution mitigation policies need to consider ultrafine particles emanating from the secondary aerosol formation process from traffic emissions.

Seasonal Abundance and Source Attribution of Carbonaceous Aerosols at Different Altitude of Mountainous Locations in Uttarakhand Himalaya

The present study reports on carbonaceous aerosol concentrations determined in total suspended particles (TSP) from three mountainous sites Devasthal (2450 m asl), Manora Peak (1940 m asl), and Bhimtal (1413 m asl) in Kumaun province of Uttarakhand Himalaya, India. The concentrations of organic carbon (OC) and elemental carbon (EC) were measured using IMPROVE_thermal optical reflectance protocol. Results showed that TSP and carbonaceous species varied significantly and decreased with increasing altitudes. Seasonal/(diurnal) analysis indicated that TSP and carbonaceous species were significantly higher during summer than winter, while day-night-time variation was not statistically significant. Correlation analysis was performed between carbonaceous species and meteorological factors which showed significant positive correlations with planetary boundary layer, temperature, and solar radiation. OC and EC were noted to be strongly correlated (correlation coefficient > 0.8), implying similar emission sources and atmospheric processes. The ratios of OC/EC varied from 2.4 to 9.3 (Devasthal), 2.1 to 8.6 (Manora Peak) and 1.9 to 4.3 (Bhimtal), which suggested mixed sources of biomass burning, coal combustion and vehicular emissions. The large variations in OC/EC ratios suggested the presence of secondary organic carbon (SOC) and it contributed higher during winter (~ 40–45%) to total OC than summer (~ 26–35%) at all sites could be attributed to higher condensation of secondary species, low temperature and large emissions of VOC precursors during winter.

생활밀착형 사업장에서 사용되는 유기용제의 오존전구 VOC 물질 목록화 및 오존생성 기여도 평가

생활밀착형 사업장에서 사용되는 유기용제의 오존전구 VOC 물질 목록화 및 오존생성 기여도 평가

Long-term observations of oxygenated volatile organic compounds (OVOCs) in an urban atmosphere in southern China, 2014-2019.

Oxygenated volatile organic compounds (OVOCs) are important precursors and intermediate products of atmospheric photochemical reactions, which can promote the formation of secondary pollutants such as ozone (O3) and secondary organic aerosol (SOA). However, there have been few studies on the sources of and long-term variation in ambient OVOCs. This study combined sensitive, near real-time measurements of VOCs by proton transfer reaction-mass spectrometry (PTR-MS) with an improved photochemical age parameterization method to quantify daytime sources of OVOCs in an urban atmosphere in China from 2014 to 2019, permitting the observation of the impacts of emission control strategies that were implemented during this period. Temporal variation in six key OVOCs (methanol, acetaldehyde, acetone, methyl ethyl ketone (MEK), formic acid, and acetic acid) were observed. The sum of concentrations of OVOCs was averagely 13% higher during the dry season (November to April), when winds transported polluted air masses to Shenzhen from the continent, than during the wet season, and peak diurnal levels occurred during the daytime year-round due to photochemical production and higher daytime anthropogenic emissions. The average dry season concentration of OVOCs declined from a peak of 30.3ppb in 2015 to 18.7ppb in 2019. The results of source apportionment showed that primary anthropogenic sources contributed the most to methanol, MEK, and acetic acid (32-51%); the dominant sources of acetaldehyde and formic acid were both primary and secondary anthropogenic sources; and biomass burning contributed a small fraction (5-11%) to the six OVOCs. From 2014 to 2019, contributions from primary anthropogenic sources of OVOCs decreased significantly by 50-60% due to intensive pollution control measures in Shenzhen, whereas pollution control measures had no observable impact on secondary OVOCs, indicating their formation was not limited by availability of their primary VOC precursors.

Resolving ambient organic aerosol formation and aging pathways with simultaneous molecular composition and volatility observations.

Organic aerosol (OA) constitutes a significant fraction of atmospheric fine particle mass. However, the precursors and chemical processes responsible for a majority of OA are rarely conclusively identified. We use online observations of hundreds of simultaneously measured molecular components obtained from 15 laboratory OA formation experiments with constraints on their effective saturation vapor concentrations to attribute the VOC precursors and subsequent chemical pathways giving rise to the vast majority of OA mass measured in two forested regions. We find that precursors and chemical pathways regulating OA composition and volatility are dynamic over hours to days, with their variations driven by coupled interactions between multiple oxidants. The extent of physical and photochemical aging, and its modulation by NOx, were key to a uniquely comprehensive combined composition-volatility description of OA. Our findings thus provide some of the most complete mechanistic-level guidance to the development of OA descriptions in air quality and Earth system models.

Regional source apportionment of summertime ozone and its precursors in the megacities of Beijing and Shanghai using a source-oriented chemical transport model

The Community Multiscale Air Quality (CMAQ) model with a source-oriented SAPRC-11 photochemical mechanism is developed in this study to quantify the source region contributions to surface O3 in Beijing and Shanghai in August 2013. Non-background O3 attributed to NOx (O3_NOx) and volatile organic compounds (O3_VOC) emitted from different source regions is determined using a three-regime approach that correctly attributes O3 to NOx and VOC precursors throughout the entire range of NOx-VOC-O3 formation sensitivity. Averaged over the entire month and all grid cells, local emissions (51%) and emissions from Hebei (31%) are the two major contributors to non-background daily maximum 8-h (DM8H) O3 in Beijing. In Shanghai, local, Zhejiang and Jiangsu emissions account for 53%, 19% and 14% of the non-background DM8H O3. Significant variations in local emission contributions are predicted among different model grid cells for both cities (Beijing, 6–80%; Shanghai, 3–76%). On high O3 days in Beijing, the wind is persistently from the south with high wind speed (~5 m s−1) in the evening and night. This leads to significant regional contributions of O3 from Hebei, along with regional transport of VOCs and NOx. In Shanghai, high O3 days are associated with southwesterly/westerly wind in the morning, rotating to southeast in the early afternoon in a counter-clockwise direction. The surface wind then gradually turns back to southwest in the afternoon until the next morning, along with reduced wind speed. In Shanghai, daytime O3 at the urban center is almost entirely due to local emissions. Low wind speed in the evening and night time allows local NOx emissions to efficiently titrate regional O3. In both cities, NOx emissions are not transported regionally as efficiently as VOCs. Source region contribution analysis of the concentration weighted maximum incremental reactivity (CWMIR) shows that VOCs from other regions are less reactive than locally emitted VOCs. HCHO and acetaldehyde (CCHO) generated from the oxidation of other VOCs are important contributors to regionally transported reactive VOCs. In both regions, the overall CWMIR in both cities is quite similar (~4 mol O3 per mole of VOC).

Trends of inorganic and organic aerosols and precursor gases in Europe: insights from the EURODELTA multi-model experiment over the 1990–2010 period

Abstract. In the framework of the EURODELTA-Trends (EDT) modeling experiment, several chemical transport models (CTMs) were applied for the 1990–2010 period to investigate air quality changes in Europe as well as the capability of the models to reproduce observed long-term air quality trends. Five CTMs have provided modeled air quality data for 21 continuous years in Europe using emission scenarios prepared by the International Institute for Applied Systems Analysis/Greenhouse Gas – Air Pollution Interactions and Synergies (IIASA/GAINS) and corresponding year-by-year meteorology derived from ERA-Interim global reanalysis. For this study, long-term observations of particle sulfate (SO42-), total nitrate (TNO3), total ammonium (TNHx) as well as sulfur dioxide (SO2) and nitrogen dioxide (NO2) for multiple sites in Europe were used to evaluate the model results. The trend analysis was performed for the full 21 years (referred to as PT) but also for two 11-year subperiods: 1990–2000 (referred to as P1) and 2000–2010 (referred to as P2). The experiment revealed that the models were able to reproduce the faster decline in observed SO2 concentrations during the first decade, i.e., 1990–2000, with a 64 %–76 % mean relative reduction in SO2 concentrations indicated by the EDT experiment (range of all the models) versus an 82 % mean relative reduction in observed concentrations. During the second decade (P2), the models estimated a mean relative reduction in SO2 concentrations of about 34 %–54 %, which was also in line with that observed (47 %). Comparisons of observed and modeled NO2 trends revealed a mean relative decrease of 25 % and between 19 % and 23 % (range of all the models) during the P1 period, and 12 % and between 22 % and 26 % (range of all the models) during the P2 period, respectively. Comparisons of observed and modeled trends in SO42- concentrations during the P1 period indicated that the models were able to reproduce the observed trends at most of the sites, with a 42 %–54 % mean relative reduction indicated by the EDT experiment (range of all models) versus a 57 % mean relative reduction in observed concentrations and with good performance also during the P2 and PT periods, even though all the models overpredicted the number of statistically significant decreasing trends during the P2 period. Moreover, especially during the P1 period, both modeled and observational data indicated smaller reductions in SO42- concentrations compared with their gas-phase precursor (i.e., SO2), which could be mainly attributed to increased oxidant levels and pH-dependent cloud chemistry. An analysis of the trends in TNO3 concentrations indicated a 28 %–39 % and 29 % mean relative reduction in TNO3 concentrations for the full period for model data (range of all the models) and observations, respectively. Further analysis of the trends in modeled HNO3 and particle nitrate (NO3-) concentrations revealed that the relative reduction in HNO3 was larger than that for NO3- during the P1 period, which was mainly attributed to an increased availability of “free ammonia”. By contrast, trends in modeled HNO3 and NO3- concentrations were more comparable during the P2 period. Also, trends of TNHx concentrations were, in general, underpredicted by all models, with worse performance for the P1 period than for P2. Trends in modeled anthropogenic and biogenic secondary organic aerosol (ASOA and BSOA) concentrations together with the trends in available emissions of biogenic volatile organic compounds (BVOCs) were also investigated. A strong decrease in ASOA was indicated by all the models, following the reduction in anthropogenic non-methane VOC (NMVOC) precursors. Biogenic emission data provided by the modeling teams indicated a few areas with statistically significant increase in isoprene emissions and monoterpene emissions during the 1990–2010 period over Fennoscandia and eastern European regions (i.e., around 14 %–27 %), which was mainly attributed to the increase of surface temperature. However, the modeled BSOA concentrations did not linearly follow the increase in biogenic emissions. Finally, a comprehensive evaluation against positive matrix factorization (PMF) data, available during the second period (P2) at various European sites, revealed a systematic underestimation of the modeled SOA fractions of a factor of 3 to 11, on average, most likely because of missing SOA precursors and formation pathways, with reduced biases for the models that accounted for chemical aging of semi-volatile SOA components in the atmosphere.

The formation of nitro-aromatic compounds under high NO&amp;lt;sub&amp;gt;&amp;lt;i&amp;gt;x&amp;lt;/i&amp;gt;&amp;lt;/sub&amp;gt; and anthropogenic VOC conditions in urban Beijing, China

Abstract. Nitro-aromatic compounds (NACs), as important contributors to the light absorption by brown carbon, have been widely observed in various ambient atmospheres; however, their formation in the urban atmosphere was little studied. In this work, we report an intensive field study of NACs in summer 2016 at an urban Beijing site, characterized by both high-NOx and anthropogenic VOC dominated conditions. We investigated the factors that influence NAC formation (e.g., NO2, VOC precursors, RH and photolysis) through quantification of eight NACs, along with major components in fine particulate matter, selected volatile organic compounds, and gases. The average total concentration of the quantified NACs was 6.63 ng m−3, higher than those reported in other summertime studies (0.14–6.44 ng m−3). 4-Nitrophenol (4NP, 32.4 %) and 4-nitrocatechol (4NC, 28.5 %) were the top two most abundant NACs, followed by methyl-nitrocatechol (MNC), methyl-nitrophenol (MNP), and dimethyl-nitrophenol (DMNP). The oxidation of toluene and benzene in the presence of NOx was found to be a more dominant source of NACs than primary biomass burning emissions. The NO2 concentration level was found to be an important factor influencing the secondary formation of NACs. A transition from low- to high-NOx regimes coincided with a shift from organic- to inorganic-dominated oxidation products. The transition thresholds were NO2 ∼ 20 ppb for daytime and NO2∼25 ppb for nighttime conditions. Under low-NOx conditions, NACs increased with NO2, while the NO3- concentrations and (NO3-)/NACs ratios were lower, implying organic-dominated products. Under high-NOx conditions, NAC concentrations did not further increase with NO2, while the NO3- concentrations and (NO3-)/NACs ratios showed increasing trends, signaling a shift from organic- to inorganic-dominated products. Nighttime enhancements were observed for 3M4NC and 4M5NC, while daytime enhancements were noted for 4NP, 2M4NP, and DMNP, indicating different formation pathways for these two groups of NACs. Our analysis suggested that the aqueous-phase oxidation was likely the major formation pathway of 4M5NC and 3M5NC, while photo-oxidation of toluene and benzene in the presence of NO2 could be more important for the formation of nitrophenol and its derivatives. Using the (3M4NC+4M5NC) ∕ 4NP ratios as an indicator of the relative contribution of aqueous-phase and gas-phase oxidation pathways to NAC formation, we observed that the relative contribution of aqueous-phase pathways increased at elevated ambient RH and remained constant at RH &gt; 30 %. We also found that the concentrations of VOC precursors (e.g., toluene and benzene) and aerosol surface area acted as important factors in promoting NAC formation, and photolysis as an important loss pathway for nitrophenols.

Quantification of Particle-Bound Organic Radicals in Secondary Organic Aerosol.

The chemical composition and evolution of secondary organic aerosol (SOA) in the atmosphere represents one of the largest uncertainties in our current understanding of air quality. Despite vast research, the toxicological mechanisms relating to adverse human health effects upon exposure to particulate matter are still poorly understood. Particle-bound reactive oxygen species (ROS) may substantially contribute to observed health effects by influencing aerosol oxidative potential (OP). The role of radicals in both the formation and aging of aerosol, as well as their contribution to aerosol OP, remains highly uncertain. The profluorescent spin trap BPEAnit (9,10-bis(phenylethynyl)anthracenenitroxide), previously utilized to study combustion-generated aerosol, has been applied to provide the first estimate of particle-bound radical concentrations in SOA. We demonstrate that SOA from different atmospherically important VOC precursors have different particle-bound radical concentrations, estimated for the ozonolysis of α-pinene (0.020 ± 0.0050 nmol/μg), limonene (0.0059 ± 0.0010 nmol/μg), and β-caryophyllene (0.0025 ± 0.00080 nmol/μg), highlighting the potential importance of OH-initiated formation of particle-bound organic radicals. Additionally, the lifetime of particle-bound radical species in α-pinene SOA was estimated, and a pseudo-first-order rate constant of k = 7.3 ± 1.7 × 10-3 s-1 was derived, implying a radical lifetime on the order of minutes.

Seasonal changes in carbonaceous aerosols over a tropical coastal location in response to meteorological processes

Near-surface atmospheric aerosols (PM10) collected from a tropical coastal location in south-west peninsular Indian region for a duration of 6 years (2012–18) (N = 461) were analysed for carbonaceous aerosol components, the less studied aerosol species. Organic carbon (OC), its water soluble-insoluble (WSOC and WIOC) components, primary-secondary (POC and SOC) fractions and elemental carbon (EC) were examined for understanding the annual, seasonal, day-night variations in abundance pattern along with associated physical and meteorological processes. Total carbonaceous aerosols accounting for 36% of the collected aerosol mass with 31.5% organic matter (OM) and 4.5% EC respectively, exhibited consistent seasonal pattern throughout the study period with high concentration during winter followed by post-monsoon, pre-monsoon and monsoon. Delineation of marine and continental components of carbonaceous species based on their relative dominance during different air-mass periods, shows that while marine aerosols were a combination of natural sources comprising of volatile, semi-volatile species and secondary organics (from marine VOC precursors); the continental aerosols were composed of anthropogenic combustion sources (fossil fuel, biomass emissions etc). Based on the measurements of OC and EC during 2005–09 and 2012–18, their long term trends (for more than a decade) were investigated. Although OC showed an increasing tendency, EC exhibited a decrease with the total carbonaceous aerosols exhibiting a gradual decreasing trend over the years, indicating that they do not strictly reverberate the reported increasing trend observed over north-central parts of India. This can be presumed to be due to the reduced anthropogenic inputs over the location owing to the control measures and policies. The strong convective activity and large scale monsoon phenomena also helps in the effective dispersion of pollutants. Making use of comprehensive measurement of carbonaceous aerosols and the previous measurements of other aerosol components, an improved chemical composition model is presented.