Organic Aerosol Formation Research Articles

Pollution Characteristics，Sources，and Secondary Generation of Organic Acids in PM2.5 in Zhengzhou

Organic acids in atmospheric particulate matter are widely involved in various physical and chemical reactions in the atmosphere and contribute greatly to the formation of secondary organic aerosols and haze pollutions. Therefore， the concentration distribution characteristics， sources， and secondary formation of organic acids in particulate matter are of great significance for further investigation of organic aerosols and their secondary transformation. Fine particulate matter （PM2.5） samples were collected in Zhengzhou， and three types of organic acids， including dicarboxylic acids， fatty acids， and resin acids， were analyzed to explore their species distribution， seasonal variations， source contribution， and secondary generation. Malonic acid （di-C3） and succinate acid （di-C4） were the most abundant in the identified dicarboxylic acids， which showed obvious seasonal variations in the order of summer > autumn > winter > spring. Fatty acids had the highest concentration in winter and the lowest concentration in spring， showing obvious bimodal advantages， with the most abundant compounds being palmitic acid and stearic acid （C18）. Principal component analysis and multiple linear regression （MLR） were used to analyze the source of organic acids in PM2.5 in Zhengzhou； the results showed that 35% of the organic acids came from combustion and traffic sources， 24% from cooking sources， 23% from secondary formation， and 17% from natural sources. The ratios of the selected marker species （i.e.， di-C3 / di-C4， F/M， and C18：1 / C18） were used as tracers for the secondary formation of the organic aerosol and its aging process. The results showed that the photochemical reaction was intense in summer， and the proportion of organic aerosol aging or secondary production was high， whereas the photochemical reaction was weak in winter， and the aging degree of organic aerosol was low. Correlation analysis and MLR were used in combination to quantify the relative contribution of gas-phase oxidation and liquid-phase oxidation to dicarboxylic acid formation， and the results showed that gas-phase oxidation played a dominant role in the sampling period （accounting for 58%）， especially in summer （61%）.

Role of sources of NMVOCs in O3, OH reactivity, and secondary organic aerosol formation over Delhi

Non-methane volatile organic compounds (NMVOCs) play a crucial role in atmospheric chemistry of ozone formation potential (OFP), secondary organic aerosol formation potential (SOAFP), and reactivity of OH ion (LOH). We have estimated LOH, OFP, and SOAFP of 25 ambient NMVOC species measured at the CSIR- National Physical Laboratory, New Delhi from February 2022 to February 2023. Alkenes contributed the highest to the OFP (75.63%) and LOH (68.11%), whereas, aromatics to the SOAFP (81.01%). The source apportionment was performed by positive matrix factorization (PMF) receptor model using the advanced ME-2 engine. Six anthropogenic sources of NMVOCs were identified namely liquified petroleum gas (LPG) + gasoline vehicular emission (GVE), diesel vehicular emission (DVE), painting usage, biomass burning, organic solvent usage, and chemical plant emission respectively. The mixed source (LPG + GVE) is primarily characterized by lower alkanes and aromatics, while DVE is mainly composed of aromatics and higher alkanes. Together, these sources contributed approximately 53% of the total VOCs. Painting usage was dominated by higher alkanes with a contribution of 11.2%, biomass burning is primarily composed of ethane, ethylene, and benzene, contributing 13.54%, and chemical plant emissions are dominated by n-hexane and benzene, contributing 13.78% of the total VOCs. The least contributing source (8.64%) is organic solvent usage, characterized by benzene, isopropyl benzene, and higher alkanes (C9 and C12). Mixed source was the highest contributor to LOH (42.09%), OFP (58.73%), and SOAFP (58.73%). A recent study underscores the importance of prioritizing reactivity-based strategies, focusing on OFP and SOAFP to control NMVOCs and ozone pollution.

Differences in Secondary Organic Aerosol Formation from α-Pinene Photooxidation in a Chamber with Purified Air and Ambient Air as Matrices: Preliminary Results

α-Pinene is a biogenic volatile organic compound (BVOC) that significantly contributes to secondary organic aerosols (SOA) in the atmosphere due to its high emission rate, reactivity, and SOA yield. However, the SOA yield measured in chamber studies from α-pinene photooxidation is limited in a purified air matrix. Assessing SOA formation from α-pinene photooxidation in real urban ambient air based on studies conducted in purified air matrices may be subject to uncertainties. In this study, α-pinene photooxidation and SOA yield were investigated in a smog chamber in the presence of NO and SO2 under purified air and ambient air matrices. With the accumulation of ozone (O3) during the photooxidation, an increasing part of α-pinene was consumed by O3 and finally nearly half of the α-pinene was oxidized by O3, facilitating the production of highly oxidized organic molecules and thereby SOA formation. Although the ambient air we introduced as matrix air was largely clean, with initial organic aerosol mass concentrations of ~1.5 μg m−3, the α-pinene SOA yield in the ambient air matrix was 42.3 ± 5.3%, still higher than that of 32.4 ± 0.4% in the purified air matrix. The chemical characterization of SOA by the high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) revealed that CxHy accounted for 53.7 ± 1.1% of the total signal in the ambient air matrix experiments, higher than 48.1 ± 0.3% in the purified air, while CxHyO and CxHyO>1 together constituted 45.0 ± 0.9% in the ambient air matrix, lower than 50.1 ± 1.0% in the purified air. The O:C ratio in the ambient air matrix experiments was 0.41 ± 0.01, lower than 0.46 ± 0.01 in the purified air. The higher SOA yield of α-pinene in the ambient air matrix compared to that in the purified air matrix was partly due to the presence of initial aerosols in the ambient air, which facilitated the low volatile organic compounds produced from photochemical oxidation to enter the aerosol phase through gas-particle partitioning. The in-situ aerosol acidity calculated by the ISORROPIA-II model in the ambient air matrix experiments was approximately six times higher than that in purified air, and the higher SOA yield in the ambient air matrix experiments might also be attributed to acid-catalyzed SOA formation.

Sources and Distribution of Light NMHCs in the Marine Boundary Layer of the Northern Indian Ocean During Winter: Implications to Aerosol Formation

AbstractNon‐methane hydrocarbons (NMHCs) are ubiquitous trace gases and profoundly affect the Earth's atmosphere and climate change. Mixing ratios of light NMHCs were measured over the northern Indian Ocean during winter‐2018 as part of the Integrated Campaign for Aerosols, gases, and Radiation Budget (ICARB‐2018). Higher levels of NMHCs over the coastal regions were due to the efficient transport of anthropogenic and biogenic air masses and higher air‐sea exchanges due to the higher biological productivity. Although oceanic emissions dominated the open ocean, the transport of aged continental air also influenced the levels of some NMHCs. The higher and lower propane/ethane ratios of 2.41 ± 0.34 and 1.13 ± 0.78 ppbv ppbv−1 over coastal and open oceans indicated the prevalence of fresh and aged air masses, respectively. Ethene and propene show a strong correlation, but the ethene/propene ratios over open ocean (2.2 ± 0.25 ppbv ppbv−1) were slightly lower than the coastal region (2.5 ± 0.34 ppbv ppbv−1). Principal component analysis reveals the major associated sources identified in this study are from oceanic and nearby anthropogenic sources, explaining nearly 51% and 21% of variance. Light alkenes accounted for ∼70% of the total ozone and secondary organic aerosol formation potential. A higher alkene/alkane ratio, strong correlation of alkene with organic aerosol mass, and new particle formation events highlight the role of alkenes in secondary aerosol formation over the equatorial Indian Ocean. Overall, the levels of NMHCs were much higher than those measured nearly two decades ago during the Indian Ocean Experiment (INDOEX)‐1999.

Impact of Nitrate and Iron Ions on Uptake Coefficients and Condensed Phase Products From the Reaction of Gaseous NO2 With HULIS Proxies

AbstractHumic‐like substances (HULIS) are a ubiquitous reactive component of atmospheric aerosol. They participate in the formation of secondary organic aerosols via chemical reactions with atmospheric oxidants. Here, we assess the influence of transition metal ions (namely ferric iron, Fe(III)), and nitrate ions () on the heterogeneous reaction of gaseous NO2 with an aqueous film containing gallic acid (GA) or tannic acid (TA) as proxies for HULIS. Using a vertical wetted wall flow tube technique, the uptake coefficients of gaseous NO2 on GA and TA increased nonlinearly with increasing [Fe(III)], in dark and under light irradiation. However, the combined effect of both ions, Fe(III) and , led to a substantial decrease in NO2 uptake in the dark and under simulated near‐UV sunlight irradiation (300 < λ < 400 nm). The lifetime of GA in dilute aqueous phase, which corresponds to cloud water, due to reaction with NO2 would be 6 hr during both nighttime and daytime. However, the lifetime of GA in aerosol particles which contain both ions, that is, Fe(III) and , would increase to 27 hr during nighttime and 11 days and 6 hr due to light‐induced reaction with NO2. Also, we observed, using Fourier transform ion cyclotron resonance mass spectrometry, the formation of nitrocatechols compounds (e.g., methyl‐nitrocatechol), which contribute to brown carbon. Compounds with reduced functional groups such as amines were also observed in the presence of iron and nitrate ions in the dark and under irradiation, indicating that Fe(III) and , can influence the kinetics and product distribution in deliquescent aerosol particles.

Unraveling the atmospheric oxidation mechanism and kinetics of naphthalene: Insights from theoretical exploration

Naphthalene, the most abundant polycyclic aromatic hydrocarbon in the atmosphere, significantly influences OH consumption and secondary organic aerosol (SOA) formation. Naphthoquinone (NQ) is a significant contributor to ring-retaining SOA from naphthalene degradation, impacting the redox properties and toxicity of ambient particles. However, inconsistencies persist regarding concentrations of its isomers, 1,2-NQ and 1,4-NQ. In present work, our theoretical investigation into naphthalene's reaction with OH and subsequent oxygenation unveils their role in SOA formation. The reaction kinetics of initial OH and subsequent O2 oxidation was extensively studied using high-level quantum chemical methods (DLPNO-CCSD(T)/aug-ccpVQZ//M052x-D3/6–311++G(d,p)) combined with RRKM/master equation simulations. The reactions mainly proceed through electrophilic addition and abstraction from the aromatic ring. The total rate coefficient of naphthalene + OH at 300 K and 1 atm from our calculation (7.2 × 10−12 cm3 molecule−1 s−1) agrees well with previous measurements (∼1 × 10−11 cm3 molecule−1 s−1). The computed branching ratios facilitate accurate product yield determination. The largest yield of 1-hydroxynaphthalen-1-yl radical (add1) producing the major precursor of RO2 is computed to be 93.8 % in the ambient environment. Our calculated total rate coefficient (5.2 × 10−16 cm3 molecule−1 s−1) for add1 + O2 closely matches that of limited experimental data (8.0 × 10−16 cm3 molecule−1 s−1). Peroxy radicals (RO2) generated from add1 + O2 include 4-cis/trans-(1-hydroxynaphthalen-1-yl)-peroxy radical (add1-4OOadd-cis/trans, 66.0 %/17.5 %), 2-cis/trans-(1-hydroxynaphthalen-1-yl)-peroxy radical (add1-2OOadd-cis/trans, 10.3 %/6.3 %). Regarding the debated predominance of 1,4-NQ (corresponding to the parent RO2, i.e., add1-4OOadd-cis/trans) and 1,2-NQ (corresponding to the parent RO2, i.e., add1-2OOadd-cis/trans) in the atmosphere, our findings substantiate the dominance of 1,4-NQ. This study also indicates potential weakening of 1,4-NQ's dominance due to competition from decomposition reactions of add1-4OOadd-cis/trans and add1-2OOadd-cis/trans. Precise reaction kinetics data are essential for characterizing SOA transformation derived from naphthalene and assessing their climatic impacts within modeling frameworks.

Wall loss of semi-volatile organic compounds in a Teflon bag chamber for the temperature range of 262–298 K: mechanistic insight on temperature dependence

Abstract. ​​​​​​​Teflon bag chambers have long been used for investigating atmospheric chemical processes, including secondary organic aerosol formation. The wall-loss process of gas-phase species in Teflon bag chambers has typically been investigated at around room temperature. Recent laboratory studies started employing Teflon bag chambers at sub-273 K conditions for simulating wintertime and upper-tropospheric environments. However, temperature dependence in vapor-wall-loss processes of semi-volatile organic compounds (SVOCs) in a Teflon bag chamber has not been well investigated. In this study, we experimentally investigated wall-loss processes of C14–C19 n-alkanes in a 1 m3 Teflon bag for the temperature range of 262 to 298 K. Enhanced wall losses of the tested n-alkanes were observed following the decrease in temperature. For instance, 65 %​​​​​​​ of C14 n-alkane was lost to the wall 15 h after injection at room temperature, while the corresponding value was 95 % at 262 K. The experimental data were analyzed using a two-layer kinetic model, which considers both absorption of gas-phase species to the surface layer of the Teflon wall and diffusion to the inner layer. The experimental data demonstrated that absorption of gas-phase species by the surface layer was enhanced at lower temperatures. The temperature dependence in absorption was well accounted for using the equilibrium-dissolution model of organic compounds to the Teflon surface by considering reduced saturation vapor pressure at lower temperatures. On the contrary, diffusion of n-alkanes from the surface to the inner layer slowed down at reduced temperatures. Mechanistic studies on these processes will need to be conducted in the future to quantitatively predict the influence of temperature-dependent wall-loss processes of SVOCs on laboratory experimental results.

Risk assessment of volatile organic compounds from aged asphalt: Implications for environment and human health

The recycling of aged asphalt offers significant economic benefits. However, its utilization may pose environmental and health risks. Limited research has been conducted to assess the health and environmental risks associated with volatile organic compounds (VOCs) emitted from aged asphalt. To investigate the environmental affects and health risks of VOCs from aged asphalt, this study conducted quantitative research through indoor simulation experiments, where different types of aged asphalt were prepared and analyzed for their VOCs release characteristics and associated risks. The findings of the study indicate noticeable differences in the VOCs release characteristics, environmental impacts, and health risks of aged asphalt, influenced by the asphalt type and aging method. Compared to the virgin asphalt, the concentration of VOCs in aged asphalt can be reduced by up to 88.38 %, resulting in a decreased impact on the environment and health. The content of alkanes, alkenes & alkynes, aromatics, and halogenated hydrocarbons in asphalt decreases, and oxygenated volatile organic compounds (OVOCs) became the primary components. In 70# and 90# virgin asphalt, alkanes, alkenes, and aromatics contribute 82.9 % and 87.3 %, respectively, to ozone generation, while in aged bitumen (except UV90#), OVOCs contribute more than 90 %. Alkanes and aromatics in the VOCs of the original asphalt contribute more than 90 % to the formation of secondary organic aerosols, while alkanes and OVOCs play this role in the aged asphalt. Although the release concentration of VOCs and the associated environmental and health risks are reduced after asphalt aging, they should not be disregarded. This study will contribute to accelerating the prevention and control of traffic pollution promoting green and sustainable development in transportation.

Spatial-temporal characteristics of ambient isoprene and monoterpene and their ozone and secondary organic aerosol formation potentials in China

Biogenic volatile organic compounds (BVOCs) are important precursors of forming ozone (O3) and secondary organic aerosols (SOA), which have important impacts on air quality and climate change. Using a literature search, this review analyzed the concentration levels and spatial-temporal distributions of isoprene and monoterpene in the atmosphere in China, mainly from biogenic emissions, and estimated their impact on O3 and SOA generation. The existing observations were mainly in the Beijing-Tianjin-Hebei region, the Pearl River Delta region, central China, and in remote mountainous areas. The results showed that isoprene is the dominant component of BVOCs in the atmosphere, and its ambient concentration is much higher than monoterpene. The site-average concentrations of isoprene and monoterpene were 0.004–3.80 and 0.0003–6.31 ppb, respectively. At vegetation sites, the concentrations of isoprene and monoterpene were 0.006–3.80 and 0.007–6.31 ppb, respectively, whereas they were 0.004–2.70 and 0.0003–1.10 ppb at urban sites. For urban sites, the higher concentrations of annual isoprene occurred mainly in several central megacities, in the Sichuan-Chongqing region, and in southern regions. For vegetation sites, higher concentrations mainly occurred in southern regions. Ambient concentrations of BVOCs in the western region were the lowest for both urban and vegetation sites. Both isoprene and monoterpene showed higher concentrations in summer. The potential of isoprene and monoterpene to form O3 were 0.05–57.21 and 0.003–72.35 ppb, while those that form SOA were 0.0002–0.21 and 0.0006–10.46 μg/m3, respectively. For urban sites, the average annual O3 formation potential (OFP) by isoprene and monoterpene were 8.70 and 2.58 ppb, and their SOA formation potential (SOAP) were 0.03 and 0.37 μg/m3. For vegetation sites, they were 7.95 and 5.31 ppb and 0.03 and 0.75 μg/m3, respectively. The annual average contributions of isoprene and monoterpene to O3 and SOA formation were higher in the Beijing-Tianjin-Hebei region, Pearl River Delta region, and central China, where experience severe air pollution in China.

Carbonyl-amine condensation coupled ozonolysis of dipropylamine and styrene: Decay kinetics, reaction mechanism, secondary organic aerosol formation and cytotoxicity

Oxidation of organic amines (OAs) or aromatic hydrocarbons (AHs) produces carbonyls, which further react with OAs to form carbonyl-amine condensation products, threatening environmental quality and human health. However, there is still a lack of systematic understanding of the carbonyl-amine condensation reaction processes of OAs or between OAs and AHs, and subsequent environmental health impact. This work systematically investigated the carbonyl-amine condensation coupled ozonolysis kinetics, reaction mechanism, secondary organic aerosol (SOA) formation and cytotoxicity from the mixture of dipropylamine (DPA) and styrene (STY) by a combined method of product mass spectrometry identification, particle property analysis and cell exposure evaluation. The results from ozonolysis of DPA and STY mixture revealed that STY inhibited the ozonolysis of DPA to different degrees to accelerate its own decay rate. The barycenter of carbonyl-amine condensation reactions was shifted from inside of DPA to between DPA and STY, which accelerated STY ozonolysis, but slowed down DPA ozonolysis. For the first time, ozonolysis of DPA and STY mixture to complex carbonyl-amine condensation products through the reactions of DPA with its carbonyl products, DPA with STY's carbonyl products and DPA's bond breakage product with STY's carbonyl products was confirmed. These condensation products significantly contributed to the formation and growth of SOA. The SOA containing particulate carbonyl-amine condensation products showed definite cytotoxicity. These findings are helpful to deeply and comprehensively understand the transformation, fate and environmental health effects of mixed organics in atmospheric environment.

On the formation of biogenic secondary organic aerosol in chemical transport models: an evaluation of the WRF-CHIMERE (v2020r2) model with a focus over the Finnish boreal forest

Abstract. We present an evaluation of the regional chemical transport model (CTM) WRF-CHIMERE (v2020r2) for the formation of biogenic secondary organic aerosol (BSOA) with a focus over the Finnish boreal forest. Formation processes of biogenic aerosols are still affected by different sources of uncertainties, and model predictions vary greatly depending on the levels of details of the adopted chemical and emissions schemes. In this study, air quality simulations were conducted for the summer of 2019 using different organic aerosol (OA) schemes (as currently available in the literature) to treat the formation of BSOA. First, we performed a set of simulations in the framework of the volatility basis set (VBS) scheme carrying different assumptions for the treatment of the aging processes of BSOA. The results of the model were compared against high-resolution (i.e., 1 h) organic aerosol mass and size distribution measurements performed at the Station for Measuring Ecosystem–Atmosphere Relations (SMEAR-II) site located in Hyytiälä, in addition to other gas-phase species such as ozone (O3), nitrogen oxides (NOx), and biogenic volatile organic compound (BVOC) measurements of isoprene (C5H10) and monoterpenes. We show that WRF-CHIMERE could reproduce well the diurnal variation of the measured OA concentrations for all the investigated scenarios (along with the standard meteorological parameters) as well as the increase in concentrations during specific heat wave episodes. However, the modeled OA concentrations varied greatly between the schemes used to describe the aging processes of BSOA, as also confirmed by an additional evaluation using organic carbon (OC) measurement data retrieved from the EBAS European databases. Comparisons with isoprene and monoterpene air concentrations revealed that the model captured the observed monoterpene concentrations, but isoprene was largely overestimated, a feature that was mainly attributed to the overstated biogenic emissions of isoprene. We investigated the potential consequences of such an overestimation by inhibiting isoprene emissions from the modeling system. Results indicated that the modeled BSOA concentrations increased in the northern regions of the domain (e.g., Finland) compared to southern European countries, possibly due to a shift in the reactions of monoterpene compounds against available radicals, as further suggested by the reduction in α-pinene modeled air concentrations. Finally, we briefly analyze the differences in the modeled cloud liquid water content (clwc) among the simulations carrying different chemical schemes for the treatment of the aging processes of BSOA. The results of the model indicated an increase in clwc values at the SMEAR-II site, for simulations with higher biogenic organic aerosol loads, most likely as a result of the increased number of biogenic aerosol particles capable of activating cloud droplets.

Airmass history, night-time particulate organonitrates, and meteorology impact urban SOA formation rate

With respect to air quality, the San Antonio metropolitan area, with a population of 1.45 million and the second largest city in Texas, has been designated as non-attainment by the United States Environmental Protection Agency in recent years. Despite the operation of multiple stationary air quality monitoring sites by the Texas Commission on Environmental Quality, the in-situ measurements of submicron aerosol and its precursors in the region is limited. To better understand the formation of secondary organic aerosol (SOA) in the San Antonio urban core, we conducted observations of a range of trace gases, volatile organic compounds, submicron aerosol, and meteorological parameters in May 2017. Data from a High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS) show that organic aerosol (OA) was the dominant component of non-refractory submicron particulate matter (average±1σ, 55 ± 32 %, 5.86 ± 3.40 μg m−3), followed by sulfate (33 ± 23 %, 3.52 ± 2.47 μg m−3). Aerosol liquid water contents predicted by ISORROPIA-II greatly increase from Continental to Oceanic airmass history scenarios, while inorganic aerosol pH remains very acidic. Positive matrix factorization (PMF) analysis of the OA mass spectra indicates that two classes of oxygenated OA (less and more-oxidized OOA, LO and MO) together constituted the bulk of OA mass during the study period (MO-OOA: 44 ± 39 %, 2.35 ± 2.07 μg m−3; LO-OOA: 42 ± 34 %, 2.22 ± 1.77 μg m−3), while the fraction of hydrocarbon-like OA was limited (13 ± 21 %, 0.71 ± 1.11 μg m−3). Using in-situ meteorological data and location-specific empirical coefficients, a zero-dimensional model that utilized PMF factors as proxies to calculate the net rate of formation of types of SOA has been developed; similar calculations were used to estimate the formation rate of particulate organonitrates (pON). The results from the model reveal the importance of pON formation in LO-OOA formation overnight and the influence of temperature and photochemistry during the day. The relationships between local atmospheric factors and the net rate of formation of MO-OOA are not statistically significant. These results emphasize how HR-ToF-AMS-PMF factors could be incorporated into chemistry modeling to evaluate quantitatively the rates of formation of SOA and reveal diurnal differences in SOA formation pathways in a major urban area in southern United States.

Parameterizations of US wildfire and prescribed fire emission ratios and emission factors based on FIREX-AQ aircraft measurements

Abstract. Extensive airborne measurements of non-methane organic gases (NMOGs), methane, nitrogen oxides, reduced nitrogen species, and aerosol emissions from US wild and prescribed fires were conducted during the 2019 NOAA/NASA Fire Influence on Regional to Global Environments and Air Quality campaign (FIREX-AQ). Here, we report the atmospheric enhancement ratios (ERs) and inferred emission factors (EFs) for compounds measured on board the NASA DC-8 research aircraft for nine wildfires and one prescribed fire, which encompass a range of vegetation types. We use photochemical proxies to identify young smoke and reduce the effects of chemical degradation on our emissions calculations. ERs and EFs calculated from FIREX-AQ observations agree within a factor of 2, with values reported from previous laboratory and field studies for more than 80 % of the carbon- and nitrogen-containing species. Wildfire emissions are parameterized based on correlations of the sum of NMOGs with reactive nitrogen oxides (NOy) to modified combustion efficiency (MCE) as well as other chemical signatures indicative of flaming/smoldering combustion, including carbon monoxide (CO), nitrogen dioxide (NO2), and black carbon aerosol. The sum of primary NMOG EFs correlates to MCE with an R2 of 0.68 and a slope of −296 ± 51 g kg−1, consistent with previous studies. The sum of the NMOG mixing ratios correlates well with CO with an R2 of 0.98 and a slope of 137 ± 4 ppbv of NMOGs per parts per million by volume (ppmv) of CO, demonstrating that primary NMOG emissions can be estimated from CO. Individual nitrogen-containing species correlate better with NO2, NOy, and black carbon than with CO. More than half of the NOy in fresh plumes is NO2 with an R2 of 0.95 and a ratio of NO2 to NOy of 0.55 ± 0.05 ppbv ppbv−1, highlighting that fast photochemistry had already occurred in the sampled fire plumes. The ratio of NOy to the sum of NMOGs follows trends observed in laboratory experiments and increases exponentially with MCE, due to increased emission of key nitrogen species and reduced emission of NMOGs at higher MCE during flaming combustion. These parameterizations will provide more accurate boundary conditions for modeling and satellite studies of fire plume chemistry and evolution to predict the downwind formation of secondary pollutants, including ozone and secondary organic aerosol.

Contribution of Ship Emission to Volatile Organic Compounds Based on One‐Year Monitoring at a Coastal Site in the Pearl River Delta Region

AbstractShip emission impacts ambient air quality, especially in coastal regions, by emitting air pollutants such as fine particles, nitrogen oxides (NOx), and sulfur dioxide (SO2), yet its contributions to volatile organic compounds (VOCs) and the formation of secondary organic aerosol (SOA) and ozone (O3) are much less constrained with the challenge in distinguish ship emission from land diesel emission. In this study, we conducted a 1‐year online measurement of VOCs with a 1‐hr resolution at a coastal site in south China's Pearl River Delta region, which holds three of the world's top 10 container ports. The results revealed that C10–C12 n‐alkanes, as typical diesel‐related emission tracers, were significantly enhanced and strongly related to oceanic air masses. Receptor modeling revealed two diesel‐related sources of land diesel emission and ship emission, which could be differentiated based on their source profiles, seasonal trends and air mass back trajectories. Ship emissions contributed 6.4%, 5.0%, and 13.6% of total VOC mixing ratios, ozone formation potentials (OFPs), and secondary organic aerosol formation potentials (SOAFPs), while these percentages were 3.4%, 14.7%, and 15.9% for land diesel emission, respectively. In particular, in July, ship emissions could contribute 21.7%, 14.6%, and 31.2% of VOCs, OFPs, and SOAFPs, respectively. Our results highlight the important contribution of diesel‐related emission VOCs in forming O3 and SOA in coastal regions, and ship emission is a non‐negligible source of VOCs, particularly after the strict control of land emission sources.

Exploring the discrepancies between SMPS and AMS measurements in secondary organic aerosol formation experiments

Exploring the discrepancies between SMPS and AMS measurements in secondary organic aerosol formation experiments

Review of Smog Chamber Experiments for Secondary Organic Aerosol Formation

In this study, we reviewed smog chamber systems and methodologies used in secondary organic aerosol (SOA) formation studies. Many important chambers across the world have been reviewed, including 18 American, 24 European, and 8 Asian chambers. The characteristics of the chambers (location, reactor size, wall materials, and light sources), measurement systems (popular equipment and working principles), and methodologies (SOA yield calculation and wall-loss correction) are summarized. This review discussed key experimental parameters such as surface-to-volume ratio (S/V), temperature, relative humidity, light intensity, and wall effect that influence the results of the experiment, and how the methodologies have evolved for more accurate simulation of atmospheric processes. In addition, this review identifies the sources of uncertainties in finding SOA yields that are originated from experimental systems and methodologies used in previous studies. The intensity of the installed artificial lights (photolysis rate of NO2 varied from 0.1/min to 0.40/min), SOA density assumption (varied from 1 g/cm3 to 1.45 g/cm3), wall-loss management, and background contaminants were identified as important sources of uncertainty. The methodologies developed in previous studies to minimize those uncertainties are also discussed.

CAMx–UNIPAR simulation of secondary organic aerosol mass formed from multiphase reactions of hydrocarbons under the Central Valley urban atmospheres of California

Abstract. The UNIfied Partitioning-Aerosol phase Reaction (UNIPAR) model was integrated into the Comprehensive Air quality Model with extensions (CAMx) to process secondary organic aerosol (SOA) formation by capturing multiphase reactions of hydrocarbons (HCs) in regional scales. SOA growth was simulated using a wide range of anthropogenic HCs, including 10 aromatics and linear alkanes with different carbon lengths. The atmospheric processes of biogenic HCs (isoprene, terpenes, and sesquiterpene) were simulated for major oxidation paths (ozone, OH radicals, and nitrate radicals) to predict day and night SOA formation. The UNIPAR model streamlined the multiphase partitioning of the lumping species originating from semi-explicitly predicted gas products and their heterogeneous chemistry to form non-volatile oligomeric species in both organic aerosol and inorganic aqueous phase. The CAMx–UNIPAR model predicted SOA formation at four ground urban sites (San Jose, Sacramento, Fresno, and Bakersfield) in California, United States, during wintertime 2018. Overall, the simulated mass concentrations of the total organic matter, consisting of primary organic aerosol and SOA, showed a good agreement with the observations. The simulated SOA mass in the urban areas of California was predominated by alkane and terpene oxidation products. During the daytime, low-volatility products originating from the autoxidation of long-chain alkanes considerably contributed to the SOA mass. In contrast, a significant amount of nighttime SOA was produced by the reaction of terpene with ozone or nitrate radicals. The spatial distributions of anthropogenic SOA associated with aromatic and alkane HCs were noticeably affected by the southward wind direction, owing to the relatively long lifetime of their atmospheric oxidation, whereas those of biogenic SOA were nearly insensitive to wind direction. During wintertime 2018, the impact of inorganic aerosol hygroscopicity on the total SOA budget was not evident because of the small contribution of aromatic and isoprene products, which are hydrophilic and reactive in the inorganic aqueous phase. However, an increased isoprene SOA mass was predicted during the wet periods, although its contribution to the total SOA was little.

Current status of model predictions of volatile organic compounds and impacts on surface ozone predictions during summer in China

Abstract. Volatile organic compounds (VOCs) play a crucial role in the formation of tropospheric ozone (O3) and secondary organic aerosols. VOC emissions are generally considered to have larger uncertainties compared to other pollutants, such as sulfur dioxide and fine particulate matter (PM2.5). Although predictions of O3 and PM2.5 have been extensively evaluated in air quality modeling studies, there has been limited reporting on the evaluation of VOCs, mainly due to a lack of routine VOC measurements at multiple sites. In this study, we utilized VOC measurements from the “Towards an Air Toxic Management System in China” (ATMSYC) project at 28 sites across China and assessed the predicted VOC concentrations using the Community Multiscale Air Quality (CMAQ) model with the widely used Multi-resolution Emission Inventory for China (MEIC). The ratio of predicted to observed total VOCs was found to be 0.74 ± 0.40, with underpredictions ranging from 2.05 to 50.61 ppbv (5.77 % to 85.40 %) at 24 sites. A greater bias in VOC predictions was observed in industrial cities in the north and southwest, such as Jinan, Shijiazhuang, Lanzhou, Chengdu, and Guiyang. In terms of different VOC components, alkanes, alkenes, non-naphthalene aromatics (ARO2MN), alkynes, and formaldehyde (HCHO) had prediction-to-observation ratios of 0.53 ± 0.38, 0.51 ± 0.48, 0.31 ± 0.38, 0.41 ± 0.47, and 1.21 ± 1.61, respectively. Sensitivity experiments were conducted to assess the impact of the VOC prediction bias on O3 predictions. While emission adjustments improved the model performance for VOCs, resulting in a change in the ratio of total VOCs to 0.86 ± 0.47, they also exacerbated O3 overprediction relative to the base case by 0.62 % to 6.27 % across the sites. This study demonstrates that current modeling setups and emission inventories are likely to underpredict VOC concentrations, and this underprediction of VOCs contributes to lower O3 predictions in China.

Formation of secondary organic aerosol from wildfire emissions enhanced by long-time ageing

Formation of secondary organic aerosol from wildfire emissions enhanced by long-time ageing

Uncovering the dominant contribution of intermediate volatility compounds in secondary organic aerosol formation from biomass-burning emissions.

Organic vapors from biomass burning are a major source of secondary organic aerosols (SOAs). Previous smog chamber studies found that the SOA contributors in biomass-burning emissions are mainly volatile organic compounds (VOCs). While intermediate volatility organic compounds (IVOCs) are efficient SOA precursors and contribute a considerable fraction of biomass-burning emissions, their contribution to SOA formation has not been directly observed. Here, by deploying a newly-developed oxidation flow reactor to study SOA formation from wood burning, we find that IVOCs can contribute ∼70% of the formed SOA, i.e. >2 times more than VOCs. This previously missing SOA fraction is interpreted to be due to the high wall losses of semi-volatile oxidation products of IVOCs in smog chambers. The finding in this study reveals that SOA production from biomass burning is much higher than previously thought, and highlights the urgent need for more research on the IVOCs from biomass burning and potentially other emission sources.