Comment on amt-2022-221

Abstract. Particulate matter (PM) largely consists of secondary organic aerosol (SOA) that is formed via oxidation of biogenic and anthropogenic volatile organic compounds (VOCs). Unambiguous identification of SOA molecules and their assignment to their precursor vapors are challenges that have so far only succeeded for a few SOA marker compounds, which are now well characterized and (partly) available as authentic standards. In this work, we resolve the complex composition of SOA by means of a top-down approach based on the newly created Aerosolomics database, which is fed by non-target analysis results of filter samples from oxidation flow reactor experiments. We investigated the oxidation products from the five biogenic VOCs α-pinene, β-pinene, limonene, 3-carene, and trans-caryophyllene and from the four anthropogenic VOCs toluene, o-xylene, 1,2,4-trimethylbenzene, and naphthalene. Using ultrahigh-performance liquid chromatography coupled to a high-resolution (Orbitrap) mass spectrometer, we determine the molecular formula of 596 chromatographically separated compounds based on exact mass and isotopic pattern. We utilize retention time and fragmentation mass spectra as a basis for unambiguous attribution of the oxidation products to their parent VOCs. Based on the molecular-resolved application of the database, we are able to assign roughly half of the total signal of oxygenated hydrocarbons in ambient suburban PM2.5 to one of the nine studied VOCs. The application of the database enabled us to interpret the appearance of diurnal compound clusters that are formed by different oxidation processes. Furthermore, by performing a hierarchical cluster analysis (HCA) on the same set of filter samples, we identified compound clusters that depend on sulfur dioxide mixing ratio and temperature. This study demonstrates how Aerosolomics tools (database and HCA) applied to PM filter samples can improve our understanding of SOA sources, their formation pathways, and temperature-driven partitioning of SOA compounds.

Abstract. In order to investigate the variability of the secondary organic aerosol (SOA) distributions and budget and provide a measure for the robustness of the conclusions on human induced changes of SOA, a global 3-dimensional chemistry transport model describing both the gas and the particulate phase chemistry of the troposphere has been applied. The response of the global budget of SOA to temperature and moisture changes as well as to biogenic emission changes over a decade (1984-1993) has been evaluated. The considered emissions of biogenic non-methane volatile organic compounds (VOC) are driven by temperature, light and vegetation. They vary between 756 and 810 Tg Cy-1 and are therefore about 5.5 times higher than the anthropogenic VOC emissions. All secondary aerosols (sulphuric, nitrates and organics) are computed on-line together with the aerosol associated water. Over the studied decade, the computed natural variations (8%) in the chemical SOA production from biogenic VOC oxidation equal the chemical SOA production from anthropogenic VOC oxidation. Maximum values are calculated for 1990 (warmer and drier) and minimum values for 1986 (colder and wetter). The SOA computed variability results from a 7% increase in biogenic VOC emissions from 1986 to 1990 combined with 8.5% and 6% increases in the wet and dry deposition of SOA and leads to about 11.5% increase in the SOA burden of biogenic origin. The present study also demonstrates the importance of the hydrological cycle in determining the built up and fate of SOA in the atmosphere. It also reveals the existence of significant positive and negative feedback mechanisms in the atmosphere responsible for the non linear relationship between emissions of biogenic VOC and SOA burden.

Assessing the role of volatile organic compounds (VOCs) in production of ozone and secondary organic aerosol (SOA) is especially important in light of ongoing policy goals. Here, we estimated the ozone formation potential (OFP) and SOA formation potential (SOAP) of anthropogenic and biogenic VOC emissions to evaluate (1) anthropogenic VOCs and associated sectors that dominate OFP and SOAP and (2) the potential impacts of enhanced biogenic VOCs from urban greening programs on air quality in Los Angeles county. In the present-day scenario, ethylene had the largest OFP followed by m & p-xylene, toluene, propylene, and formaldehyde. The top five contributors to SOAP were toluene, mineral spirits, benzene, heptadecane, and hexadecane. Mobile and solvent sources were the dominant VOC sources for both OFP and SOAP. The potential increases in biogenic VOC emissions due to future urban greening had significant effects on urban air quality that offset the benefits of reducing anthropogenic VOC emissions. This study demonstrates that urban greening programs in Los Angeles county, and likely other cities as well, need to account for both anthropogenic and biogenic VOC contributions to secondary pollution, and greening cities should consider using vegetation types with low VOC emissions to avoid further degradation to urban air quality.

<strong class="journal-contentHeaderColor">Abstract.</strong> Secondary organic aerosols (SOA) are an important component of atmospheric fine particulate matter (PM_2.5) in China, and elsewhere, with contributions from anthropogenic and biogenic volatile organic compounds (AVOC and BVOC) and semi- (SVOC) and intermediate volatility organic compounds (IVOC). Policy makers need to know which SOA precursors are important but accurate simulation of SOA magnitude and contributions remains uncertain. We reviewed SOA modelling studies in the past decade that have reported the relative contributions of different precursors to SOA concentration and the findings have many inconsistencies due to differing emission inventory methodologies/assumptions, air quality model (AQM) algorithms, and other aspects of study methodologies. We investigated the role of different AQM SOA algorithms by applying two commonly used models, CAMx and CMAQ, with consistent emission inventories to simulate SOA concentrations and contributions for July and November 2018 in China. Both models have a volatility basis set (VBS) SOA algorithm but with different parameters and treatments of SOA photochemical aging. BSOA (SOA produced from BVOC) is found to be more important over southern China whereas SOA generated from anthropogenic precursors is more prevalent in the North China Plain (NCP), Yangtze River Delta (YRD), Sichuan Basin and Central China. Both models indicate negligible SOA formation from SVOC emissions as compared to other precursors. In July when BVOC emissions are abundant, SOA is predominantly contributed by BSOA (except for NCP), followed by IVOC-SOA (i.e. SOA produced from IVOC) and ASOA (i.e. SOA produced from anthropogenic VOC). In contrast in November, IVOC becomes the leading SOA contributor for all selected regions except PRD, illustrating the important contribution of IVOC emissions to SOA formation. Therefore, future control policies should aim at reducing IVOC emissions as well as traditional VOC emissions. While both models generally agree in terms of the spatial distributions and seasonal variations of different SOA components, CMAQ tends to predict higher BSOA while CAMx generates higher ASOA concentrations. As a result, CMAQ results suggest that BSOA concentration is always higher than ASOA in November while CAMx emphasizes the importance of ASOA. Utilizing a conceptual model, we found that different treatment of SOA aging between the two models is a major cause of differences in simulated ASOA concentrations. The step-wise SOA aging scheme implemented in CAMx (based on gas-phase reactions with OH radical and similar to other models) exhibits a strong enhancement effect on simulated ASOA concentrations and this effect increases with the ambient OA concentrations. The CMAQ VBS implements a different SOA aging scheme that represents particle-phase oligomerization and has smaller impacts, or no impact, on total OA. A brief literature survey shows that different structure and/or parameters of the SOA aging schemes are being used in current models, which could greatly affect model simulations of OA in ways that are difficult to anticipate. Our results indicate that large uncertainties still exist in the simulation of SOA in current air quality models due to the aging schemes as well as uncertainties of the emission inventory. More sophisticated measurement data and/or chamber experiments are needed to better characterize SOA aging and constrain model parameterizations.

Modeling of secondary organic aerosols (SOA) based on two commonly used air quality models in China: Consistent S/IVOCs contribution but large differences in SOA aging

The formation and evolution of secondary organic aerosol during haze events in Beijing in wintertime

Secondary organic aerosols (SOA) produced in the atmosphere from sequential oxidation of biogenic or anthropogenic volatile organic compounds (VOC) represent a significant part of the atmospheric organic aerosol. Aerosol particles can act as cloud condensation nuclei or can be scavenged by cloud droplets, where organic carbon undergo chemical and biological transformations. Due to its high complexity, a nontargeted analysis by FT-ICR MS (Fourier-transform ion cyclotron resonance mass spectrometry) has been used to characterize the dissolved organic matter at a molecular level. SOA compounds have been detected in six aqueous samples collected in 2017 at the Puy de Dome station (PUY, France). SOA tracers, produced by VOC oxidation in environmental chambers or in ambient air and characterized in previous studies by mass spectrometry, were searched by FT-ICR MS in cloudwaters. Results clearly indicate the presence of oxidation products of isoprene, α- and β-pinene, and other monoterpenes and sesquiterpenes. I...

Abstract. Contrary to most regions in the US, ozone in the northern Front Range metropolitan area (NFRMA) of Colorado was either stagnant or increasing between 2000 and 2015, despite substantial reductions in NOx emissions. We used available long-term ozone and NOx data in the NFRMA to investigate these trends. Ozone increased from weekdays to weekends for a number of sites in the NFRMA with weekend reductions in NO2 at two sites in downtown Denver, indicating that the region was in a NOx-saturated ozone production regime. The stagnation and increases in ozone in the NFRMA are likely due to a combination of decreasing NOx emissions in a NOx-saturated environment and increased anthropogenic volatile organic compound (VOC) emissions in the NFRMA. Further investigation of the weekend–weekday effect showed that the region outside of the most heavily trafficked Denver area was transitioning to peak ozone production towards NOx-limited chemistry. This transition implies that continued NOx decreases will result in ozone being less sensitive to changes in either anthropogenic or biogenic VOC reactivity in the NFRMA. In contrast to anthropogenic VOCs, biogenic VOCs are unlikely to have increased in the NFRMA between 2000 and 2015, but are temperature dependent and likely vary by drought year. Ozone in the NFRMA has a temperature dependence, albeit smaller than many other US locations, consistent with biogenic VOC contributions to ozone production in the region. We show that while ozone increased with temperature in the NFRMA, which is consistent with a NOx-saturated regime coupled to temperature-dependent VOCs, this relationship is suppressed in drought years. We attribute this drought year suppression to decreased biogenic isoprene emissions due to long-term drought stress. Thus, while anthropogenic NOx and VOCs likely dominate ozone production regimes in the NFRMA, biogenic VOCs may also impact regional ozone and its temperature dependence.

Plants produce a variety of volatile organic compounds (VOCs). Under abiotic and biotic stresses, the number and amount of produced compounds can increase. Due to their long life span and large size, trees can produce biogenic VOCs (BVOCs) in much higher amounts than many other plants. It has been suggested that at cellular and tree physiological levels, induced production of VOCs is aimed at improving plant resistance to damage by reactive oxygen species generated by multiple abiotic stresses. In the few reported cases when biosynthesis of plant volatiles is inhibited or enhanced, the observed response to stress can be attributed to plant volatiles. Reported increase, e.g., in photosynthesis has mostly ranged between 5 and 50%. A comprehensive model to explain similar induction of VOCs under multiple biotic stresses is not yet available. As a result of pathogen or herbivore attack on forest trees, the induced production of VOCs is localized to the damage site but systemic induction of emissions has also been detected. These volatiles can affect fungal pathogens and the arrival rate of herbivorous insects on damaged trees, but also act as signalling compounds to maintain the trophic cascades that may improve tree fitness by improved efficiency of herbivore natural enemies. On the forest scale, biotic induction of VOC synthesis and release leads to an amplified flow of BVOCs in atmospheric reactions, which in atmospheres rich in oxides of nitrogen (NOx) results in ozone formation, and in low NOx atmospheres results in oxidation of VOCs, removal in ozone from the troposphere and the resulting formation of biogenic secondary organic aerosol (SOA) particles. I will summarize recent advances in the understanding of stress-induced VOC emissions from trees, with special focus on Populus spp. Particular importance is given to the ecological and atmospheric feedback systems based on BVOCs and biogenic SOA formation.

<strong class="journal-contentHeaderColor">Abstract.</strong> Secondary organic aerosol (SOA) is formed through the oxidation of volatile organic compounds (VOC), which can be of both natural and anthropogenic origin. While the hydroxyl radical (OH) and ozone (O₃) are the main atmospheric oxidants during the day, the nitrate radical (NO₃) becomes more important during the night time. Yet, atmospheric nitrate chemistry has received less attention compared to OH and O₃. The Nitrate Aerosol and Volatility Experiment (NArVE) aimed to study the NO₃-induced SOA formation and evolution from three biogenic VOCs (BVOC), namely isoprene, &alpha;-pinene and &beta;-caryophyllene. The volatility of aerosol particles was studied using isothermal evaporation chambers, temperature-dependent evaporation in a volatility tandem differential mobility analyzer (VTDMA), and thermal desorption in a filter inlet for gases and aerosols coupled to a chemical ionization mass spectrometer (FIGAERO-CIMS). Data from these three setups present a cohesive picture of the volatility of the SOA formed in the dark from the three biogenic precursors. Under our experimental conditions, the SOA formed from NO₃ + &alpha;-pinene was generally more volatile than SOA from &alpha;-pinene ozonolysis, while the NO₃ oxidation of isoprene produced similar, although slightly less volatile SOA than &alpha;-pinene under our experimental conditions. &beta;-caryophyllene reactions with NO₃ resulted in the least volatile species. Three different parametrizations for estimating the saturation vapor pressure of the oxidation products were tested for reproducing the observed evaporation in a kinetic modelling framework. Our results show that the SOA from nitrate oxidation of &alpha;-pinene or isoprene is dominated by low volatility organic compounds (LVOC) and semivolatile organic compounds (SVOC), while the corresponding SOA from &beta;-caryophyllene consists primarily of extremely low volatility organic compounds (ELVOC) and LVOC. The parameterizations yielded variable results in terms of reproducing the observed evaporation, and generally the comparisons pointed to a need for re-evaluating the treatment of the nitrate group in such parameterizations. Strategies for improving the predictive power of the volatility parameterizations, particularly in relation to the contribution from the nitrate group, are discussed.

Abstract. Organic nitrates are important atmospheric species that significantly affect the cycling of NOx and ozone production. However, characterization of particulate organic nitrates and their sources in polluted atmosphere is a big challenge and has not been comprehensively studied in Asia. In this study, an aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) was deployed at an urban site in China from 2015 to 2016 to characterize particulate organic nitrates in total nitrates with a high time resolution. Based on the cross-validation of two different data processing methods, organic nitrates were effectively quantified to contribute a notable fraction of organic aerosol (OA), namely 9 %–21 % in spring, 11 %–25 % in summer, and 9 %–20 % in autumn, while contributing a very small fraction in winter. The good correlation between organic nitrates and fresh secondary organic aerosol (SOA) at night, as well as the diurnal trend of size distribution of organic nitrates, indicated a key role of nighttime local secondary formation of organic nitrates. Furthermore, theoretical calculations of nighttime SOA production of NO3 reactions with volatile organic compounds (VOCs) measured during the spring campaign were performed, resulting in three biogenic VOCs (α-pinene, limonene, and camphene) and one anthropogenic VOC (styrene) identified as the possible key VOC precursors to particulate organic nitrates. The comparison with similar studies in the literature implied that nighttime particulate organic nitrate formation is highly relevant to NOx levels. This study proposes that unlike the documented cases in the United States and Europe, modeling nighttime particulate organic nitrate formation in China should incorporate not only biogenic VOCs but also anthropogenic VOCs for urban air pollution, which needs the support of relevant smog chamber studies in the future.

Chemical formation pathways of secondary organic aerosols in the Beijing-Tianjin-Hebei region in wintertime

Secondary organic aerosol (SOA) makes a sizable contribution to fine particulate matter (PM2.5) pollution, especially during episodic hours. Past studies of SOA evolution at episode-scale mainly rely on measurements of bulk SOA mass and few studies probe individual SOA molecular tracers. In this study, we continuously monitored at a bihourly resolution SOA tracers specific to a few common volatile organic compound (VOC) precursors at a suburban site in Hong Kong for four-month from the end of Aug. to Dec. 2020. The SOA molecules include tracers for SOA derived from biomass burning emissions, monoaromatics, naphthalene/methylnaphthalenes, and three biogenic VOCs (i.e., isoprene, monoterpene and sesquiterpene). Generally, the SOA tracers showed regional characteristics for both anthropogenic and biogenic SOA, as well as the biomass burning-derived SOA. This work focused on the seasonal variation and evolution characteristics of SOA tracers during eleven city-wide PM2.5 episodes, which are defined to be periods of PM2.5 exceeding 35 μg/m3 at three or more of the 15 general air quality monitoring stations cross the city. Mass increment ratios (MIR), calculated as the ratio of mass concentration between before and during an episode, were examined for individual species in each episode. During most episodes, the SOA tracers were enhanced in their concentrations (i.e., MIR > 1) and maximum MIR values were in the range of 5.5–11.0 for SOA tracers of different precursors. Episodes on summer and fall days showed notably larger MIR values than those falling on winter days, indicating a higher importance of SOA to formation of summer/fall PM2.5 episodes. Simultaneous monitoring of six tracers for isoprene SOA revealed the dominance of the low-NOx pathway in forming isoprene SOA in our study region. The multiple monoterpene SOA products suggested fresher SOA in winter, evidenced by an increased presence of the early generation products. The current study has shown by example the precursor-specific SOA chemical evolution characteristics during PM2.5 episodes in different seasons. This study also suggests the necessity to apply the high time resolution organic marker measurement at multiple sites to fully capture the spatial heterogeneity of the haze pollution at the city scale.

Abstract. Secondary organic aerosol (SOA) makes a sizable contribution to fine-particulate-matter (PM2.5) pollution, especially during high-PM episodes. Past studies of SOA evolution at the episode scale mainly rely on measurements of bulk SOA mass, with few studies probing individual SOA molecular tracers. In this study, we continuously monitored (at a bi-hourly resolution) SOA tracers specific to a few common volatile organic compound (VOC) precursors at a suburban site in Hong Kong for a 4-month period from the end of August to December 2020. The SOA molecules include tracers for SOA derived from biomass burning (BB) emissions, monoaromatics, naphthalene/methylnaphthalenes, and three biogenic VOCs (isoprene, monoterpene, and sesquiterpene). Generally, the SOA tracers showed regional characteristics for both anthropogenic and biogenic SOA as well as for the BB-derived SOA. This work focused on the seasonal variation and evolution characteristics of SOA tracers during 11 city-wide PM2.5 episodes, which are defined as periods with PM2.5 concentrations exceeding 35 µg m−3 at 3 or more of the 15 general air quality monitoring stations cross the city. Mass increment ratios (MIR), calculated as the ratio of the mass concentration prior to an episode to that during an episode, were examined for individual species during each episode. During most episodes, the SOA tracer concentrations were enhanced (i.e. MIR &gt;1), and the maximum MIR values were in the range of 5.5–11.0 for SOA tracers of different precursors. Episodes on summer and fall days showed notably larger MIR values than those falling on winter days, indicating the higher importance of SOA to the formation of summer/fall PM2.5 episodes. Simultaneous monitoring of six tracers for isoprene SOA revealed the dominance of the low-NOx pathway in forming isoprene SOA in our study region. The multiple monoterpene SOA products suggested fresher SOA in winter, evidenced by the increased presence of the early-generation products. Thus, the current study has shown by example the precursor-specific SOA chemical evolution characteristics during PM2.5 episodes in different seasons. This study also suggests the necessity to apply high-time-resolution organic marker measurement at multiple sites in order to fully capture the spatial heterogeneity of haze pollution at the city scale.

Abstract. The budget of atmospheric secondary organic aerosol (SOA) is very uncertain, with recent estimates suggesting a global source of between 12 and 1820 Tg (SOA) a−1. We used a dataset of aerosol mass spectrometer (AMS) observations from 34 different surface locations to evaluate the GLOMAP global chemical transport model. The standard model simulation (which included SOA from monoterpenes only) underpredicted organic aerosol (OA) observed by the AMS and had little skill reproducing the variability in the dataset. We simulated SOA formation from biogenic (monoterpenes and isoprene), lumped anthropogenic and lumped biomass burning volatile organic compounds (VOCs) and varied the SOA yield from each precursor source to produce the best overall match between model and observations. We assumed that SOA is essentially non-volatile and condenses irreversibly onto existing aerosol. Our best estimate of the SOA source is 140 Tg (SOA) a−1 but with a large uncertainty range which we estimate to be 50–380 Tg (SOA) a−1. We found the minimum in normalised mean error (NME) between model and the AMS dataset when we assumed a large SOA source (100 Tg (SOA) a−1) from sources that spatially matched anthropogenic pollution (which we term antropogenically controlled SOA). We used organic carbon observations compiled by Bahadur et al. (2009) to evaluate our estimated SOA sources. We found that the model with a large anthropogenic SOA source was the most consistent with these observations, however improvement over the model with a large biogenic SOA source (250 Tg (SOA) a−1) was small. We used a dataset of 14C observations from rural locations to evaluate our estimated SOA sources. We estimated a maximum of 10 Tg (SOA) a−1 (10 %) of the anthropogenically controlled SOA source could be from fossil (urban/industrial) sources. We suggest that an additional anthropogenic source is most likely due to an anthropogenic pollution enhancement of SOA formation from biogenic VOCs. Such an anthropogenically controlled SOA source would result in substantial climate forcing. We estimated a global mean aerosol direct effect of −0.26 ± 0.15 Wm−2 and indirect (cloud albedo) effect of −0.6+0.24−0.14 Wm−2 from anthropogenically controlled SOA. The biogenic and biomass SOA sources are not well constrained with this analysis due to the limited number of OA observations in regions and periods strongly impacted by these sources. To further improve the constraints by this method, additional OA observations are needed in the tropics and the Southern Hemisphere.