Organic Aerosol Concentrations Research Articles

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

A regional air quality model system (RAQMS) with a volatility basis set approach for secondary organic aerosol (SOA) formation and an emission inventory of semi-volatile (SVOC) and intermediate volatile organic compounds (IVOC) are applied to investigate the distribution and evolution of organic aerosols over the Beijing-Tianjin-Hebei (BTH) region in winter 2014, with focus on Beijing. Model validation demonstrates the model is capable of reproducing meteorological variables and major aerosol components, and the model significantly improves SOA and organic aerosol (OA) simulations by taking S/IVOCs (SVOC + IVOC) and relevant aging processes into account. SVOC and IVOC emissions in the BTH region are estimated to be 0.47 Tg and in a range of 0.09–0.36 Tg, respectively, which are about 18% and 4–14% of the emission amounts of volatile organic compounds (VOCs). The distribution of mean organic aerosols is characterized by a high concentration belt oriented southwest-northeast from southern Hebei to Beijing, with the maximum concentration up to 50 μg m−3 in Beijing and Shijiazhuang. The simulated SOA concentration is comparable in magnitude to primary organic aerosol (POA) concentration, and the SOA/OA ratio is around 50% in most areas of the BTH region. In terms of domain average, the percentage contributions to SOA mass concentration from anthropogenic volatile organic compounds (AVOCs), SVOCs, IVOCs and biogenic VOCs are estimated to be 46.1%, 40.1%, 9.4% and 4.4%, respectively, in the BTH region during the study period, which indicates an important role of S/IVOCs in SOA formation. From clean to haze periods, both POA and SOA concentrations apparently increase, with an increasing (decreasing) trend of the SOA/OA (POA/OA) ratio. SOA dominates over POA in fine organic aerosols during the haze periods. The increase of POA in hazy days is mainly due to the weakened vertical diffusion and accumulation near the surface, whereas the increase of SOA is likely attributed to both the reduced diffusivity and a series of competing chemical processes, in which the decreased photolysis rate by aerosol attenuation tends to decrease SOA concentration by about 6% during the most severe haze day, whereas the lower surface air temperature and higher POA and S/IVOC concentrations in haze days both enhance gas to particle partition, and consequently lead to higher SOA concentration.

Retrofitting and re-powering as a control strategies for curtailment of exposure of underground miners to diesel aerosols.

A study was conducted to examine the potential of diesel emissions control strategies based on retrofitting existing power packages with exhaust aftertreatment devices and repowering with advanced power packages. The retrofit systems, a diesel oxidation catalyst (DOC) and diesel particulate filter (DPF), were evaluated individually using a US EPA tier 2 (ter 2) engine operated under four steady-state conditions and one transient cycle. The DOC effectively curtailed emissions of CO, and to some extent organic carbon (OC), elemental carbon (EC), and aerosol number concentration. The DPF system offered substantially higher reductions in OC and EC mass and aerosol number concentrations. Both, the DOC and DPF achieved reductions in the aforementioned emissions without adversely affecting emissions of NO2 and nano-sized aerosols. The strategy of repowering with an advanced system was examined using a US EPA tier 4 final (tier 4f) engine equipped with a cooled exhaust gas recirculation system and diesel exhaust fluid-based selective catalytic reduction system, but not with a DPF system. The tier 4f engine contributed substantially less than the tier 2 engine to the EC and OC mass, aerosol number, and CO, NO, and NO2 concentrations. The tier 4f engine was very effective in reducing aerosol mass, NO, and NO2 concentrations, but it was not equally effective in reducing aerosol number concentrations. The implementation of viable exhaust after treatment systems and advanced diesel power packages could be instrumental to the underground mining industry to secure a clean, economical, and dependable source of power for mobile equipment.

Biogenic secondary organic aerosol sensitivity to organic aerosol simulation schemes in climate projections

Abstract. Organic aerosol (OA) can have important impacts on air quality and human health because of its large contribution to atmospheric fine aerosol and its chemical composition, including many toxic compounds. Simulation of this type of aerosol is difficult, since there are many unknowns in its nature and mechanism and processes involved in its formation. These uncertainties become even more important in the context of a changing climate because different mechanisms, and their representation in atmospheric models, imply different sensitivities to changes in climate variables. In this work, the effects caused by using different schemes to simulate OA are explored. Three schemes are used in this work: (1) a molecular scheme; (2) a standard volatility basis set (VBS) scheme with anthropogenic aging; and (3) a modified VBS scheme containing functionalization, fragmentation and formation of nonvolatile secondary organic aerosol (SOA) for all semi-volatile organic compounds (SVOCs). Five years of historic and five years of future simulations were performed using the RCP8.5 climatic scenario. The years were chosen in a way to maximize the differences between future and historic simulations. The study focuses on biogenic SOA (BSOA), since the contribution of this fraction of BSOA among OA is major in both historic and future scenarios (40 % to 78 % for different schemes in historic simulations). Simulated OA and BSOA concentrations with different schemes are different, with the molecular scheme showing the highest concentrations among the three schemes. The comparisons show that for the European area, the modified VBS scheme shows the highest relative change between future and historic simulations, while the molecular scheme shows the lowest (a factor of 2 lower). These changes are largest over the summer period for BSOA because the higher temperatures increase terpene and isoprene emissions, the major precursors of BSOA. This increase is partially offset by a temperature-induced shift of SVOCs to the gas phase. This shift is indeed scheme dependent, and it is shown that it is the least pronounced for the modified VBS scheme including a full suite of aerosol aging processes, comprising also formation of nonvolatile aerosol. For the Mediterranean Sea, without BVOC emissions, the OA changes are less pronounced and, at least on an annual average, more similar between different schemes. Our results warrant further developments in organic aerosol schemes used for air quality modeling to reduce their uncertainty, including sensitivity to climate variables (temperature).

Influence of High Relative Humidity on Secondary Organic Carbon: Observations at a Background Site in East China

To investigate the impacts of relative humidity (RH) on secondary organic aerosol (SOA) concentrations and chemical reactions, the carbonaceous aerosol components [i.e., organic carbon (OC) and element carbon (EC)] were quantified in daily PM2.5 samples collected at a background site in East China during summer 2015. Based on the method of EC-tracer, the concentration of secondary organic carbon (SOC) demonstrated an obvious negative relationship with RH higher than 60%. Moreover, the ratio of SOC/EC also exhibited obvious decreasing trends with increasing RH, indicating negative effects for chemical production of SOA under high RH conditions. Due to high RH, photochemistry was weakened, gaseous oxidant concentrations was lowered (e.g., significantly decreased O3 levels), and the production rates of SOA were relatively low. On the other hand, because of more water uptake under higher RH conditions, the aerosol droplet acidity was reduced and enhancement of SOA formation by acidity was accordingly absent. In addition, high RH also plays an important role in changing viscosity of pre-existing aerosol coatings, which can affect reactive uptake yield of SOA. Overall, the results from this study imply that SOA production may be more associated with photochemical processes, while aqueous-phase chemistry is not very important for some SOA formation in a moist ambient environment. In the ambient atmosphere, oxidant concentrations, reaction rates, airborne species, etc., are highly variable. How do these factors affect SOA yields under given ambient environment warrants further detailed investigations.

Nonlinear behavior of organic aerosol in biomass burning plumes: a microphysical model analysis

Abstract. Organic aerosol (OA) is a major component of smoke plumes from open biomass burning (BB). Therefore, adequate representation of the atmospheric transformations of BB OA in chemistry-transport and climate models is an important prerequisite for accurate estimates of the impact of BB emissions on air quality and climate. However, field and laboratory studies of atmospheric transformations (aging) of BB OA have yielded a wide diversity of observed effects. This diversity is still not sufficiently understood and thus not addressed in models. As OA evolution is governed by complex nonlinear processes, it is likely that at least a part of the observed variability in the BB OA aging effects is due to the factors associated with the intrinsic nonlinearity of the OA system. In this study, we performed a numerical analysis in order to gain a deeper understanding of these factors. We employ a microphysical dynamic model that represents gas–particle partitioning and OA oxidation chemistry within the volatility basis set (VBS) framework and includes a schematic parameterization of BB OA dilution due to dispersion of an isolated smoke plume. Several VBS schemes of different complexity, which have been suggested in the literature to represent BB OA aging in regional and global chemistry-transport models, are applied to simulate BB OA evolution over a 5 d period representative of the BB aerosol lifetime in the dry atmosphere. We consider the BB OA mass enhancement ratio (EnR), which is defined as the ratio of the mass concentration of BB OA to that of an inert tracer and allows us to eliminate the linear part of the dilution effects. We also analyze the behavior of the hygroscopicity parameter, κ, that was simulated in a part of our numerical experiments. As a result, five qualitatively different regimes of OA evolution are identified, which comprise (1) a monotonic saturating increase in EnR, (2) an increase in EnR followed by a decrease, (3) an initial rapid decrease in EnR followed by a gradual increase, (4) an EnR increase between two intermittent stages of its decrease, or (5) a gradual decrease in EnR. We find that the EnR for BB aerosol aged from a few hours to a few tens of hours typically increases for larger initial sizes of the smoke plume (and therefore smaller dilution rates) or for lower initial OA concentrations (and thus more organic gases available to form secondary OA – SOA). However, these dependencies can be weakened or even reversed, depending on the BB OA age and on the ratio between the fragmentation and functionalization oxidation pathways. Nonlinear behavior of BB OA is also exhibited in the dependencies of κ on the parameters of the plume. Application of the different VBS schemes results in large quantitative and qualitative differences between the simulations, although our analysis suggests also that the main qualitative features of OA evolution simulated with a complex two-dimensional VBS scheme can also be reproduced with a much simpler scheme. Overall, this study indicates that the BB aerosol evolution may strongly depend on parameters of the individual BB smoke plumes (such as the initial organic aerosol concentration and plume size) that are typically not resolved in chemistry-transport models.

Light absorption properties and potential sources of particulate brown carbon in the Pearl River Delta region of China

Abstract. Brown carbon (BrC) is a special type of organic aerosol (OA), capable of absorbing solar radiation from near-ultraviolet (UV) to visible wavelengths, which may lead to an increased aerosol radiative effect in the atmosphere. While high concentrations of OAs have been observed in the Pearl River Delta (PRD) region of China, the optical properties and corresponding radiative forcing of BrC in the PRD are still not well understood. In this work, we conducted a set of comprehensive measurements of atmospheric particulate matter from 29 November 2014 to 2 January 2015 to investigate aerosol compositions, optical properties, source origins, and radiative forcing effects at a suburban station in Guangzhou. The particle absorption Ångström exponent (AAE) was deduced and utilized to distinguish light absorption by BrC from that by black carbon (BC). The results showed that the average absorption contributions of BrC were 34.1±8.0 % at 370 nm, 23.7±7.3 % at 470 nm, 16.0±6.7 % at 520 nm, 13.0±5.4 % at 590 nm, and 8.7±4.3 % at 660 nm. A sensitivity analysis of the evaluation of the absorption Ångström exponent of BC (AAEBC) was conducted based on the Mie theory calculation assuming that the BC-containing aerosol was mixed with the core–shell and external configurations. The corresponding uncertainty in AAEBC was acquired. We found that variations in the imaginary refractive index (RI) of the BC core can significantly affect the estimation of AAEBC. However, AAEBC was relatively less sensitive to the real part of the RI of the BC core and was least sensitive to the real part of the RI of the non-light-absorbing shell. BrC absorption was closely related to aerosol potassium cation content (K+), a common tracer of biomass burning emissions, which was most likely associated with straw burning in the rural area of the western PRD. Diurnal variation in BrC absorption revealed that primary organic aerosols had a larger BrC absorption capacity than secondary organic aerosols (SOAs). Radiative transfer simulations showed that BrC absorption may cause 2.3±1.8 W m−2 radiative forcing at the top of the atmosphere (TOA) and contribute to 15.8±4.4 % of the aerosol warming effect. A chart was constructed to conveniently assess the BrC radiative forcing efficiency in the studied area with reference to certain aerosol single-scattering albedo (SSA) and BrC absorption contributions at various wavelengths. Evidently, the BrC radiative forcing efficiency was higher at shorter wavelengths.

Source apportionment of organic pollutants in fine and coarse atmospheric particles in Doha, Qatar

ABSTRACT In this study, we investigated the sources of organic pollutants associated with fine (PM2.5) and coarse (PM2.5–10) atmospheric particulate matter in Doha, Qatar based on an eight-month sampling campaign conducted from May to December 2015. Multiple organic compound tracers including 36 PAH members, 25 n-alkane homologs, 17 hopanes, and 12 steranes were used for organic aerosols source apportionment. Source apportionment based on specific molecular markers, molecular diagnostic ratios/indices, and positive matrix factorization (PMF) modeling showed that similar sources are responsible for both fine- and coarse-particle organic pollutants. PMF analysis showed that biogenic aerosols, fugitive dust emissions, gasoline engine emissions, diesel engine emissions, and heavy oil combustion were the five main pollution sources of organic aerosols, which agreed well with the results from the diagnostic ratios analysis. The conditional bivariate probability functions (CPF) and potential source contribution function (PSCF) indicated that both regional (i.e., mixed biogenic/secondary particles and oil refinery/shipping emissions) and local sources contributed to airborne organic aerosol concentrations observed at the site, depending on the wind speed and direction. It appears that the relatively high levels of organic pollutants were contributed by local anthropogenic sources, such as fossil fuel combustion, vehicular emissions, and fugitive dust emissions. The high levels of local contributions indicated that there might be great opportunities for Qatar to considerably reduce emissions so that population exposures to carbonaceous aerosols and the public health risks associated with air pollution can be minimized. Implications: Multiple organic tracers and various source apportionment techniques have been used for convincing source apportionment. It was found that both long-range and local sources have a significant impact on atmospheric carbonaceous particles in the area, depending on the wind conditions. Relatively high levels of organic pollutants attributed to local anthropogenic sources indicate that there are great opportunities for Qatar to establish and implement more efficient pollution control measures and policies. Regional sources such as petroleum refineries and shipping-vessels emissions in the Gulf region should also be regulated and managed through regional cooperation to improve the air quality in the region.

Quantification of the impact of cooking processes on indoor concentrations of volatile organic species and primary and secondary organic aerosols.

Cooking is recognized as an important source of particulate pollution in indoor and outdoor environments. We conducted more than 100 individual experiments to characterize the particulate and non‐methane organic gas emissions from various cooking processes, their reaction rates, and their secondary organic aerosol yields. We used this emission data to develop a box model, for simulating the cooking emission concentrations in a typical European home and the indoor gas‐phase reactions leading to secondary organic aerosol production. Our results suggest that about half of the indoor primary organic aerosol emission rates can be explained by cooking. Emission rates of larger and unsaturated aldehydes likely are dominated by cooking while the emission rates of terpenes are negligible. We found that cooking dominates the particulate and gas‐phase air pollution in non‐smoking European households exceeding 1000 μg m−3. While frying processes are the main driver of aldehyde emissions, terpenes are mostly emitted due to the use of condiments. The secondary aerosol production is negligible with around 2 μg m−3. Our results further show that ambient cooking organic aerosol concentrations can only be explained by super‐polluters like restaurants. The model offers a comprehensive framework for identifying the main parameters controlling indoor gas‐ and particle‐phase concentrations.

Is water vapor a key player of the wintertime haze in North China Plain?

Abstract. Water vapor has been proposed to amplify the severe haze pollution in China by enhancing the aerosol–radiation feedback (ARF). Observations have revealed that the near-surface PM2.5 concentrations ([PM2.5]) generally exhibit an increasing trend with relative humidity (RH) in the North China Plain (NCP) during 2015 wintertime, indicating that the aerosol liquid water (ALW) caused by hygroscopic growth could play an important role in the PM2.5 formation and accumulation. Simulations during a persistent and heavy haze pollution episode from 5 December 2015 to 4 January 2016 in the NCP were conducted using the WRF-Chem Model to comprehensively quantify contributions of the ALW effect to near-surface [PM2.5]. The WRF-Chem Model generally performs reasonably well in simulating the temporal variations in RH against measurements in the NCP. The factor separation approach (FSA) was used to evaluate the contribution of the ALW effect on the ARF, photochemistry, and heterogeneous reactions to [PM2.5]. The ALW not only augments particle sizes to enhance aerosol backward scattering but also increases the effective radius to favor aerosol forward scattering. The contribution of the ALW effect on the ARF and photochemistry to near-surface [PM2.5] is not significant, being generally within 1.0 µg m−3 on average in the NCP during the episode. Serving as an excellent substrate for heterogeneous reactions, the ALW substantially enhances the secondary aerosol (SA) formation, with an average contribution of 71 %, 10 %, 26 %, and 48 % to near-surface sulfate, nitrate, ammonium, and secondary organic aerosol concentrations. Nevertheless, the SA enhancement due to the ALW decreases the aerosol optical depth and increases the effective radius to weaken the ARF, reducing near-surface primary aerosols. The contribution of the ALW total effect to near-surface [PM2.5] is 17.5 % on average, which is overwhelmingly dominated by enhanced SA. Model sensitivities also show that when the RH is less than 80 %, the ALW progressively increases near-surface [PM2.5] but commences to decrease when the RH exceeds 80 % due to the high occurrence frequencies of precipitation.

Investigating secondary organic aerosol formation pathways in China during 2014

The concentrations of organic aerosol (OA) in central and eastern China are much higher than those in Europe and North America. Compared with observations, recent numerical modeling studies have largely underestimated the concentrations of OA, especially the secondary components. Based on the volatility basis set framework, a secondary OA (SOA) module is developed and coupled into the nested air quality prediction modeling system (NAQPMS). This model is applied to investigate the concentration and formation pathways of SOA in central and eastern China during 2014, and the simulation performance is validated through observation. The oxidation of intermediate volatile organic compounds (IVOCs) is significant to SOA formation and could reduce the great discrepancy between simulations and observations. In winter, the contribution of IVOCs accounted for 60%–80% of SOA formation. In spring and autumn, IVOCs and volatile organic compounds (VOCs) have a considerable effect on SOA formation. In summer, the contributions of VOCs reach 40%–60% due to an increase in the emissions of biogenic VOCs. The mass yields and other parameters of IVOCs remain largely uncertain. By using the latest mass yields obtained from chamber experiments, the simulated SOA concentrations in winter increase by 10–20 μg m−3 compared with the base scenario. To more thoroughly understand SOA formation in China, further research on the emission sources and mass yields of IVOCs is warranted.

Investigating the Urban Air Quality Effects of Cool Walls and Cool Roofs in Southern California.

Solar reflective cool roofs and walls can be used to mitigate the urban heat island effect. While many past studies have investigated the climate impacts of adopting cool surfaces, few studies have investigated their effects on air pollution, especially on particulate matter (PM). This research for the first time investigates the influence of widespread deployment of cool walls on urban air pollutant concentrations, and systematically compares cool wall to cool roof effects. Simulations using a coupled meteorology-chemistry model (WRF-Chem) for a representative summertime period show that cool walls and roofs can reduce urban air temperatures, wind speeds, and planetary boundary heights in the Los Angeles Basin. Consequently, increasing wall (roof) albedo by 0.80, an upper bound scenario, leads to maximum daily 8-h average ozone concentration reductions of 0.35 (0.83) ppbv in Los Angeles County. However, cool walls (roofs) increase daily average PM2.5 concentrations by 0.62 (0.85) μg m-3. We investigate the competing processes driving changes in concentrations of speciated PM2.5. Increases in primary PM (elemental carbon and primary organic aerosols) concentrations can be attributed to reductions in ventilation of the Los Angeles Basin. Increases in concentrations of semivolatile species (e.g., nitrate) are mainly driven by increases in gas-to-particle conversion due to reduced atmospheric temperatures.

More Than Emissions and Chemistry: Fire Size, Dilution, and Background Aerosol Also Greatly Influence Near‐Field Biomass Burning Aerosol Aging

AbstractBiomass burning emits particles (black carbon and primary organic aerosol) and precursor vapors to the atmosphere that chemically and physically age in the atmosphere. This theoretical study explores the relationships between fire size (determining the initial plume width and concentration), dilution rate, and entrainment of background aerosol on particle coagulation, organic aerosol (OA) evaporation, and secondary organic aerosol (SOA) condensation in smoke plumes. We examine the impacts of these processes on aged smoke OA mass, geometric mean diameter (Dg), peak lognormal modal width (σg), particle extinction (E), and cloud condensation nuclei (CCN) concentrations. In our simulations, aging OA mass is controlled by competition between OA evaporation and SOA condensation. Large, slowly diluting plumes evaporate little in our base set of simulations, which may allow for net increases in mass, E, CCN , and Dg from SOA condensation. Smaller, quickly diluting fire plumes lead to faster evaporation, which favors decreases in mass, E, CCN, and Dg. However, the SOA fraction of the smoke OA increases more rapidly in smaller fires due to faster primary organic aerosol evaporation leading to more SOA precursors. Net mass changes for smaller fires depend on background OA concentrations; increasing background aerosol concentrations decrease evaporation rates. Although coagulation does not change mass, it can decrease the number of particles in large/slowly diluting plumes, increasing Dg and E, and decreasing σg. While our conclusions are limited by being a theoretical study, we hope they help motivate future smoke‐plume analyses to consider the effects of fire size, meteorology, and background OA concentrations.

Assessment of dicarbonyl contributions to secondary organic aerosols over China using RAMS-CMAQ

Abstract. The concentration of secondary organic aerosol (SOA) is underestimated in current model studies. Recent research suggests that the reactive uptake of dicarbonyls contributes to the production of SOA, although few models have included this pathway. Glyoxal, an important representative component of dicarbonyls in models, is significantly underestimated. We therefore incorporated the reactive uptake of dicarbonyls into the regional air quality modeling system RAMS-CMAQ (the Regional Atmospheric Modeling System-Community Multiscale Air Quality) to evaluate the contribution of dicarbonyls to SOA, and we then assess the impact of the underestimation of glyoxal on the production of SOA in China during two time periods: 3 June to 11 July 2014 (episode 1) and 14 October to 14 November 2014 (episode 2). When the reactive uptake process was added, the modeled mean concentration of SOA in episode 1 increased by 3.65 µg m−3, which explained 34.8 % of the unaccounted-for source of SOA. Meanwhile the increase in the concentration of SOA in episode 2 was 1.82 µg m−3 as a result of the lower liquid water content and the lower amount of dicarbonyls produced from biogenic precursors in the fall. On this basis, when the glyoxal simulation was improved, the modeled mean dicarbonyl-derived SOA (AAQ) increased by more than a factor of 2 in both episodes relative to case 1. AAQ in episode 1 contributed, on average, 60.6 % of the total concentration of SOA and the increase in this contribution represented 69.1 % of the unaccounted-for concentration of SOA, whereas the mean AAQ in episode 2 accounted for 64.5 % of total concentration of SOA. Based on the results, the mean AAQ over China was generally higher in the east than in the west during the two episodes. The highest value (10–15 µg m−3) of episode 1 appeared in the areas around the lower reaches of the Yellow River, whereas the highest value of 5–10 µg m−3 in episode 2 was concentrated over regions from south of the lower reaches of the Yellow River to the south of Guangzhou Province as well as the Sichuan Basin. The contribution of AAQ to the concentration of SOA in episode 1 varied from 10 % to 90 % throughout China, with the highest contributions (70 %–90 %) in the coastal regions and offshore along the East China Sea to the South China Sea and in the southwestern regions. The fraction of AAQ to SOA in episode 2 was in the range of 10 %–80 % over China, with the fraction up to 80 % in a small portion of northeastern China.

Predicting the importance of oxidative aging on indoor organic aerosol concentrations using the two-dimensional volatility basis set (2D-VBS).

Organic aerosol (OA) is chemically dynamic, continuously evolving by oxidative chemistry, for instance, via hydroxyl radical (OH) reactions. Studies have explored this evolution (so-called OA aging) in the atmosphere, but none have investigated it indoors. Aging organic molecules in both particle and gas-phases undergo changes in oxygen content and volatility, which may ultimately either enhance or reduce the condensed-phase OA concentration (COA ). This work models OH-induced aging using the two-dimensional volatility basis set (2D-VBS) within an indoor model and explores its significance on COA relative to prior modeling methodologies which neglect aging transformations. Lagrangian, time-averaged, and transient indoor simulations were conducted. The time-averaged simulations included a Monte Carlo procedure and sensitivity analysis, using input distributions typical of U.S. residences. Results demonstrate that indoors, aging generally leads to COA augmentation. The extent to which this is significant is conditional upon several factors, most notably temperature, OH exposure, and OA mass loading. Time-averaged COA was affected minimally in typical residences (<5% increase). However, some plausible cases may cause stronger COA enhancements, such as in a sunlit room where photolysis facilitates significant OH production (~20% increase), or during a transient OH-producing cleaning event (~35% peak increase).

Impacts of six potential HONO sources on HOx budgets and SOA formation during a wintertime heavy haze period in the North China Plain

The Weather Research and Forecasting/Chemistry (WRF-Chem) model updated with six potential HONO sources (i.e., traffic, soil, biomass burning and indoor emissions, and heterogeneous reactions on aerosol and ground surfaces) was used to quantify the impact of the six potential HONO sources on the production and loss rates of OH and HO2 radicals and the concentrations of secondary organic aerosol (SOA) in the Beijing-Tianjin-Heibei (BTH) region of China during a winter heavy haze period of Nov. 29–Dec. 3, 2017. The updated WRF-Chem model well simulated the observed HONO concentrations at the Wangdu site, especially in the daytime, and well reproduced the observed diurnal variations of regional-mean O3 in the BTH region. The traffic emission source was an important HONO source during nighttime but not significant during daytime, heterogeneous reactions on ground/aerosol surfaces were important during nighttime and daytime. We found that the six potential HONO sources led to a significant enhancement in the dominant production and loss rates of HOx on the wintertime heavy haze and nonhaze days (particularly on the heavy haze day), an enhancement of 5–25 μg m−3 (75–200%) in the ground SOA in the studied heavy haze event, and an enhancement of 2–15 μg m−3 in the meridional-mean SOA on the heavy haze day, demonstrating that the six potential HONO sources accelerate the HOx cycles and aggravate haze events. HONO was the key precursor of primary OH in the BTH region in the studied wintertime period, and the photolysis of HONO produced a daytime mean OH production rate of 2.59 ppb h−1 on the heavy haze day, much higher than that of 0.58 ppb h−1 on the nonhaze day. Anthropogenic SOA dominated in the BTH region in the studied wintertime period, and its main precursors were xylenes (42%), BIGENE (31%) and toluene (21%).

Simulation of summer ozone and its sensitivity to emission changes in China

Rapid economic growth and associated emission increase in China have led to severe air pollution in recent decades. As fine particulate matter concentration is decreasing due to strict control measures, ozone (O3) concentration has an increasing trend with adverse effects on human health and ecosystems. In this study, the Community Multi-scale Air Quality (CMAQ) model was used to investigate the formation of O3 in China during three high concentration episodes in summer 2013 and analyzed its sensitivity to emission changes. Compared with observation data, O3 performance met the EPA criteria of mean normalized bias (MNB) within ±0.15 in major parts of China including five megacities. The diurnal variation of O3 had similar trend with temperature. The August episode (6–12) had the highest daily maximum 1-h O3 of ∼100 ppb in North China Plain (NCP), while the July episode (11–19) had the lowest concentrations of ∼50 ppb. The O3 production rates (OPR) were higher at NCP and the Yangzi River Delta (YRD), but O3 production efficiencies (OPE) acted in contrary. O3 isopleth showed that NOx controlled O3 concentration in most areas of China. Reducing VOC would have minor effects on O3 concentrations while reducing NOx could largely reduce O3 concentration except for urban areas such as Shanghai and Guangzhou. Linear correlations were observed between secondary organic aerosol (SOA) and Ox (O3+NO2) concentrations in August at Shanghai and Guangzhou, indicating correlations between O3 and other photochemical compounds. This study provides valuable information for designing effective control strategies for O3 in China.

Precursors and formation of secondary organic aerosols from wildfires in the Euro-Mediterranean region

Abstract. This work aims at quantifying the relative contribution of secondary organic aerosol (SOA) precursors emitted by wildfires to organic aerosol (OA) formation during summer of 2007 over the Euro-Mediterranean region, where intense wildfires occurred. A new SOA formation mechanism, H2Oaro, including recently identified aromatic volatile organic compounds (VOCs) emitted from wildfires, is developed based on smog chamber experiment measurements under low- and high-NOx regimes. The aromatic VOCs included in the mechanism are toluene, xylene, benzene, phenol, cresol, catechol, furan, naphthalene, methylnaphthalene, syringol, guaiacol, and structurally assigned and unassigned compounds with at least six carbon atoms per molecule (USC&gt;6). This mechanism H2Oaro is an extension of the H2O (hydrophilic–hydrophobic organic) aerosol mechanism: the oxidation of the precursor forms surrogate species with specific thermodynamic properties (volatility, oxidation degree and affinity to water). The SOA concentrations over the Euro-Mediterranean region in summer of 2007 are simulated using the chemistry transport model (CTM) Polair3D of the air-quality platform Polyphemus, where the mechanism H2Oaro was implemented. To estimate the relative contribution of the aromatic VOCs, intermediate volatility, semi-volatile and low-volatility organic compounds (I/S/L-VOCs), to wildfires OA concentrations, different estimations of the gaseous I/S/L-VOC emissions (from primary organic aerosol – POA – using a factor of 1.5 or from non-methanic organic gas – NMOG – using a factor of 0.36) and their ageing (one-step oxidation vs. multi-generational oxidation) are also tested in the CTM. Most of the particle OA concentrations are formed from I/S/L-VOCs. On average during the summer of 2007 and over the Euro-Mediterranean domain, they are about 10 times higher than the OA concentrations formed from VOCs. However, locally, the OA concentrations formed from VOCs can represent up to 30 % of the OA concentrations from biomass burning. Amongst the VOCs, the main contributors to SOA formation are phenol, benzene and catechol (CAT; 47 %); USC&gt;6 compounds (23 %); and toluene and xylene (12 %). Sensitivity studies of the influence of the VOCs and the I/S/L-VOC emissions and chemical ageing mechanisms on PM2.5 concentrations show that surface PM2.5 concentrations are more sensitive to the parameterization used for gaseous I/S/L-VOC emissions than for ageing. Estimating the gaseous I/S/L-VOC emissions from POA or from NMOG has a high impact on local surface PM2.5 concentrations (reaching −30 % in the Balkans, −8 % to −16 % in the fire plume and +8 % to +16 % in Greece). Considering the VOC as SOA precursors results in a moderate increase in PM2.5 concentrations mainly in the Balkans (up to 24 %) and in the fire plume (+10 %).

Effects of two different biogenic emission models on modelled ozone and aerosol concentrations in Europe

Abstract. Biogenic volatile organic compound (BVOC) emissions are one of the essential inputs for chemical transport models (CTMs), but their estimates are associated with large uncertainties, leading to significant influence on air quality modelling. This study aims to investigate the effects of using different BVOC emission models on the performance of a CTM in simulating secondary pollutants, i.e. ozone, organic, and inorganic aerosols. European air quality was simulated for the year 2011 by the regional air quality model Comprehensive Air Quality Model with Extensions (CAMx) version 6.3, using BVOC emissions calculated by two emission models: the Paul Scherrer Institute (PSI) model and the Model of Emissions of Gases and Aerosol from Nature (MEGAN) version 2.1. Comparison of isoprene and monoterpene emissions from both models showed large differences in their general amounts, as well as their spatial distribution in both summer and winter. MEGAN produced more isoprene emissions by a factor of 3 while the PSI model generated 3 times the monoterpene emissions in summer, while there was negligible difference (∼4 %) in sesquiterpene emissions associated with the two models. Despite the large differences in isoprene emissions (i.e. 3-fold), the resulting impact in predicted summertime ozone proved to be minor (&lt;10 %; MEGAN O3 was higher than PSI O3 by ∼7 ppb). Comparisons with measurements from the European air quality database (AirBase) indicated that PSI emissions might improve the model performance at low ozone concentrations but worsen performance at high ozone levels (&gt;60 ppb). A much larger effect of the different BVOC emissions was found for the secondary organic aerosol (SOA) concentrations. The higher monoterpene emissions (a factor of ∼3) by the PSI model led to higher SOA by ∼110 % on average in summer, compared to MEGAN, and lead to better agreement between modelled and measured organic aerosol (OA): the mean bias between modelled and measured OA at nine measurement stations using Aerodyne aerosol chemical speciation monitors (ACSMs) or Aerodyne aerosol mass spectrometers (AMSs) was reduced by 21 %–83 % at rural or remote stations. Effects on inorganic aerosols (particulate nitrate, sulfate, and ammonia) were relatively small (&lt;15 %).

Wintertime secondary organic aerosol formation in Beijing–Tianjin–Hebei (BTH): contributions of HONO sources and heterogeneous reactions

Abstract. Organic aerosol (OA) concentrations are simulated over the Beijing–Tianjin–Hebei (BTH) region from 9 to 26 January 2014 using the Weather Research and Forecasting model coupled with chemistry (WRF-CHEM), with the goal of examining the impact of heterogeneous HONO sources on SOA formation and SOA formation from different pathways during wintertime haze days. The model generally shows good performance with respect to simulating air pollutants and organic aerosols against measurements in BTH. Model results show that heterogeneous HONO sources substantially enhance near-surface SOA formation, increasing the regional average near-surface SOA concentration by about 46.3 % during the episode. Oxidation and partitioning of primary organic aerosols treated as semi-volatile dominate SOA formation, contributing 58.9 % of the near-surface SOA mass in BTH. Irreversible uptake of glyoxal and methylglyoxal on aerosol surfaces constitutes the second most important SOA formation pathway during the episode, with the SOA contribution increasing from 8.5 % under non-haze conditions to 30.2 % under haze conditions. Additionally, direct emissions of glyoxal and methylglyoxal from residential sources contribute about 25.5 % of the total SOA mass on average in BTH. Our study highlights the importance of heterogeneous HONO sources and primary residential emissions of glyoxal and methylglyoxal to SOA formation over the BTH region in winter.

Modeling organic aerosol concentrations and properties during winter 2014 in the northwestern Mediterranean region

Abstract. Organic aerosols are measured at a remote site (Ersa) on the cape of Corsica in the northwestern Mediterranean basin during the winter campaign of 2014 of the CHemistry and AeRosols Mediterranean EXperiment (CharMEx), when high organic concentrations from anthropogenic origins are observed. This work aims to represent the observed organic aerosol concentrations and properties (oxidation state) using the air-quality model Polyphemus with a surrogate approach for secondary organic aerosol (SOA) formation. Because intermediate and semi-volatile organic compounds (I/S-VOCs) are the main precursors of SOAs at Ersa during winter 2014, different parameterizations to represent the emission and aging of I/S-VOCs were implemented in the chemistry-transport model of Polyphemus (different volatility distribution emissions and single-step oxidation vs multi-step oxidation within a volatility basis set – VBS – framework, inclusion of non-traditional volatile organic compounds – NTVOCs). Simulations using the different parameterizations are compared to each other and to the measurements (concentration and oxidation state). The highly observed organic concentrations are well reproduced in all the parameterizations. They are slightly underestimated in most parameterizations. The volatility distribution at emissions influences the concentrations more strongly than the choice of the parameterization that may be used for aging (single-step oxidation vs multi-step oxidation), stressing the importance of an accurate characterization of emissions. Assuming the volatility distribution of sectors other than residential heating to be the same as residential heating may lead to a strong underestimation of organic concentrations. The observed organic oxidation and oxygenation states are strongly underestimated in all simulations, even when multigenerational aging of I/S-VOCs from all sectors is modeled. This suggests that uncertainties in the emissions and aging of I/S-VOC emissions remain to be elucidated, with a potential role of formation of organic nitrate and low-volatility highly oxygenated organic molecules.