Organic Aerosol Concentrations Research Articles

Evaluation of Biogenic Organic Aerosols in the Amazon Rainforest Using WRF‐Chem With MOSAIC

AbstractBiogenic secondary organic aerosol (BSOA) accounts for 70%–80% of submicron aerosol over the Amazon rainforest. However, uncertainties with regard to the chemical formation pathway, mass budget, and radiative impact of BSOA in the region still remain high. To address the issue, we used a regional chemistry transport model (WRF‐Chem‐MOSAIC) to evaluate the budget of BSOA in the Amazon forest during the wet season (March) of 2014 when the air mass was clean from influences from anthropogenic and biomass burning emissions. We found that the default model underestimated the surface concentration of submicron organic aerosol (OA) by 57% at a ground measurement site (T3). We subsequently updated the WRF‐Chem‐MOSAIC model by including SOA formation from isoprene epoxydiols (IEPOX‐SOA) and SOA aging schemes. The updated model reproduced the observed submicron OA concentration well with an overestimation of only 2.5%. With the updated model, we will show that IEPOX‐SOA accounts for 23% of surface submicron OA averaged over the entire Amazon rainforest. The modeled surface SOA (smaller than 2.5 μm in diameter) concentration in the Amazon region was about a factor of 14 larger than the global mean. Finally, a sensitivity study was conducted which showed that convective plumes can remove more than 40% of submicron OA below 5 km in the Amazon region. Overall, our study highlights the importance of IEPOX chemistry as well as the convective removal processes in the global SOA budget.

Cryptogamic organisms are a substantial source and sink for volatile organic compounds in the Amazon region

Cryptogamic organisms such as bryophytes and lichens cover most surfaces within tropical forests, yet their impact on the emission of biogenic volatile organic compounds is unknown. These compounds can strongly influence atmospheric oxidant levels as well as secondary organic aerosol concentrations, and forest canopy leaves have been considered the dominant source of these emissions. Here we present cuvette flux measurements, made in the Amazon rainforest between 2016–2018, and show that common bryophytes emit large quantities of highly reactive sesquiterpenoids and that widespread lichens strongly uptake atmospheric oxidation products. A spatial upscaling approach revealed that cryptogamic organisms emit sesquiterpenoids in quantities comparable to current canopy attributed estimates, and take up atmospheric oxidation products at rates comparable to hydroxyl radical chemistry. We conclude that cryptogamic organisms play an important and hitherto overlooked role in atmospheric chemistry above and within tropical rainforests.

Process-based and observation-constrained SOA simulations in China: the role of semivolatile and intermediate-volatility organic compounds and OH levels

Abstract. Organic aerosol (OA) is a major component of tropospheric submicron aerosol that contributes to air pollution and causes adverse effects on human health. Chemical transport models have difficulties in reproducing the variability in OA concentrations in polluted areas, hindering understanding of the OA budget and sources. Herein, we apply both process-based and observation-constrained schemes to simulate OA in GEOS-Chem. Comprehensive data sets of surface OA, OA components, secondary organic aerosol (SOA) precursors, and oxidants were used for model–observation comparisons. The base models generally underestimate the SOA concentrations in China. In the revised schemes, updates were made on the emissions, volatility distributions, and SOA yields of semivolatile and intermediate-volatility organic compounds (SVOCs and IVOCs) and additional nitrous acid sources. With all the model improvements, both the process-based and observation-constrained SOA schemes can reproduce the observed mass concentrations of SOA and show spatial and seasonal consistency with each other. Our best model simulations suggest that anthropogenic SVOCs and IVOCs are the dominant source of SOA, with a contribution of over 50 % in most of China, which should be considered for pollution mitigation in the future. The residential sector may be the predominant source of SVOCs and IVOCs in winter, despite large uncertainty remaining in the emissions of IVOCs from the residential sector in northern China. The industry sector is also an important source of IVOCs, especially in summer. More SVOC and IVOC measurements are needed to constrain their emissions. Besides, the results highlight the sensitivity of SOA to hydroxyl radical (OH) levels in winter in polluted environments. The addition of nitrous acid sources can lead to over 30 % greater SOA mass concentrations in winter in northern China. It is important to have good OH simulations in air quality models.

Quantifying ambient concentrations of primary and secondary organic aerosol in central Los Angeles using an integrated approach coupling source apportionment with regression analysis

The main objective of this study was to explore the correlations between carbonaceous PM2.5 species (i.e., primary and secondary organic aerosols (POAs and SOAs) and elemental carbon (EC)) with various criteria gaseous pollutants over the 2015–2019 period in order to devise a simple way of estimating the 24-hr concentration of these PM species in central Los Angeles. The Positive Matrix Factorization (PMF) model was used to determine the contribution of various sources to organic carbon (OC) and its volatility fractions (OC1-OC3) in the atmosphere in years of 2015, 2017, and 2019. A 5-factor solution that includes vehicular exhaust emissions (traced by EC and OC1), non-tailpipe emissions (characterized by Ti, Cu, and Zn), SOAs (identified by sulfate and ozone), biomass burning (associated with high loadings of K+/K), and local industrial activities (traced by Cr) was identified as the most physically interpretable solution for each of the investigated years. The SOA concentrations determined using the PMF model output and the POA concentrations, calculated by subtracting the SOA concentrations from the total OC mass, were employed in our regression analysis with criteria gaseous pollutants, the concentrations of which are routinely reported by the air quality agencies. The result of the regression analysis revealed high correlation between the concentrations of SOA and ozone (R2 > 0.74) in different years, probably because they are originated from synchronized photochemical reactions in the atmosphere. The SOA/O3 ratios were between ∼47-56 μg/m3/ppm in the time period of 2015–2019. A strong correlation between POA and CO was also observed (R2 > 0.70); the POA/CO ratios decreased from about 6.5 to 5 μg/m3/ppm from 2015 to 2019, which is consistent with the trend of tailpipe emission contributions to total OC concentrations in our monitoring site. EC was also strongly correlated with NO2 (R2 > 0.73) and CO (R2 > 0.70) because they are emitted from the same combustion sources (e.g., vehicular emissions in central Los Angeles). Our results show persistent and significant correlations between the concentrations of criteria gaseous pollutants and carbonaceous PM2.5 species (i.e., POA, SOA, and EC) in different years, offering a straightforward approach to estimate the 24-h average concentration of these PM species in central Los Angeles.

Nighttime chemistry of biomass burning emissions in urban areas: A dual mobile chamber study

Abstract. Residential biomass burning for heating purposes is an important source of air pollutants during winter. Here we test the hypothesis that significant secondary organic aerosol production can take place even during winter nights through oxidation of the emitted organic vapors by the nitrate (NO3) radical produced during the reaction of ozone and nitrogen oxides. We use a mobile dual smog chamber system which allows the study of chemical aging of ambient air against a control reference. Ambient urban air sampled during a wintertime campaign during nighttime periods with high concentrations of biomass burning emissions was used as the starting point for the aging experiments. Biomass burning organic aerosol (OA) was, on average, 70 % of the total OA at the beginning of our experiments. Ozone was added in the perturbed chamber to simulate mixing with background air (and subsequent NO3 radical production and aging), while the second chamber was used as a reference. Following the injection of ozone, rapid OA formation was observed in all experiments, leading to increases in the OA concentration by 20 %–70 %. The oxygen-to-carbon ratio of the OA increased on average by 50 %, and the mass spectra of the produced OA was quite similar to the oxidized OA mass spectra reported during winter in urban areas. Furthermore, good correlation was found for the OA mass spectra between the ambient-derived emissions in this study and the nocturnal aged laboratory-derived biomass burning emissions from previous work. Concentrations of NO3 radicals as high as 25 ppt (parts per trillion) were measured in the perturbed chamber, with an accompanying production of 0.1–3.2 µg m−3 of organic nitrate in the aerosol phase. Organic nitrate represented approximately 10 % of the mass of the secondary OA formed. These results strongly indicate that the OA in biomass burning plumes can chemically evolve rapidly even during wintertime periods with low photochemical activity.

Estimating organic aerosol emissions from cooking in winter over the Pearl River Delta region, China

Cooking is an important source of organic aerosols (OA), particularly in urban areas, but it has not been explicitly included in current emission inventories in China. This study estimated the organic aerosol emissions from cooking during winter over the Pearl River Delta (PRD) region, China. Using the retrieved hourly cooking organic aerosol (COA) concentrations at two sites in Hong Kong and Guangzhou, population density, and daily per capita COA emissions, we determined the spatial and temporal distribution of COA emissions over the PRD region based on two approaches by treating COA as non-volatile (NVCOA) and semi-volatile (SVCOA), respectively. By using the estimated COA emissions and the Weather Research and Forecasting model coupled with chemistry (WRF-Chem) model, we reproduced the diurnal cycles of COA concentrations at the PolyU site in Hong Kong and Panyu site in Guangzhou. We also resolved the different patterns of COA between weekdays and weekends. The mean COA concentration during wintertime over the urban areas of the PRD region was 0.7 μg m−3 and 0.9 μg m−3 for the NVCOA and SVCOA cases, respectively, contributing 5.1% and 6.9% to the urban OA concentrations. The total COA emissions in winter over the PRD region were estimated to be 3.5 × 108 g month−1 and 3.8 × 108 g month−1 for the NVCOA and SVCOA cases, respectively, adding 34.8% and 37.8% to the total primary organic aerosol emissions. Considering COA emissions in the model increased the mean regional OA concentrations by 4.6% and 7.4% for the NVCOA and SVCOA cases, respectively. Our study therefore highlights the importance of cooking activities to OA concentrations in winter over the PRD region.

Modeling Volatility-Based Aerosol Phase State Predictions in the Amazon Rainforest

Organic aerosol (OA) is a complex matrix of various constituents—fresh (primary organic aerosols—POA) and aged via oxidation (secondary organic aerosols—SOA), generated from biogenic, anthropogenic, and biomass burning sources. The viscosity of OA can be critical in influencing new particle formation, reactive uptake processes that impact evaporation-growth kinetics, and the lifetime of particles in the atmosphere. This work utilizes a well-defined relationship between volatility and viscosity for pure compounds, which we incorporated within the Weather Research and Forecasting Model coupled to chemistry (WRF-Chem) to simulate the phase state and viscosity of bulk OA during the dry-to-wet transition season (September–October) in the Amazon rainforest during 2014. Our simulations indicate spatial and temporal heterogeneity in aerosol phase state often not captured by global-scale models. We show the strong role of water associated with organic aerosol (ws) as the dominant factor that can be used to quantitatively estimate OA viscosity. Analysis of WRF-Chem simulations across the entire atmospheric column indicates a strong inverse log-linear relationship between ws and OA viscosity with a correlation coefficient approaching 1, in the background and biomass burning-influenced conditions. At high altitudes where relative humidity (RH) and temperatures are low, our simulations indicate that OA exists in a semisolid-/solid-like phase state, consistent with previous studies. OA hygroscopicity is strongly correlated (ca. −0.8) with OA viscosity at RH ca. 30–50%, but this RH range is found mostly at low OA concentrations and the middle troposphere (ca. 6–10 km altitudes) in our simulated domain. OA hygroscopicity is uncorrelated with viscosity at higher-RH (near surface) and lower-RH (upper troposphere) regimes. At the urban site near surface, where day–night differences in RH are significant, RH is found to drive the phase state. At the background forested site near surface, where day–night RH differences are small, biomass burning-influenced OA is semisolid and a significant OA associated with background conditions is liquid-like. Simulations indicate a long tail of OA viscosity frequency distributions extending in the semisolid/solid regimes over background biogenic-influenced conditions due to the role of low-volatility OA components such as monoterpene oxidation products.

Significance of the organic aerosol driven climate feedback in the boreal area

Aerosol particles cool the climate by scattering solar radiation and by acting as cloud condensation nuclei. Higher temperatures resulting from increased greenhouse gas levels have been suggested to lead to increased biogenic secondary organic aerosol and cloud condensation nuclei concentrations creating a negative climate feedback mechanism. Here, we present direct observations on this feedback mechanism utilizing collocated long term aerosol chemical composition measurements and remote sensing observations on aerosol and cloud properties. Summer time organic aerosol loadings showed a clear increase with temperature, with simultaneous increase in cloud condensation nuclei concentration in a boreal forest environment. Remote sensing observations revealed a change in cloud properties with an increase in cloud reflectivity in concert with increasing organic aerosol loadings in the area. The results provide direct observational evidence on the significance of this negative climate feedback mechanism.

Simulation of the cooking organic aerosol concentration variability in an urban area

Cooking activities are a source of urban air pollution that has been often ignored. The corresponding particulate matter (PM) emissions are not included or are seriously underestimated in urban emission inventories. However, several field studies suggest that cooking organic aerosol (COA) can be an important component of the organic PM in urban areas. In this study we propose and evaluate a methodology for the simulation of the COA concentration and its variability in space and time in an urban area. The city of Patras, the third biggest in Greece, is used for this first application during a typical late summer period.The spatial distribution of COA emissions was based on the exact location of restaurants and grills, while the emission rates on the per person meat consumption in Greece. We estimated COA emissions of 0.6 g d−1 per person that corresponds to 150 kg d−1 for Patras. The temporal distribution of COA emissions was based on the known cooking times and the results of past field studies in the area. We estimated that half of the daily COA is emitted during dinner time (21:00–0:00 LT), while approximately 25% during lunch time (13:00–16:00 LT). The COA is simulated using the Volatility Basis Set approach and is treated as semivolatile and reactive. Its volatility distribution is based on laboratory measurements of COA from meat grilling.The chemical transport model PMCAMx predicts that the COA concentration reaches values up to 15 μg m−3 during the nights of the simulated summertime period in an area with high restaurant density. The average predicted COA concentration is around 1.2 μg m−3 in the center and 0.1–0.2 μg m−3 in the suburbs of the city. COA has a distinct daily profile that peaks during lunch (13:00–15:00 LT) and dinner (21:00–23:00 LT) periods. The local production of secondary COA is predicted to be slow and it represents just a few percent of the total COA. The model reproduces well the average PM2.5 concentrations at the outskirts of Patras and its overall performance for hourly PM2.5 values is rated as good. A 50% uncertainty of the reported COA emissions is estimated based on the results of the sensitivity tests and the observations in the city core. The emissions can be further constrained and the corresponding uncertainty can be further reduced with measurements focusing on COA and not on total PM2.5 as was the case in this study. These should take place in different areas of the city, selected based on the model predictions, to also improve our estimates of the spatial distribution of the emissions.

Seasonal characteristics of PM1 in Seoul, Korea, measured using HR-ToF-Aerosol Mass Spectrometer in 2018

In Korea, the characteristics of aerosols vary according to the four distinct seasons (spring, summer, fall, and winter); the seasonal variations are influenced by different air mass inflows of each season. Therefore, research is required to analyze the composition and characteristics of aerosols in different seasons. In this study, high-resolution time-of-flight aerosol mass spectrometry (HR-ToF-AMS) and positive matrix factorization (PMF) analyses were conducted in 2018 to examine the seasonal characteristics of aerosols with focus on organic aerosol in Seoul metropolitan area of South Korea. The results indicated that the seasonal non-refractory submicron particle (NR-PM1) concentration in Seoul metropolitan area ranged from 6.3 to 41.0 μg/m3, which was lower than those in other metropolitan areas of Northeast Asia and slightly higher than those in suburban and rural areas of South Asia and Europe. The organic aerosol concentration, which was the highest among PM1 components, ranged 3.5–14.24 μg/m3. In addition, a large increase in nitrate content was observed in high-concentration episodes. In all seasons, the O:C ratio and oxidation state were higher than those in previous studies, and it was estimated that the oxidation state was higher than those in other countries due to the influx of aged aerosols by long-range transport. In summer, the odd oxygen (Ox) concentration tends to be proportional to temperature and inversely proportional to humidity, indicating that the formation of fresh organic aerosol (OA) by active photochemical reaction is the main process of organic aerosol generation. In spring, fall, and winter, the Van Krevelen graph showed a slope of −0.68 ~ –0.99, indicating that carboxylic acid production was an important process for OA production. In addition, the causes of the high concentration episodes observed in spring and winter were estimated through the oxidation state of organic aerosols, PMF factor, and backward trajectory analyses.

Predicting the Nonlinear Response of PM2.5 and Ozone to Precursor Emission Changes with a Response Surface Model.

Reducing PM2.5 and ozone concentrations is important to protect human health and the environment. Chemical transport models, such as the Community Multiscale Air Quality (CMAQ) model, are valuable tools for exploring policy options for improving air quality but are computationally expensive. Here, we statistically fit an efficient polynomial function in a response surface model (pf-RSM) to CMAQ simulations over the eastern U.S. for January and July 2016. The pf-RSM predictions were evaluated using out-of-sample CMAQ simulations and used to examine the nonlinear response of air quality to emission changes. Predictions of the pf-RSM are in good agreement with the out-of-sample CMAQ simulations, with some exceptions for cases with anthropogenic emission reductions approaching 100%. NOX emission reductions were more effective for reducing PM2.5 and ozone concentrations than SO2, NH3, or traditional VOC emission reductions. NH3 emission reductions effectively reduced nitrate concentrations in January but increased secondary organic aerosol (SOA) concentrations in July. More work is needed on SOA formation under conditions of low NH3 emissions to verify the responses of SOA to NH3 emission changes predicted here. Overall, the pf-RSM performs well in the eastern U.S., but next-generation RSMs based on deep learning may be needed to meet the computational requirements of typical regulatory applications.

Size−resolved source apportionment of particulate matter from a megacity in northern China based on one-year measurement of inorganic and organic components

This research apportioned size-resolved particulate matter (PM) contributions in a megacity in northern China based on a full year of measurements of both inorganic and organic markers. Ions, elements, carbon fractions, n-alkanes, polycyclic aromatic hydrocarbons (PAHs), hopanes and steranes in 9 p.m. size fractions were analyzed. High molecular weight PAHs concentrated in fine PM, while most other organic compounds showed two peaks. Both two-way and three-way receptor models were used for source apportionment of PM in different size ranges. The three-way receptor model gave a clearer separation of factors than the two-way model, because it uses a combination of chemical composition and size distributions, so that factors with similar composition but distinct size distributions (like more mature and less mature coal combustion) can be resolved. The three-way model resolved six primary and three secondary factors. Gasoline vehicles and coal and biomass combustion, nitrate and high relative humidity related secondary aerosol, and resuspended dust and diesel vehicles (exhaust and non-exhaust) are the top two contributors to pseudo-ultrafine (<0.43 μm), fine (0.43–2.1 μm) and coarse mode (>2.1 μm) PM, respectively. Mass concentration of PM from coal and biomass combustion, industrial emissions, and diesel vehicle sources showed a bimodal size distribution, but gasoline vehicles and resuspended dust exhibited a peak in the fine and coarse mode, separately. Mass concentration of sulphate, nitrate and secondary organic aerosol exhibited a bimodal distribution and were correlated with temperature, indicating strong photochemical processing and repartitioning. High relative humidity related secondary aerosol was strongly associated with size shifts of PM, NO3− and SO42− from the usual 0.43–0.65 μm to 1.1–2.1 μm. Our results demonstrated the dominance of primary combustion sources in the <0.43 μm particle mass, in contrast to that of secondary aerosol in fine particle mass, and dust in coarse particle mass in the Northern China megacity.

Characterization of primary and aged wood burning and coal combustion organic aerosols in an environmental chamber and its implications for atmospheric aerosols

Abstract. Particulate matter (PM) affects visibility, climate, and public health. Organic matter (OM), a uniquely complex portion of PM, can make up more than half of total atmospheric fine PM mass. We investigated the effect of aging on secondary organic aerosol (SOA) concentration and composition for wood burning (WB) and coal combustion (CC) emissions, two major atmospheric OM sources, using mid-infrared (MIR) spectroscopy and aerosol mass spectrometry (AMS). For this purpose, primary emissions were injected into an environmental chamber and aged using hydroxyl (diurnal aging) and nitrate (nocturnal aging) radicals to reach an atmospherically relevant oxidative age. A time-of-flight AMS instrument was used to measure the high-time-resolution composition of non-refractory fine PM, while fine PM was collected on PTFE filters before and after aging for MIR analysis. AMS and MIR spectroscopy indicate an approximately 3-fold enhancement of organic aerosol (OA) concentration after aging (not wall-loss corrected). The OM:OC ratios also agree closely between the two methods and increase, on average, from 1.6 before aging to 2 during the course of aging. MIR spectroscopy, which is able to differentiate among oxygenated groups, shows a distinct functional group composition for aged WB (high abundance of carboxylic acids) and CC OA (high abundance of non-acid carbonyls) and detects aromatics and polycyclic aromatic hydrocarbons (PAHs) in emissions of both sources. The MIR spectra of fresh WB and CC aerosols are reminiscent of their parent compounds with differences in specific oxygenated functional groups after aging, consistent with expected oxidation pathways for volatile organic compounds (VOCs) of each emission source. The AMS mass spectra also show variations due to source and aging that are consistent with the MIR functional group (FG) analysis. Finally, a comparison of the MIR spectra of aged chamber WB OA with that of ambient samples affected by residential wood burning and wildfires reveals similarities regarding the high abundance of organics, especially acids, and the visible signatures of lignin and levoglucosan. This finding is beneficial for the source identification of atmospheric aerosols and interpretation of their complex MIR spectra.

Role of ecosystem-atmosphere exchanges of semi-volatile organic compounds in organic aerosol formation

Deposition of the gas fraction of Semi-Volatile Organic Compounds (SVOC) may be an important removal pathway and may strongly influence concentrations of organic aerosols due to the gas-particle partitioning of SVOC. All the studies on this process are based on the classic Wesely resistance approach that uses Henry's law constants to calculate a deposition rate scaled on the deposition rate of SO2. However, even highly hydrophobic SVOC could be efficiently removed by the vegetation and soils as shown by numerous studies on Persistent Organic Pollutant (POP) modeling. Moreover, the re-volatilization of deposited SVOC is possible and could influence organic aerosol concentrations.An atmosphere-soil-vegetation module was developed and implemented in the 3D air quality model CHIMERE 2017β to represent the accumulation of compounds in the different compartments of the biosphere and the exchanges between them. The soil compartment was represented with a multi-layer approach (the layers corresponding to different in-soil depths) to simulate the multiphase diffusion of compounds inside the soil. Exchanges of SVOC between the air, soil and vegetation compartments were simulated using bi-directional approaches based on Rg (the gas-phase partitioning in the soil compartment) and Kva the vegetation-air partitioning coefficient. Parameters were estimated based on the physical properties of the compounds and their molecular structure.Simulations performed over Europe show that air-vegetation-soil exchanges may be a more efficient removal pathway than dry deposition of particles for SVOC with a gas-phase fraction above 10%. Considering air-vegetation-soil exchanges in the simulations lead to a decrease of organic aerosol concentrations by 15% and primary SVOC (considered as hydrophobic compounds) may be efficiently removed by those pathways (contrary to what is calculated with the Wesely approach). This decrease of concentrations is mainly due to air-vegetation exchanges. During summer, the use of the Wesely approach may lead to a slight overestimation of deposition fluxes (leading to an underestimation of concentration by 1%).Re-volatilization may limit the amount of deposited SVOC. Depending on assumptions, simulations showed that re-emissions (inversion of exchanges toward the emissions) in summer of SVOC accumulated during winter is theoretically possible and may be a minor source of organic aerosol.

Improving Predictions of Indoor Aerosol Concentrations of Outdoor Origin by Considering the Phase Change of Semivolatile Material Driven by Temperature and Mass-Loading Gradients.

Outdoor aerosols experience environmental changes as they are transported indoors, including outdoor-to-indoor temperature and mass-loading gradients, which can reduce or enhance their indoor concentrations due to repartitioning driven by changes in thermodynamic equilibrium states. However, the complexity required to model repartitioning typically hinders its inclusion in studies predicting indoor exposure to ambient aerosols. To facilitate exposure predictions, this work used an explicit thermodynamic indoor aerosol model to simulate outdoor-to-indoor aerosol repartitioning typical for residential and office buildings across the 16 U.S. climate zones over an annual time horizon. Results demonstrate that neglecting repartitioning when predicting indoor concentrations can produce errors of up to 80-100% for hydrocarbon-like organic aerosol, 40-60% for total organic aerosol, 400% for ammonium nitrate, and 60% (typically 3 μg/m3) for the total PM2.5 aerosol. Underpredictions were more likely for buildings in hotter than colder regions, and for residences than offices, since both cooler indoor air and more meaningful residential organic aerosol concentrations encourage condensation of semivolatile organics. Furthermore, a method for computing correction factors to more easily account for thermodynamic repartitioning is provided. Applying these correction factors to mechanical-only aerosol predictions significantly reduced errors to <0.5 μg/m3 for the total indoor PM2.5 while bypassing explicit thermodynamic simulations.

Regional modeling of secondary organic aerosol formation over eastern China: The impact of uptake coefficients of dicarbonyls and semivolatile process of primary organic aerosol

Capturing the secondary organic aerosol (SOA) concentration using the chemical transport model is difficult due to a large knowledge gap of its formation mechanism. Previous studies demonstrated the uptake of dicarbonyls and semivolatile process of primary organic aerosol (POA) emissions are the significant sources of SOA. However, the uptake coefficients of dicarbonyls have large uncertainties and the SOA from the semivolatile process of POA emission remains unclear. We applied the revised reactive uptake parameterization, with “salting effects” for dicarbonyls, and updated approaches for POA to the Community Multiscale Air Quality Modeling System (CMAQ) simulations for October 2014 to study their impacts on modeling the SOA formation over eastern China. We introduce a method of quantifying crystalized or deliquescent aerosols to further improve the parameterization. The revised glyoxal uptake coefficients results in higher glyoxal SOA in the Beijing-Tianjin-Hebei region, where is typically under low relative humidity (RH) and high aerosol pH conditions. It gives lower glyoxal SOA in the Pearl River Delta region, where is typically under high RH and low pH conditions. The updated parameterization gives negligible methylglyoxal SOA due to the low uptake coefficients. The implementation of semivolatile process of POA and the approach for potential SOA from combustion sources will largely decrease the predicted POA and increase the modeled SOA concentrations over eastern China. The increased SOA from POA emissions could improve the model performance for organic carbon and SOA. It slightly improves the performance in PM2.5 modeling by compensating the reduction of modeled POA. This study indicates the mixed impact of a parameterization considering “salting effects” on modeling the dicarbonyls SOA in key regions of eastern China. It also demonstrates the improved performance by implementing the POA approaches in aerosol modeling using CMAQ. Meanwhile, the uncertainty in the revised reactive uptake parameterization and POA approaches is discussed.

Ambient PM2.5 organic and elemental carbon in New York City: Changing source contributions during a decade of large emission reductions

ABSTRACT Fine particle (PM2.5) exposure is a public health issue affecting millions of people worldwide. In New York State, significant emission reductions occurred during the past decades due to fuel switching, increased renewable energy, and transformations in buildings and transportation. Between 2002 and 2018, anthropogenic emissions of CO, NOx, SO2, VOCs, and primary PM2.5 declined by 58%, 61%, 89%, 47%, and 29%, respectively, in New York and three adjoining states. Ambient PM2.5 mass concentrations decreased but contributions of source types to changes in PM2.5 elemental carbon (EC) and organic carbon (OC) are incompletely understood. Receptor modeling was used to estimate changing source contributions to EC and OC in New York City (NYC) between 2007 and 2019. Source identification was facilitated by incorporating measurements of CO, NO, NO2, O3, SO2, and speciated hydrocarbons (1,3-butadiene, n-butane, isobutane, n-pentane, isopentane, isoprene, benzene, toluene, xylenes, acetaldehyde, and formaldehyde). Hydrocarbon species identified mobile-source emissions, evaporative emissions, biogenics, and photochemical secondary organic aerosol. At three study locations, predicted reductions of TC (OC + EC) summed over all source types were 1.3 ± 0.2 μg m−3, compared with a measured TC reduction of 1.5 ± 0.2 μg m−3. Declining sulfate concentrations and cleaner mobile sources together reduced the predicted average TC by a combined 1 μg m−3. Smaller changes occurred in other source contributions, e.g., 0.15 ± 0.01 μg m−3 reduction likely in response to NYC regulations related to heating fuel oil. Biomass burning PM2.5 increased between 2007 and 2011, then declined between 2015 and 2019. Reductions contrast with a non-significant increase of 0.05 μg m−3 in photochemical TC. Further opportunities to decrease PM2.5 concentrations include wood burning and photochemical-related OC. Continued temporal analysis and source apportionment will be needed to track changes in air quality and source contributions as jurisdictions expand renewable energy and energy efficiency goals. Implications: Large emission reductions that occurred in the eastern U.S. between 2002 and 2019 lowered average fine particle concentrations in New York City by a factor of two. Secondary organic aerosol concentrations declined as sulfate decreased but increased non-significantly with rising ozone. Cleaner mobile-source emissions lowered elemental and organic carbon concentrations. Opportunities for further reductions of PM2.5 concentrations include biomass burning and photochemical secondary aerosol.

Organic aerosol volatility and viscosity in the North China Plain: contrast between summer and winter

Abstract. Volatility and viscosity have substantial impacts on gas–particle partitioning, formation and evolution of aerosol and hence the predictions of aerosol-related air quality and climate effects. Here aerosol volatility and viscosity at a rural site (Gucheng) and an urban site (Beijing) in the North China Plain (NCP) in summer and winter were investigated by using a thermodenuder coupled with a high-resolution aerosol mass spectrometer. The effective saturation concentration (C*) of organic aerosol (OA) in summer was smaller than that in winter (0.55 µg m−3 vs. 0.71–0.75 µg m−3), indicating that OA in winter in the NCP is more volatile due to enhanced primary emissions from coal combustion and biomass burning. The volatility distributions varied and were largely different among different OA factors. In particular, we found that hydrocarbon-like OA (HOA) contained more nonvolatile compounds compared to coal-combustion-related OA. The more oxidized oxygenated OA (MO-OOA) showed overall lower volatility than less oxidized OOA (LO-OOA) in both summer and winter, yet the volatility of MO-OOA was found to be relative humidity (RH) dependent showing more volatile properties at higher RH. Our results demonstrated the different composition and chemical formation pathways of MO-OOA under different RH levels. The glass transition temperature (Tg) and viscosity of OA in summer and winter are estimated using the recently developed parameterization formula. Our results showed that the Tg of OA in summer in Beijing (291.5 K) was higher than that in winter (289.7–290.0 K), while it varied greatly among different OA factors. The viscosity suggested that OA existed mainly as solid in winter in Beijing (RH = 29 ± 17 %), but as semisolids in Beijing in summer (RH = 48 ± 25 %) and Gucheng in winter (RH = 68 ± 24 %). These results have the important implication that kinetically limited gas–particle partitioning may need to be considered when simulating secondary OA formation in the NCP.

Effect of chemical aging of monoterpene products on biogenic secondary organic aerosol concentrations

Capturing the effects of the complex processes of chemical aging of biogenic secondary organic aerosol (SOA) in chemical transport models (CTMs) has been challenging. Recent laboratory results from atmospheric simulation chambers are used in this study to develop a parameterization for biogenic SOA formation as a result of aging for use in CTMs using the Volatility Basis Set framework. This parameterization was implemented in PMCAMx which was then applied over the eastern United States to simulate summertime conditions. Using the base case parameterization of monoterpene SOA chemical aging resulted in modest increases (17–21%) in predicted domain average biogenic SOA. An alternative parameterization was developed fitting the same laboratory results, but assuming higher volatility products of chemical aging reactions. Use of this parameterization resulted in small increases (1–4%) of the predicted biogenic SOA. The PMCAMx predictions in sites where most of the SOA was biogenic were evaluated against measurements from the EPA IMPROVE network in July 2001 and during the Southern Oxidant and Aerosol Study in June 2013. The differences in the model performance were modest and mixed, a result consistent with the relatively small effect of the proposed parameterization on total organic aerosol levels.

Effects of Early Pollution Control Measures on Secondary Species of PM2.5 in Jiaozuo, China.

Various measures for reducing air pollution have been promulgated since 2013 in China. To investigate the synergistic results of emission control and meteorological environment, PM2.5 samples collected from October 2013 to July 2016 and November 2018 to October 2019 in Jiaozuo city were analyzed for their compositions, secondary species (Ss) variations, and factors changing for Ss formation. The results showed that the concentrations of sulfate, nitrate, ammonium, and secondary organic aerosols (SOAs) generally decreased over the same seasonal period during these years. In addition, the concentrations and proportions of each Ss increased with the increase in the PM2.5 level in these years, implying that although PM2.5 levels have been reduced by various control policies, Ss formation would remain the major contributor to PM elevations. The enhanced effects of gas-phase reactions on intensification of sulfate, SOA, and PM were observed in 2018–2019, which was consistent with the elevation of nitrate and SOA at PM levels of >150 μg/m3. Only sulfate in all PM levels sharply decreased after 2015, showing the fine effect of coal-related pollution control and the importance of collaborative control of NOx, volatile organic compounds, and organic aerosol emissions with SO2 emissions in the future.