Primary Organic Aerosol Emissions Research Articles

Molecular composition and the impact of fuel moisture content on fresh primary organic aerosol emissions during laboratory combustion of ponderosa pine needles

Environmental context Wildland fire smoke and its impacts on air quality and human health are increasing globally. However, uncertainties in organic emissions from these fires hinder our understanding of downwind atmospheric photochemical processes driving the formation of hazardous air pollutants. In this study, we investigated the impact of fuel moisture content on organic species emission during the combustion of ponderosa pine needles, an important fuel source in the western United States. Rationale Pine needles represent an important fuel source in coniferous forest systems in the western United States. During forest fires, they can be easily ignited and help sustain flame on the ground. Methodology In this study, a comprehensive chemical analysis was conducted to examine oxygenated organic compounds (OOCs) present in PM2.5 (particles ≤ 2.5 µm in aerodynamic diameter) formed from burning dry and moist ponderosa pine (Pinus ponderosa) needles (PPN) in the presence and absence of fine woody debris (FWD). The effect of fuel moisture content (FMC), a key parameter that influences smoke formation, has not received much attention. Therefore, we also investigated the effect of FMC on PM2.5 formation and its composition. Thirty three experiments were conducted at the US Forest Service Fire Science Laboratory. PM2.5 was collected onto 47-mm Teflon filters, and silylated extracts were analysed by gas chromatography–mass spectrometry. Results More than 50 OOCs were identified, including levoglucosan and mannosan; n-dodecanoic acid and n-hexadecanoic acid; dihydroabietic acid, and dehydroabietic acid; and a series of intermediate volatile and semivolatile organic compounds. Mass spectra of a wide variety of compounds in electron and chemical ionisation mode are provided. Most of these OOCs were identified in this study for the first time in PPN aerosol, although some were previously reported in pine wood and other biomass burning aerosol. Our results show significant changes in the composition and abundance of particles depending on the amount and type of PPN burned. When compared with dry PPN, moist PPN showed decreased emissions of PM2.5 and OOCs, due likely to the presence of water in the system that partially suppressed the production of OOCs. Discussion Incorporating pine needles in atmospheric models as a contributor to smoke particles generated during forest fires is an essential step towards reducing the current uncertainties regarding the influence of these aerosols on chemical/air mass characteristics, regional meteorology, and the climate.

Primary and Secondary Organic Aerosol Formation from Asphalt Pavements.

Asphalt is ubiquitous across cities and a source of organic compounds spanning a wide range of volatility and may be an overlooked source of urban organic aerosols. The emission rate and composition depend strongly on temperature, but emissions have been observed at both application temperatures and surface temperatures during warm sunny days. Here we report primary organic aerosol (POA) emissions and secondary organic aerosol (SOA) production from asphalt. We reheated real-world asphalt samples to application-relevant temperatures (∼130 °C) and typical summertime road-surface temperatures (∼55 °C) and then flushed the emitted vapors into an environmental oxidation chamber containing ammonium sulfate seed particles. SOA was then formed following the photo-oxidation of emissions under high-NOx conditions typical of urban atmospheres. We find that POA only forms at application temperature as it does not require further oxidation, whereas SOA forms under both conditions; with the resulting POA and SOA both being semi-volatile. While total OA formation rates were substantially greater under the limited time spent under application conditions, SOA formation from passive asphalt heating presents a potential long-term source, as heating continues for the lifetime of the road surface. This suggests that persistent asphalt solar heating is likely a considerable and continued source of summertime SOA in urban environments.

Substantially positive contributions of new particle formation to cloud condensation nuclei under low supersaturation in China based on numerical model improvements

Abstract. New particle formation (NPF) and subsequent particle growth are important sources of condensation nuclei (CN) and cloud condensation nuclei (CCN). While many observations have shown positive contributions of NPF to CCN at low supersaturation, negative NPF contributions were often simulated in polluted environments. Using the observations in a coastal city of Qingdao, Beijing, and Gucheng in north China, we thoroughly evaluate the simulated number concentrations of CN and CCN using an NPF-explicit parameterization embedded in the WRF-Chem model. For CN, the initial simulation shows large biases of particle number concentrations at 10–40 and 40–100 nm. By adjusting the process of gas–particle partitioning, including the mass accommodation coefficient (MAC) of sulfuric acid, the phase changes in primary organic aerosol emissions, and the condensational amount of nitric acid, the improvement of the particle growth process yields substantially reduced overestimation of CN. Regarding CCN, secondary organic aerosol (SOA) formed from the oxidation of semi-volatile and intermediate-volatility organic compounds (S/IVOCs) is called SI-SOA, the yield of which is an important contributor. At default settings, the SI-SOA yield is too high without considering the differences in precursor oxidation rates. Lowering the SI-SOA yield under linear H2SO4 nucleation scheme results in much-improved CCN simulations compared to observations. On the basis of the bias-corrected model, we find substantially positive contributions of NPF to CCN at low supersaturation (∼ 0.2 %) over broad areas of China, primarily due to competing effects of increasing particle hygroscopicity, a result of reductions in SI-SOA amount, surpassing that of particle size decreases. The bias-corrected model is robustly applicable to other schemes, such as the quadratic H2SO4 nucleation scheme, in terms of CN and CCN, though the dependence of CCN on SI-SOA yield is diminished likely due to changes in particle composition. This study highlights potentially much larger NPF contributions to CCN on a regional and even global basis.

Volatility distribution of primary organic aerosol emissions from household crop waste combustion in China

Biomass-burning emissions are a significant source of primary organic aerosol (POA). Volatility is one of the most important physical properties of organic aerosol (OA). Dilution and thermodenuder (TD) measurements were used to investigate the volatility of POA from household crop waste combustion in China. Between 10% and 30% of the POA desorbed when diluted from 20:1 to 120:1, while 10%–40% of POA evaporated in the TD when heated to 150 °C. Thus, a considerable proportion of the POA emissions were volatile. A dynamic mass transfer model was applied to derived volatility distributions of POA based on TD data. A best fit volatility distributions for POA and associated mass accommodation coefficients (α), and the enthalpy of vaporization (ΔHvap) were presented. The emissions factors and volatility distribution of POA emission from household crop waste combustion in this study can be used to improve emission inventories and simulate gas-particle partitioning of organic aerosol in chemical transport models.

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.

Primary emissions and secondary production of organic aerosols from heated animal fats

Cooking is an important source of primary organic aerosol (POA) in urban areas, and it may also generate abundant non-methane organic gases (NMOGs), which form oxidized organic aerosol (OOA) after atmospheric oxidation. Edible fats play an important role in a balanced diet and are part of various types of cooking. We conducted laboratory studies to examine the primary emissions of POA and NMOGs and OOA formation using an oxidation flow reactor (OFR) for three animal fats (i.e., lard, beef and chicken fats) heated at two different temperatures (160 and 180 °C). Positive matrix factorization (PMF) revealed that OOA formed together with POA loss after photochemical aging, suggesting the conversion of some POA to OOA. The maximum OOA production rates (PRs) from heated animal fats, occurring under OH exposures (OHexp) of 8.3–15 × 1010 molecules cm−3 s, ranged from 8.9 to 24.7 μg min−1, 1.6–14.5 times as high as initial POA emission rates (ERs). NMOG emissions from heated animal fats were dominated by aldehydes, which contributed 14–71% of the observed OOA. We estimated that cooking-related OOA could contribute to as high as ~10% of total organic aerosol (OA) in an urban area in Hong Kong, where cooking OA (COA) dominated the POA. This study provides insights into the potential contribution of cooking to urban OOA, which might be especially pronounced when cooking contributions dominate the primary emissions.

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.

Aqueous production of secondary organic aerosol from fossil-fuel emissions in winter Beijing haze

Secondary organic aerosol (SOA) produced by atmospheric oxidation of primary emitted precursors is a major contributor to fine particulate matter (PM2.5) air pollution worldwide. Observations during winter haze pollution episodes in urban China show that most of this SOA originates from fossil-fuel combustion but the chemical mechanisms involved are unclear. Here we report field observations in a Beijing winter haze event that reveal fast aqueous-phase conversion of fossil-fuel primary organic aerosol (POA) to SOA at high relative humidity. Analyses of aerosol mass spectra and elemental ratios indicate that ring-breaking oxidation of POA aromatic species, leading to functionalization as carbonyls and carboxylic acids, may serve as the dominant mechanism for this SOA formation. A POA origin for SOA could explain why SOA has been decreasing over the 2013-2018 period in response to POA emission controls even as emissions of volatile organic compounds (VOCs) have remained flat.

New SOA Treatments Within the Energy Exascale Earth System Model (E3SM): Strong Production and Sinks Govern Atmospheric SOA Distributions and Radiative Forcing

AbstractSecondary organic aerosols (SOA) are large contributors to fine particle mass loading and number concentration and interact with clouds and radiation. Several processes affect the formation, chemical transformation, and removal of SOA in the atmosphere. For computational efficiency, global models use simplified SOA treatments, which often do not capture the dynamics of SOA formation. Here we test more complex SOA treatments within the global Energy Exascale Earth System Model (E3SM) to investigate how simulated SOA spatial distributions respond to some of the important but uncertain processes affecting SOA formation, removal, and lifetime. We evaluate model predictions with a suite of surface, aircraft, and satellite observations that span the globe and the full troposphere. Simulations indicate that both a strong production (achieved here by multigenerational aging of SOA precursors that includes moderate functionalization) and a strong sink of SOA (especially in the middle upper troposphere, achieved here by adding particle‐phase photolysis) are needed to reproduce the vertical distribution of organic aerosol (OA) measured during several aircraft field campaigns; without this sink, the simulated middle upper tropospheric OA is too large. Our results show that variations in SOA chemistry formulations change SOA wet removal lifetime by a factor of 3 due to changes in horizontal and vertical distributions of SOA. In all the SOA chemistry formulations tested here, an efficient chemical sink, that is, particle‐phase photolysis, was needed to reproduce the aircraft measurements of OA at high altitudes. Globally, SOA removal rates by photolysis are equal to the wet removal sink, and photolysis decreases SOA lifetimes from 10 to ~3 days. A recent review of multiple field studies found no increase in net OA formation over and downwind biomass burning regions, so we also tested an alternative, empirical SOA treatment that increases primary organic aerosol (POA) emissions near source region and converts POA to SOA with an aging time scale of 1 day. Although this empirical treatment performs surprisingly well in simulating OA loadings near the surface, it overestimates OA loadings in the middle and upper troposphere compared to aircraft measurements, likely due to strong convective transport to high altitudes where wet removal is weak. The default improved model formulation (multigenerational aging with moderate fragmentation and photolysis) performs much better than the empirical treatment in these regions. Differences in SOA treatments greatly affect the SOA direct radiative effect, which ranges from −0.65 (moderate fragmentation and photolysis) to −2 W m−2 (moderate fragmentation without photolysis). Notably, most SOA formulations predict similar global indirect forcing of SOA calculated as the difference in cloud forcing between present‐day and preindustrial simulations.

Light Absorption Properties of Organic Aerosol from Wood Pyrolysis: Measurement Method Comparison and Radiative Implications.

Growing evidence indicates that organic aerosol (OA) is a significant absorber of solar radiation. Such absorptive OA is known as "brown carbon" (BrC). However, a formal analytical method for BrC is currently lacking although several methods have been applied to determine its absorption properties. Reported imaginary refractive index (kOA) values from various combustion sources span 2 orders of magnitude. Measurement methods are an important factor affecting this kOA variation. In this work, isolated OA from wood pyrolysis was used to compare four methods to determine absorbing properties of OA. The generated aerosol was lognormally distributed, spherical, and nearly pure organic matter. Optical closure was considered as the reference method. kOA calculated from the extract bulk light absorbance measurement was comparable to that determined by optical closure. kOA and mass absorption cross section obtained by online and offline filter-based transmission measurements were similar, but 3.5 to 5.0 times greater than those determined by optical closure. Absorption Ångström Exponents determined by the four methods were comparable and ranged from 6.1 to 6.8. A clear-sky radiative transfer model implied that using the optical parameters derived from different methods in the full climate model could produce different radiative impacts of primary OA emissions.

Optimization of a thermal desorption-gas chromatography/mass spectrometry method for characterization of semi-volatile organic compounds in high time resolved PM2.5

Organic aerosol (OA) is an important fraction of fine particulate matter. Most primary OA emissions comprise semivolatile organic compounds (SVOCs) that are reactive and may partition into particle and vapor phases. Collection of SVOCs in the particle phase at high time resolution reduces positive and negative artifacts, but requires sensitive analytical techniques for chemical characterization. In this work, we investigated the effect of thermal desorption-gas chromatography/mass spectrometry (TD-GC-MS) analytical variables on 16 polycyclic aromatic hydrocarbons (PAHs) and 29 n-alkanes. Analytical responses of target compounds were mostly influenced by trap desorption time and GC column pressure. The optimal TD-GC-MS trap desorption conditions were 350 °C for 10 min at GC constant pressure mode of 17 psi. Good linearity (R2 > 0.99) was observed for all target analytes (with the exception of 6 ring PAHs and C35–C39n-alkanes). Method detection limits were 0.038–0.157 ng m−3 and 0.028–0.355 ng m−3 for PAHs and n-alkanes, respectively. The optimized method was tested on PM2.5 samples collected with the high-volume sampling technique at high temporal resolution of 2 h. Analysis of a sample, followed by analysis of a blank, did not show carryover. The optimized TD-GC-MS method showed the capability to resolve diurnal variations of target analytes in high time resolved PM2.5. Using TD-GC-MS for analysis of high time resolved PM2.5 will contribute to the improvement of source apportionment, emission inventories, and global chemistry-climate models.

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.

Primary emissions and secondary organic aerosol formation from in-use diesel vehicle exhaust: Comparison between idling and cruise mode

Diesel vehicle exhaust is an important source of carbonaceous aerosols, especially in developing countries, like China. Driving condition impacts diesel vehicle emissions, yet its influence needs further understanding especially on secondary organic aerosol (SOA) formation. In this study tailpipe exhaust from an in-use light duty diesel vehicle at idling and driving speeds of 20 and 40 km h−1 was introduced respectively into a 30 m−3 indoor smog chamber to investigate primary emissions and SOA formation during photo-oxidation. The emission factors of SO2 at 20 and 40 km h−1 were higher than those at idling, whereas the emission factors of aromatic hydrocarbons (AHs), polycyclic aromatic hydrocarbons (PAHs) and oxygenated volatile organic compounds (OVOCs) decreased when driving speeds increased. The emission factors of black carbon (BC) and primary organic aerosol (POA) at idling were comparable to those at 20 and 40 km h−1. The SOA production factors were 0.41 ± 0.09 g kg-fuel−1 at idling, approximately 2.5 times as high as those at 20 km h−1 (0.16 ± 0.09 g kg-fuel−1) or 40 km h−1 (0.17 ± 0.09 g kg-fuel−1). Total carbonaceous aerosols, including BC, POA and SOA, from diesel vehicles at 20 and 40 km h−1 were 60–75% of those at idling, due largely to a reduction in SOA production. Measured AHs and PAHs altogether were estimated to explain <10% of SOA production, and eight major OVOCs could contribute 8.4–23% of SOA production. A preliminary comparison was further made for the same diesel vehicle at idling using diesel oils upgraded from China 3 to China 5 standard. The emission factors of total particle numbers decreased by 38% owing to less nuclei mode particles, which was probably caused by the reducing fuel sulfur content; the emission factors of BC were almost unchanged, the POA emission factors and SOA production factors however decreased by 72% and 37%.

Global Modeling of Secondary Organic Aerosol With Organic Nucleation

AbstractOrganic nucleation has been identified as an important way to form secondary organic aerosol (SOA) and change the number concentration of aerosol and thus its climate effect. A global atmospheric chemistry model is developed to include a comprehensive organic nucleation scheme that includes heteromolecular nucleation of sulfuric acid and organics, neutral pure organic nucleation, and ion‐induced pure organic nucleation. Our model simulation shows reasonable agreement with the seasonal as well as spatial pattern of organic carbon concentration in America, while it fails to predict the seasonal pattern of organic carbon in Europe due to the lack of sharp increases in primary organic aerosol emissions in the winter. Including organic nucleation decreases the bias of the annual average particle number concentration at 54% of the available observation sites and increases the temporal correlation coefficients at 58% of the sites. Ion‐induced pure organic nucleation contributes the most to the total organic nucleation rate, which peaks around 400 hPa in the tropics. Heteromolecular nucleation of sulfuric acid and organics dominates the total organic nucleation rate in the summer and mostly occurs in the lower troposphere. The number concentration of particles formed from organic nucleation (newSOA) in the nucleation and Aitken modes is highest in the tropics, while accumulation mode newSOA is highest in the Northern Hemisphere due to growth as a result of the condensation of sulfate. Three sensitivity experiments suggest that more studies are needed to investigate the formation mechanism of newSOA, so that a more accurate simulation of the spatial and size distribution of newSOA can be developed.

Detailed Speciation of Intermediate Volatility and Semivolatile Organic Compound Emissions from Gasoline Vehicles: Effects of Cold-Starts and Implications for Secondary Organic Aerosol Formation.

Over the past two decades vehicle emission standards in the United States have been dramatically tightened with the goal of reducing urban air pollution. Secondary organic aerosol (SOA) is the dominant contributor to urban organic aerosol. Experiments were conducted at the California Air Resources Board Haagen-Smit Laboratory to characterize exhaust organics from 20 gasoline vehicles recruited from the California in-use fleet. The vehicles spanned a wide range of emission certification standards. We comprehensively characterized intermediate volatility and semivolatile organic compound emissions using thermal desorption two-dimensional gas-chromatography-mass-spectrometry with electron impact (GC × GC-EI-MS) and vacuum-ultraviolet (GC × GC-VUV-MS) ionization. Single-ring aromatic compounds with unsaturated C4 and C5 substituents contribute a large fraction of the intermediate volatility organic compound (IVOC) emissions in gasoline vehicle exhaust. The analyses of quartz filters used in GC × GC-VUV-MS show that primary organic aerosol emissions were dominated by motor oil. We combined our new emissions data with published SOA yield parametrizations to estimate SOA formation potential. After 24 h of oxidation, IVOC emissions contributed 45% of SOA formation; BTEX compounds (benzene, toluene, xylenes, and ethylbenzene),40%; other VOC aromatics, 15%. The composition of IVOC emissions was consistent across the test fleet, suggesting that future reductions in vehicular emissions will continue to reduce SOA formation and ambient particulate mass levels.

Intermediate Volatility Organic Compound Emissions from a Large Cargo Vessel Operated under Real-World Conditions.

Intermediate volatility organic compound (IVOC) emissions from a large cargo vessel were characterized under real-world operating conditions using an on-board measurement system. Test ship fuel-based emission factors (EFs) of total IVOCs were determined for two fuel types and seven operating conditions. The average total IVOC EF was 1003 ± 581 mg·kg-fuel-1, approximately 0.76 and 0.29 times the EFs of primary organic aerosol (POA) emissions from low-sulfur fuel (LSF, 0.38 wt % S) and high-sulfur fuel (HSF, 1.12 wt % S), respectively. The average total IVOC EF from LSF was 2.4 times that from HSF. The average IVOC EF under low engine load (15%) was 0.5-1.6 times higher than those under 36%-74% loads. An unresolved complex mixture (UCM) contributed 86.1 ± 1.9% of the total IVOC emissions. Ship secondary organic aerosol (SOA) production was estimated to be 546.5 ± 284.1 mg·kg-fuel-1; IVOCs contributed 98.9 ± 0.9% of the produced SOA on average. Fuel type was the dominant determinant of ship IVOC emissions, IVOC volatility distributions, and SOA production. The ship emitted more IVOC mass, produced higher proportions of volatile organic components, and produced more SOA mass when fueled with LSF than when fueled with HSF. When reducing ship POA emissions, more attention should be paid to commensurate control of ship SOA formation potential.

Additional Benefits of Federal Air-Quality Rules: Model Estimates of Controllable Biogenic Secondary Organic Aerosol.

Atmospheric models that accurately describe the fate and transport of trace species for the right reasons aid in the development of effective air-quality management strategies that safeguard human health. Controllable emissions facilitate the formation of biogenic secondary organic aerosol (BSOA) to enhance the atmospheric fine particulate matter (PM2.5) burden. Previous modeling with the EPA's Community Multiscale Air Quality (CMAQ) model predicted that anthropogenic primary organic aerosol (POA) emissions had the greatest impact on BSOA. That experiment included formation processes involving semivolatile partitioning but not aerosol liquid water (ALW), a ubiquitous PM constituent. We conduct 17 summertime CMAQ simulations with updated chemistry and evaluate changes in BSOA due to the removal of individual pollutants and source sectors for the contiguous U.S. CMAQ predicts SO2 from electricity generating units, and mobile source NOX emissions have the largest impacts on BSOA. The removal of anthropogenic NOX, SO2, and POA emissions during the simulation reduces the nationally averaged BSOA by 23, 14, and 8% and PM2.5 by 9.2, 14, and 5.3%, respectively. ALW mass concentrations decrease by 10 and 35% in response to the removal of NOX and SO2 emissions. This work contributes chemical insight into ancillary benefits of Federal NOX and SO2 rules that concurrently reduce organic PM2.5 mass.

Emission of intermediate, semi and low volatile organic compounds from traffic and their impact on secondary organic aerosol concentrations over Greater Paris

Exhaust particle emissions are mostly made of black carbon and/or organic compounds, with some of these organic compounds existing in both the gas and particle phases. Although emissions of volatile organic compounds (VOC) are usually measured at the exhaust, emissions in the gas phase of lower volatility compounds (POAvapor) are not. However, these gas-phase emissions may be oxidised after emission and enhance the formation of secondary organic aerosols (SOA). They are shown here to contribute to most of the SOA formation in Central Paris. POAvapor emissions are usually estimated from primary organic aerosol emissions in the particle phase (POA). However, they could also be estimated from VOC emissions for both gasoline and diesel vehicles using previously published measurements from chamber measurements. Estimating POAvapor from VOC emissions and ageing exhaust emissions with a simple model included in the Polyphemus air-quality platform compare well to measurements of SOA formation performed in chamber experiments. Over Greater Paris, POAvapor emissions estimated using POA and VOC emissions are compared using the HEAVEN bottom-up traffic emissions model. The impact on the simulated atmospheric concentrations is then assessed using the Polyphemus/Polair3D chemistry-transport model. Estimating POAvapor emissions from VOC emissions rather than POA emissions lead to lower emissions along motorway axes (between −50% and −70%) and larger emissions in urban areas (up to between +120% and +140% in Central Paris). The impact on total organic aerosol concentrations (gas plus particle) is lower than the impact on emissions: between −8% and 25% along motorway axes and in urban areas respectively. Particle-phase organic concentrations are lower when POAvapor emissions are estimated from VOC than POA emissions, even in Central Paris where the total organic aerosol concentration is higher, because of different assumptions on the emission volatility distribution, stressing the importance of characterizing not only the emission strength, but also the emission volatility distribution.

Significant Production of Secondary Organic Aerosol from Emissions of Heated Cooking Oils

Cooking emissions have been identified as a major source of primary organic aerosol (POA) in urban environments. Cooking may also be a potential source of secondary organic aerosol (SOA) because of the abundant emissions of non-methane organic gases. We studied SOA formation from the photooxidation of emissions from seven vegetable oils heated at 200 °C under high-NOx conditions in a smog chamber. After the samples had been aged under an OH exposure of 1.0 × 1010 molecules cm–3 s, the SOA formation rate was generally 1 order of magnitude higher than the POA emission rate. We determined that alkenals, which are not traditional SOA precursors in chemical transport models, accounted for 5–34% of the observed SOA. The unexplained SOA may be attributed to the oxidation of primary semivolatile and intermediate-volatility organic compounds (SVOCs and IVOCs, respectively), which were estimated to contribute an additional 9–106% of the observed SOA assuming the volatility distribution of heated cooking oils is the...

CCN activity and organic hygroscopicity of aerosols downwind of an urban region in central Amazonia: seasonal and diel variations and impact of anthropogenic emissions

Abstract. During the Observations and Modeling of the Green Ocean Amazon (GoAmazon2014/5) campaign, size-resolved cloud condensation nuclei (CCN) spectra were characterized at a research site (T3) 60 km downwind of the city of Manaus, Brazil, in central Amazonia for 1 year (12 March 2014 to 3 March 2015). Particle hygroscopicity (κCCN) and mixing state were derived from the size-resolved CCN spectra, and the hygroscopicity of the organic component of the aerosol (κorg) was then calculated from κCCN and concurrent chemical composition measurements. The annual average κCCN increased from 0.13 at 75 nm to 0.17 at 171 nm, and the increase was largely due to an increase in sulfate volume fraction. During both wet and dry seasons, κCCN, κorg, and particle composition under background conditions exhibited essentially no diel variations. The constant κorg of ∼ 0. 15 is consistent with the largely uniform and high O : C value (∼ 0. 8), indicating that the aerosols under background conditions are dominated by the aged regional aerosol particles consisting of highly oxygenated organic compounds. For air masses strongly influenced by urban pollution and/or local biomass burning, lower values of κorg and organic O : C atomic ratio were observed during night, due to accumulation of freshly emitted particles, dominated by primary organic aerosol (POA) with low hygroscopicity, within a shallow nocturnal boundary layer. The O : C, κorg, and κCCN increased from the early morning hours and peaked around noon, driven by the formation and aging of secondary organic aerosol (SOA) and dilution of POA emissions into a deeper boundary layer, while the development of the boundary layer, which leads to mixing with aged particles from the residual layer aloft, likely also contributed to the increases. The hygroscopicities associated with individual organic factors, derived from PMF (positive matrix factorization) analysis of AMS (aerosol mass spectrometry) spectra, were estimated through multivariable linear regression. For the SOA factors, the variation of the κ value with O : C agrees well with the linear relationship reported from earlier laboratory studies of SOA hygroscopicity. On the other hand, the variation in O : C of ambient aerosol organics is largely driven by the variation in the volume fractions of POA and SOA factors, which have very different O : C values. As POA factors have hygroscopicity values well below the linear relationship between SOA hygroscopicity and O : C, mixtures with different POA and SOA fractions exhibit a steeper slope for the increase in κorg with O : C, as observed during this and earlier field studies. This finding helps better understand and reconcile the differences in the relationships between κorg and O : C observed in laboratory and field studies, therefore providing a basis for improved parameterization in global models, especially in a tropical context.