scholarly journals Modeling secondary organic aerosol formation from volatile chemical products

2021 ◽  
Vol 21 (24) ◽  
pp. 18247-18261
Author(s):  
Elyse A. Pennington ◽  
Karl M. Seltzer ◽  
Benjamin N. Murphy ◽  
Momei Qin ◽  
John H. Seinfeld ◽  
...  
Keyword(s):  
Los Angeles ◽  
Organic Compounds ◽  
Urban Areas ◽  
Secondary Organic Aerosol ◽  
Current Model ◽  
Regional Scale ◽  
Organic Aerosol ◽  
Aerosol Formation ◽  
Emissions Inventory ◽  
Chemical Products

Abstract. Volatile chemical products (VCPs) are commonly used consumer and industrial items that are an important source of anthropogenic emissions. Organic compounds from VCPs evaporate on atmospherically relevant timescales and include many species that are secondary organic aerosol (SOA) precursors. However, the chemistry leading to SOA, particularly that of intermediate-volatility organic compounds (IVOCs), has not been fully represented in regional-scale models such as the Community Multiscale Air Quality (CMAQ) model, which tend to underpredict SOA concentrations in urban areas. Here we develop a model to represent SOA formation from VCP emissions. The model incorporates a new VCP emissions inventory and employs three new classes of emissions: siloxanes, oxygenated IVOCs, and nonoxygenated IVOCs. VCPs are estimated to produce 1.67 µg m−3 of noontime SOA, doubling the current model predictions and reducing the SOA mass concentration bias from −75 % to −58 % when compared to observations in Los Angeles in 2010. While oxygenated and nonoxygenated intermediate-volatility VCP species are emitted in similar quantities, SOA formation is dominated by the nonoxygenated IVOCs. Formaldehyde and SOA show similar relationships to temperature and bias signatures, indicating common sources and/or chemistry. This work suggests that VCPs contribute up to half of anthropogenic SOA in Los Angeles and models must better represent SOA precursors from VCPs to predict the urban enhancement of SOA.

scholarly journals Modeling secondary organic aerosol formation from volatile chemical products

2021 ◽  
Author(s):  
Elyse A. Pennington ◽  
Karl M. Seltzer ◽  
Benjamin N. Murphy ◽  
Momei Qin ◽  
John H. Seinfeld ◽  
...  
Keyword(s):  
Los Angeles ◽  
Organic Compounds ◽  
Urban Areas ◽  
Secondary Organic Aerosol ◽  
Current Model ◽  
Regional Scale ◽  
Organic Aerosol ◽  
Aerosol Formation ◽  
Emissions Inventory ◽  
Chemical Products

Abstract. Volatile chemical products (VCPs) are commonly-used consumer and industrial items that are an important source of anthropogenic emissions. Organic compounds from VCPs evaporate on atmospherically relevant time scales and include many species that are secondary organic aerosol (SOA) precursors. However, the chemistry leading to SOA, particularly that of intermediate volatility organic compounds (IVOCs), has not been fully represented in regional-scale models such as the Community Multiscale Air Quality (CMAQ) model, which tend to underpredict SOA concentrations in urban areas. Here we develop a model to represent SOA formation from VCP emissions. The model incorporates a new VCP emissions inventory and employs three new classes of emissions: siloxanes, oxygenated IVOCs, and nonoxygenated IVOCs. VCPs are estimated to produce 1.67 μg m−3 of noontime SOA, doubling the current model predictions and reducing the SOA mass concentration bias from −75 % to −58 % when compared to observations in Los Angeles in 2010. While oxygenated and nonoxygenated intermediate volatility VCP species are emitted in similar quantities, SOA formation is dominated by the nonoxygenated IVOCs. Formaldehyde and SOA show similar relationships to temperature and bias signatures indicating common sources and/or chemistry. This work suggests that VCPs contribute up to half of anthropogenic SOA in Los Angeles and models must better represent SOA precursors from VCPs to predict the urban enhancement of SOA.

scholarly journals Measurement report: Distinct emissions and volatility distribution of intermediate-volatility organic compounds from on-road Chinese gasoline vehicles: implication of high secondary organic aerosol formation potential

2021 ◽  
Vol 21 (4) ◽  
pp. 2569-2583
Author(s):  
Rongzhi Tang ◽  
Quanyang Lu ◽  
Song Guo ◽  
Hui Wang ◽  
Kai Song ◽  
...  
Keyword(s):  
Organic Compounds ◽  
Urban Areas ◽  
Secondary Organic Aerosol ◽  
Organic Aerosol ◽  
Aerosol Formation ◽  
Test Cycle ◽  
Yield Data ◽  
Formation Potential ◽  
Gasoline Vehicles ◽  
Light Duty Vehicle

Abstract. In the present work, we performed chassis dynamometer experiments to investigate the emissions and secondary organic aerosol (SOA) formation potential of intermediate-volatility organic compounds (IVOCs) from an on-road Chinese gasoline vehicle. High IVOC emission factors (EFs) and distinct volatility distribution were recognized. The IVOC EFs for the China V vehicle ranged from 12.1 to 226.3 mg per kilogram fuel, with a median value of 83.7 mg per kilogram fuel, which was higher than that from US vehicles. Besides, a large discrepancy in volatility distribution and chemical composition of IVOCs from Chinese gasoline vehicle exhaust was discovered, with larger contributions of B14–B16 compounds (retention time bins corresponding to C14-C16 n-alkanes) and a higher percentage of n-alkanes. Further we investigated the possible reasons that influence the IVOC EFs and volatility distribution and found that fuel type, starting mode, operating cycles and acceleration rates did have an impact on the IVOC EF. When using E10 (ethanol volume ratio of 10 %, v/v) as fuel, the IVOC EF of the tested vehicle was lower than that using commercial China standard V fuel. The average IVOC-to-THC (total hydrocarbon) ratios for gasoline-fueled and E10-fueled gasoline vehicles were 0.07±0.01 and 0.11±0.02, respectively. Cold-start operation had higher IVOC EFs than hot-start operation. The China Light-Duty Vehicle Test Cycle (CLTC) produced 70 % higher IVOCs than those from the Worldwide Harmonized Light Vehicles Test Cycle (WLTC). We found that the tested vehicle emitted more IVOCs at lower acceleration rates, which leads to high EFs under CLTC. The only factor that may influence the volatility distribution and compound composition is the engine aftertreatment system, which has compound and volatility selectivity in exhaust purification. These distinct characteristics in EFs and volatility may result in higher SOA formation potential in China. Using published yield data and a surrogate equivalent method, we estimated SOA formation under different OA (organic aerosol) loading and NOx conditions. Results showed that under low- and high-NOx conditions at different OA loadings, IVOCs contributed more than 80 % of the predicted SOA. Furthermore, we built up a parameterization method to simply estimate the vehicular SOA based on our bottom-up measurement of VOCs (volatile organic compounds) and IVOCs, which would provide another dimension of information when considering the vehicular contribution to the ambient OA. Our results indicate that vehicular IVOCs contribute significantly to SOA, implying the importance of reducing IVOCs when making air pollution controlling policies in urban areas of China.

scholarly journals Reducing secondary organic aerosol formation from gasoline vehicle exhaust

2017 ◽  
Vol 114 (27) ◽  
pp. 6984-6989 ◽  
Author(s):  
Yunliang Zhao ◽  
Rawad Saleh ◽  
Georges Saliba ◽  
Albert A. Presto ◽  
Timothy D. Gordon ◽  
...  
Keyword(s):  
Los Angeles ◽  
Atmospheric Chemistry ◽  
Urban Areas ◽  
Secondary Organic Aerosol ◽  
Organic Aerosol ◽  
Peroxy Radicals ◽  
Oxides Of Nitrogen ◽  
Aerosol Formation ◽  
Vehicle Exhaust ◽  
Gasoline Vehicles

On-road gasoline vehicles are a major source of secondary organic aerosol (SOA) in urban areas. We investigated SOA formation by oxidizing dilute, ambient-level exhaust concentrations from a fleet of on-road gasoline vehicles in a smog chamber. We measured less SOA formation from newer vehicles meeting more stringent emissions standards. This suggests that the natural replacement of older vehicles with newer ones that meet more stringent emissions standards should reduce SOA levels in urban environments. However, SOA production depends on both precursor concentrations (emissions) and atmospheric chemistry (SOA yields). We found a strongly nonlinear relationship between SOA formation and the ratio of nonmethane organic gas to oxides of nitrogen (NOx) (NMOG:NOx), which affects the fate of peroxy radicals. For example, changing the NMOG:NOxfrom 4 to 10 ppbC/ppbNOxincreased the SOA yield from dilute gasoline vehicle exhaust by a factor of 8. We investigated the implications of this relationship for the Los Angeles area. Although organic gas emissions from gasoline vehicles in Los Angeles are expected to fall by almost 80% over the next two decades, we predict no reduction in SOA production from these emissions due to the effects of rising NMOG:NOxon SOA yields. This highlights the importance of integrated emission control policies for NOxand organic gases.

scholarly journals Secondary Organic Aerosol Yields from the Oxidation of Benzyl Alcohol

2020 ◽  
Author(s):  
Sophia M. Charan ◽  
Reina S. Buenconsejo ◽  
John H. Seinfeld
Keyword(s):  
Benzyl Alcohol ◽  
Urban Areas ◽  
Secondary Organic Aerosol ◽  
Organic Aerosol ◽  
Aerosol Formation ◽  
Aerosol Mass ◽  
Aerosol Exposure ◽  
Chemical Products ◽  
Secondary Organic Aerosol Formation ◽  
Urban Conditions

Abstract. Recent inventory-based analysis suggests that emissions of volatile chemical products in urban areas are now competitive with those from the transportation sector. Understanding the potential for secondary organic aerosol formation from these volatile chemical products is, therefore, critical to predicting levels of aerosol and for formulating policy to reduce aerosol exposure. It is clear that a plethora of oxygenated compounds are either emitted directly into the atmosphere or emitted indoors and later escape into the outdoors. Experimental and computationally simulated environmental chamber data provide an understanding of aerosol yield and chemistry under relevant urban conditions (5–200 ppb NO and 291–312 K) and give insight into the effect of volatile chemical products on the production of secondary organic aerosol. Benzyl alcohol, one of these volatile chemical products, is found to have a large secondary organic aerosol formation potential. At NO concentrations of ~ 80 ppb and 291 K, secondary organic aerosol mass yields for benzyl alcohol can reach 1.

scholarly journals Gasoline aromatics: a critical determinant of urban secondary organic aerosol formation

2017 ◽  
Vol 17 (17) ◽  
pp. 10743-10752 ◽  
Author(s):  
Jianfei Peng ◽  
Min Hu ◽  
Zhuofei Du ◽  
Yinhui Wang ◽  
Jing Zheng ◽  
...  
Keyword(s):  
Volatile Organic Compounds ◽  
Organic Compounds ◽  
Urban Areas ◽  
Secondary Organic Aerosol ◽  
Organic Aerosol ◽  
Urban Atmosphere ◽  
Aerosol Formation ◽  
Vehicle Exhaust ◽  
Aromatic Content ◽  
Volatile Organic

Abstract. Gasoline vehicle exhaust is an important contributor to secondary organic aerosol (SOA) formation in urban atmosphere. Fuel composition has a potentially considerable impact on gasoline SOA production, but the link between fuel components and SOA production is still poorly understood. Here, we present chamber experiments to investigate the impacts of gasoline aromatic content on SOA production through chamber oxidation approach. A significant amplification factor of 3–6 for SOA productions from gasoline exhausts is observed as gasoline aromatic content rose from 29 to 37 %. Considerably higher emission of aromatic volatile organic compounds (VOCs) using high-aromatic fuel plays an essential role in the enhancement of SOA production, while semi-volatile organic compounds (e.g., gas-phase PAHs) may also contribute to the higher SOA production. Our findings indicate that gasoline aromatics significantly influence ambient PM2. 5 concentration in urban areas and emphasize that more stringent regulation of gasoline aromatic content will lead to considerable benefits for urban air quality.

scholarly journals Simulation of organic aerosol formation during the CalNex study: updated mobile emissions and simplified secondary organic aerosol parameterization for intermediate volatility organic compounds

2019 ◽  
Author(s):  
Quanyang Lu ◽  
Benjamin N. Murphy ◽  
Momei Qin ◽  
Peter J. Adams ◽  
Yunliang Zhao ◽  
...  
Keyword(s):  
Los Angeles ◽  
Mass Balance ◽  
Organic Compounds ◽  
Organic Aerosol ◽  
Aerosol Formation ◽  
Mobile Source ◽  
Mobile Source Emissions ◽  
Mobile Sources ◽  
Mobile Emissions ◽  
Chemical Products

Abstract. We describe simulations using an updated version of the Community Multiscale Air Quality model version 5.3 (CMAQ v5.3) to investigate the contribution of intermediate volatile organic compounds (IVOCs) to secondary organic aerosol formation (SOA) in Southern California during the CalNex study. We first derive a model-ready parameterization for SOA formation from IVOC emissions from mobile sources. To account for SOA formation from both diesel and gasoline sources, the parameterization has six lumped precursor species that account for differences in both volatility and molecular structure (aromatic versus aliphatic) of unspeciated IVOC emissions. We also implement new mobile source emission profiles that quantify all IVOCs based on direct measurements. The profiles have been released in SPECIATE 5.0. In the Los Angeles region, gasoline sources emit 4 times more non-methane organic gases (NMOG) than diesel sources, but diesel emits roughly 3 times more IVOCs on an absolute basis. When accounting for IVOCs, the model predicts all mobile sources (including on- and off-road gasoline, aircraft and on- and off-road diesel) contribute ~1 μg m−3 of SOA in Pasadena, CA, which corresponds to 12 % of the measured SOA concentrations during CalNex. Adding mobile-source IVOCs increases the predicted SOA concentration by ~ 70 %. Therefore, IVOCs in mobile source emissions contribute almost as much SOA as traditional precursors such as single-ring aromatics. However, addition of these emissions still does not close either the ambient SOA or IVOC mass balance. To explore the potential contribution of other IVOC sources, we perform two exploratory simulations with varying amounts of IVOC emissions from non-mobile sources. To close the mass balance of primary hydrocarbon IVOCs, IVOCs would need to account for 12 % of NMOG emissions from non-mobile sources (or equivalently 30.7 Ton day−1 in Los Angeles-Pasadena region), a value that is well within the reported range of IVOC content from volatile chemical products. To close the SOA mass balance and explain mildly oxygenated IVOCs in Pasadena, an additional 14.8 % of non-mobile source NMOG emissions would need to be IVOCs, but assigning an IVOC-to-NMOG ratio of 26.8 % (or equivalently 68.5 Ton day−1 in Los Angeles-Pasadena region) for non-mobile sources seems unrealistically high. By incorporating the most comprehensive mobile emissions profiles for SVOCs and IVOCs along with experimentally constrained SOA yields from mobile IVOCs, this CMAQ configuration represents the most accurate photochemical model prediction of the contribution of mobile sources to urban and regional ambient OA to date. Our results highlight the important contribution of IVOCs to SOA production in Los Angeles region, but also underscore that other uncertainties must be addressed (multigenerational aging, aqueous chemistry, and vapor wall losses) to close the SOA mass balance. This research also highlights the effectiveness of regulations to reduce mobile source emissions, which have, in turn, increased the relative importance of other sources, such as volatile chemical products.

scholarly journals Secondary Organic Aerosol Formation from the Oxidation of Decamethylcyclopentasiloxane at Atmospherically Relevant OH Concentrations

2021 ◽  
Author(s):  
Sophia M. Charan ◽  
Yuanlong Huang ◽  
Reina S. Buenconsejo ◽  
Qi Li ◽  
David R. Cocker III ◽  
...  
Keyword(s):  
Particulate Matter ◽  
Urban Areas ◽  
Secondary Organic Aerosol ◽  
Organic Aerosol ◽  
Aerosol Formation ◽  
Yield Data ◽  
Mixing Ratios ◽  
Outdoor Concentration ◽  
Chemical Products ◽  
Atmospherically Relevant

Abstract. Decamethylcyclopentasiloxane (D5, C10H30O5Si5) is measured at ppt levels outdoors and ppb levels indoors. Primarily used in personal care products, its outdoor concentration is correlated to population density. Since understanding the aerosol formation potential of volatile chemical products is critical to understanding particulate matter in urban areas, the secondary organic aerosol yield of D5 was studied under a range of OH concentrations, OH exposures, NOx concentrations, and temperatures. The secondary organic aerosol (SOA) yield from the oxidation of D5 is extremely dependent on the OH concentration, and differing measurements of the SOA yield from the literature are resolved in this study. Here, we compare experimental results from environmental chambers and flow tube reactors. Generally, there are high SOA yields (> 68 %) at OH mixing ratios of 5 × 109 molec cm−3. At atmospherically relevant OH concentrations, the SOA yield is largely < 5 % and usually ~1 %. This is significantly lower than SOA yields used in emission and particulate matter inventories and demonstrates the necessity of OH concentrations similar to the ambient environment when extrapolating SOA yield data to the outdoor atmosphere.

scholarly journals Secondary organic aerosol yields from the oxidation of benzyl alcohol

2020 ◽  
Vol 20 (21) ◽  
pp. 13167-13190
Author(s):  
Sophia M. Charan ◽  
Reina S. Buenconsejo ◽  
John H. Seinfeld
Keyword(s):  
Benzyl Alcohol ◽  
Urban Areas ◽  
Secondary Organic Aerosol ◽  
Organic Aerosol ◽  
Aerosol Formation ◽  
Aerosol Mass ◽  
Aerosol Exposure ◽  
Chemical Products ◽  
Secondary Organic Aerosol Formation ◽  
Urban Conditions

Abstract. Recent inventory-based analysis suggests that emissions of volatile chemical products in urban areas are competitive with those from the transportation sector. Understanding the potential for secondary organic aerosol formation from these volatile chemical products is therefore critical to predicting levels of aerosol and for formulating policy to reduce aerosol exposure. Experimental and computationally simulated environmental chamber data provide an understanding of aerosol yield and chemistry under relevant urban conditions (5–200 ppb NO and 291–312 K) and give insight into the effect of volatile chemical products on the production of secondary organic aerosol. Benzyl alcohol, one of these volatile chemical products, is found to have a large secondary organic aerosol formation potential. At NO concentrations of ∼ 80 ppb and 291 K, secondary organic aerosol mass yields for benzyl alcohol can reach 1.

scholarly journals Simulation of organic aerosol formation during the CalNex study: updated mobile emissions and secondary organic aerosol parameterization for intermediate-volatility organic compounds

2020 ◽  
Vol 20 (7) ◽  
pp. 4313-4332 ◽  
Author(s):  
Quanyang Lu ◽  
Benjamin N. Murphy ◽  
Momei Qin ◽  
Peter J. Adams ◽  
Yunliang Zhao ◽  
...  
Keyword(s):  
Los Angeles ◽  
Mass Balance ◽  
Organic Compounds ◽  
Secondary Organic Aerosol ◽  
Organic Aerosol ◽  
Mobile Source ◽  
Mobile Source Emissions ◽  
Mobile Sources ◽  
Chemical Products ◽  
Source Emission

Abstract. We describe simulations using an updated version of the Community Multiscale Air Quality model version 5.3 (CMAQ v5.3) to investigate the contribution of intermediate-volatility organic compounds (IVOCs) to secondary organic aerosol (SOA) formation in southern California during the CalNex study. We first derive a model-ready parameterization for SOA formation from IVOC emissions from mobile sources. To account for SOA formation from both diesel and gasoline sources, the parameterization has six lumped precursor species that resolve both volatility and molecular structure (aromatic versus aliphatic). We also implement new mobile-source emission profiles that quantify all IVOCs based on direct measurements. The profiles have been released in SPECIATE 5.0. By incorporating both comprehensive mobile-source emission profiles for semivolatile organic compounds (SVOCs) and IVOCs and experimentally constrained SOA yields, this CMAQ configuration best represents the contribution of mobile sources to urban and regional ambient organic aerosol (OA). In the Los Angeles region, gasoline sources emit 4 times more non-methane organic gases (NMOGs) than diesel sources, but diesel emits roughly 3 times more IVOCs on an absolute basis. The revised model predicts all mobile sources (including on- and off-road gasoline, aircraft, and on- and off-road diesel) contribute ∼1 µg m−3 to the daily peak SOA concentration in Pasadena. This represents a ∼70 % increase in predicted daily peak SOA formation compared to the base version of CMAQ. Therefore, IVOCs in mobile-source emissions contribute almost as much SOA as traditional precursors such as single-ring aromatics. However, accounting for these emissions in CMAQ does not reproduce measurements of either ambient SOA or IVOCs. To investigate the potential contribution of other IVOC sources, we performed two exploratory simulations with varying amounts of IVOC emissions from nonmobile sources. To close the mass balance of primary hydrocarbon IVOCs, IVOCs would need to account for 12 % of NMOG emissions from nonmobile sources (or equivalently 30.7 t d−1 in the Los Angeles–Pasadena region), a value that is well within the reported range of IVOC content from volatile chemical products. To close the SOA mass balance and also explain the mildly oxygenated IVOCs in Pasadena, an additional 14.8 % of nonmobile-source NMOG emissions would need to be IVOCs (assuming SOA yields from the mobile IVOCs apply to nonmobile IVOCs). However, an IVOC-to-NMOG ratio of 26.8 % (or equivalently 68.5 t d−1 in the Los Angeles–Pasadena region) for nonmobile sources is likely unrealistically high. Our results highlight the important contribution of IVOCs to SOA production in the Los Angeles region but underscore that other uncertainties must be addressed (multigenerational aging, aqueous chemistry and vapor wall losses) to close the SOA mass balance. This research also highlights the effectiveness of regulations to reduce mobile-source emissions, which have in turn increased the relative importance of other sources, such as volatile chemical products.

scholarly journals Impact of aftertreatment devices on primary emissions and secondary organic aerosol formation potential from in-use diesel vehicles: results from smog chamber experiments

2010 ◽  
Vol 10 (6) ◽  
pp. 16055-16109 ◽  
Author(s):  
R. Chirico ◽  
P. F. DeCarlo ◽  
M. F. Heringa ◽  
T. Tritscher ◽  
R. Richter ◽  
...  
Keyword(s):  
Urban Areas ◽  
Secondary Organic Aerosol ◽  
Organic Aerosol ◽  
Oxidation Catalyst ◽  
Particulate Filter ◽  
Exhaust Aftertreatment ◽  
Smog Chamber ◽  
Aerosol Formation ◽  
Diesel Particulate ◽  
Diesel Vehicles

Abstract. Diesel particulate matter (DPM) is a significant source of aerosol in urban areas and has been linked to adverse health effects. Although newer European directives have introduced increasingly stringent standards for primary PM emissions, gaseous organics emitted from diesel cars can still lead to large amounts of secondary organic aerosol (SOA) in the atmosphere. Here we present results from smog chamber investigations characterizing the primary organic aerosol (POA) and the corresponding SOA formation at atmospherically relevant concentrations for three in-use diesel vehicles with different exhaust aftertreatment systems. One vehicle lacked exhaust aftertreatment devices, one vehicle was equipped with a diesel oxidation catalyst (DOC) and the final vehicle used both a DOC and diesel particulate filter (DPF). The experiments presented here were obtained from the vehicles at conditions representative of idle mode, and for one car in addition at a speed of 60 km/h. An Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) was used to measure the organic aerosol (OA) concentration and to obtain information on the chemical composition. For the conditions explored in this paper, primary aerosols from vehicles without a particulate filter consisted mainly of black carbon (BC) with a low fraction of organic matter (OM, OM/BC<0.5), while the subsequent aging by photooxidation resulted in a consistent production of SOA only for the vehicles without a DOC and with a deactivated DOC. After 5 h of aging ~80% of the total organic aerosol was on average secondary and the estimated "emission factor" for SOA was 0.23–0.56 g/kg fuel burned. In presence of both a DOC and a DPF, primary particles with a mobility diameter above 5 nm were 300±19 cm−3, and only 0.01 g SOA per kg fuel burned was produced within 5 h after lights on. The mass spectra indicate that POA was mostly a non-oxidized OA with an oxygen to carbon atomic ratio (O/C) ranging from 0.097 to 0.190. Five hours of oxidation led to a more oxidized OA with an O/C range of 0.208 to 0.369.

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