Molecular structure impacts on secondary organic aerosol formation from glycol ethers

NASA Astrophysics Data System (ADS)

Li, Lijie; Cocker, David R.

2018-05-01

Glycol ethers, a class of widely used solvents in consumer products, are often considered exempt as volatile organic compounds based on their vapor pressure or boiling points by regulatory agencies. However, recent studies found that glycol ethers volatilize at ambient conditions nearly as rapidly as the traditional high-volatility solvents indicating the potential of glycol ethers to form secondary organic aerosol (SOA). This is the first work on SOA formation from glycol ethers. The impact of molecular structure, specifically -OH, on SOA formation from glycol ethers and related ethers are investigated in the work. Ethers with and without -OH, with methyl group hindrance on -OH and with -OH at different location are studied in the presence of NOX and under "NOX free" conditions. Photooxidation experiments under different oxidation conditions confirm that the processing of ethers is a combination of carbonyl formation, cyclization and fragmentation. Bulk SOA chemical composition analysis and oxidation products identified in both gas and particle phase suggests that the presence and location of -OH in the carbon bond of ethers determine the occurrence of cyclization mechanism during ether oxidation. The cyclization is proposed as a critical SOA formation mechanism to prevent the formation of volatile compounds from fragmentation during the oxidation of ethers. Glycol ethers with -CH2-O-CH2CH2OH structure is found to readily form cyclization products, especially with the presence of NOx, which is more relevant to urban atmospheric conditions than without NOx. Glycol ethers are evaluated as dominating SOA precursors among all ethers studied. It is estimated that the contribution of glycol ethers to anthropogenic SOA is roughly 1% of the current organic aerosol from mobile sources. The contribution of glycol ethers to anthropogenic SOA is roughly 1% of the current organic aerosol from mobile sources and will play a more important role in future anthropogenic SOA formation.

Simulation of SOA formation and composition from oxidation of toluene and m-xylene in chamber experiments

NASA Astrophysics Data System (ADS)

Xu, J.; Liu, Y.; Nakao, S.; Cocker, D.; Griffin, R. J.

2013-12-01

Aromatic hydrocarbons contribute an important fraction of anthropogenic reactive volatile organic compounds (VOCs) in the urban atmosphere. Photo-oxidation of aromatic hydrocarbons leads to secondary organic products that have decreased volatilities or increased solubilities and can form secondary organic aerosol (SOA). Despite the crucial role of aromatic-derived SOA in deteriorating air quality and harming human health, its formation mechanism is not well understood and model simulation of SOA formation still remains difficult. The dependence of aromatic SOA formation on nitrogen oxides (NOx) is not captured fully by most SOA formation models. Most models predict SOA formation under high NOx levels well but underestimate SOA formation under low NOx levels more representative of the ambient atmosphere. Thus, it is crucial to investigate the NOx-dependent chemistry in aromatic photo-oxidation systems and correspondingly update SOA formation models. In this study, NOx-dependent mechanisms of toluene and m-xylene SOA formation are updated using the gas-phase Caltech Atmospheric Chemistry Mechanism (CACM) coupled to a gas/aerosol partitioning model. The updated models were optimized by comparing to eighteen University of California, Riverside United States Environmental Protection Agency (EPA) chamber experiment runs under both high and low NOx conditions. Correction factors for vapor pressures imply uncharacterized aerosol-phase association chemistry. Simulated SOA speciation implies the importance of ring-opening products in governing SOA formation (up to 40%~60% for both aromatics). The newly developed model can predict strong decreases of m-xylene SOA yield with increasing NOx. Speciation distributions under varied NOx levels implies that the well-known competition between RO2 + HO2 and RO2 + NO (RO2 = peroxide bicyclic radical) may not be the only factor influencing SOA formation. The reaction of aromatic peroxy radicals with NO competing with its self-cyclization also affects NOx-dependence of SOA formation. Comparison of SOA formation yield and composition between two aromatics implies aldehyde/ketone chemistry from ring-opening route and chemistry for phenolic route play important roles in governing SOA formation and that ring-opening aldehydes and phenolic nitrates are produced to a greater extent in the toluene system, leading to higher SOA yields for toluene than for m-xylene.

Secondary organic aerosol formation from photochemical aging of light-duty gasoline vehicle exhausts in a smog chamber

NASA Astrophysics Data System (ADS)

Liu, T.; Wang, X.; Deng, W.; Hu, Q.; Ding, X.; Zhang, Y.; He, Q.; Zhang, Z.; Lü, S.; Bi, X.; Chen, J.; Yu, J.

2015-04-01

In China, fast increase in passenger vehicles has procured the growing concern about vehicle exhausts as an important source of anthropogenic secondary organic aerosols (SOA) in megacities hard-hit by haze. However, there are still no chamber simulation studies in China on SOA formation from vehicle exhausts. In this study, the SOA formation of emissions from two idling light-duty gasoline vehicles (LDGVs) (Euro 1 and Euro 4) in China was investigated in a 30 m3 smog chamber. Five photo-oxidation experiments were carried out at 25 °C with the relative humidity around 50%. After aging at an OH exposure of 5 × 106 molecules cm-3 h, the formed SOA was 12-259 times as high as primary OA (POA). The SOA production factors (PF) were 0.001-0.044 g kg-1 fuel, comparable with those from the previous studies at the quite similar OH exposure. This quite lower OH exposure than that in typical atmospheric condition might however lead to the underestimation of the SOA formation potential from LDGVs. Effective SOA yield data in this study were well fit by a one-product gas-particle partitioning model and quite lower than those of a previous study investigating SOA formation form three idling passenger vehicles (Euro 2-Euro 4). Traditional single-ring aromatic precursors and naphthalene could explain 51-90% of the formed SOA. Unspeciated species such as branched and cyclic alkanes might be the possible precursors for the unexplained SOA. A high-resolution time-of-flight aerosol mass spectrometer was used to characterize the chemical composition of SOA. The relationship between f43 (ratio of m/z 43, mostly C2H3O+, to the total signal in mass spectrum) and f44 (mostly CO2+) of the gasoline vehicle exhaust SOA is similar to the ambient semi-volatile oxygenated organic aerosol (SV-OOA). We plot the O : C and H : C molar ratios of SOA in a Van Krevelen diagram. The slopes of ΔH : C/ΔO : C ranged from -0.59 to -0.36, suggesting that the oxidation chemistry in these experiments was a combination of carboxylic acid and alcohol/peroxide formation.

SOA formation from photooxidation of naphthalene and methylnaphthalenes with m-xylene and surrogate mixtures

NASA Astrophysics Data System (ADS)

Chen, Chia-Li; Li, Lijie; Tang, Ping; Cocker, David R.

2018-05-01

SOA formation is not well predicted in current models in urban area. The interaction among multiple anthropogenic volatile organic compounds is essential for the SOA formation in the complex urban atmosphere. Secondary organic aerosol (SOA) from the photooxidation of naphthalene, 1-methylnaphthalene, and 2-methylnaphthalene as well as individual polycyclic aromatic hydrocarbons (PAHs) mixed with m-xylene or an atmospheric surrogate mixture was explored in the UCR CE-CERT environmental chamber under urban relevant low NOx and extremely low NOx (H2O2) conditions. Addition of m-xylene suppressed SOA formation from the individual PAH precursor. A similar suppression effect on SOA formation was observed during the surrogate mixture photooxidation suggesting the importance of gas-phase chemical reactivity to SOA formation. The SOA growth rate for different PAH-m-xylene mixtures was strongly correlated with initial [HO2]/[RO2] ratio but negatively correlated with initial m-xylene/NO ratio. Decreasing SOA formation was observed for increasing m-xylene/PAHs ratios and increasing initial m-xylene/NO ratio. The SOA chemical composition characteristics such as f44 versus f43, H/C ratio, O/C ratio, and the oxidation state of the carbon OSbarc were consistent with a continuously aging with the SOA exhibiting characteristics of both individual precursors. SOA formation from PAHs was also suppressed within an atmospheric surrogate mixture compared to the SOA formed from individual PAHs, indicating that atmospheric reactivity directly influences SOA formation from PAHs.

Secondary organic aerosol formation from photochemical aging of light-duty gasoline vehicle exhausts in a smog chamber

NASA Astrophysics Data System (ADS)

Liu, T.; Wang, X.; Deng, W.; Hu, Q.; Ding, X.; Zhang, Y.; He, Q.; Zhang, Z.; Lü, S.; Bi, X.; Chen, J.; Yu, J.

2015-08-01

In China, a rapid increase in passenger vehicles has led to the growing concern of vehicle exhaust as an important source of anthropogenic secondary organic aerosol (SOA) in megacities hard hit by haze. In this study, the SOA formation of emissions from two idling light-duty gasoline vehicles (LDGVs) (Euro 1 and Euro 4) operated in China was investigated in a 30 m3 smog chamber. Five photo-oxidation experiments were carried out at 25 °C with relative humidity at around 50 %. After aging at an OH exposure of 5 × 106 molecules cm-3 h, the formed SOA was 12-259 times as high as primary organic aerosol (POA). The SOA production factors (PF) were 0.001-0.044 g kg-1 fuel, comparable with those from the previous studies at comparable OH exposure. This quite lower OH exposure than that in typical atmospheric conditions might however lead to the underestimation of the SOA formation potential from LDGVs. Effective SOA yields in this study were well fit by a one-product gas-particle partitioning model but quite lower than those of a previous study investigating SOA formation from three idling passenger vehicles (Euro 2-4). Traditional single-ring aromatic precursors and naphthalene could explain 51-90 % of the formed SOA. Unspeciated species such as branched and cyclic alkanes might be the possible precursors for the unexplained SOA. A high-resolution time-of-flight aerosol mass spectrometer was used to characterize the chemical composition of SOA. The relationship between f43 (ratio of m/z 43, mostly C2H3O+, to the total signal in mass spectrum) and f44 (mostly CO2+) of the gasoline vehicle exhaust SOA is similar to the ambient semi-volatile oxygenated organic aerosol (SV-OOA). We plot the O : C and H : C molar ratios of SOA in a Van Krevelen diagram. The slopes of ΔH : C / ΔO : C ranged from -0.59 to -0.36, suggesting that the oxidation chemistry in these experiments was a combination of carboxylic acid and alcohol/peroxide formation.

In situ secondary organic aerosol formation from ambient pine forest air using an oxidation flow reactor

DOE PAGES

Palm, Brett B.; Campuzano-Jost, Pedro; Ortega, Amber M.; ...

2016-03-08

An oxidation flow reactor (OFR) is a vessel inside which the concentration of a chosen oxidant can be increased for the purpose of studying SOA formation and aging by that oxidant. During the BEACHON-RoMBAS (Bio-hydro-atmosphere interactions of Energy, Aerosols, Carbon, H 2O, Organics & Nitrogen–Rocky Mountain Biogenic Aerosol Study) field campaign, ambient pine forest air was oxidized by OH radicals in an OFR to measure the amount of SOA that could be formed from the real mix of ambient SOA precursor gases, and how that amount changed with time as precursors changed. High OH concentrations and short residence times allowedmore » for semicontinuous cycling through a large range of OH exposures ranging from hours to weeks of equivalent (eq.) atmospheric aging. A simple model is derived and used to account for the relative timescales of condensation of low-volatility organic compounds (LVOCs) onto particles; condensational loss to the walls; and further reaction to produce volatile, non-condensing fragmentation products. More SOA production was observed in the OFR at nighttime (average 3 µg m –3 when LVOC fate corrected) compared to daytime (average 0.9 µg m –3 when LVOC fate corrected), with maximum formation observed at 0.4–1.5 eq. days of photochemical aging. SOA formation followed a similar diurnal pattern to monoterpenes, sesquiterpenes, and toluene+ p-cymene concentrations, including a substantial increase just after sunrise at 07:00 local time. Higher photochemical aging (>10 eq. days) led to a decrease in new SOA formation and a loss of preexisting OA due to heterogeneous oxidation followed by fragmentation and volatilization. When comparing two different commonly used methods of OH production in OFRs (OFR185 and OFR254-70), similar amounts of SOA formation were observed. We recommend the OFR185 mode for future forest studies. Concurrent gas-phase measurements of air after OH oxidation illustrate the decay of primary VOCs, production of small oxidized organic compounds, and net production at lower ages followed by net consumption of terpenoid oxidation products as photochemical age increased. New particle formation was observed in the reactor after oxidation, especially during times when precursor gas concentrations and SOA formation were largest. Approximately 4.4 times more SOA was formed in the reactor from OH oxidation than could be explained by the VOCs measured in ambient air. To our knowledge this is the first time that this has been shown when comparing VOC concentrations with SOA formation measured at the same time, rather than comparing measurements made at different times. Several recently developed instruments have quantified ambient semivolatile and intermediate-volatility organic compounds (S/IVOCs) that were not detected by a proton transfer reaction time-of-flight mass spectrometer (PTR-TOF-MS). An SOA yield of 18–58 % from those compounds can explain the observed SOA formation. S/IVOCs were the only pool of gas-phase carbon that was large enough to explain the observed SOA formation. This work suggests that these typically unmeasured gases play a substantial role in ambient SOA formation. Our results allow ruling out condensation sticking coefficients much lower than 1. Lastly, these measurements help clarify the magnitude of potential SOA formation from OH oxidation in forested environments and demonstrate methods for interpretation of ambient OFR measurements.« less

In situ secondary organic aerosol formation from ambient pine forest air using an oxidation flow reactor

NASA Astrophysics Data System (ADS)

Palm, Brett B.; Campuzano-Jost, Pedro; Ortega, Amber M.; Day, Douglas A.; Kaser, Lisa; Jud, Werner; Karl, Thomas; Hansel, Armin; Hunter, James F.; Cross, Eben S.; Kroll, Jesse H.; Peng, Zhe; Brune, William H.; Jimenez, Jose L.

2016-03-01

An oxidation flow reactor (OFR) is a vessel inside which the concentration of a chosen oxidant can be increased for the purpose of studying SOA formation and aging by that oxidant. During the BEACHON-RoMBAS (Bio-hydro-atmosphere interactions of Energy, Aerosols, Carbon, H2O, Organics & Nitrogen-Rocky Mountain Biogenic Aerosol Study) field campaign, ambient pine forest air was oxidized by OH radicals in an OFR to measure the amount of SOA that could be formed from the real mix of ambient SOA precursor gases, and how that amount changed with time as precursors changed. High OH concentrations and short residence times allowed for semicontinuous cycling through a large range of OH exposures ranging from hours to weeks of equivalent (eq.) atmospheric aging. A simple model is derived and used to account for the relative timescales of condensation of low-volatility organic compounds (LVOCs) onto particles; condensational loss to the walls; and further reaction to produce volatile, non-condensing fragmentation products. More SOA production was observed in the OFR at nighttime (average 3 µg m-3 when LVOC fate corrected) compared to daytime (average 0.9 µg m-3 when LVOC fate corrected), with maximum formation observed at 0.4-1.5 eq. days of photochemical aging. SOA formation followed a similar diurnal pattern to monoterpenes, sesquiterpenes, and toluene+p-cymene concentrations, including a substantial increase just after sunrise at 07:00 local time. Higher photochemical aging (> 10 eq. days) led to a decrease in new SOA formation and a loss of preexisting OA due to heterogeneous oxidation followed by fragmentation and volatilization. When comparing two different commonly used methods of OH production in OFRs (OFR185 and OFR254-70), similar amounts of SOA formation were observed. We recommend the OFR185 mode for future forest studies. Concurrent gas-phase measurements of air after OH oxidation illustrate the decay of primary VOCs, production of small oxidized organic compounds, and net production at lower ages followed by net consumption of terpenoid oxidation products as photochemical age increased. New particle formation was observed in the reactor after oxidation, especially during times when precursor gas concentrations and SOA formation were largest. Approximately 4.4 times more SOA was formed in the reactor from OH oxidation than could be explained by the VOCs measured in ambient air. To our knowledge this is the first time that this has been shown when comparing VOC concentrations with SOA formation measured at the same time, rather than comparing measurements made at different times. Several recently developed instruments have quantified ambient semivolatile and intermediate-volatility organic compounds (S/IVOCs) that were not detected by a proton transfer reaction time-of-flight mass spectrometer (PTR-TOF-MS). An SOA yield of 18-58 % from those compounds can explain the observed SOA formation. S/IVOCs were the only pool of gas-phase carbon that was large enough to explain the observed SOA formation. This work suggests that these typically unmeasured gases play a substantial role in ambient SOA formation. Our results allow ruling out condensation sticking coefficients much lower than 1. These measurements help clarify the magnitude of potential SOA formation from OH oxidation in forested environments and demonstrate methods for interpretation of ambient OFR measurements.

Secondary organic aerosol formation through cloud processing of aromatic VOCs

NASA Astrophysics Data System (ADS)

Herckes, P.; Hutchings, J. W.; Ervens, B.

2010-12-01

Field observations have shown substantial concentrations (20-5,500 ng L-1) of aromatic volatile organic compounds (VOC) in cloud droplets. The potential generation of secondary organic aerosol mass through the processing of these anthropogenic VOCs was investigated through laboratory and modeling studies. Under simulated atmospheric laboratory conditions, in idealized solutions, benzene, toluene, ethylbenzene, and xylene (BTEX) degraded quickly in the aqueous phase. The degradation process yielded less volatile products which would contribute to new aerosol mass upon cloud evaporation. However, when realistic cloud solutions containing natural organic matter were used in the experiments, the reaction rates decreased with increasing organic carbon content. Kinetic data derived from these experiments were used as input to a multiphase box model in order to evaluate the secondary organic aerosol (SOA) mass formation potential of cloud processing of BTEX. Model results will be presented that quantify the SOA amounts from these aqueous phase pathways. The efficiency of this multiphase SOA source will be compared to SOA yields from the same aromatics as treated in traditional SOA models that are restricted to gas phase oxidation and subsequent condensation on particles.

Secondary organic aerosol formation from in situ OH, O3, and NO3 oxidation of ambient forest air in an oxidation flow reactor

NASA Astrophysics Data System (ADS)

Palm, Brett B.; Campuzano-Jost, Pedro; Day, Douglas A.; Ortega, Amber M.; Fry, Juliane L.; Brown, Steven S.; Zarzana, Kyle J.; Dube, William; Wagner, Nicholas L.; Draper, Danielle C.; Kaser, Lisa; Jud, Werner; Karl, Thomas; Hansel, Armin; Gutiérrez-Montes, Cándido; Jimenez, Jose L.

2017-04-01

Ambient pine forest air was oxidized by OH, O3, or NO3 radicals using an oxidation flow reactor (OFR) during the BEACHON-RoMBAS (Bio-hydro-atmosphere interactions of Energy, Aerosols, Carbon, H2O, Organics and Nitrogen - Rocky Mountain Biogenic Aerosol Study) campaign to study biogenic secondary organic aerosol (SOA) formation and organic aerosol (OA) aging. A wide range of equivalent atmospheric photochemical ages was sampled, from hours up to days (for O3 and NO3) or weeks (for OH). Ambient air processed by the OFR was typically sampled every 20-30 min, in order to determine how the availability of SOA precursor gases in ambient air changed with diurnal and synoptic conditions, for each of the three oxidants. More SOA was formed during nighttime than daytime for all three oxidants, indicating that SOA precursor concentrations were higher at night. At all times of day, OH oxidation led to approximately 4 times more SOA formation than either O3 or NO3 oxidation. This is likely because O3 and NO3 will only react with gases containing C = C bonds (e.g., terpenes) to form SOA but will not react appreciably with many of their oxidation products or any species in the gas phase that lacks a C = C bond (e.g., pinonic acid, alkanes). In contrast, OH can continue to react with compounds that lack C = C bonds to produce SOA. Closure was achieved between the amount of SOA formed from O3 and NO3 oxidation in the OFR and the SOA predicted to form from measured concentrations of ambient monoterpenes and sesquiterpenes using published chamber yields. This is in contrast to previous work at this site (Palm et al., 2016), which has shown that a source of SOA from semi- and intermediate-volatility organic compounds (S/IVOCs) 3.4 times larger than the source from measured VOCs is needed to explain the measured SOA formation from OH oxidation. This work suggests that those S/IVOCs typically do not contain C = C bonds. O3 and NO3 oxidation produced SOA with elemental O : C and H : C similar to the least-oxidized OA observed in local ambient air, and neither oxidant led to net mass loss at the highest exposures, in contrast to OH oxidation. An OH exposure in the OFR equivalent to several hours of atmospheric aging also produced SOA with O : C and H : C values similar to ambient OA, while higher aging (days-weeks) led to formation of SOA with progressively higher O : C and lower H : C (and net mass loss at the highest exposures). NO3 oxidation led to the production of particulate organic nitrates (pRONO2), while OH and O3 oxidation (under low NO) did not, as expected. These measurements of SOA formation provide the first direct comparison of SOA formation potential and chemical evolution from OH, O3, and NO3 oxidation in the real atmosphere and help to clarify the oxidation processes that lead to SOA formation from biogenic hydrocarbons.

Real-time measurements of secondary organic aerosol formation and aging from ambient air in an oxidation flow reactor in the Los Angeles area

DOE PAGES

Ortega, Amber M.; Hayes, Patrick L.; Peng, Zhe; ...

2016-06-15

Field studies in polluted areas over the last decade have observed large formation of secondary organic aerosol (SOA) that is often poorly captured by models. The study of SOA formation using ambient data is often confounded by the effects of advection, vertical mixing, emissions, and variable degrees of photochemical aging. An oxidation flow reactor (OFR) was deployed to study SOA formation in real-time during the California Research at the Nexus of Air Quality and Climate Change (CalNex) campaign in Pasadena, CA, in 2010. A high-resolution aerosol mass spectrometer (AMS) and a scanning mobility particle sizer (SMPS) alternated sampling ambient andmore » reactor-aged air. The reactor produced OH concentrations up to 4 orders of magnitude higher than in ambient air. OH radical concentration was continuously stepped, achieving equivalent atmospheric aging of 0.8 days–6.4 weeks in 3 min of processing every 2 h. Enhancement of organic aerosol (OA) from aging showed a maximum net SOA production between 0.8–6 days of aging with net OA mass loss beyond 2 weeks. Reactor SOA mass peaked at night, in the absence of ambient photochemistry and correlated with trimethylbenzene concentrations. Reactor SOA formation was inversely correlated with ambient SOA and O x, which along with the short-lived volatile organic compound correlation, indicates the importance of very reactive ( τ OH ~ 0.3 day) SOA precursors (most likely semivolatile and intermediate volatility species, S/IVOCs) in the Greater Los Angeles Area. Evolution of the elemental composition in the reactor was similar to trends observed in the atmosphere (O : C vs. H : C slope ~ –0.65). Oxidation state of carbon (OSc) in reactor SOA increased steeply with age and remained elevated (OS C ~ 2) at the highest photochemical ages probed. The ratio of OA in the reactor output to excess CO (ΔCO, ambient CO above regional background) vs. photochemical age is similar to previous studies at low to moderate ages and also extends to higher ages where OA loss dominates. The mass added at low-to-intermediate ages is due primarily to condensation of oxidized species, not heterogeneous oxidation. The OA decrease at high photochemical ages is dominated by heterogeneous oxidation followed by fragmentation/evaporation. A comparison of urban SOA formation in this study with a similar study of vehicle SOA in a tunnel suggests the importance of vehicle emissions for urban SOA. Pre-2007 SOA models underpredict SOA formation by an order of magnitude, while a more recent model performs better but overpredicts at higher ages. Furthermore, these results demonstrate the value of the reactor as a tool for in situ evaluation of the SOA formation potential and OA evolution from ambient air.« less

Real-time measurements of secondary organic aerosol formation and aging from ambient air in an oxidation flow reactor in the Los Angeles area

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ortega, Amber M.; Hayes, Patrick L.; Peng, Zhe

Field studies in polluted areas over the last decade have observed large formation of secondary organic aerosol (SOA) that is often poorly captured by models. The study of SOA formation using ambient data is often confounded by the effects of advection, vertical mixing, emissions, and variable degrees of photochemical aging. An oxidation flow reactor (OFR) was deployed to study SOA formation in real-time during the California Research at the Nexus of Air Quality and Climate Change (CalNex) campaign in Pasadena, CA, in 2010. A high-resolution aerosol mass spectrometer (AMS) and a scanning mobility particle sizer (SMPS) alternated sampling ambient andmore » reactor-aged air. The reactor produced OH concentrations up to 4 orders of magnitude higher than in ambient air. OH radical concentration was continuously stepped, achieving equivalent atmospheric aging of 0.8 days–6.4 weeks in 3 min of processing every 2 h. Enhancement of organic aerosol (OA) from aging showed a maximum net SOA production between 0.8–6 days of aging with net OA mass loss beyond 2 weeks. Reactor SOA mass peaked at night, in the absence of ambient photochemistry and correlated with trimethylbenzene concentrations. Reactor SOA formation was inversely correlated with ambient SOA and O x, which along with the short-lived volatile organic compound correlation, indicates the importance of very reactive ( τ OH ~ 0.3 day) SOA precursors (most likely semivolatile and intermediate volatility species, S/IVOCs) in the Greater Los Angeles Area. Evolution of the elemental composition in the reactor was similar to trends observed in the atmosphere (O : C vs. H : C slope ~ –0.65). Oxidation state of carbon (OSc) in reactor SOA increased steeply with age and remained elevated (OS C ~ 2) at the highest photochemical ages probed. The ratio of OA in the reactor output to excess CO (ΔCO, ambient CO above regional background) vs. photochemical age is similar to previous studies at low to moderate ages and also extends to higher ages where OA loss dominates. The mass added at low-to-intermediate ages is due primarily to condensation of oxidized species, not heterogeneous oxidation. The OA decrease at high photochemical ages is dominated by heterogeneous oxidation followed by fragmentation/evaporation. A comparison of urban SOA formation in this study with a similar study of vehicle SOA in a tunnel suggests the importance of vehicle emissions for urban SOA. Pre-2007 SOA models underpredict SOA formation by an order of magnitude, while a more recent model performs better but overpredicts at higher ages. Furthermore, these results demonstrate the value of the reactor as a tool for in situ evaluation of the SOA formation potential and OA evolution from ambient air.« less

Modeling Secondary Organic Aerosol Formation From Emissions of Combustion Sources

NASA Astrophysics Data System (ADS)

Jathar, Shantanu Hemant

Atmospheric aerosols exert a large influence on the Earth's climate and cause adverse public health effects, reduced visibility and material degradation. Secondary organic aerosol (SOA), defined as the aerosol mass arising from the oxidation products of gas-phase organic species, accounts for a significant fraction of the submicron atmospheric aerosol mass. Yet, there are large uncertainties surrounding the sources, atmospheric evolution and properties of SOA. This thesis combines laboratory experiments, extensive data analysis and global modeling to investigate the contribution of semi-volatile and intermediate volatility organic compounds (SVOC and IVOC) from combustion sources to SOA formation. The goals are to quantify the contribution of these emissions to ambient PM and to evaluate and improve models to simulate its formation. To create a database for model development and evaluation, a series of smog chamber experiments were conducted on evaporated fuel, which served as surrogates for real-world combustion emissions. Diesel formed the most SOA followed by conventional jet fuel / jet fuel derived from natural gas, gasoline and jet fuel derived from coal. The variability in SOA formation from actual combustion emissions can be partially explained by the composition of the fuel. Several models were developed and tested along with existing models using SOA data from smog chamber experiments conducted using evaporated fuel (this work, gasoline, fischertropschs, jet fuel, diesels) and published data on dilute combustion emissions (aircraft, on- and off-road gasoline, on- and off-road diesel, wood burning, biomass burning). For all of the SOA data, existing models under-predicted SOA formation if SVOC/IVOC were not included. For the evaporated fuel experiments, when SVOC/IVOC were included predictions using the existing SOA model were brought to within a factor of two of measurements with minor adjustments to model parameterizations. Further, a volatility-only model suggested that differences in the volatility of the precursors were able to explain most of the variability observed in the SOA formation. For aircraft exhaust, the previous methods to simulate SOA formation from SVOC and IVOC performed poorly. A more physically-realistic modeling framework was developed, which was then used to show that SOA formation from aircraft exhaust was (a) higher for petroleum-based than synthetically derived jet fuel and (b) higher at lower engine loads and vice versa. All of the SOA data from combustion emissions experiments were used to determine source-specific parameterizations to model SOA formation from SVOC, IVOC and other unspeciated emissions. The new parameterizations were used to investigate their influence on the OA budget in the United States. Combustion sources were estimated to emit about 2.61 Tg yr-1 of SVOC, 1VOC and other unspeciated emissions (sixth of the total anthropogenic organic emissions), which are predicted to double SOA production from combustion sources in the United States. The contribution of SVOC and IVOC emissions to global SOA formation was assessed using a global climate model. Simulations were performed using a modified version of GISS GCM 11'. The modified model predicted that SVOC and IVOC contributed to half of the OA mass in the atmosphere. Their inclusion improved OA model-measurement comparisons for absolute concentrations, POA-SOA split and volatility (gas-particle partitioning) globally suggesting that atmospheric models need to incorporate SOA formation from SVOC and IVOC if they are to reasonably predict the abundance and properties of aerosols. This thesis demonstrates that SVOC/IVOC and possibly other unspeciated organics emitted by combustion sources are very important precursors of SOA and potentially large contributors to the atmospheric aerosol mass. Models used for research and policy applications need to represent them to improve model-predictions of aerosols on climate and health outcomes. The improved modeling frameworks developed in this dissertation are suitable for implementation into chemical transport models.

Assessing the impact of anthropogenic pollution on isoprene-derived secondary organic aerosol formation in PM2.5 collected from the Birmingham, Alabama, ground site during the 2013 Southern Oxidant and Aerosol Study

NASA Astrophysics Data System (ADS)

Rattanavaraha, Weruka; Chu, Kevin; Hapsari Budisulistiorini, Sri; Riva, Matthieu; Lin, Ying-Hsuan; Edgerton, Eric S.; Baumann, Karsten; Shaw, Stephanie L.; Guo, Hongyu; King, Laura; Weber, Rodney J.; Neff, Miranda E.; Stone, Elizabeth A.; Offenberg, John H.; Zhang, Zhenfa; Gold, Avram; Surratt, Jason D.

2016-04-01

In the southeastern US, substantial emissions of isoprene from deciduous trees undergo atmospheric oxidation to form secondary organic aerosol (SOA) that contributes to fine particulate matter (PM2.5). Laboratory studies have revealed that anthropogenic pollutants, such as sulfur dioxide (SO2), oxides of nitrogen (NOx), and aerosol acidity, can enhance SOA formation from the hydroxyl radical (OH)-initiated oxidation of isoprene; however, the mechanisms by which specific pollutants enhance isoprene SOA in ambient PM2.5 remain unclear. As one aspect of an investigation to examine how anthropogenic pollutants influence isoprene-derived SOA formation, high-volume PM2.5 filter samples were collected at the Birmingham, Alabama (BHM), ground site during the 2013 Southern Oxidant and Aerosol Study (SOAS). Sample extracts were analyzed by gas chromatography-electron ionization-mass spectrometry (GC/EI-MS) with prior trimethylsilylation and ultra performance liquid chromatography coupled to electrospray ionization high-resolution quadrupole time-of-flight mass spectrometry (UPLC/ESI-HR-QTOFMS) to identify known isoprene SOA tracers. Tracers quantified using both surrogate and authentic standards were compared with collocated gas- and particle-phase data as well as meteorological data provided by the Southeastern Aerosol Research and Characterization (SEARCH) network to assess the impact of anthropogenic pollution on isoprene-derived SOA formation. Results of this study reveal that isoprene-derived SOA tracers contribute a substantial mass fraction of organic matter (OM) ( ˜ 7 to ˜ 20 %). Isoprene-derived SOA tracers correlated with sulfate (SO42-) (r2 = 0.34, n = 117) but not with NOx. Moderate correlations between methacrylic acid epoxide and hydroxymethyl-methyl-α-lactone (together abbreviated MAE/HMML)-derived SOA tracers with nitrate radical production (P[NO3]) (r2 = 0.57, n = 40) were observed during nighttime, suggesting a potential role of the NO3 radical in forming this SOA type. However, the nighttime correlation of these tracers with nitrogen dioxide (NO2) (r2 = 0.26, n = 40) was weaker. Ozone (O3) correlated strongly with MAE/HMML-derived tracers (r2 = 0.72, n = 30) and moderately with 2-methyltetrols (r2 = 0.34, n = 15) during daytime only, suggesting that a fraction of SOA formation could occur from isoprene ozonolysis in urban areas. No correlation was observed between aerosol pH and isoprene-derived SOA. Lack of correlation between aerosol acidity and isoprene-derived SOA is consistent with the observation that acidity is not a limiting factor for isoprene SOA formation at the BHM site as aerosols were acidic enough to promote multiphase chemistry of isoprene-derived epoxides throughout the duration of the study. All in all, these results confirm previous studies suggesting that anthropogenic pollutants enhance isoprene-derived SOA formation.

Monoterpene SOA - Contribution of first-generation oxidation products to formation and chemical composition

NASA Astrophysics Data System (ADS)

Mutzel, Anke; Rodigast, Maria; Iinuma, Yoshiteru; Böge, Olaf; Herrmann, Hartmut

2016-04-01

Investigation of the consecutive reactions of first-generation terpene oxidation products provides insight into the formation of secondary organic aerosol (SOA). To this end, OH radical reactions with α-pinene, β-pinene, and limonene were examined along with the OH-oxidation of nopinone as a β-pinene oxidation product and pinonaldehyde and myrtenal as α-pinene oxidation products. The SOA yield of β-pinene (0.50) was much higher than that of α-pinene (0.35) and the limonene/OH system (0.30). This is opposite to the ozonolysis SOA yields described in the literature. The growth curve of SOA from β-pinene shows the contribution of secondary reactions, such as further reaction of nopinone. This contribution (17%) and the high SOA yield of nopinone (0.24) might lead to the high SOA formation potential observed for β-pinene. The majority of the C9 oxidation products observed from β-pinene can be attributed to the consecutive reaction of nopinone, whereas in the case of pinonaldehyde, only a few α-pinene oxidation products were identified. Nopinone contributes significantly to the formation of pinic acid (51%), homoterpenylic acid (74%), and 3-methyl-1,2,3-butane-tricarboxylic acid (MBTCA, 88%) during β-pinene oxidation. The oxidation of pinonaldehyde was expected to produce important SOA markers, but only negligible amounts were identified. This indicates that their formation by oxidation of α-pinene must proceed via different pathways from the further oxidation of pinonaldehyde. Only pinonic acid and MBTCA were found in considerable amounts and were formed in α-pinene oxidation with 57% yield, while that for the pinonaldehyde/OH reaction was 33%. The lack of important SOA marker compounds might cause the low SOA yield (0.07) observed for pinonaldehyde. Based on the low SOA yield, pinonaldehyde contributes only 4.5% to α-pinene SOA. Myrtenal was identified among the gas-phase products of α-pinene oxidation. A majority of α-pinene SOA marker compounds was indeed formed by myrtenal oxidation, especially terebic acid (84%), pinic acid (76%), and diaterpenylic acid acetate (DTAA; 40%). In general, the contribution of myrtenal to α-pinene SOA is estimated to be as high as 23%. Among the detected compounds, homoterpenylic acid was positively identified as a new SOA marker compound, which was formed from β-pinene/OH and nopinone/OH but not from α-pinene/OH. A new reaction pathway yielding MBTCA was also identified in the β-pinene/OH system formed by the oxidation of nopinone, while in the case of α-pinene, the oxidation of pinonaldehyde yielded MBTCA.

Phase, composition, and growth mechanism for secondary organic aerosol from the ozonolysis of α-cedrene

NASA Astrophysics Data System (ADS)

Zhao, Yue; Wingen, Lisa M.; Perraud, Véronique; Finlayson-Pitts, Barbara J.

2016-03-01

Sesquiterpenes are an important class of biogenic volatile organic compounds (BVOCs) and have a high secondary organic aerosol (SOA) forming potential. However, SOA formation from sesquiterpene oxidation has received less attention compared to other BVOCs such as monoterpenes, and the underlying mechanisms remain poorly understood. In this work, we present a comprehensive experimental investigation of the ozonolysis of α-cedrene both in a glass flow reactor (27-44 s reaction times) and in static Teflon chambers (30-60 min reaction times). The SOA was collected by impaction or filters, followed by analysis using attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy and electrospray ionization mass spectrometry (ESI-MS), or measured online using direct analysis in real-time mass spectrometry (DART-MS) and aerosol mass spectrometry (AMS). The slow evaporation of 2-ethylhexyl nitrate that was incorporated into the SOA during its formation and growth gives an estimated diffusion coefficient of 3 × 10-15 cm2 s-1 and shows that SOA is a highly viscous semisolid. Possible structures of four newly observed low molecular weight (MW ≤ 300 Da) reaction products with higher oxygen content than those previously reported were identified. High molecular weight (HMW) products formed in the early stages of the oxidation have structures consistent with aldol condensation products, peroxyhemiacetals, and esters. The size-dependent distributions of HMW products in the SOA, as well as the effects of stabilized Criegee intermediate (SCI) scavengers on HMW products and particle formation, confirm that HMW products and reactions of SCI play a crucial role in early stages of particle formation. Our studies provide new insights into mechanisms of SOA formation and growth in α-cedrene ozonolysis and the important role of sesquiterpenes in new particle formation as suggested by field measurements.

Phase, composition and growth mechanism for secondary organic aerosol from the ozonolysis of α-cedrene

NASA Astrophysics Data System (ADS)

Zhao, Y.; Wingen, L. M.; Perraud, V.; Finlayson-Pitts, B. J.

2015-12-01

Sesquiterpenes are an important class of biogenic volatile organic compounds (BVOCs) and have a high secondary organic aerosol (SOA) forming potential. However, SOA formation from sesquiterpene oxidation has received less attention compared to other BVOCs such as monoterpenes, and the underlying mechanisms remain poorly understood. In this work, we present a comprehensive experimental investigation of the ozonolysis of α-cedrene both in a glass flow reactor (27-44 s reaction times) and in static Teflon chambers (30-60 min reaction times). The SOA was collected by impaction or filters, followed by analysis using attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR) and electrospray ionization mass spectrometry (ESI-MS), or measured on line using direct analysis in real time (DART-MS) and aerosol mass spectrometry (AMS). The slow evaporation of 2-ethylhexyl nitrate that was incorporated into the SOA during its formation and growth gives an estimated diffusion coefficient of 3 × 10-15 cm2 s-1 and shows that SOA is a highly viscous semi-solid. Possible structures of four newly observed low molecular weight (MW ≤ 300 Da) reaction products with higher oxygen content than those previously reported were identified. High molecular weight (HMW) products formed in the early stages of the oxidation have structures consistent with aldol condensation products, peroxyhemiacetals, and esters. The size-dependent distributions of HMW products in the SOA, as well as the effects of stabilized Criegee intermediate (SCI) scavengers on HMW products and particle formation, confirm that HMW products and reactions of Criegee intermediates play a crucial role in early stages of particle formation. Our studies provide new insights into mechanisms of SOA formation and growth in α-cedrene ozonolysis and the important role of sesquiterpenes in new particle formation as suggested by field measurements.

Impact of chamber wall loss of gaseous organic compounds on secondary organic aerosol formation: Explicit modeling of SOA formation from alkane and alkene oxidation

DOE PAGES

La, Y. S.; Camredon, M.; Ziemann, P. J.; ...

2016-02-08

Recent studies have shown that low volatility gas-phase species can be lost onto the smog chamber wall surfaces. Although this loss of organic vapors to walls could be substantial during experiments, its effect on secondary organic aerosol (SOA) formation has not been well characterized and quantified yet. Here the potential impact of chamber walls on the loss of gaseous organic species and SOA formation has been explored using the Generator for Explicit Chemistry and Kinetics of the Organics in the Atmosphere (GECKO-A) modeling tool, which explicitly represents SOA formation and gas–wall partitioning. The model was compared with 41 smog chambermore » experiments of SOA formation under OH oxidation of alkane and alkene series (linear, cyclic and C 12-branched alkanes and terminal, internal and 2-methyl alkenes with 7 to 17 carbon atoms) under high NO x conditions. Simulated trends match observed trends within and between homologous series. The loss of organic vapors to the chamber walls is found to affect SOA yields as well as the composition of the gas and the particle phases. Simulated distributions of the species in various phases suggest that nitrates, hydroxynitrates and carbonylesters could substantially be lost onto walls. The extent of this process depends on the rate of gas–wall mass transfer, the vapor pressure of the species and the duration of the experiments. Furthermore, this work suggests that SOA yields inferred from chamber experiments could be underestimated up a factor of 2 due to the loss of organic vapors to chamber walls.« less

Photolysis of α-KETO Acids in Model Atmospheric Water

NASA Astrophysics Data System (ADS)

Eugene, A. J.; Guzman, M. I.

2017-12-01

Recent work has reported the potential of aqueous-phase photochemistry to promote secondary organic aerosol (SOA) formation. New aqueous photochemical SOA sources may contribute to bridging the gap between field measurements of SOA and models of SOA formation. The ubiquitous α-ketocarboxylic acids pyruvic and glyoxylic acid are known products of the atmospheric oxidation of polycyclic aromatic hydrocarbons (PAHs) as well as of biogenic volatile organic compounds (VOCs). The combination of a carbonyl chromophore (absorbing at wavelengths λ ≥ 300 nm) and hydrophilic functional groups makes these acids likely candidates for forming aqueous SOA by direct sunlight photolysis. We use a variety of analytical techniques including: 2,4-dinitrophenylhydrazine (DNPH) derivatization; ultra-high performance liquid chromatography (UHPLC) and ion chromatography (IC) coupled to mass spectrometry;1H and 13C NMR; and 13C gCOSY NMR to probe the kinetics and mechanisms of the direct photolysis of model solutions of pyruvic acid and glyoxylic acid. The results indicate that despite the structural similarity between the two acids, they each react via very different primary photochemical pathways. Pyruvic acid undergoes a proton-coupled electron transfer (PCET) mechanism with radical recombination, resulting in CO2 and 6-8 carbon organic acids. In contrast, glyoxylic acid primarily undergoes α-cleavage to generate CO, CO2, and glyoxal which is a key species in SOA formation. This work demonstrates that aqueous photolysis is a very competitive atmospheric sink for both pyruvic and glyoxylic acid, indicating that these photoreactions are capable of contributing substantially to SOA formation.

Formation and evolution of molecular products in α-pinene secondary organic aerosol.

PubMed

Zhang, Xuan; McVay, Renee C; Huang, Dan D; Dalleska, Nathan F; Aumont, Bernard; Flagan, Richard C; Seinfeld, John H

2015-11-17

Much of our understanding of atmospheric secondary organic aerosol (SOA) formation from volatile organic compounds derives from laboratory chamber measurements, including mass yield and elemental composition. These measurements alone are insufficient to identify the chemical mechanisms of SOA production. We present here a comprehensive dataset on the molecular identity, abundance, and kinetics of α-pinene SOA, a canonical system that has received much attention owing to its importance as an organic aerosol source in the pristine atmosphere. Identified organic species account for ∼58-72% of the α-pinene SOA mass, and are characterized as semivolatile/low-volatility monomers and extremely low volatility dimers, which exhibit comparable oxidation states yet different functionalities. Features of the α-pinene SOA formation process are revealed for the first time, to our knowledge, from the dynamics of individual particle-phase components. Although monomeric products dominate the overall aerosol mass, rapid production of dimers plays a key role in initiating particle growth. Continuous production of monomers is observed after the parent α-pinene is consumed, which cannot be explained solely by gas-phase photochemical production. Additionally, distinct responses of monomers and dimers to α-pinene oxidation by ozone vs. hydroxyl radicals, temperature, and relative humidity are observed. Gas-phase radical combination reactions together with condensed phase rearrangement of labile molecules potentially explain the newly characterized SOA features, thereby opening up further avenues for understanding formation and evolution mechanisms of α-pinene SOA.

Formation of secondary organic aerosols from gas-phase emissions of heated cooking oils

NASA Astrophysics Data System (ADS)

Liu, Tengyu; Li, Zijun; Chan, ManNin; Chan, Chak K.

2017-06-01

Cooking emissions can potentially contribute to secondary organic aerosol (SOA) but remain poorly understood. In this study, formation of SOA from gas-phase emissions of five heated vegetable oils (i.e., corn, canola, sunflower, peanut and olive oils) was investigated in a potential aerosol mass (PAM) chamber. Experiments were conducted at 19-20 °C and 65-70 % relative humidity (RH). The characterization instruments included a scanning mobility particle sizer (SMPS) and a high-resolution time-of-flight aerosol mass spectrometer (HR-TOF-AMS). The efficiency of SOA production, in ascending order, was peanut oil, olive oil, canola oil, corn oil and sunflower oil. The major SOA precursors from heated cooking oils were related to the content of monounsaturated fat and omega-6 fatty acids in cooking oils. The average production rate of SOA, after aging at an OH exposure of 1. 7 × 1011 molecules cm-3 s, was 1. 35 ± 0. 30 µg min-1, 3 orders of magnitude lower compared with emission rates of fine particulate matter (PM2. 5) from heated cooking oils in previous studies. The mass spectra of cooking SOA highly resemble field-derived COA (cooking-related organic aerosol) in ambient air, with R2 ranging from 0.74 to 0.88. The average carbon oxidation state (OSc) of SOA was -1.51 to -0.81, falling in the range between ambient hydrocarbon-like organic aerosol (HOA) and semi-volatile oxygenated organic aerosol (SV-OOA), indicating that SOA in these experiments was lightly oxidized.

Potential of secondary aerosol formation from Chinese gasoline engine exhaust.

PubMed

Du, Zhuofei; Hu, Min; Peng, Jianfei; Guo, Song; Zheng, Rong; Zheng, Jing; Shang, Dongjie; Qin, Yanhong; Niu, He; Li, Mengren; Yang, Yudong; Lu, Sihua; Wu, Yusheng; Shao, Min; Shuai, Shijin

2018-04-01

Light-duty gasoline vehicles have drawn public attention in China due to their significant primary emissions of particulate matter and volatile organic compounds (VOCs). However, little information on secondary aerosol formation from exhaust for Chinese vehicles and fuel conditions is available. In this study, chamber experiments were conducted to quantify the potential of secondary aerosol formation from the exhaust of a port fuel injection gasoline engine. The engine and fuel used are common in the Chinese market, and the fuel satisfies the China V gasoline fuel standard. Substantial secondary aerosol formation was observed during a 4-5hr simulation, which was estimated to represent more than 10days of equivalent atmospheric photo-oxidation in Beijing. As a consequence, the extreme case secondary organic aerosol (SOA) production was 426±85mg/kg-fuel, with high levels of precursors and OH exposure. The low hygroscopicity of the aerosols formed inside the chamber suggests that SOA was the dominant chemical composition. Fourteen percent of SOA measured in the chamber experiments could be explained through the oxidation of speciated single-ring aromatics. Unspeciated precursors, such as intermediate-volatility organic compounds and semi-volatile organic compounds, might be significant for SOA formation from gasoline VOCs. We concluded that reductions of emissions of aerosol precursor gases from vehicles are essential to mediate pollution in China. Copyright © 2017. Published by Elsevier B.V.

Project Final Report: Linking Plant Stress, Biogenic SOA, and CCN Production - A New Feedback in the Climate System?

DOE Office of Scientific and Technical Information (OSTI.GOV)

VanReken, Timothy; Balasingam, Muhunthan

2017-05-01

This project worked toward understanding the role of variable biogenic emissions in the formation of secondary organic aerosol (SOA), and in turn the potential for this aerosol to affect cloud droplet formation. It was premised on the idea that a changing climate could impose biogenic and abiogenic stresses on plants that would affect the emissions of volatile organic compounds (VOCs). The transformation of these VOCs to SOA and cloud condensation nuclei (CCN) implied the possibility of a feedback mechanism within the biosphere/atmosphere/climate system. The project’s activities centered on laboratory experiments to study the effects of stresses on plants and plant-derivedmore » material under controlled conditions, observing both the VOC emissions and the aerosol that formed from the oxidation of those VOCs. The results highlighted the potentially important contributions of stress and decomposition mechanisms to biogenic SOA formation. Related field measurements elucidated the conditions when these factors could be important in the ambient environment. The project also revealed repeated the complexity of the stress/VOC emission relationship, and the difficulty in expressing these relationships in a comprehensive manner.« less

Secondary organic aerosol formation from in situ OH, O 3, and NO 3 oxidation of ambient forest air in an oxidation flow reactor

DOE Office of Scientific and Technical Information (OSTI.GOV)

Palm, Brett B.; Campuzano-Jost, Pedro; Day, Douglas A.

Ambient pine forest air was oxidized by OH, O 3, or NO 3 radicals using an oxidation flow reactor (OFR) during the BEACHON-RoMBAS (Bio–hydro–atmosphere interactions of Energy, Aerosols, Carbon, H 2O, Organics and Nitrogen – Rocky Mountain Biogenic Aerosol Study) campaign to study biogenic secondary organic aerosol (SOA) formation and organic aerosol (OA) aging. A wide range of equivalent atmospheric photochemical ages was sampled, from hours up to days (for O 3 and NO 3) or weeks (for OH). Ambient air processed by the OFR was typically sampled every 20–30 min, in order to determine how the availability of SOAmore » precursor gases in ambient air changed with diurnal and synoptic conditions, for each of the three oxidants. More SOA was formed during nighttime than daytime for all three oxidants, indicating that SOA precursor concentrations were higher at night. At all times of day, OH oxidation led to approximately 4 times more SOA formation than either O 3 or NO 3 oxidation. This is likely because O 3 and NO 3 will only react with gases containing C = C bonds (e.g., terpenes) to form SOA but will not react appreciably with many of their oxidation products or any species in the gas phase that lacks a C = C bond (e.g., pinonic acid, alkanes). In contrast, OH can continue to react with compounds that lack C = C bonds to produce SOA. Closure was achieved between the amount of SOA formed from O 3 and NO 3 oxidation in the OFR and the SOA predicted to form from measured concentrations of ambient monoterpenes and sesquiterpenes using published chamber yields. This is in contrast to previous work at this site (Palm et al., 2016), which has shown that a source of SOA from semi- and intermediate-volatility organic compounds (S/IVOCs) 3.4 times larger than the source from measured VOCs is needed to explain the measured SOA formation from OH oxidation. This work suggests that those S/IVOCs typically do not contain C = C bonds. O 3 and NO 3 oxidation produced SOA with elemental O : C and H : C similar to the least-oxidized OA observed in local ambient air, and neither oxidant led to net mass loss at the highest exposures, in contrast to OH oxidation. An OH exposure in the OFR equivalent to several hours of atmospheric aging also produced SOA with O : C and H : C values similar to ambient OA, while higher aging (days–weeks) led to formation of SOA with progressively higher O : C and lower H : C (and net mass loss at the highest exposures). NO 3 oxidation led to the production of particulate organic nitrates (pRONO 2), while OH and O 3 oxidation (under low NO) did not, as expected. As a result, these measurements of SOA formation provide the first direct comparison of SOA formation potential and chemical evolution from OH, O 3, and NO 3 oxidation in the real atmosphere and help to clarify the oxidation processes that lead to SOA formation from biogenic hydrocarbons.« less

Secondary organic aerosol formation from in situ OH, O 3, and NO 3 oxidation of ambient forest air in an oxidation flow reactor

DOE PAGES

Palm, Brett B.; Campuzano-Jost, Pedro; Day, Douglas A.; ...

2017-04-25

Ambient pine forest air was oxidized by OH, O 3, or NO 3 radicals using an oxidation flow reactor (OFR) during the BEACHON-RoMBAS (Bio–hydro–atmosphere interactions of Energy, Aerosols, Carbon, H 2O, Organics and Nitrogen – Rocky Mountain Biogenic Aerosol Study) campaign to study biogenic secondary organic aerosol (SOA) formation and organic aerosol (OA) aging. A wide range of equivalent atmospheric photochemical ages was sampled, from hours up to days (for O 3 and NO 3) or weeks (for OH). Ambient air processed by the OFR was typically sampled every 20–30 min, in order to determine how the availability of SOAmore » precursor gases in ambient air changed with diurnal and synoptic conditions, for each of the three oxidants. More SOA was formed during nighttime than daytime for all three oxidants, indicating that SOA precursor concentrations were higher at night. At all times of day, OH oxidation led to approximately 4 times more SOA formation than either O 3 or NO 3 oxidation. This is likely because O 3 and NO 3 will only react with gases containing C = C bonds (e.g., terpenes) to form SOA but will not react appreciably with many of their oxidation products or any species in the gas phase that lacks a C = C bond (e.g., pinonic acid, alkanes). In contrast, OH can continue to react with compounds that lack C = C bonds to produce SOA. Closure was achieved between the amount of SOA formed from O 3 and NO 3 oxidation in the OFR and the SOA predicted to form from measured concentrations of ambient monoterpenes and sesquiterpenes using published chamber yields. This is in contrast to previous work at this site (Palm et al., 2016), which has shown that a source of SOA from semi- and intermediate-volatility organic compounds (S/IVOCs) 3.4 times larger than the source from measured VOCs is needed to explain the measured SOA formation from OH oxidation. This work suggests that those S/IVOCs typically do not contain C = C bonds. O 3 and NO 3 oxidation produced SOA with elemental O : C and H : C similar to the least-oxidized OA observed in local ambient air, and neither oxidant led to net mass loss at the highest exposures, in contrast to OH oxidation. An OH exposure in the OFR equivalent to several hours of atmospheric aging also produced SOA with O : C and H : C values similar to ambient OA, while higher aging (days–weeks) led to formation of SOA with progressively higher O : C and lower H : C (and net mass loss at the highest exposures). NO 3 oxidation led to the production of particulate organic nitrates (pRONO 2), while OH and O 3 oxidation (under low NO) did not, as expected. As a result, these measurements of SOA formation provide the first direct comparison of SOA formation potential and chemical evolution from OH, O 3, and NO 3 oxidation in the real atmosphere and help to clarify the oxidation processes that lead to SOA formation from biogenic hydrocarbons.« less

Potential of select intermediate-volatility organic compounds and consumer products for secondary organic aerosol and ozone formation under relevant urban conditions

NASA Astrophysics Data System (ADS)

Li, Weihua; Li, Lijie; Chen, Chia-li; Kacarab, Mary; Peng, Weihan; Price, Derek; Xu, Jin; Cocker, David R.

2018-04-01

Emissions of certain low vapor pressure-volatile organic compounds (LVP-VOCs) are considered exempt to volatile organic compounds (VOC) regulations due to their low evaporation rates. However, these compounds may still play a role in ambient secondary organic aerosol (SOA) and ozone formation. The LVP-VOCs selected for this work are categorized as intermediate-volatility organic compounds (IVOCs) according to their vapor pressures and molecular formulas. In this study, the evaporation rates of 14 select IVOCs are investigated with half of them losing more than 95% of their mass in less than one month. Further, SOA and ozone formation are presented from 11 select IVOCs and 5 IVOC-containing generic consumer products under atmospherically relevant conditions using varying radical sources (NOx and/or H2O2) and a surrogate reactive organic gas (ROG) mixture. Benzyl alcohol (0.41), n-heptadecane (0.38), and diethylene glycol monobutyl ether (0.16) are determined to have SOA yields greater than 0.1 in the presence of NOx and a surrogate urban hydrocarbon mixture. IVOCs also influence ozone formation from the surrogate urban mixture by impacting radical levels and NOx availability. The addition of lab created generic consumer products has a weak influence on ozone formation from the surrogate mixture but strongly affects SOA formation. The overall SOA and ozone formation of the generic consumer products could not be explained solely by the results of the pure IVOC experiments.

Seasonal cycles of secondary organic aerosol tracers in rural Guangzhou, Southern China: The importance of atmospheric oxidants.

PubMed

Yuan, Qi; Lai, Senchao; Song, Junwei; Ding, Xiang; Zheng, Lishan; Wang, Xinming; Zhao, Yan; Zheng, Junyu; Yue, Dingli; Zhong, Liuju; Niu, Xiaojun; Zhang, Yingyi

2018-05-21

Thirteen secondary organic aerosol (SOA) tracers of isoprene (SOA I ), monoterpenes (SOA M ), sesquiterpenes (SOA S ) and aromatics (SOA A ) in fine particulate matter (PM 2.5 ) were measured at a Pearl River Delta (PRD) regional site for one year. The characteristics including their seasonal cycles and the factors influencing their formation in this region were studied. The seasonal patterns of SOA I , SOA M and SOA S tracers were characterized over three enhancement periods in summer (I), autumn (II) and winter (III), while the elevations of SOA A tracer (i.e., 2,3-dihydroxy-4-oxopentanoic acid, DHOPA) were observed in Periods II and III. We found that SOA formed from different biogenic precursors could be driven by several factors during a one-year seasonal cycle. Isoprene emission controlled SOA I formation throughout the year, while monoterpene and sesquiterpene emissions facilitated SOA M and SOA S formation in summer rather than in other seasons. The influence of atmospheric oxidants (O x ) was found to be an important factor of the formation of SOA M tracers during the enhancement periods in autumn and winter. The formation of SOA S tracer was influenced by the precursor emissions in summer, atmospheric oxidation in autumn and probably also by biomass burning in both summer and winter. In this study, we could not see the strong contribution of biomass burning to DHOPA as suggested by previous studies in this region. Instead, good correlations between observed DHOPA and O x as well as [NO 2 ][O 3 ] suggest the involvement of both ozone (O 3 ) and nitrogen dioxide (NO 2 ) in the formation of DHOPA. The results showed that regional air pollution may not only increase the emissions of aromatic precursors but also can greatly promote the formation processes. Copyright © 2018 Elsevier Ltd. All rights reserved.

Development and Application of an Oxidation Flow Reactor to Study Secondary Organic Aerosol Formation from Ambient Air

NASA Astrophysics Data System (ADS)

Palm, Brett Brian

Secondary organic aerosols (SOA) in the atmosphere play an important role in air quality, human health, and climate. However, the sources, formation pathways, and fate of SOA are poorly constrained. In this dissertation, I present development and application of the oxidation flow reactor (OFR) technique for studying SOA formation from OH, O3, and NO3 oxidation of ambient air. With a several-minute residence time and a portable design with no inlet, OFRs are particularly well-suited for this purpose. I first introduce the OFR concept, and discuss several advances I have made in performing and interpreting OFR experiments. This includes estimating oxidant exposures, modeling the fate of low-volatility gases in the OFR (wall loss, condensation, and oxidation), and comparing SOA yields of single precursors in the OFR with yields measured in environmental chambers. When these experimental details are carefully considered, SOA formation in an OFR can be more reliably compared with ambient SOA formation processes. I then present an overview of what OFR measurements have taught us about SOA formation in the atmosphere. I provide a comparison of SOA formation from OH, O3, and NO3 oxidation of ambient air in a wide variety of environments, from rural forests to urban air. In a rural forest, the SOA formation correlated with biogenic precursors (e.g., monoterpenes). In urban air, it correlated instead with reactive anthropogenic tracers (e.g., trimethylbenzene). In mixed-source regions, the SOA formation did not correlate well with any single precursor, but could be predicted by multilinear regression from several precursors. Despite these correlations, the concentrations of speciated ambient VOCs could only explain approximately 10-50% of the total SOA formed from OH oxidation. In contrast, ambient VOCs could explain all of the SOA formation observed from O3 and NO3 oxidation. Evidence suggests that lower-volatility gases (semivolatile and intermediate-volatility organic compounds; S/IVOCs) were present in ambient air and were the likely source of SOA formation that could not be explained by VOCs. These measurements show that S/IVOCs likely play an important intermediary role in ambient SOA formation in all of the sampled locations, from rural forests to urban air.

Kinetic modeling of secondary organic aerosol formation: effects of particle- and gas-phase reactions of semivolatile products

NASA Astrophysics Data System (ADS)

Chan, A. W. H.; Kroll, J. H.; Ng, N. L.; Seinfeld, J. H.

2007-08-01

The distinguishing mechanism of formation of secondary organic aerosol (SOA) is the partitioning of semivolatile hydrocarbon oxidation products between the gas and aerosol phases. While SOA formation is typically described in terms of partitioning only, the rate of formation and ultimate yield of SOA can also depend on the kinetics of both gas- and aerosol-phase processes. We present a general equilibrium/kinetic model of SOA formation that provides a framework for evaluating the extent to which the controlling mechanisms of SOA formation can be inferred from laboratory chamber data. With this model we examine the effect on SOA formation of gas-phase oxidation of first-generation products to either more or less volatile species, of particle-phase reaction (both first- and second-order kinetics), of the rate of parent hydrocarbon oxidation, and of the extent of reaction of the parent hydrocarbon. The effect of pre-existing organic aerosol mass on SOA yield, an issue of direct relevance to the translation of laboratory data to atmospheric applications, is examined. The importance of direct chemical measurements of gas- and particle-phase species is underscored in identifying SOA formation mechanisms.

Kinetic modeling of Secondary Organic Aerosol formation: effects of particle- and gas-phase reactions of semivolatile products

NASA Astrophysics Data System (ADS)

Chan, A. W. H.; Kroll, J. H.; Ng, N. L.; Seinfeld, J. H.

2007-05-01

The distinguishing mechanism of formation of secondary organic aerosol (SOA) is the partitioning of semivolatile hydrocarbon oxidation products between the gas and aerosol phases. While SOA formation is typically described in terms of partitioning only, the rate of formation and ultimate yield of SOA can also depend on the kinetics of both gas- and aerosol-phase processes. We present a general equilibrium/kinetic model of SOA formation that provides a framework for evaluating the extent to which the controlling mechanisms of SOA formation can be inferred from laboratory chamber data. With this model we examine the effect on SOA formation of gas-phase oxidation of first-generation products to either more or less volatile species, of particle-phase reaction (both first- and second-order kinetics), of the rate of parent hydrocarbon oxidation, and of the extent of reaction of the parent hydrocarbon. The effect of pre-existing organic aerosol mass on SOA yield, an issue of direct relevance to the translation of laboratory data to atmospheric applications, is examined. The importance of direct chemical measurements of gas- and particle-phase species is underscored in identifying SOA formation mechanisms.

Role of methyl group number on SOA formation from aromatic hydrocarbons photooxidation under low NOx conditions

NASA Astrophysics Data System (ADS)

Li, L.; Tang, P.; Nakao, S.; Chen, C.-L.; Cocker, D. R., III

2015-11-01

Substitution of methyl groups onto the aromatic ring determines the SOA formation from the aromatic hydrocarbon precursor. This study links the number of methyl groups on the aromatic ring to SOA formation from aromatic hydrocarbons photooxidation under low NOx conditions (HC / NO > 10 ppb C : ppb). Aromatic hydrocarbons with increasing numbers of methyl groups are systematically studied. SOA formation from pentamethylbenzene and hexamethylbenzene are reported for the first time. A decreasing SOA yield with increasing number of methyl groups is observed. Linear trends are found in both f44 vs. f43 and O / C vs. H / C for SOA from aromatic hydrocarbons with zero to six methyl groups. An SOA oxidation state predictive method based on benzene is used to examine the effect of added methyl groups on aromatic oxidation under low NOx conditions. Further, the impact of methyl group number on density and volatility of SOA from aromatic hydrocarbons is explored. Finally, a mechanism for methyl group impact on SOA formation is suggested. Overall, this work suggests as more methyl groups are attached on the aromatic ring, SOA products from these aromatic hydrocarbons become less oxidized per mass/carbon.

Contrasting Secondary Organic Aerosol Formation in Aerosol Liquid Water During Summer and Winter

NASA Astrophysics Data System (ADS)

El-Sayed, M.; Hennigan, C. J.

2017-12-01

In this study, we characterize the formation of aqueous secondary organic aerosols (aqSOA) in the eastern United States during summer and winter. The aim was to identify the main factors affecting the reversible and irreversible uptake of water-soluble organic gases to aerosol liquid water under variable influence from biogenic and anthropogenic sources. The reversible and irreversible uptake of water-soluble organic gases to aerosol water was measured in Baltimore, MD using a recently developed on-line method. The formation of aqSOA was observed during the summer and the winter; however, the amount of aqSOA varied significantly between the two seasons, as did the reversible and irreversible nature of the uptake. While the availability of aerosol liquid water (ALW) predominantly controlled aqSOA formation in the summer, wintertime aqSOA formation was limited by precursor VOCs as well. During the summer, aqSOA formation was tightly linked with isoprene oxidation, while the aqSOA formed in the winter was associated with biomass burning. Irreversible aqSOA was formed in both seasons; however, reversible aqSOA was only observed in the summer. Overall, these results demonstrate the importance of multi-phase chemistry in aerosol formation and underscore the significance of soluble organic gases partitioning to aerosol water both reversibly and irreversibly.

Role of methyl group number on SOA formation from monocyclic aromatic hydrocarbons photooxidation under low-NOx conditions

NASA Astrophysics Data System (ADS)

Li, L.; Tang, P.; Nakao, S.; Chen, C.-L.; Cocker, D. R., III

2016-02-01

Substitution of methyl groups onto the aromatic ring determines the secondary organic aerosol (SOA) formation from the monocyclic aromatic hydrocarbon precursor (SOA yield and chemical composition). This study links the number of methyl groups on the aromatic ring to SOA formation from monocyclic aromatic hydrocarbons photooxidation under low-NOx conditions (HC/NO > 10 ppbC : ppb). Monocyclic aromatic hydrocarbons with increasing numbers of methyl groups are systematically studied. SOA formation from pentamethylbenzene and hexamethylbenzene are reported for the first time. A decreasing SOA yield with increasing number of methyl groups is observed. Linear trends are found in both f44 vs. f43 and O / C vs. H / C for SOA from monocyclic aromatic hydrocarbons with zero to six methyl groups. An SOA oxidation state predictive method based on benzene is used to examine the effect of added methyl groups on aromatic oxidation under low-NOx conditions. Further, the impact of methyl group number on density and volatility of SOA from monocyclic aromatic hydrocarbons is explored. Finally, a mechanism for methyl group impact on SOA formation is suggested. Overall, this work suggests that, as more methyl groups are attached on the aromatic ring, SOA products from these monocyclic aromatic hydrocarbons become less oxidized per mass/carbon on the basis of SOA yield or chemical composition.

Temperature Effects on Secondary Organic Aerosol (SOA) from the Dark Ozonolysis and Photo-Oxidation of Isoprene.

PubMed

Clark, Christopher H; Kacarab, Mary; Nakao, Shunsuke; Asa-Awuku, Akua; Sato, Kei; Cocker, David R

2016-06-07

Isoprene is globally the most ubiquitous nonmethane hydrocarbon. The biogenic emission is found in abundance and has a propensity for SOA formation in diverse climates. It is important to characterize isoprene SOA formation with varying reaction temperature. In this work, the effect of temperature on SOA formation, physical properties, and chemical nature is probed. Three experimental systems are probed for temperature effects on SOA formation from isoprene, NO + H2O2 photo-oxidation, H2O2 only photo-oxidation, and dark ozonolysis. These experiments show that isoprene readily forms SOA in unseeded chamber experiments, even during dark ozonolysis, and also reveal that temperature affects SOA yield, volatility, and density formed from isoprene. As temperature increases SOA yield is shown to generally decrease, particle density is shown to be stable (or increase slightly), and formed SOA is shown to be less volatile. Chemical characterization is shown to have a complex trend with both temperature and oxidant, but extensive chemical speciation are provided.

Simulating Aqueous-Phase Isoprene-Epoxydiol (IEPOX) ...

EPA Pesticide Factsheets

The lack of statistically robust relationships between IEPOX (isoprene epoxydiol)-derived SOA (IEPOX SOA) and aerosol liquid water and pH observed during the 2013 Southern Oxidant and Aerosol Study (SOAS) emphasizes the importance of modeling the whole system to understand the controlling factors governing IEPOX SOA formation. We present a mechanistic modeling investigation predicting IEPOX SOA based on Community Multiscale Air Quality (CMAQ) model algorithms and a recently introduced photochemical box model, simpleGAMMA. We aim to (1) simulate IEPOX SOA tracers from the SOAS Look Rock ground site, (2) compare the two model formulations, (3) determine the limiting factors in IEPOX SOA formation, and (4) test the impact of a hypothetical sulfate reduction scenario on IEPOX SOA. The estimated IEPOX SOA mass variability is in similar agreement (r2 ∼ 0.6) with measurements. Correlations of the estimated and measured IEPOX SOA tracers with observed aerosol surface area (r2 ∼ 0.5–0.7), rate of particle-phase reaction (r2 ∼ 0.4–0.7), and sulfate (r2 ∼ 0.4–0.5) suggest an important role of sulfate in tracer formation via both physical and chemical mechanisms. A hypothetical 25% reduction of sulfate results in ∼70% reduction of IEPOX SOA formation, reaffirming the importance of aqueous phase chemistry in IEPOX SOA production. The National Exposure Research Laboratory (NERL) Computational Exposure Division (CED) develops and evaluates data, decision-suppor

Modeling the formation and properties of traditional and non-traditional secondary organic aerosol: problem formulation and application to aircraft exhaust

NASA Astrophysics Data System (ADS)

Jathar, S. H.; Miracolo, M. A.; Presto, A. A.; Adams, P. J.; Robinson, A. L.

2012-04-01

We present a methodology to model secondary organic aerosol (SOA) formation from the photo-oxidation of low-volatility organics (semi-volatile and intermediate volatility organic compounds). The model is parameterized and tested using SOA data collected during two field campaigns that characterized the atmospheric evolution of dilute gas-turbine engine emissions using a smog chamber. Photo-oxidation formed a significant amount of SOA, much of which cannot be explained based on the emissions of traditional, speciated precursors; we refer to this as non-traditional SOA (NT-SOA). The NT-SOA can be explained by emissions of low-volatility organic vapors measured using sorbents. Since these vapors could not be speciated, we employ a volatility-based approach to model NT-SOA formation. We show that the method proposed by Robinson et al. (2007) is unable to explain the timing of NT-SOA formation because it assumes a very modest reduction in volatility of the precursors with every oxidation reaction. In contrast, a Hybrid method, similar to models of traditional SOA formation, assumes a larger reduction in volatility with each oxidation step and results in a better reproduction of NT-SOA formation. The NT-SOA yields estimated for the low-volatility organic vapor emissions are similar to literature data for large n-alkanes and other low-volatility organics. The yields vary with fuel composition (JP8 versus Fischer-Tropsch) and engine load (idle versus non-idle). These differences are consistent with the expected contribution of high (aromatics and n-alkanes) and low (branched alkanes and oxygenated species) SOA forming species to the exhaust.

Organosulfates as Tracers for Secondary Organic Aerosol (SOA) Formation from 2-Methyl-3-Buten-2 ol (MBO) in the Atmosphere

EPA Science Inventory

2-Methyl-3-buten-2-ol (MBO) is an important biogenic volatile organic compound (BVOC) emitted by pine trees and a potential precursor of atmospheric secondary organic aerosol (SOA) in forested regions. In the present study, hydroxyl radical (OH)-initiated oxidation of MBO was exa...

SOA formation by biogenic and carbonyl compounds: data evaluation and application.

PubMed

Ervens, Barbara; Kreidenweis, Sonia M

2007-06-01

The organic fraction of atmospheric aerosols affects the physical and chemical properties of the particles and their role in the climate system. Current models greatly underpredict secondary organic aerosol (SOA) mass. Based on a compilation of literature studies that address SOA formation, we discuss different parameters that affect the SOA formation efficiency of biogenic compounds (alpha-pinene, isoprene) and aliphatic aldehydes (glyoxal, hexanal, octanal, hexadienal). Applying a simple model, we find that the estimated SOA mass after one week of aerosol processing under typical atmospheric conditions is increased by a few microg m(-3) (low NO(x) conditions). Acid-catalyzed reactions can create > 50% more SOA mass than processes under neutral conditions; however, other parameters such as the concentration ratio of organics/NO(x), relative humidity, and absorbing mass are more significant. The assumption of irreversible SOA formation not limited by equilibrium in the particle phase or by depletion of the precursor leads to unrealistically high SOA masses for some of the assumptions we made (surface vs volume controlled processes).

Different roles of water in secondary organic aerosol formation from toluene and isoprene

NASA Astrophysics Data System (ADS)

Jia, Long; Xu, YongFu

2018-06-01

Roles of water in the formation of secondary organic aerosol (SOA) from the irradiations of toluene-NO2 and isoprene-NO2 were investigated in a smog chamber. Experimental results show that the yield of SOA from toluene almost doubled as relative humidity increased from 5 to 85 %, whereas the yield of SOA from isoprene under humid conditions decreased by 2.6 times as compared to that under dry conditions. The distinct difference of RH effects on SOA formation from toluene and isoprene is well explained with our experiments and model simulations. The increased SOA from humid toluene-NO2 irradiations is mainly contributed by O-H-containing products such as polyalcohols formed from aqueous reactions. The major chemical components of SOA in isoprene-NO2 irradiations are oligomers formed from the gas phase. SOA formation from isoprene-NO2 irradiations is controlled by stable Criegee intermediates (SCIs) that are greatly influenced by water. As a result, high RH can obstruct the oligomerization reaction of SCIs to form SOA.

In vitro exposure to isoprene-derived secondary organic aerosol by direct deposition and its effects on COX-2 and IL-8 gene expression

NASA Astrophysics Data System (ADS)

Arashiro, Maiko; Lin, Ying-Hsuan; Sexton, Kenneth G.; Zhang, Zhenfa; Jaspers, Ilona; Fry, Rebecca C.; Vizuete, William G.; Gold, Avram; Surratt, Jason D.

2016-11-01

Atmospheric oxidation of isoprene, the most abundant non-methane hydrocarbon emitted into Earth's atmosphere primarily from terrestrial vegetation, is now recognized as a major contributor to the global secondary organic aerosol (SOA) burden. Anthropogenic pollutants significantly enhance isoprene SOA formation through acid-catalyzed heterogeneous chemistry of epoxide products. Since isoprene SOA formation as a source of fine aerosol is a relatively recent discovery, research is lacking on evaluating its potential adverse effects on human health. The objective of this study was to examine the effect of isoprene-derived SOA on inflammation-associated gene expression in human lung cells using a direct deposition exposure method. We assessed altered expression of inflammation-related genes in human bronchial epithelial cells (BEAS-2B) exposed to isoprene-derived SOA generated in an outdoor chamber facility. Measurements of gene expression of known inflammatory biomarkers interleukin 8 (IL-8) and cyclooxygenase 2 (COX-2) in exposed cells, together with complementary chemical measurements, showed that a dose of 0.067 µg cm-2 of SOA from isoprene photooxidation leads to statistically significant increases in IL-8 and COX-2 mRNA levels. Resuspension exposures using aerosol filter extracts corroborated these findings, supporting the conclusion that isoprene-derived SOA constituents induce the observed changes in mRNA levels. The present study is an attempt to examine the early biological responses of isoprene SOA exposure in human lung cells.

Elemental Composition Analysis to Investigate NOx Effects on Secondary Organic Aerosol from α-Pinene Using Ultrahigh Resolution Mass Spectrometry

NASA Astrophysics Data System (ADS)

Lim, H. J.; Park, J. H.; Babar, Z.

2015-12-01

Secondary organic aerosol (SOA) accounts for 20-70% of atmospheric fine aerosol. NOx plays crucial roles in SOA formation and consequently affects the composition and yield of SOA. SOA component speciation is incomplete due to its complex composition of polar oxygenated and multifunctional species. In this study, ultrahigh resolution mass spectrometry (UHR MS) was applied to improve the understanding of NOx effects on biogenic SOA formation by identifying the elemental composition of SOA. Additional research aim was to investigate oligomer components that are considered as a driving force for SOA formation and growth. In this study α-pinene SOA from photochemical reaction was examined. SOA formation was performed in the absence and presence of NOx at dry condition (<5% RH) of room temperature (~25oC) in ~8 m3 KNU smog chamber. SOA was collected on Teflon-coated glass fiber filter, which was extracted using acetonitrile and analyzed by ultrahigh resolution 15T FT-ICR MS. UHR MS data were interpreted in various ways including molecular formula, Kendrick diagram, van Krevelen diagram, and double bond equivalent values. Substantially large fractions of them are nitrogen containing species. Thousands of individual species of SOA were identified. For SOA in the absence of NOx. intensity normalized mean O/C, H/C, N/C, OM/OC ratios were 0.43, 1.52, 0.02, and 1.68, respectively. For SOA in the presence of NOx, those ratios were 0.52, 0.95, 0.08, and 1.48, respectively. 4 different oligomer formation mechanisms (addition, H abstraction, hydrolysis and de-hydrolysis reaction) were examined on the basis of SOA compositions. Detailed discussion will be presented on the molecular structure and building block of oligomers in SOA as well as the evolution of individual elemental composition by multi-generation reactions. This work was supported by the National Research Foundation of Korea (NRF) grant funded by the Korea government (MEST) (No. 2011-01350000).

Incremental Reactivity Effects on Secondary Organic Aerosol Formation in Urban Atmospheres with and without Biogenic Influence

NASA Astrophysics Data System (ADS)

Kacarab, Mary; Li, Lijie; Carter, William P. L.; Cocker, David R., III

2016-04-01

Two different surrogate mixtures of anthropogenic and biogenic volatile organic compounds (VOCs) were developed to study secondary organic aerosol (SOA) formation at atmospheric reactivities similar to urban regions with varying biogenic influence levels. Environmental chamber simulations were designed to enable the study of the incremental aerosol formation from select anthropogenic (m-Xylene, 1,2,4-Trimethylbenzene, and 1-Methylnaphthalene) and biogenic (α-pinene) precursors under the chemical reactivity set by the two different surrogate mixtures. The surrogate reactive organic gas (ROG) mixtures were based on that used to develop the maximum incremental reactivity (MIR) factors for evaluation of O3 forming potential. Multiple incremental aerosol formation experiments were performed in the University of California Riverside (UCR) College of Engineering Center for Environmental Research and Technology (CE-CERT) dual 90m3 environmental chambers. Incremental aerosol yields were determined for each of the VOCs studied and compared to yields found from single precursor studies. Aerosol physical properties of density, volatility, and hygroscopicity were monitored throughout experiments. Bulk elemental chemical composition from high-resolution time of flight aerosol mass spectrometer (HR-ToF-AMS) data will also be presented. Incremental yields and SOA chemical and physical characteristics will be compared with data from previous single VOC studies conducted for these aerosol precursors following traditional VOC/NOx chamber experiments. Evaluation of the incremental effects of VOCs on SOA formation and properties are paramount in evaluating how to best extrapolate environmental chamber observations to the ambient atmosphere and provides useful insights into current SOA formation models. Further, the comparison of incremental SOA from VOCs in varying surrogate urban atmospheres (with and without strong biogenic influence) allows for a unique perspective on the impacts different compounds have on aerosol formation in different urban regions.

Elucidating secondary organic aerosol from diesel and gasoline vehicles through detailed characterization of organic carbon emissions

PubMed Central

Gentner, Drew R.; Isaacman, Gabriel; Worton, David R.; Chan, Arthur W. H.; Dallmann, Timothy R.; Davis, Laura; Liu, Shang; Day, Douglas A.; Russell, Lynn M.; Wilson, Kevin R.; Weber, Robin; Guha, Abhinav; Harley, Robert A.; Goldstein, Allen H.

2012-01-01

Emissions from gasoline and diesel vehicles are predominant anthropogenic sources of reactive gas-phase organic carbon and key precursors to secondary organic aerosol (SOA) in urban areas. Their relative importance for aerosol formation is a controversial issue with implications for air quality control policy and public health. We characterize the chemical composition, mass distribution, and organic aerosol formation potential of emissions from gasoline and diesel vehicles, and find diesel exhaust is seven times more efficient at forming aerosol than gasoline exhaust. However, both sources are important for air quality; depending on a region’s fuel use, diesel is responsible for 65% to 90% of vehicular-derived SOA, with substantial contributions from aromatic and aliphatic hydrocarbons. Including these insights on source characterization and SOA formation will improve regional pollution control policies, fuel regulations, and methodologies for future measurement, laboratory, and modeling studies. PMID:23091031

Elucidating secondary organic aerosol from diesel and gasoline vehicles through detailed characterization of organic carbon emissions.

PubMed

Gentner, Drew R; Isaacman, Gabriel; Worton, David R; Chan, Arthur W H; Dallmann, Timothy R; Davis, Laura; Liu, Shang; Day, Douglas A; Russell, Lynn M; Wilson, Kevin R; Weber, Robin; Guha, Abhinav; Harley, Robert A; Goldstein, Allen H

2012-11-06

Emissions from gasoline and diesel vehicles are predominant anthropogenic sources of reactive gas-phase organic carbon and key precursors to secondary organic aerosol (SOA) in urban areas. Their relative importance for aerosol formation is a controversial issue with implications for air quality control policy and public health. We characterize the chemical composition, mass distribution, and organic aerosol formation potential of emissions from gasoline and diesel vehicles, and find diesel exhaust is seven times more efficient at forming aerosol than gasoline exhaust. However, both sources are important for air quality; depending on a region's fuel use, diesel is responsible for 65% to 90% of vehicular-derived SOA, with substantial contributions from aromatic and aliphatic hydrocarbons. Including these insights on source characterization and SOA formation will improve regional pollution control policies, fuel regulations, and methodologies for future measurement, laboratory, and modeling studies.

Degradation of indoor limonene by outdoor ozone: A cascade of secondary organic aerosols.

PubMed

Rösch, Carolin; Wissenbach, Dirk K; Franck, Ulrich; Wendisch, Manfred; Schlink, Uwe

2017-07-01

In indoor air, terpene-ozone reactions can form secondary organic aerosols (SOA) in a transient process. 'Real world' measurements conducted in a furnished room without air conditioning were modelled involving the indoor background of airborne particulate matter, outdoor ozone infiltrated by natural ventilation, repeated transient limonene evaporations, and different subsequent ventilation regimes. For the given setup, we disentangled the development of nucleated, coagulated, and condensed SOA fractions in the indoor air and calculated the time dependence of the aerosol mass fraction (AMF) by means of a process model. The AMF varied significantly between 0.3 and 5.0 and was influenced by the ozone limonene ratio and the background particles which existed prior to SOA formation. Both influencing factors determine whether nucleation or adsorption processes are preferred; condensation is strongly intensified by particulate background. The results provide evidence that SOA levels in natural indoor environments can surpass those known from chamber measurements. An indicator for the SOA forming potential of limonene was found to be limona ketone. Multiplying its concentration (in μg/m 3 ) by 450(±100) provides an estimate of the concentration of the reacted limonene. This can be used to detect a high particle formation potential due to limonene pollution, e.g. in epidemiological studies considering adverse health effects of indoor air pollutants. Copyright © 2017 Elsevier Ltd. All rights reserved.

Reducing secondary organic aerosol formation from gasoline vehicle exhaust

PubMed Central

Zhao, Yunliang; Saleh, Rawad; Presto, Albert A.; Gordon, Timothy D.; Drozd, Greg T.; Goldstein, Allen H.; Robinson, Allen L.

2017-01-01

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:NOx from 4 to 10 ppbC/ppbNOx increased 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:NOx on SOA yields. This highlights the importance of integrated emission control policies for NOx and organic gases. PMID:28630318

Gene Expression Profiling in Human Lung Cells Exposed to Isoprene-Derived Secondary Organic Aerosol.

PubMed

Lin, Ying-Hsuan; Arashiro, Maiko; Clapp, Phillip W; Cui, Tianqu; Sexton, Kenneth G; Vizuete, William; Gold, Avram; Jaspers, Ilona; Fry, Rebecca C; Surratt, Jason D

2017-07-18

Secondary organic aerosol (SOA) derived from the photochemical oxidation of isoprene contributes a substantial mass fraction to atmospheric fine particulate matter (PM 2.5 ). The formation of isoprene SOA is influenced largely by anthropogenic emissions through multiphase chemistry of its multigenerational oxidation products. Considering the abundance of isoprene SOA in the troposphere, understanding mechanisms of adverse health effects through inhalation exposure is critical to mitigating its potential impact on public health. In this study, we assessed the effects of isoprene SOA on gene expression in human airway epithelial cells (BEAS-2B) through an air-liquid interface exposure. Gene expression profiling of 84 oxidative stress and 249 inflammation-associated human genes was performed. Our results show that the expression levels of 29 genes were significantly altered upon isoprene SOA exposure under noncytotoxic conditions (p < 0.05), with the majority (22/29) of genes passing a false discovery rate threshold of 0.3. The most significantly affected genes belong to the nuclear factor (erythroid-derived 2)-like 2 (Nrf2) transcription factor network. The Nrf2 function is confirmed through a reporter cell line. Together with detailed characterization of SOA constituents, this study reveals the impact of isoprene SOA exposure on lung responses and highlights the importance of further understanding its potential health outcomes.

Comparison of secondary organic aerosol formation from toluene on initially wet and dry ammonium sulfate particles at moderate relative humidity

NASA Astrophysics Data System (ADS)

Liu, Tengyu; Huang, Dan Dan; Li, Zijun; Liu, Qianyun; Chan, ManNin; Chan, Chak K.

2018-04-01

The formation of secondary organic aerosol (SOA) has been widely studied in the presence of dry seed particles at low relative humidity (RH). At higher RH, initially dry seed particles can exist as wet particles due to water uptake by the seeds as well as the SOA. Here, we investigated the formation of SOA from the photooxidation of toluene using an oxidation flow reactor in the absence of NOx under a range of OH exposures on initially wet or dry ammonium sulfate (AS) seed particles at an RH of 68 %. The ratio of the SOA yield on wet AS seeds to that on dry AS seeds, the relative SOA yield, decreased from 1.31 ± 0.02 at an OH exposure of 4.66 × 1010 molecules cm-3 s to 1.01 ± 0.01 at an OH exposure of 5.28 × 1011 molecules cm-3 s. This decrease may be due to the early deliquescence of initially dry AS seeds after being coated by highly oxidized toluene-derived SOA. SOA formation lowered the deliquescence RH of AS and resulted in the uptake of water by both AS and SOA. Hence the initially dry AS seeds contained aerosol liquid water (ALW) soon after SOA formed, and the SOA yield and ALW approached those of the initially wet AS seeds as OH exposure and ALW increased, especially at high OH exposure. However, a higher oxidation state of the SOA on initially wet AS seeds than that on dry AS seeds was observed at all levels of OH exposure. The difference in mass fractions of m / z 29, 43 and 44 of SOA mass spectra, obtained using an aerosol mass spectrometer (AMS), indicated that SOA formed on initially wet seeds may be enriched in earlier-generation products containing carbonyl functional groups at low OH exposures and later-generation products containing acidic functional groups at high exposures. Our results suggest that inorganic dry seeds become at least partially deliquesced particles during SOA formation and hence that ALW is inevitably involved in the SOA formation at moderate RH. More laboratory experiments conducted with a wide variety of SOA precursors and inorganic seeds under different NOx and RH conditions are warranted.

Secondary organic aerosol formation from ambient air in an oxidation flow reactor in central Amazonia

DOE PAGES

Palm, Brett B.; de Sá, Suzane S.; Day, Douglas A.; ...

2018-01-17

Secondary organic aerosol (SOA) formation from ambient air was studied using an oxidation flow reactor (OFR) coupled to an aerosol mass spectrometer (AMS) during both the wet and dry seasons at the Observations and Modeling of the Green Ocean Amazon (GoAmazon2014/5) field campaign. Measurements were made at two sites downwind of the city of Manaus, Brazil. Ambient air was oxidized in the OFR using variable concentrations of either OH or O 3, over ranges from hours to days (O 3) or weeks (OH) of equivalent atmospheric aging. The amount of SOA formed in the OFR ranged from 0 to asmore » much as 10 μg m -3, depending on the amount of SOA precursor gases in ambient air. Typically, more SOA was formed during nighttime than daytime, and more from OH than from O 3 oxidation. SOA yields of individual organic precursors under OFR conditions were measured by standard addition into ambient air, and confirmed to be consistent with published environmental chamber-derived SOA yields. Positive matrix factorization of organic aerosol (OA) after OH oxidation showed formation of typical oxidized OA factors and a loss of primary OA factors as OH aging increased. After OH oxidation in the OFR, the hygroscopicity of the OA increased with increasing elemental O : C up to O : C ~ 1.0, and then decreased as O : C increased further. Some possible reasons for this decrease are discussed. The measured SOA formation was compared to the amount predicted from the concentrations of measured ambient SOA precursors and their SOA yields. And while measured ambient precursors were sufficient to explain the amount of SOA formed from O 3, they could only explain 10–50 % of the SOA formed from OH. This is consistent with previous OFR studies which showed that typically unmeasured semivolatile and intermediate volatility gases (that tend to lack C = C bonds) are present in ambient air and can explain such additional SOA formation. To investigate the sources of the unmeasured SOA-forming gases during this campaign, multilinear regression analysis was performed between measured SOA formation and the concentration of gas-phase tracers representing different precursor sources. The majority of SOA-forming gases present during both seasons were of biogenic origin. Urban sources also contributed substantially in both seasons, while biomass burning sources were more important during the dry season. Our study enables a better understanding of SOA formation in environments with diverse emission sources.« less

Secondary organic aerosol formation from ambient air in an oxidation flow reactor in central Amazonia

NASA Astrophysics Data System (ADS)

Palm, Brett B.; de Sá, Suzane S.; Day, Douglas A.; Campuzano-Jost, Pedro; Hu, Weiwei; Seco, Roger; Sjostedt, Steven J.; Park, Jeong-Hoo; Guenther, Alex B.; Kim, Saewung; Brito, Joel; Wurm, Florian; Artaxo, Paulo; Thalman, Ryan; Wang, Jian; Yee, Lindsay D.; Wernis, Rebecca; Isaacman-VanWertz, Gabriel; Goldstein, Allen H.; Liu, Yingjun; Springston, Stephen R.; Souza, Rodrigo; Newburn, Matt K.; Lizabeth Alexander, M.; Martin, Scot T.; Jimenez, Jose L.

2018-01-01

Secondary organic aerosol (SOA) formation from ambient air was studied using an oxidation flow reactor (OFR) coupled to an aerosol mass spectrometer (AMS) during both the wet and dry seasons at the Observations and Modeling of the Green Ocean Amazon (GoAmazon2014/5) field campaign. Measurements were made at two sites downwind of the city of Manaus, Brazil. Ambient air was oxidized in the OFR using variable concentrations of either OH or O3, over ranges from hours to days (O3) or weeks (OH) of equivalent atmospheric aging. The amount of SOA formed in the OFR ranged from 0 to as much as 10 µg m-3, depending on the amount of SOA precursor gases in ambient air. Typically, more SOA was formed during nighttime than daytime, and more from OH than from O3 oxidation. SOA yields of individual organic precursors under OFR conditions were measured by standard addition into ambient air and were confirmed to be consistent with published environmental chamber-derived SOA yields. Positive matrix factorization of organic aerosol (OA) after OH oxidation showed formation of typical oxidized OA factors and a loss of primary OA factors as OH aging increased. After OH oxidation in the OFR, the hygroscopicity of the OA increased with increasing elemental O : C up to O : C ˜ 1.0, and then decreased as O : C increased further. Possible reasons for this decrease are discussed. The measured SOA formation was compared to the amount predicted from the concentrations of measured ambient SOA precursors and their SOA yields. While measured ambient precursors were sufficient to explain the amount of SOA formed from O3, they could only explain 10-50 % of the SOA formed from OH. This is consistent with previous OFR studies, which showed that typically unmeasured semivolatile and intermediate volatility gases (that tend to lack C = C bonds) are present in ambient air and can explain such additional SOA formation. To investigate the sources of the unmeasured SOA-forming gases during this campaign, multilinear regression analysis was performed between measured SOA formation and the concentration of gas-phase tracers representing different precursor sources. The majority of SOA-forming gases present during both seasons were of biogenic origin. Urban sources also contributed substantially in both seasons, while biomass burning sources were more important during the dry season. This study enables a better understanding of SOA formation in environments with diverse emission sources.

Secondary organic aerosol formation from ambient air in an oxidation flow reactor in central Amazonia

DOE Office of Scientific and Technical Information (OSTI.GOV)

Palm, Brett B.; de Sá, Suzane S.; Day, Douglas A.

Secondary organic aerosol (SOA) formation from ambient air was studied using an oxidation flow reactor (OFR) coupled to an aerosol mass spectrometer (AMS) during both the wet and dry seasons at the Observations and Modeling of the Green Ocean Amazon (GoAmazon2014/5) field campaign. Measurements were made at two sites downwind of the city of Manaus, Brazil. Ambient air was oxidized in the OFR using variable concentrations of either OH or O 3, over ranges from hours to days (O 3) or weeks (OH) of equivalent atmospheric aging. The amount of SOA formed in the OFR ranged from 0 to asmore » much as 10 μg m -3, depending on the amount of SOA precursor gases in ambient air. Typically, more SOA was formed during nighttime than daytime, and more from OH than from O 3 oxidation. SOA yields of individual organic precursors under OFR conditions were measured by standard addition into ambient air, and confirmed to be consistent with published environmental chamber-derived SOA yields. Positive matrix factorization of organic aerosol (OA) after OH oxidation showed formation of typical oxidized OA factors and a loss of primary OA factors as OH aging increased. After OH oxidation in the OFR, the hygroscopicity of the OA increased with increasing elemental O : C up to O : C ~ 1.0, and then decreased as O : C increased further. Some possible reasons for this decrease are discussed. The measured SOA formation was compared to the amount predicted from the concentrations of measured ambient SOA precursors and their SOA yields. And while measured ambient precursors were sufficient to explain the amount of SOA formed from O 3, they could only explain 10–50 % of the SOA formed from OH. This is consistent with previous OFR studies which showed that typically unmeasured semivolatile and intermediate volatility gases (that tend to lack C = C bonds) are present in ambient air and can explain such additional SOA formation. To investigate the sources of the unmeasured SOA-forming gases during this campaign, multilinear regression analysis was performed between measured SOA formation and the concentration of gas-phase tracers representing different precursor sources. The majority of SOA-forming gases present during both seasons were of biogenic origin. Urban sources also contributed substantially in both seasons, while biomass burning sources were more important during the dry season. Our study enables a better understanding of SOA formation in environments with diverse emission sources.« less

Secondary organic aerosol formation from ambient air in an oxidation flow reactor in central Amazonia

DOE Office of Scientific and Technical Information (OSTI.GOV)

Palm, Brett B.; de Sá, Suzane S.; Day, Douglas A.

Secondary organic aerosol (SOA) formation from ambient air was studied using an oxidation flow reactor (OFR) coupled to an aerosol mass spectrometer (AMS) during both the wet and dry seasons at the Observations and Modeling of the Green Ocean Amazon (GoAmazon2014/5) field campaign. Measurements were made at two sites downwind of the city of Manaus, Brazil. Ambient air was oxidized in the OFR using variable concentrations of either OH or O 3, over ranges from hours to days (O 3) or weeks (OH) of equivalent atmospheric aging. The amount of SOA formed in the OFR ranged from 0 to asmore » much as 10 µg m −3, depending on the amount of SOA precursor gases in ambient air. Typically, more SOA was formed during nighttime than daytime, and more from OH than from O 3 oxidation. SOA yields of individual organic precursors under OFR conditions were measured by standard addition into ambient air and were confirmed to be consistent with published environmental chamber-derived SOA yields. Positive matrix factorization of organic aerosol (OA) after OH oxidation showed formation of typical oxidized OA factors and a loss of primary OA factors as OH aging increased. After OH oxidation in the OFR, the hygroscopicity of the OA increased with increasing elemental O : C up to O : C ∼ 1.0, and then decreased as O : C increased further. Possible reasons for this decrease are discussed. The measured SOA formation was compared to the amount predicted from the concentrations of measured ambient SOA precursors and their SOA yields. While measured ambient precursors were sufficient to explain the amount of SOA formed from O 3, they could only explain 10–50 % of the SOA formed from OH. This is consistent with previous OFR studies, which showed that typically unmeasured semivolatile and intermediate volatility gases (that tend to lack C = C bonds) are present in ambient air and can explain such additional SOA formation. To investigate the sources of the unmeasured SOA-forming gases during this campaign, multilinear regression analysis was performed between measured SOA formation and the concentration of gas-phase tracers representing different precursor sources. The majority of SOA-forming gases present during both seasons were of biogenic origin. Urban sources also contributed substantially in both seasons, while biomass burning sources were more important during the dry season. This study enables a better understanding of SOA formation in environments with diverse emission sources.« less

Investigation of a Particle into Liquid Sampler to Study the Formation & Ageing of Secondary Organic Aerosol

NASA Astrophysics Data System (ADS)

Pereira, K. L.; Hamilton, J. F.; Rickard, A. R.; Bloss, W. J.; Alam, M. S.; Camredon, M.; Munoz, A.; Vazquez, M.; Rodenas, M.; Vera, T.; Borrás, E.

2012-12-01

The atmospheric oxidation of Volatile Organic Compounds (VOCs) in the presence of NOx results in the formation of tropospheric ozone and Secondary Organic Aerosol (SOA) [Hallquist et al., 2009]. Whilst SOA is known to affect both climate and human health, the VOC oxidation pathways leading to SOA formation are poorly understood [Solomon et al., 2007]. This is in part due to the vast number and the low concentration of SOA species present in the ambient atmosphere. It has been estimated as many as 10,000 to 100,000 VOCs have been detected in the atmosphere, all of which can undergo photo-chemical oxidation and contribute to SOA formation [Goldstein and Galbally, 2007]. Atmospheric simulation chambers such as the EUropean PHOtoREactor (EUPHORE) in Valencia, Spain, are often used to study SOA formation from a single VOC precursor under controlled conditions. SOA composition and formation can be studied using online techniques such as Aerosol Mass Spectrometry (AMS), which provide high time resolution but limited structural information [Zhang et al., 2007]. Offline techniques, such as collection onto filters, extraction and subsequent analysis, provide detailed SOA composition but only usually one or two samples per experiment. In this work we report time resolved SOA composition analysis using a Particle into Liquid Sampler (PILS) followed by Liquid Chromatography Ion-Trap Mass Spectrometry (LC-IT-MS/MS) and Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FTICR-MS/MS). Experiments were performed at EUPHORE investigating the formation and composition of Methyl Chavicol SOA. Methyl Chavicol (also known as Estragole) was identified as the highest floral emission from an oil palm plantation in Malaysian Borneo and has also been observed in US pine forests [Bouvier-Brown et al., 2009; Misztal et al., 2010]. Previous studies indicate a high SOA yield from Methyl Chavicol at around 40 % [Lee et al., 2006], however currently there have been very few literature reports of the atmospheric degradation of Methyl Chavicol. Methyl Chavicol oxidation was investigated using a series of photosmog and ozonolysis experiments with varying ratios of NOx:VOC. An extensive range of instruments were used to monitor radical and product formation [including: LIF (HOx intermediates), LOPAP (HONO), FT-IR, PTR-MS, GC-FID, and SMPS]. Samples were collected using the PILS at 30 minute intervals with filters taken at the end of each experiment for comparison. A number of key oxidation products have been identified. Time profiles can be used to determine the importance of first, second & higher oxidation products and may indicate which species are undergoing oxidation or heterogeneous reactions during aerosol ageing. This data will allow for modelled vs. measured SOA composition comparison, with the potential to determine the rates of reactions for the condensed phase oxidation products formed. References Bouvier-Brown et al., Atmos. Chem. Phys. 9, 2061-2074, 2009. Goldstein and Galbally, Environ. Sci. Technol. 41, 1514-1521, 2007. Hallquist et al., Atmos. Chem. Phys. 9, 5155-5236, 2009. Lee et al., J. Geophys. Res. 111, D17305, 2006. Misztal et al., Atmos. Chem. Phys. Discuss. 10, 1517-1557, 2010. Solomon et al., Climate Change 2007: IPCC Report. Cambridge, 2007. Zhang et al., Geophys. Res. Lett. 34, L13801, 2007.

Secondary organic aerosol formation from road vehicle emissions

NASA Astrophysics Data System (ADS)

Pieber, Simone M.; Platt, Stephen M.; El Haddad, Imad; Zardini, Alessandro A.; Suarez-Bertoa, Ricardo; Slowik, Jay G.; Huang, Ru-Jin; Hellebust, Stig; Temime-Roussel, Brice; Marchand, Nicolas; Drinovec, Luca; Mocnik, Grisa; Baltensperger, Urs; Astorga, Covadogna; Prévôt, André S. H.

2014-05-01

Organic aerosol particles (OA) are a major fraction of the submicron particulate matter. OA consists of directly emitted primary (POA) and secondary OA (SOA). SOA is formed in-situ in the atmosphere via the reaction of volatile organic precursors. The partitioning of SOA species depends not only on the exposure to oxidants, but for instance also on temperature, relative humidity (RH), and the absorptive mass chemical composition (presence of inorganics) and concentration. Vehicle exhaust is a known source of POA and likely contributes to SOA formation in urban areas [1;2]. This has recently been estimated by (i) analyzing ambient data from urban areas combined with fuel consumption data [3], (ii) by examining the chemical composition of raw fuels [4], or (iii) smog chamber studies [5, 6]. Contradictory and thus somewhat controversial results in the relative quantity of SOA from diesel vs. gasoline vehicle exhaust were observed. In order to elucidate the impact of variable ambient conditions on the potential SOA formation of vehicle exhaust, and its relation to the emitted gas phase species, we studied SOA formed from the exhaust of passenger cars and trucks as a function of fuel and engine type (gasoline, diesel) at different temperatures (T 22 vs. -7oC) and RH (40 vs. 90%), as well as with different levels of inorganic salt concentrations. The exhaust was sampled at the tailpipe during regulatory driving cycles on chassis dynamometers, diluted (200 - 400x) and introduced into the PSI mobile smog chamber [6], where the emissions were subjected to simulated atmospheric ageing. Particle phase instruments (HR-ToF-AMS, aethalometers, CPC, SMPS) and gas phase instruments (PTR-TOF-MS, CO, CO2, CH4, THC, NH3 and other gases) were used online during the experiments. We found that gasoline emissions, because of cold starts, were generally larger than diesel, especially during cold temperatures driving cycles. Gasoline vehicles also showed the highest SOA formation. Furthermore, we observed that vehicle emissions and SOA are significantly affected by temperature and RH: doubling the RH in the chamber resulted in significantly increased SOA formation. Primary emissions and secondary aerosol formation from diesel and gasoline vehicles will be compared at different temperature and RH. Also the interaction and influence of inorganics on organics will be discussed. References: [1] Robinson, A.L., et al. (2007) Science 315, 1259. [2] Weitkamp, E.A., et al. (2007) Environ. Sci. Technol. 41, 6969. [3] Bahreini, R., et al. (2012) Geophys. Res. Lett. 39, L06805. [4] Gentner, D.R. et al. (2012) PNAS 109, 18318. [5] Gordon, T.D. et al. (2013) Atmos. Chem. Phys. Discuss 13, 23173. [6] Platt, S.M., et al. (2013) Atmos. Chem. Phys. Discuss. 12, 28343.

Modeling SOA formation from the oxidation of intermediate volatility n-alkanes

NASA Astrophysics Data System (ADS)

Aumont, B.; Valorso, R.; Mouchel-Vallon, C.; Camredon, M.; Lee-Taylor, J.; Madronich, S.

2012-08-01

The chemical mechanism leading to SOA formation and ageing is expected to be a multigenerational process, i.e. a successive formation of organic compounds with higher oxidation degree and lower vapor pressure. This process is here investigated with the explicit oxidation model GECKO-A (Generator of Explicit Chemistry and Kinetics of Organics in the Atmosphere). Gas phase oxidation schemes are generated for the C8-C24 series of n-alkanes. Simulations are conducted to explore the time evolution of organic compounds and the behavior of secondary organic aerosol (SOA) formation for various preexisting organic aerosol concentration (COA). As expected, simulation results show that (i) SOA yield increases with the carbon chain length of the parent hydrocarbon, (ii) SOA yield decreases with decreasing COA, (iii) SOA production rates increase with increasing COA and (iv) the number of oxidation steps (i.e. generations) needed to describe SOA formation and evolution grows when COA decreases. The simulated oxidative trajectories are examined in a two dimensional space defined by the mean carbon oxidation state and the volatility. Most SOA contributors are not oxidized enough to be categorized as highly oxygenated organic aerosols (OOA) but reduced enough to be categorized as hydrocarbon like organic aerosols (HOA), suggesting that OOA may underestimate SOA. Results show that the model is unable to produce highly oxygenated aerosols (OOA) with large yields. The limitations of the model are discussed.

Modeling SOA formation from the oxidation of intermediate volatility n-alkanes

NASA Astrophysics Data System (ADS)

Aumont, B.; Valorso, R.; Mouchel-Vallon, C.; Camredon, M.; Lee-Taylor, J.; Madronich, S.

2012-06-01

The chemical mechanism leading to SOA formation and ageing is expected to be a multigenerational process, i.e. a successive formation of organic compounds with higher oxidation degree and lower vapor pressure. This process is here investigated with the explicit oxidation model GECKO-A (Generator of Explicit Chemistry and Kinetics of Organics in the Atmosphere). Gas phase oxidation schemes are generated for the C8-C24 series of n-alkanes. Simulations are conducted to explore the time evolution of organic compounds and the behavior of secondary organic aerosol (SOA) formation for various preexisting organic aerosol concentration (COA). As expected, simulation results show that (i) SOA yield increases with the carbon chain length of the parent hydrocarbon, (ii) SOA yield decreases with decreasing COA, (iii) SOA production rates increase with increasing COA and (iv) the number of oxidation steps (i.e. generations) needed to describe SOA formation and evolution grows when COA decreases. The simulated oxidative trajectories are examined in a two dimensional space defined by the mean carbon oxidation state and the volatility. Most SOA contributors are not oxidized enough to be categorized as highly oxygenated organic aerosols (OOA) but reduced enough to be categorized as hydrocarbon like organic aerosols (HOA), suggesting that OOA may underestimate SOA. Results show that the model is unable to produce highly oxygenated aerosols (OOA) with large yields. The limitations of the model are discussed.

Linking Load, Fuel, and Emission Controls to Photochemical Production of Secondary Organic Aerosol from a Diesel Engine.

PubMed

Jathar, Shantanu H; Friedman, Beth; Galang, Abril A; Link, Michael F; Brophy, Patrick; Volckens, John; Eluri, Sailaja; Farmer, Delphine K

2017-02-07

Diesel engines are important sources of fine particle pollution in urban environments, but their contribution to the atmospheric formation of secondary organic aerosol (SOA) is not well constrained. We investigated direct emissions of primary organic aerosol (POA) and photochemical production of SOA from a diesel engine using an oxidation flow reactor (OFR). In less than a day of simulated atmospheric aging, SOA production exceeded POA emissions by an order of magnitude or more. Efficient combustion at higher engine loads coupled to the removal of SOA precursors and particle emissions by aftertreatment systems reduced POA emission factors by an order of magnitude and SOA production factors by factors of 2-10. The only exception was that the retrofitted aftertreatment did not reduce SOA production at idle loads where exhaust temperatures were low enough to limit removal of SOA precursors in the oxidation catalyst. Use of biodiesel resulted in nearly identical POA and SOA compared to diesel. The effective SOA yield of diesel exhaust was similar to that of unburned diesel fuel. While OFRs can help study the multiday evolution, at low particle concentrations OFRs may not allow for complete gas/particle partitioning and bias the potential of precursors to form SOA.

Evaluating the impact of new observational constraints on P-S/IVOC emissions, multi-generation oxidation, and chamber wall losses on SOA modeling for Los Angeles, CA

NASA Astrophysics Data System (ADS)

Ma, Prettiny K.; Zhao, Yunliang; Robinson, Allen L.; Worton, David R.; Goldstein, Allen H.; Ortega, Amber M.; Jimenez, Jose L.; Zotter, Peter; Prévôt, André S. H.; Szidat, Sönke; Hayes, Patrick L.

2017-08-01

Secondary organic aerosol (SOA) is an important contributor to fine particulate matter (PM) mass in polluted regions, and its modeling remains poorly constrained. A box model is developed that uses recently published literature parameterizations and data sets to better constrain and evaluate the formation pathways and precursors of urban SOA during the CalNex 2010 campaign in Los Angeles. When using the measurements of intermediate-volatility organic compounds (IVOCs) reported in Zhao et al. (2014) and of semi-volatile organic compounds (SVOCs) reported in Worton et al. (2014) the model is biased high at longer photochemical ages, whereas at shorter photochemical ages it is biased low, if the yields for VOC oxidation are not updated. The parameterizations using an updated version of the yields, which takes into account the effect of gas-phase wall losses in environmental chambers, show model-measurement agreement at longer photochemical ages, even though some low bias at short photochemical ages still remains. Furthermore, the fossil and non-fossil carbon split of urban SOA simulated by the model is consistent with measurements at the Pasadena ground site. Multi-generation oxidation mechanisms are often employed in SOA models to increase the SOA yields derived from environmental chamber experiments in order to obtain better model-measurement agreement. However, there are many uncertainties associated with these aging mechanisms. Thus, SOA formation in the model is compared to data from an oxidation flow reactor (OFR) in order to constrain SOA formation at longer photochemical ages than observed in urban air. The model predicts similar SOA mass at short to moderate photochemical ages when the aging mechanisms or the updated version of the yields for VOC oxidation are implemented. The latter case has SOA formation rates that are more consistent with observations from the OFR though. Aging mechanisms may still play an important role in SOA chemistry, but the additional mass formed by functionalization reactions during aging would need to be offset by gas-phase fragmentation of SVOCs. All the model cases evaluated in this work show a large majority of the urban SOA (70-83 %) at Pasadena coming from the oxidation of primary SVOCs (P-SVOCs) and primary IVOCs (P-IVOCs). The importance of these two types of precursors is further supported by analyzing the percentage of SOA formed at long photochemical ages (1.5 days) as a function of the precursor rate constant. The P-SVOCs and P-IVOCs have rate constants that are similar to highly reactive VOCs that have been previously found to strongly correlate with SOA formation potential measured by the OFR. Finally, the volatility distribution of the total organic mass (gas and particle phase) in the model is compared against measurements. The total SVOC mass simulated is similar to the measurements, but there are important differences in the measured and modeled volatility distributions. A likely reason for the difference is the lack of particle-phase reactions in the model that can oligomerize and/or continue to oxidize organic compounds even after they partition to the particle phase.

Evaporation kinetics and phase of laboratory and ambient secondary organic aerosol.

PubMed

Vaden, Timothy D; Imre, Dan; Beránek, Josef; Shrivastava, Manish; Zelenyuk, Alla

2011-02-08

Field measurements of secondary organic aerosol (SOA) find significantly higher mass loads than predicted by models, sparking intense effort focused on finding additional SOA sources but leaving the fundamental assumptions used by models unchallenged. Current air-quality models use absorptive partitioning theory assuming SOA particles are liquid droplets, forming instantaneous reversible equilibrium with gas phase. Further, they ignore the effects of adsorption of spectator organic species during SOA formation on SOA properties and fate. Using accurate and highly sensitive experimental approach for studying evaporation kinetics of size-selected single SOA particles, we characterized room-temperature evaporation kinetics of laboratory-generated α-pinene SOA and ambient atmospheric SOA. We found that even when gas phase organics are removed, it takes ∼24 h for pure α-pinene SOA particles to evaporate 75% of their mass, which is in sharp contrast to the ∼10 min time scale predicted by current kinetic models. Adsorption of "spectator" organic vapors during SOA formation, and aging of these coated SOA particles, dramatically reduced the evaporation rate, and in some cases nearly stopped it. Ambient SOA was found to exhibit evaporation behavior very similar to that of laboratory-generated coated and aged SOA. For all cases studied in this work, SOA evaporation behavior is nearly size-independent and does not follow the evaporation kinetics of liquid droplets, in sharp contrast with model assumptions. The findings about SOA phase, evaporation rates, and the importance of spectator gases and aging all indicate that there is need to reformulate the way SOA formation and evaporation are treated by models.

Evaporation kinetics and phase of laboratory and ambient secondary organic aerosol

PubMed Central

Vaden, Timothy D.; Imre, Dan; Beránek, Josef; Shrivastava, Manish; Zelenyuk, Alla

2011-01-01

Field measurements of secondary organic aerosol (SOA) find significantly higher mass loads than predicted by models, sparking intense effort focused on finding additional SOA sources but leaving the fundamental assumptions used by models unchallenged. Current air-quality models use absorptive partitioning theory assuming SOA particles are liquid droplets, forming instantaneous reversible equilibrium with gas phase. Further, they ignore the effects of adsorption of spectator organic species during SOA formation on SOA properties and fate. Using accurate and highly sensitive experimental approach for studying evaporation kinetics of size-selected single SOA particles, we characterized room-temperature evaporation kinetics of laboratory-generated α-pinene SOA and ambient atmospheric SOA. We found that even when gas phase organics are removed, it takes ∼24 h for pure α-pinene SOA particles to evaporate 75% of their mass, which is in sharp contrast to the ∼10 min time scale predicted by current kinetic models. Adsorption of “spectator” organic vapors during SOA formation, and aging of these coated SOA particles, dramatically reduced the evaporation rate, and in some cases nearly stopped it. Ambient SOA was found to exhibit evaporation behavior very similar to that of laboratory-generated coated and aged SOA. For all cases studied in this work, SOA evaporation behavior is nearly size-independent and does not follow the evaporation kinetics of liquid droplets, in sharp contrast with model assumptions. The findings about SOA phase, evaporation rates, and the importance of spectator gases and aging all indicate that there is need to reformulate the way SOA formation and evaporation are treated by models. PMID:21262848

Size distribution dynamics reveal particle-phase chemistry in organic aerosol formation

PubMed Central

Shiraiwa, Manabu; Yee, Lindsay D.; Schilling, Katherine A.; Loza, Christine L.; Craven, Jill S.; Zuend, Andreas; Ziemann, Paul J.; Seinfeld, John H.

2013-01-01

Organic aerosols are ubiquitous in the atmosphere and play a central role in climate, air quality, and public health. The aerosol size distribution is key in determining its optical properties and cloud condensation nucleus activity. The dominant portion of organic aerosol is formed through gas-phase oxidation of volatile organic compounds, so-called secondary organic aerosols (SOAs). Typical experimental measurements of SOA formation include total SOA mass and atomic oxygen-to-carbon ratio. These measurements, alone, are generally insufficient to reveal the extent to which condensed-phase reactions occur in conjunction with the multigeneration gas-phase photooxidation. Combining laboratory chamber experiments and kinetic gas-particle modeling for the dodecane SOA system, here we show that the presence of particle-phase chemistry is reflected in the evolution of the SOA size distribution as well as its mass concentration. Particle-phase reactions are predicted to occur mainly at the particle surface, and the reaction products contribute more than half of the SOA mass. Chamber photooxidation with a midexperiment aldehyde injection confirms that heterogeneous reaction of aldehydes with organic hydroperoxides forming peroxyhemiacetals can lead to a large increase in SOA mass. Although experiments need to be conducted with other SOA precursor hydrocarbons, current results demonstrate coupling between particle-phase chemistry and size distribution dynamics in the formation of SOAs, thereby opening up an avenue for analysis of the SOA formation process. PMID:23818634

Size distribution dynamics reveal particle-phase chemistry in organic aerosol formation.

PubMed

Shiraiwa, Manabu; Yee, Lindsay D; Schilling, Katherine A; Loza, Christine L; Craven, Jill S; Zuend, Andreas; Ziemann, Paul J; Seinfeld, John H

2013-07-16

Organic aerosols are ubiquitous in the atmosphere and play a central role in climate, air quality, and public health. The aerosol size distribution is key in determining its optical properties and cloud condensation nucleus activity. The dominant portion of organic aerosol is formed through gas-phase oxidation of volatile organic compounds, so-called secondary organic aerosols (SOAs). Typical experimental measurements of SOA formation include total SOA mass and atomic oxygen-to-carbon ratio. These measurements, alone, are generally insufficient to reveal the extent to which condensed-phase reactions occur in conjunction with the multigeneration gas-phase photooxidation. Combining laboratory chamber experiments and kinetic gas-particle modeling for the dodecane SOA system, here we show that the presence of particle-phase chemistry is reflected in the evolution of the SOA size distribution as well as its mass concentration. Particle-phase reactions are predicted to occur mainly at the particle surface, and the reaction products contribute more than half of the SOA mass. Chamber photooxidation with a midexperiment aldehyde injection confirms that heterogeneous reaction of aldehydes with organic hydroperoxides forming peroxyhemiacetals can lead to a large increase in SOA mass. Although experiments need to be conducted with other SOA precursor hydrocarbons, current results demonstrate coupling between particle-phase chemistry and size distribution dynamics in the formation of SOAs, thereby opening up an avenue for analysis of the SOA formation process.

Sources of primary and secondary organic aerosols in Chinese versus European Cities during winter time

NASA Astrophysics Data System (ADS)

Prevot, A. S.; Slowik, J.; El-Haddad, I.; Pieber, S. M.; Yuan, B.; Stefenelli, G.; Pospisilova, V.; Lopez-Hilfiker, F.; Qi, L.; Tong, Y.; Wang, L.; Daellenbach, K.; Klein, F.; Elser, M.; Junji, C.; Huang, R. J. J.; Baltensperger, U.

2017-12-01

In the recent years, aerosol mass spectrometric (AMS) measurements were performed in Beijing (China), Zurich (Switzerland) and other Chinese and European cities indicating the importance of not only primary sources but also secondary organic aerosol (SOA) sources despite low radiation levels for photooxidation. Among the primary sources, residential burning is especially important in winter including wood and coal burning. Also for secondary organic aerosols, VOC emissions of residential burning are likely an important source in winter. An interesting question is whether daytime photooxidation and/or night-time NO3 radical chemistry are important pathways for the SOA formation. Recently we developed a new measurement technique based on exctractive electrospray ionization (EESI) that allow for the study of the organic molecules in the particulate phase without fragmentation. Combined measurements with AMS and EESI will be discussed for smogchamber experiments (simulating both nighttime and daytime chemistry) SOA formation potential, the link between VOCs and SOA and the SOA composition. In-situ and off-line measurements in Europe and China are analyzed in the light of those experiments with a focus on the importance of residential burning to both primary and secondary organic aerosols in cities during winter.

The effect of gas-phase polycyclic aromatic hydrocarbons on the formation and properties of biogenic secondary organic aerosol particles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zelenyuk, Alla; Imre, Dan G.; Wilson, Jacqueline

2017-01-01

When secondary organic aerosol (SOA) particles are formed by ozonolysis in the presence of gas-phase polycyclic aromatic hydrocarbons (PAHs), their formation and properties are significantly different from SOA particles formed without PAHs. For all SOA precursors and all PAHs, discussed in this study, the presence of the gas-phase PAHs during SOA formation significantly affects particle mass loadings, composition, growth, evaporation kinetics, and viscosity. SOA particles formed in the presence of PAHs have, as part of their compositions, trapped unreacted PAHs and products of heterogeneous reactions between PAHs and ozone. Compared to ‘pure’ SOA particles, these particles exhibit slower evaporation kinetics,more » have higher fractions of non-volatile components, like oligomers, and higher viscosities, assuring their longer atmospheric lifetimes. In turn, the increased viscosity and decreased volatility provide a shield that protects PAHs from chemical degradation and evaporation, allowing for the long-range transport of these toxic pollutants. The magnitude of the effect of PAHs on SOA formation is surprisingly large. The presence of PAHs during SOA formation increases mass loadings by factors of two to five, and particle number concentrations, in some cases, by more than a factor of 100. Increases in SOA mass, particle number concentrations, and lifetime have important implications to many atmospheric processes related to climate, weather, visibility, and human health, all of which relate to the interactions between biogenic SOA and anthropogenic PAHs. The synergistic relationship between SOA and PAHs presented here are clearly complex and call for future research to elucidate further the underlying processes and their exact atmospheric implications.« less

Aqueous aerosol SOA formation: impact on aerosol physical properties.

PubMed

Woo, Joseph L; Kim, Derek D; Schwier, Allison N; Li, Ruizhi; McNeill, V Faye

2013-01-01

Organic chemistry in aerosol water has recently been recognized as a potentially important source of secondary organic aerosol (SOA) material. This SOA material may be surface-active, therefore potentially affecting aerosol heterogeneous activity, ice nucleation, and CCN activity. Aqueous aerosol chemistry has also been shown to be a potential source of light-absorbing products ("brown carbon"). We present results on the formation of secondary organic aerosol material in aerosol water and the associated changes in aerosol physical properties from GAMMA (Gas-Aerosol Model for Mechanism Analysis), a photochemical box model with coupled gas and detailed aqueous aerosol chemistry. The detailed aerosol composition output from GAMMA was coupled with two recently developed modules for predicting a) aerosol surface tension and b) the UV-Vis absorption spectrum of the aerosol, based on our previous laboratory observations. The simulation results suggest that the formation of oligomers and organic acids in bulk aerosol water is unlikely to perturb aerosol surface tension significantly. Isoprene-derived organosulfates are formed in high concentrations in acidic aerosols under low-NO(x) conditions, but more experimental data are needed before the potential impact of these species on aerosol surface tension may be evaluated. Adsorption of surfactants from the gas phase may further suppress aerosol surface tension. Light absorption by aqueous aerosol SOA material is driven by dark glyoxal chemistry and is highest under high-NO(x) conditions, at high relative humidity, in the early morning hours. The wavelength dependence of the predicted absorption spectra is comparable to field observations and the predicted mass absorption efficiencies suggest that aqueous aerosol chemistry can be a significant source of aerosol brown carbon under urban conditions.

Effects of NOx and SO2 on the secondary organic aerosol formation from photooxidation of α-pinene and limonene

NASA Astrophysics Data System (ADS)

Zhao, Defeng; Schmitt, Sebastian H.; Wang, Mingjin; Acir, Ismail-Hakki; Tillmann, Ralf; Tan, Zhaofeng; Novelli, Anna; Fuchs, Hendrik; Pullinen, Iida; Wegener, Robert; Rohrer, Franz; Wildt, Jürgen; Kiendler-Scharr, Astrid; Wahner, Andreas; Mentel, Thomas F.

2018-02-01

Anthropogenic emissions such as NOx and SO2 influence the biogenic secondary organic aerosol (SOA) formation, but detailed mechanisms and effects are still elusive. We studied the effects of NOx and SO2 on the SOA formation from the photooxidation of α-pinene and limonene at ambient relevant NOx and SO2 concentrations (NOx: < 1to 20 ppb, SO2: < 0.05 to 15 ppb). In these experiments, monoterpene oxidation was dominated by OH oxidation. We found that SO2 induced nucleation and enhanced SOA mass formation. NOx strongly suppressed not only new particle formation but also SOA mass yield. However, in the presence of SO2 which induced a high number concentration of particles after oxidation to H2SO4, the suppression of the mass yield of SOA by NOx was completely or partly compensated for. This indicates that the suppression of SOA yield by NOx was largely due to the suppressed new particle formation, leading to a lack of particle surface for the organics to condense on and thus a significant influence of vapor wall loss on SOA mass yield. By compensating for the suppressing effect on nucleation of NOx, SO2 also compensated for the suppressing effect on SOA yield. Aerosol mass spectrometer data show that increasing NOx enhanced nitrate formation. The majority of the nitrate was organic nitrate (57-77 %), even in low-NOx conditions (< ˜ 1 ppb). Organic nitrate contributed 7-26 % of total organics assuming a molecular weight of 200 g mol-1. SOA from α-pinene photooxidation at high NOx had a generally lower hydrogen to carbon ratio (H / C), compared to low NOx. The NOx dependence of the chemical composition can be attributed to the NOx dependence of the branching ratio of the RO2 loss reactions, leading to a lower fraction of organic hydroperoxides and higher fractions of organic nitrates at high NOx. While NOx suppressed new particle formation and SOA mass formation, SO2 can compensate for such effects, and the combining effect of SO2 and NOx may have an important influence on SOA formation affected by interactions of biogenic volatile organic compounds (VOCs) with anthropogenic emissions.

Indoor transient SOA formation from ozone + α-pinene reactions: Impacts of air exchange and initial product concentrations, and comparison to limonene ozonolysis

NASA Astrophysics Data System (ADS)

Youssefi, Somayeh; Waring, Michael S.

2015-07-01

The ozonolysis of reactive organic gases (ROG), e.g. terpenes, generates secondary organic aerosol (SOA) indoors. The SOA formation strength of such reactions is parameterized by the aerosol mass fraction (AMF), a.k.a. SOA yield, which is the mass ratio of generated SOA to oxidized ROG. AMFs vary in magnitude both among and for individual ROGs. Here, we quantified dynamic SOA formation from the ozonolysis of α-pinene with 'transient AMFs,' which describe SOA formation due to pulse emission of a ROG in an indoor space with air exchange, as is common when consumer products are intermittently used in ventilated buildings. We performed 19 experiments at low, moderate, and high (0.30, 0.52, and 0.94 h-1, respectively) air exchange rates (AER) at varying concentrations of initial reactants. Transient AMFs as a function of peak SOA concentrations ranged from 0.071 to 0.25, and they tended to increase as the AER and product of the initial reactant concentrations increased. Compared to our similar research on limonene ozonolysis (Youssefi and Waring, 2014), for which formation strength was driven by secondary ozone reactions, the AER impact for α-pinene was opposite in direction and weaker, while the initial reactant product impact was in the same direction but stronger for α-pinene than for limonene. Linear fits of AMFs for α-pinene ozonolysis as a function of the AER and initial reactant concentrations are provided so that future indoor models can predict SOA formation strength.

Condensed-phase biogenic-anthropogenic interactions with implications for cold cloud formation

DOE PAGES

Charnawskas, Joseph C.; Alpert, Peter A.; Lambe, Andrew; ...

2017-01-24

Anthropogenic and biogenic gas emissions contribute to the formation of secondary organic aerosol (SOA). When present, soot particles from fossil-fuel combustion can acquire a coating of SOA. We investigate SOA-soot biogenic-anthropogenic interactions and their impact on ice nucleation in relation to the particles’ organic phase state. SOA particles were generated from the OH oxidation of naphthalene, α-pinene, longifolene, or isoprene, with or without presence of sulfate or soot particles. Corresponding particle glass transition (T g) and full deliquescence relative humidity (FDRH) were estimated by a numerical diffusion model. Longifolene SOA particles are solid-like and all biogenic SOA sulfate mixtures exhibitmore » a core-shell configuration (i.e. a sulfate-rich core coated with SOA). Biogenic SOA with or without sulfate formed ice at conditions expected for homogeneous ice nucleation in agreement with respective T g and FDRH. α-pinene SOA coated soot particles nucleated ice above the homogeneous freezing temperature with soot acting as ice nuclei (IN). At lower temperatures the α-pinene SOA coating can be semisolid inducing ice nucleation. Naphthalene SOA coated soot particles acted as IN above and below the homogeneous freezing limit, which can be explained by the presence of a highly viscous SOA phase. Our results suggest that biogenic SOA does not play a significant role in mixed-phase cloud formation and the presence of sulfate further renders this even less likely. Furthermore, anthropogenic SOA may have an enhancing effect on cloud glaciation under mixed-phase and cirrus cloud conditions compared to biogenic SOA that dominate during preindustrial times or in pristine areas.« less

Condensed-phase biogenic-anthropogenic interactions with implications for cold cloud formation.

PubMed

Charnawskas, Joseph C; Alpert, Peter A; Lambe, Andrew T; Berkemeier, Thomas; O'Brien, Rachel E; Massoli, Paola; Onasch, Timothy B; Shiraiwa, Manabu; Moffet, Ryan C; Gilles, Mary K; Davidovits, Paul; Worsnop, Douglas R; Knopf, Daniel A

2017-08-24

Anthropogenic and biogenic gas emissions contribute to the formation of secondary organic aerosol (SOA). When present, soot particles from fossil fuel combustion can acquire a coating of SOA. We investigate SOA-soot biogenic-anthropogenic interactions and their impact on ice nucleation in relation to the particles' organic phase state. SOA particles were generated from the OH oxidation of naphthalene, α-pinene, longifolene, or isoprene, with or without the presence of sulfate or soot particles. Corresponding particle glass transition (T g ) and full deliquescence relative humidity (FDRH) were estimated using a numerical diffusion model. Longifolene SOA particles are solid-like and all biogenic SOA sulfate mixtures exhibit a core-shell configuration (i.e. a sulfate-rich core coated with SOA). Biogenic SOA with or without sulfate formed ice at conditions expected for homogeneous ice nucleation, in agreement with respective T g and FDRH. α-pinene SOA coated soot particles nucleated ice above the homogeneous freezing temperature with soot acting as ice nuclei (IN). At lower temperatures the α-pinene SOA coating can be semisolid, inducing ice nucleation. Naphthalene SOA coated soot particles acted as ice nuclei above and below the homogeneous freezing limit, which can be explained by the presence of a highly viscous SOA phase. Our results suggest that biogenic SOA does not play a significant role in mixed-phase cloud formation and the presence of sulfate renders this even less likely. However, anthropogenic SOA may have an enhancing effect on cloud glaciation under mixed-phase and cirrus cloud conditions compared to biogenic SOA that dominate during pre-industrial times or in pristine areas.

Modeling the formation and aging of secondary organic aerosols during CalNex 2010

NASA Astrophysics Data System (ADS)

Hayes, P. L.; Ortega, A. M.; Ahmadov, R.; McKeen, S. A.; Washenfelder, R. A.; Alvarez, S.; Rappenglueck, B.; Holloway, J. S.; Gilman, J. B.; Kuster, W. C.; De Gouw, J. A.; Zotter, P.; Prevot, A. S.; Kleindienst, T. E.; Offenberg, J. H.; Jimenez, J. L.

2012-12-01

Several traditional and recently proposed models are applied to predict the concentrations and properties of secondary organic aerosols (SOA) and organic gases at the Pasadena ground site during the CalNex campaign. The models are constrained with and compared against results from available observations. The CalNex campaign and specifically the Pasadena ground site featured a large and sophisticated suite of aerosol and gas phase instrumentation, and thus, it provides a unique opportunity to test SOA models under conditions of strong urban emissions at a range of low photochemical ages. The oxidation of volatile organic compounds (VOCs) using an updated traditional model cannot explain the observed ambient SOA, and under-predicts the measurements by a factor of ~40. Similarly, after accounting for the multi-generation oxidation of VOCs using a volatility basis set (VBS) approach as described by Tsimpidi et al. (2010), SOA is still under-predicted by a factor of ~8. For SOA formed from VOCs (V-SOA) the dominant precursors are aromatics (xylenes, toluene, and trimethylbenzenes). The model SOA formed from the oxidation of primary semivolatile and intermediate volatility organic compounds (P-S/IVOCs, producing SI-SOA) is also predicted using the parameterizations of Robinson et al. (2007) and Grieshop et al. (2009), and the properties of V-SOA + SI-SOA are compared against the measured O:C and volatility. We also compare the results of the different models against fossil/non-fossil carbon measurements as well as tracers of different SOA precursors. Potential Aerosol Mass (PAM) measurements of the SOA forming potential of the Pasadena air masses are also compared against that predicted by the models. The PAM analysis allows for model/measurement comparisons of SOA properties over a range of photochemical ages spanning almost two weeks. Using the V-SOA model, at low photochemical ages (< 1 day) the modeled PAM V-SOA is less than the measured PAM SOA, similar to the ambient results. In contrast, at high photochemical ages (i.e., more than about three days) the modeled PAM V-SOA is substantially greater than that measured, which is likely due fragmentation reactions that are not included in that model. We derive a parameterization of the measured PAM SOA as a function of the input photochemical age and the PAM photochemical age that serves as a comparison with other SOA models.

Recent advances in understanding secondary organic aerosol: Implications for global climate forcing: Advances in Secondary Organic Aerosol

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shrivastava, Manish; Cappa, Christopher D.; Fan, Jiwen

Anthropogenic emissions and land-use changes have modified atmospheric aerosol concentrations and size distributions over time. Understanding pre-industrial conditions and changes in organic aerosol due to anthropogenic activities is important because these features 1) influence estimates of aerosol radiative forcing and 2) can confound estimates of the historical response of climate to increases in greenhouse gases (e.g. the ‘climate sensitivity’). Secondary organic aerosol (SOA), formed in the atmosphere by oxidation of organic gases, represents a major fraction of global submicron-sized atmospheric organic aerosol. Over the past decade, significant advances in understanding SOA properties and formation mechanisms have occurred through a combinationmore » of laboratory and field measurements, yet current climate models typically do not comprehensively include all important SOA-relevant processes. Therefore, major gaps exist at present between current measurement-based knowledge on the one hand and model implementation of organic aerosols on the other. The critical review herein summarizes some of the important developments in understanding SOA formation that could potentially have large impacts on our understanding of aerosol radiative forcing and climate. We highlight the importance of some recently discovered processes and properties that influence the growth of SOA particles to sizes relevant for clouds and radiative forcing, including: formation of extremely low-volatility organics in the gas-phase; isoprene epoxydiols (IEPOX) multi-phase chemistry; particle-phase oligomerization; and physical properties such as viscosity. In addition, this review also highlights some of the important processes that involve interactions between natural biogenic emissions and anthropogenic emissions, such as the role of sulfate and oxides of nitrogen (NOx) on SOA formation from biogenic volatile organic compounds. Studies that relate the observed evolution of organic aerosol mass and number with knowledge of particle properties such as volatility and viscosity are crucial for improving understanding of non-linear SOA-related processes. For example, useful insights can be attained by combining bottom-up information related to the molecular speciation of gas- and particle-phase precursors with top-down insights on size evolution dynamics of SOA. Continuing efforts are also needed to rank the most influential processes affecting SOA lifecycle, so that these processes can be accurately represented in atmospheric chemistry-climate models.« less

Formation and fate of alkyl nitrates from chlorine-initiated oxidation of alkanes

NASA Astrophysics Data System (ADS)

Wang, D. S.; Hildebrandt Ruiz, L.

2017-12-01

Alkanes are a main source of anthropogenic volatile organic compounds (VOCs). Studies suggest that large alkanes, despite having high carbon mass, often do not significantly contribute to secondary organic aerosol (SOA) formation due to their low reactivity towards hydroxyl radicals. Chlorine radicals react much more quickly with alkanes; for example, the reaction of Cl with n-decane is about 50 times faster than the reaction of OH with n-decane. High reactive chlorine concentrations have been reported within continental regions as well as near coastal regions. The rapid oxidation of alkanes by chlorine radicals can therefore be a potentially significant, and overlooked source of alkylperoxy radicals and SOA formation. We present results from environmental chamber experiments on chlorine-initiated oxidation of C8, C10, and C12 linear and branched alkanes. Experiments were conducted under high NOx conditions to simulate highly polluted industrial environments. Formation of multigenerational gas-phase oxidation products were monitored using a High-Resolution Time-of-Flight Chemical Ionization Mass Spectrometer (CIMS). High SOA formation was observed using an Aerosol Chemical Speciation Monitor (ACSM). Aerosol volatility was determined using a thermodenuder and a kinetic aerosol evaporation model. Particle-phase composition was investigated using a Filter Inlet for Gases and AEROsols (FIGAERO) coupled to the CIMS, where dimer and oligomer formation were observed. Results from this study can be used to more accurately represent the fate of anthropogenic alkanes and SOA loadings in the atmosphere.

Secondary organic aerosol formation from semi- and intermediate-volatility organic compounds and glyoxal: Relevance of O/C as a tracer for aqueous multiphase chemistry

NASA Astrophysics Data System (ADS)

Waxman, Eleanor M.; Dzepina, Katja; Ervens, Barbara; Lee-Taylor, Julia; Aumont, Bernard; Jimenez, Jose L.; Madronich, Sasha; Volkamer, Rainer

2013-03-01

The role of aqueous multiphase chemistry in the formation of secondary organic aerosol (SOA) remains difficult to quantify. We investigate it here by testing the rapid formation of moderate oxygen-to-carbon (O/C) SOA during a case study in Mexico City. A novel laboratory-based glyoxal-SOA mechanism is applied to the field data, and explains why less gas-phase glyoxal mass is observed than predicted. Furthermore, we compare an explicit gas-phase chemical mechanism for SOA formation from semi- and intermediate-volatility organic compounds (S/IVOCs) with empirical parameterizations of S/IVOC aging. The mechanism representing our current understanding of chemical kinetics of S/IVOC oxidation combined with traditional SOA sources and mixing of background SOA underestimates the observed O/C by a factor of two at noon. Inclusion of glyoxal-SOA with O/C of 1.5 brings O/C predictions within measurement uncertainty, suggesting that field observations can be reconciled on reasonable time scales using laboratory-based empirical relationships for aqueous chemistry.

Secondary Organic Aerosol Production from Gasoline Vehicle Exhaust: Effects of Engine Technology, Cold Start, and Emission Certification Standard.

PubMed

Zhao, Yunliang; Lambe, Andrew T; Saleh, Rawad; Saliba, Georges; Robinson, Allen L

2018-02-06

Secondary organic aerosol (SOA) formation from dilute exhaust from 16 gasoline vehicles was investigated using a potential aerosol mass (PAM) oxidation flow reactor during chassis dynamometer testing using the cold-start unified cycle (UC). Ten vehicles were equipped with gasoline direct injection engines (GDI vehicles) and six with port fuel injection engines (PFI vehicles) certified to a wide range of emissions standards. We measured similar SOA production from GDI and PFI vehicles certified to the same emissions standard; less SOA production from vehicles certified to stricter emissions standards; and, after accounting for differences in gas-particle partitioning, similar effective SOA yields across different engine technologies and certification standards. Therefore the ongoing, dramatic shift from PFI to GDI vehicles in the United States should not alter the contribution of gasoline vehicles to ambient SOA and the natural replacement of older vehicles with newer ones certified to stricter emissions standards should reduce atmospheric SOA levels. Compared to hot operations, cold-start exhaust had lower effective SOA yields, but still contributed more SOA overall because of substantially higher organic gas emissions. We demonstrate that the PAM reactor can be used as a screening tool for vehicle SOA production by carefully accounting for the effects of the large variations in emission rates.

Condensed-phase biogenic–anthropogenic interactions with implications for cold cloud formation

DOE PAGES

Charnawskas, Joseph C.; Alpert, Peter A.; Lambe, Andrew T.; ...

2017-01-24

Anthropogenic and biogenic gas emissions contribute to the formation of secondary organic aerosol (SOA). When present, soot particles from fossil fuel combustion can acquire a coating of SOA. We investigate SOA–soot biogenic–anthropogenic interactions and their impact on ice nucleation in relation to the particles’ organic phase state. SOA particles were generated from the OH oxidation of naphthalene, α-pinene, longifolene, or isoprene, with or without the presence of sulfate or soot particles. Corresponding particle glass transition (T g) and full deliquescence relative humidity (FDRH) were estimated using a numerical diffusion model. Longifolene SOA particles are solid-like and all biogenic SOA sulfatemore » mixtures exhibit a core–shell configuration (i.e.a sulfate-rich core coated with SOA). Biogenic SOA with or without sulfate formed ice at conditions expected for homogeneous ice nucleation, in agreement with respectiveT gand FDRH. α-pinene SOA coated soot particles nucleated ice above the homogeneous freezing temperature with soot acting as ice nuclei (IN). At lower temperatures the α-pinene SOA coating can be semisolid, inducing ice nucleation. Naphthalene SOA coated soot particles acted as ice nuclei above and below the homogeneous freezing limit, which can be explained by the presence of a highly viscous SOA phase. Our results suggest that biogenic SOA does not play a significant role in mixed-phase cloud formation and the presence of sulfate renders this even less likely. However, anthropogenic SOA may have an enhancing effect on cloud glaciation under mixed-phase and cirrus cloud conditions compared to biogenic SOA that dominate during pre-industrial times or in pristine areas.« less

3rd hand smoking; heterogeneous oxidation of nicotine and secondary aerosol formation in the indoor environment

NASA Astrophysics Data System (ADS)

Petrick, Lauren; Dubowski, Yael

2010-05-01

Tobacco smoking is well known as a significant source of primary indoor air pollutants. However, only recently has it been recognized that the impact of Tobacco smoking may continue even after the cigarette has been extinguished (i.e., third hand smoke) due to the effect of indoor surfaces. These surfaces may affect the fate of tobacco smoke in the form of secondary reactions and pollutants, including secondary organic aerosol (SOA) formation. Fourier Transform Infrared spectrometry with Attenuated Total Reflection (FTIR-ATR) in tandem with a Scanning Mobility Particle Sizing (SMPS) system was used to monitor the ozonation of cellulose sorbed nicotine and resulting SOA formation. SOA formation began at onset of ozone introduction ([O3] = 60 ± 5 ppb) with a size distribution of dp ≤ 25 nm, and was determined to be a result of heterogeneous reaction (opposed to homogeneous). SOA yield from reacted surface nicotine was on the order of 10 %. Simultaneous to SOA monitoring, FTIR-ATR spectra showed surface changes in the nicotine film as the reaction progressed, revealing a pseudo first-order surface reaction rate of 0.0026 ± 0.0008 min-1. Identified surface oxidation products included: cotinine, myosmine, methylnicotinamide and nicotyrine. Surface reaction rate was found to be partially inhibited at high relative humidity. Given the toxicity of some of the identified products (e.g., cotinine has shown potential mutagenicity and teratogenicity) and that small particles may contribute to adverse health effects, the present study indicates that exposure to 3rd hand smoke ozonation products may pose additional health risks.

Simulation and analysis of OOK-to-BPSK format conversion based on gain-transparent SOA used as optical phase-modulator.

PubMed

Hong, Wei; Huang, Dexiu; Zhang, Xinliang; Zhu, Guangxi

2007-12-24

All-optical on-off keying (OOK) to binary phase-shift keying (BPSK) modulation format conversion based on gain-transparent semiconductor optical amplifier (GT-SOA) is simulated and analyzed, where GT-SOA is used as an all-optical phase-modulator (PM). Numerical simulation of the phase modulation effect of GT-SOA is performed using a wideband dynamic model of GT-SOA and the quality of the BPSK signal is evaluated using the differential-phase-Q factor. Performance improvement by holding light injection is analyzed and non-return-to-zero (NRZ) and return-to-zero (RZ) modulation formats of the OOK signal are considered.

Formation of hydroxyl radicals from photolysis of secondary organic aerosol material

NASA Astrophysics Data System (ADS)

Badali, K. M.; Zhou, S.; Aljawhary, D.; Antiñolo, M.; Chen, W. J.; Lok, A.; Mungall, E.; Wong, J. P. S.; Zhao, R.; Abbatt, J. P. D.

2015-07-01

This paper demonstrates that OH radicals are formed by photolysis of secondary organic aerosol (SOA) material formed by terpene ozonolysis. The SOA is collected on filters, dissolved in water containing a radical trap (benzoic acid), and then exposed to ultraviolet light in a photochemical reactor. The OH formation rates, which are similar for both α-pinene and limonene SOA, are measured from the formation rate of p-hydroxybenzoic acid as measured using offline HPLC analysis. To evaluate whether the OH is formed by photolysis of H2O2 or organic hydroperoxides (ROOH), the peroxide content of the SOA was measured using the horseradish peroxidase-dichlorofluorescein (HRP-DCF) assay, which was calibrated using H2O2. The OH formation rates from SOA are 5 times faster than from the photolysis of H2O2 solutions whose concentrations correspond to the peroxide content of the SOA solutions, assuming that the HRP-DCF signal arises from H2O2 alone. The higher rates of OH formation from SOA are likely due to ROOH photolysis, but we cannot rule out a contribution from secondary processes as well. This result is substantiated by photolysis experiments conducted with t-butyl hydroperoxide and cumene hydroperoxide which produce over 3 times more OH than photolysis of equivalent concentrations of H2O2. Relative to the peroxide level in the SOA and assuming that the peroxides drive most of the ultraviolet absorption, the quantum yield for OH generation from α-pinene SOA is 0.8 ± 0.4. This is the first demonstration of an efficient photolytic source of OH in SOA, one that may affect both cloud water and aerosol chemistry.

Characterization of isoprene-derived secondary organic aerosols at a rural site in North China Plain with implications for anthropogenic pollution effects.

PubMed

Li, Jianjun; Wang, Gehui; Wu, Can; Cao, Cong; Ren, Yanqin; Wang, Jiayuan; Li, Jin; Cao, Junji; Zeng, Limin; Zhu, Tong

2018-01-11

Isoprene is the most abundant non-methane volatile organic compound (VOC) and the largest contributor to secondary organic aerosol (SOA) burden on a global scale. In order to examine the influence of high concentrations of anthropogenic pollutants on isoprene-derived SOA (SOA i ) formation, summertime PM 2.5 filter samples were collected with a three-hour sampling interval at a rural site in the North China Plain (NCP), and determined for SOA i tracers and other chemical species. RO 2 +NO pathway derived 2-methylglyceric acid presented a relatively higher contribution to the SOA i due to the high-NOx (~20 ppb) conditions in the NCP that suppressed the reactive uptake of RO 2 +HO 2 reaction derived isoprene epoxydiols. Compared to particle acidity and water content, sulfate plays a dominant role in the heterogeneous formation process of SOA i . Diurnal variation and correlation of 2-methyltetrols with ozone suggested an important effect of isoprene ozonolysis on SOA i formation. SOA i increased linearly with levoglucosan during June 10-18, which can be attributed to an increasing emission of isoprene caused by the field burning of wheat straw and a favorable aqueous SOA formation during the aging process of the biomass burning plume. Our results suggested that isoprene oxidation is highly influenced by intensive anthropogenic activities in the NCP.

Simulation of semi-explicit mechanisms of SOA formation from glyoxal in a 3D model

NASA Astrophysics Data System (ADS)

Knote, C. J.; Hodzic, A.; Jimenez, J. L.; Volkamer, R.; Orlando, J. J.; Baidar, S.; Brioude, J. F.; Fast, J. D.; Gentner, D. R.; Goldstein, A. H.; Hayes, P. L.; Knighton, W. B.; Oetjen, H.; Setyan, A.; Stark, H.; Thalman, R. M.; Tyndall, G. S.; Washenfelder, R. A.; Waxman, E.; Zhang, Q.

2013-12-01

Formation of secondary organic aerosols (SOA) through multi-phase processing of glyoxal has been proposed recently as a relevant contributor to SOA mass. Glyoxal has both anthropogenic and biogenic sources, and readily partitions into the aqueous-phase of cloud droplets and aerosols. Both reversible and irreversible chemistry in the liquid-phase has been observed. A recent laboratory study indicates that the presence of salts in the liquid-phase strongly enhances the Henry';s law constant of glyoxal, allowing for much more effective multi-phase processing. In our work we investigate the contribution of glyoxal to SOA formation on the regional scale. We employ the regional chemistry transport model WRF-chem with MOZART gas-phase chemistry and MOSAIC aerosols, which we both extended to improve the description of glyoxal formation in the gas-phase, and its interactions with aerosols. The detailed description of aerosols in our setup allows us to compare very simple (uptake coefficient) parameterizations of SOA formation from glyoxal, as has been used in previous modeling studies, with much more detailed descriptions of the various pathways postulated based on laboratory studies. Measurements taken during the CARES and CalNex campaigns in California in summer 2010 allowed us to constrain the model, including the major direct precursors of glyoxal. Simulations at convection-permitting resolution over a 2 week period in June 2010 have been conducted to assess the effect of the different ways to parameterize SOA formation from glyoxal and investigate its regional variability. We find that depending on the parameterization used the contribution of glyoxal to SOA is between 1 and 15% in the LA basin during this period, and that simple parameterizations based on uptake coefficients derived from box model studies lead to higher contributions (15%) than parameterizations based on lab experiments (1%). A kinetic limitation found in experiments hinders substantial contribution of volume-based pathways to total SOA formation from glyoxal. Once removed, 5% of total SOA can be formed from glyoxal through these channels. Results from a year-long simulation over the continental US will give a broader picture of the contribution of glyoxal to SOA formation.

Aqueous-phase oxidation of green leaf volatiles by hydroxyl radical as a source of SOA: Product identification from methyl jasmonate and methyl salicylate oxidation

NASA Astrophysics Data System (ADS)

Hansel, Amie K.; Ehrenhauser, Franz S.; Richards-Henderson, Nicole K.; Anastasio, Cort; Valsaraj, Kalliat T.

2015-02-01

Green leaf volatiles (GLVs) are a group of biogenic volatile organic compounds (BVOCs) released into the atmosphere by vegetation. BVOCs produce secondary organic aerosol (SOA) via gas-phase reactions, but little is known of their aqueous-phase oxidation as a source of SOA. GLVs can partition into atmospheric water phases, e.g., fog, mist, dew or rain, and be oxidized by hydroxyl radicals (˙OH). These reactions in the liquid phase also lead to products that have higher molecular weights, increased polarity, and lower vapor pressures, ultimately forming SOA after evaporation of the droplet. To examine this process, we investigated the aqueous, ˙OH-mediated oxidation of methyl jasmonate (MeJa) and methyl salicylate (MeSa), two GLVs that produce aqueous-phase SOA. High performance liquid chromatography/electrospray ionization mass spectrometry (HPLC-ESI-MS) was used to monitor product formation. The oxidation products identified exhibit higher molecular mass than their parent GLV due to either dimerization or the addition of oxygen and hydroxyl functional groups. The proposed structures of potential products are based on mechanistic considerations combined with the HPLC/ESI-MS data. Based on the structures, the vapor pressure and the Henry's law constant were estimated with multiple methods (SPARC, SIMPOL, MPBPVP, Bond and Group Estimations). The estimated vapor pressures of the products identified are significantly (up to 7 orders of magnitude) lower than those of the associated parent compounds, and therefore, the GLV oxidation products may remain as SOA after evaporation of the water droplet. The contribution of the identified oxidation products to SOA formation is estimated based on measured HPLC-ESI/MS responses relative to previous aqueous SOA mass yield measurements.

A Review of Secondary Organic Aerosol (SOA) Formation from Isoprene

EPA Science Inventory

Recent field and laboratory evidence indicates that the oxidation of isoprene forms secondary organic aerosol (SOA). Global biogenic emissions of isoprene (600 Tg yr^-1) are sufficiently large the formation of SOA is even small yields results in substantial production ...

Mechanism of SOA formation determines magnitude of radiative effects

NASA Astrophysics Data System (ADS)

Zhu, Jialei; Penner, Joyce E.; Lin, Guangxing; Zhou, Cheng; Xu, Li; Zhuang, Bingliang

2017-11-01

Secondary organic aerosol (SOA) nearly always exists as an internal mixture, and the distribution of this mixture depends on the formation mechanism of SOA. A model is developed to examine the influence of using an internal mixing state based on the mechanism of formation and to estimate the radiative forcing of SOA in the future. For the present day, 66% of SOA is internally mixed with sulfate, while 34% is internally mixed with primary soot. Compared with using an external mixture, the direct effect of SOA is decreased due to the decrease in total aerosol surface area and the increase of absorption efficiency. Aerosol number concentrations are sharply reduced, and this is responsible for a large decrease in the cloud albedo effect. Internal mixing decreases the radiative effect of SOA by a factor of >4 compared with treating SOA as an external mixture. The future SOA burden increases by 24% due to CO2 increases and climate change, leading to a total (direct plus cloud albedo) radiative forcing of ‑0.05 W m‑2. When the combined effects of changes in climate, anthropogenic emissions, and land use are included, the SOA forcing is ‑0.07 W m‑2, even though the SOA burden only increases by 6.8%. This is caused by the substantial increase of SOA associated with sulfate in the Aitken mode. The Aitken mode increase contributes to the enhancement of first indirect radiative forcing, which dominates the total radiative forcing.

Mechanism of SOA formation determines magnitude of radiative effects

DOE PAGES

Zhu, Jialei; Penner, Joyce E.; Lin, Guangxing; ...

2017-11-13

Secondary organic aerosol (SOA) nearly always exists as an internal mixture and the distribution of this mixture depends on the formation mechanism of SOA. A model is developed to examine the influence of using an internal mixing states based on the mechanism of formation and to estimate the radiative forcing of SOA in the future. For the present day, 66 % of SOA is internally mixed with sulfate, while 34 % is internally mixed with primary soot. When compared with using an external mixture, the direct effect of SOA is decreased, due to the decrease of total aerosol surface areamore » and the increase of absorption efficiency. Aerosol number concentrations are sharply reduced and this is responsible for a large decrease in the cloud albedo effect. In total, internal mixing suppresses the radiative effect of SOA by a factor of >4 compared to treating SOA as an external mixture. The future SOA burden increases by 24% due to CO2 increases and climate change, leading to a total (direct plus cloud albedo) radiative forcing of -0.05 W m-2. When the combined effects of changes in climate, anthropogenic emissions and land use are included, the SOA forcing is -0.07 W m-2, even though the SOA burden only increases by 6.8%. This is caused by the substantial increase of SOA associated with sulfate in the Aitken mode. The Aitken mode increase contributes to the enhancement of first indirect radiative forcing, which dominates the total radiative forcing.« less

Mechanism of SOA formation determines magnitude of radiative effects

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhu, Jialei; Penner, Joyce E.; Lin, Guangxing

Secondary organic aerosol (SOA) nearly always exists as an internal mixture and the distribution of this mixture depends on the formation mechanism of SOA. A model is developed to examine the influence of using an internal mixing states based on the mechanism of formation and to estimate the radiative forcing of SOA in the future. For the present day, 66 % of SOA is internally mixed with sulfate, while 34 % is internally mixed with primary soot. When compared with using an external mixture, the direct effect of SOA is decreased, due to the decrease of total aerosol surface areamore » and the increase of absorption efficiency. Aerosol number concentrations are sharply reduced and this is responsible for a large decrease in the cloud albedo effect. In total, internal mixing suppresses the radiative effect of SOA by a factor of >4 compared to treating SOA as an external mixture. The future SOA burden increases by 24% due to CO2 increases and climate change, leading to a total (direct plus cloud albedo) radiative forcing of -0.05 W m-2. When the combined effects of changes in climate, anthropogenic emissions and land use are included, the SOA forcing is -0.07 W m-2, even though the SOA burden only increases by 6.8%. This is caused by the substantial increase of SOA associated with sulfate in the Aitken mode. The Aitken mode increase contributes to the enhancement of first indirect radiative forcing, which dominates the total radiative forcing.« less

Mechanism of SOA Formation Determines Magnitude of Radiative Effects

NASA Astrophysics Data System (ADS)

Zhu, J.; Penner, J.; Lin, G.; Zhou, C.

2017-12-01

Secondary organic aerosol (SOA) nearly always exists as an internal mixture and the distribution of this mixture depends on the formation mechanism of SOA. A model is developed to examine the influence of using an internal mixing states based on the mechanism of formation and to estimate the radiative forcing of SOA in the future. For the present day, 66 % of SOA is internally mixed with sulfate, while 34 % is internally mixed with primary soot. When compared with using an external mixture, the direct effect of SOA is decreased, due to the decrease of total aerosol surface area and the increase of absorption efficiency. Aerosol number concentrations are sharply reduced and this is responsible for a large decrease in the cloud albedo effect. In total, internal mixing suppresses the radiative effect of SOA by a factor of >4 compared to treating SOA as an external mixture. The future SOA burden increases by 24% due to CO2 increases and climate change, leading to a total (direct plus cloud albedo) radiative forcing of -0.05 W m-2. When the combined effects of changes in climate, anthropogenic emissions and land use are included, the SOA forcing is -0.07 W m-2, even though the SOA burden only increases by 6.8%. This is caused by the substantial increase of SOA associated with sulfate in the Aitken mode. The Aitken mode increase contributes to the enhancement of first indirect radiative forcing, which dominates the total radiative forcing.

Effects of inorganic seeds on secondary organic aerosol formation from photochemical oxidation of acetone in a chamber

NASA Astrophysics Data System (ADS)

Ge, Shuangshuang; Xu, Yongfu; Jia, Long

2017-12-01

Photochemical oxidations of acetone were studied under different inorganic seed (NaCl, (NH4)2SO4 and NaNO3) conditions in a self-made chamber. The results show that no secondary organic aerosol (SOA) can be formed in the experiments either in the absence of artificially added seed particles or in the presence of solid status of the added particles. Liquid water content is the key factor for the formation of SOA in the experiments with seeds. The amount of SOA was only about 4-7 μg m-3 in the experiments with the initial acetone of ∼15 ppm under different seed conditions. The analysis of SOA compositions by Exactive-Orbitrap mass spectrometer equipped with electro-spray interface (ESI-MS) shows that chlorine-containing and sulfur-containing compounds were detected in SOA formed from the experiments with NaCl and (NH4)2SO4 seeds, respectively, which were not identified in SOA from those with NaNO3. The compositions of SOA were mainly esters, organonitrates, hydroperoxides, etc. It is concluded that inorganic seed particles participated into the formation of SOA. Acetone SOA was mainly formed in the aqueous phase in which dissolved SOA precursors underwent further oxidation reactions, esterification reactions and/or radical-radical reactions. Our experiments further demonstrate that low-molecular-weight VOCs, such as acetone, can form SOA under certain conditions in the atmosphere, although their contributions to SOA may not be large.

Mechanism of SOA formation determines magnitude of radiative effects

PubMed Central

Penner, Joyce E.; Lin, Guangxing; Zhou, Cheng; Xu, Li; Zhuang, Bingliang

2017-01-01

Secondary organic aerosol (SOA) nearly always exists as an internal mixture, and the distribution of this mixture depends on the formation mechanism of SOA. A model is developed to examine the influence of using an internal mixing state based on the mechanism of formation and to estimate the radiative forcing of SOA in the future. For the present day, 66% of SOA is internally mixed with sulfate, while 34% is internally mixed with primary soot. Compared with using an external mixture, the direct effect of SOA is decreased due to the decrease in total aerosol surface area and the increase of absorption efficiency. Aerosol number concentrations are sharply reduced, and this is responsible for a large decrease in the cloud albedo effect. Internal mixing decreases the radiative effect of SOA by a factor of >4 compared with treating SOA as an external mixture. The future SOA burden increases by 24% due to CO2 increases and climate change, leading to a total (direct plus cloud albedo) radiative forcing of −0.05 W m−2. When the combined effects of changes in climate, anthropogenic emissions, and land use are included, the SOA forcing is −0.07 W m−2, even though the SOA burden only increases by 6.8%. This is caused by the substantial increase of SOA associated with sulfate in the Aitken mode. The Aitken mode increase contributes to the enhancement of first indirect radiative forcing, which dominates the total radiative forcing. PMID:29133426

Mechanism of SOA formation determines magnitude of radiative effects.

PubMed

Zhu, Jialei; Penner, Joyce E; Lin, Guangxing; Zhou, Cheng; Xu, Li; Zhuang, Bingliang

2017-11-28

Secondary organic aerosol (SOA) nearly always exists as an internal mixture, and the distribution of this mixture depends on the formation mechanism of SOA. A model is developed to examine the influence of using an internal mixing state based on the mechanism of formation and to estimate the radiative forcing of SOA in the future. For the present day, 66% of SOA is internally mixed with sulfate, while 34% is internally mixed with primary soot. Compared with using an external mixture, the direct effect of SOA is decreased due to the decrease in total aerosol surface area and the increase of absorption efficiency. Aerosol number concentrations are sharply reduced, and this is responsible for a large decrease in the cloud albedo effect. Internal mixing decreases the radiative effect of SOA by a factor of >4 compared with treating SOA as an external mixture. The future SOA burden increases by 24% due to CO 2 increases and climate change, leading to a total (direct plus cloud albedo) radiative forcing of -0.05 W m -2 When the combined effects of changes in climate, anthropogenic emissions, and land use are included, the SOA forcing is -0.07 W m -2 , even though the SOA burden only increases by 6.8%. This is caused by the substantial increase of SOA associated with sulfate in the Aitken mode. The Aitken mode increase contributes to the enhancement of first indirect radiative forcing, which dominates the total radiative forcing. Copyright © 2017 the Author(s). Published by PNAS.

Modeling the formation and properties of traditional and non-traditional secondary organic aerosol: problem formulation and application to aircraft exhaust

NASA Astrophysics Data System (ADS)

Jathar, S. H.; Miracolo, M. A.; Presto, A. A.; Donahue, N. M.; Adams, P. J.; Robinson, A. L.

2012-10-01

We present a methodology to model secondary organic aerosol (SOA) formation from the photo-oxidation of unspeciated low-volatility organics (semi-volatile and intermediate volatile organic compounds) emitted by combustion systems. It is formulated using the volatility basis-set approach. Unspeciated low-volatility organics are classified by volatility and then allowed to react with the hydroxyl radical. The new methodology allows for larger reductions in volatility with each oxidation step than previous volatility basis set models, which is more consistent with the addition of common functional groups and similar to those used by traditional SOA models. The methodology is illustrated using data collected during two field campaigns that characterized the atmospheric evolution of dilute gas-turbine engine emissions using a smog chamber. In those experiments, photo-oxidation formed a significant amount of SOA, much of which could not be explained based on the emissions of traditional speciated precursors; we refer to the unexplained SOA as non-traditional SOA (NT-SOA). The NT-SOA can be explained by emissions of unspeciated low-volatility organics measured using sorbents. We show that the parameterization proposed by Robinson et al. (2007) is unable to explain the timing of the NT-SOA formation in the aircraft experiments because it assumes a very modest reduction in volatility of the precursors with every oxidation reaction. In contrast the new method better reproduces the NT-SOA formation. The NT-SOA yields estimated for the unspeciated low-volatility organic emissions in aircraft exhaust are similar to literature data for large n-alkanes and other low-volatility organics. The estimated yields vary with fuel composition (Jet Propellent-8 versus Fischer-Tropsch) and engine load (ground idle versus non-ground idle). The framework developed here is suitable for modeling SOA formation from emissions from other combustion systems.

Mechanisms leading to oligomers and SOA through aqueous photooxidation: insights from OH radical oxidation of acetic acid and methylglyoxal

NASA Astrophysics Data System (ADS)

Tan, Y.; Lim, Y. B.; Altieri, K. E.; Seitzinger, S. P.; Turpin, B. J.

2012-01-01

Previous experiments have demonstrated that the aqueous OH radical oxidation of methylglyoxal produces low volatility products including pyruvate, oxalate and oligomers. These products are found predominantly in the particle phase in the atmosphere, suggesting that methylglyoxal is a precursor of secondary organic aerosol (SOA). Acetic acid plays a central role in the aqueous oxidation of methylglyoxal and it is a ubiquitous product of gas phase photochemistry, making it a potential "aqueous" SOA precursor in its own right. However, the fate of acetic acid upon aqueous-phase oxidation is not well understood. In this research, acetic acid (20 μM-10 mM) was oxidized by OH radicals, and pyruvic acid and methylglyoxal experimental samples were analyzed using new analytical methods, in order to better understand the formation of SOA from acetic acid and methylglyoxal. Glyoxylic, glycolic, and oxalic acids formed from acetic acid and OH radicals. In contrast to the aqueous OH radical oxidation of methylglyoxal, the aqueous OH radical oxidation of acetic acid did not produce succinic acid and oligomers. This suggests that the methylgloxal-derived oligomers do not form through the acid catalyzed esterification pathway proposed previously. Using results from these experiments, radical mechanisms responsible for oligomer formation from methylglyoxal oxidation in clouds and wet aerosols are proposed. The importance of acetic acid/acetate as an SOA precursor is also discussed. We hypothesize that this and similar chemistry is central to the daytime formation of oligomers in wet aerosols.

VOC species and emission inventory from vehicles and their SOA formation potentials estimation in Shanghai, China

NASA Astrophysics Data System (ADS)

Huang, C.; Wang, H. L.; Li, L.; Wang, Q.; Lu, Q.; de Gouw, J. A.; Zhou, M.; Jing, S. A.; Lu, J.; Chen, C. H.

2015-10-01

Volatile organic compound (VOC) species from vehicle exhausts and gas evaporation were investigated by chassis dynamometer and on-road measurements of nine gasoline vehicles, seven diesel vehicles, five motorcycles, and four gas evaporation samples. The secondary organic aerosol (SOA) mass yields of gasoline, diesel, motorcycle exhausts, and gas evaporation were estimated based on the mixing ratio of measured C2-C12 VOC species and inferred carbon number distributions. High aromatic contents were measured in gasoline exhausts and contributed comparatively more SOA yield. A vehicular emission inventory was compiled based on a local survey of on-road traffic in Shanghai and real-world measurements of vehicle emission factors from previous studies in the cities of China. The inventory-based vehicular organic aerosol (OA) productions to total CO emissions were compared with the observed OA to CO concentrations (ΔOA / ΔCO) in the urban atmosphere. The results indicate that vehicles dominate the primary organic aerosol (POA) emissions and OA production, which contributed about 40 and 60 % of OA mass in the urban atmosphere of Shanghai. Diesel vehicles, which accounted for less than 20 % of vehicle kilometers of travel (VKT), contribute more than 90 % of vehicular POA emissions and 80-90 % of OA mass derived by vehicles in urban Shanghai. Gasoline exhaust could be an important source of SOA formation. Tightening the limit of aromatic content in gasoline fuel will be helpful to reduce its SOA contribution. Intermediate-volatile organic compounds (IVOCs) in vehicle exhausts greatly contribute to SOA formation in the urban atmosphere of China. However, more experiments need to be conducted to determine the contributions of IVOCs to OA pollution in China.

Glyoxal-methylglyoxal cross-reactions in secondary organic aerosol formation.

PubMed

Schwier, Allison N; Sareen, Neha; Mitroo, Dhruv; Shapiro, Erica L; McNeill, V Faye

2010-08-15

Glyoxal (G) and methylglyoxal (MG) are potentially important secondary organic aerosol (SOA) precursors. Previous studies of SOA formation by G and MG have focused on either species separately; however, G and MG typically coexist in the atmosphere. We studied the formation of secondary organic material in aqueous aerosol mimic mixtures containing G and MG with ammonium sulfate. We characterized the formation of light-absorbing products using UV-vis spectrophotometry. We found that absorption at 280 nm can be described well using models for the formation of light-absorbing products by G and MG in parallel. Pendant drop tensiometry measurements showed that surface tension depression by G and MG in these solutions can be modeled as a linear combination of the effects of G and MG alone. Product species were identified using chemical ionization mass spectrometry with a volatilization flow tube inlet (Aerosol CIMS). Peaks consistent with G-MG cross-reaction products were observed, accounting for a significant fraction of detected product mass, but most peaks could be attributed to self-reaction. We conclude that cross-reactions contribute to SOA mass from uptake of G and MG, but they are not required to accurately model the effects of this process on aerosol surface tension or light absorption.

Secondary Organic Aerosol Formation in the Captive Aerosol Growth and Evolution (CAGE) Chambers during the Southern Oxidant and Aerosol Study (SOAS) in Centreville, AL

NASA Astrophysics Data System (ADS)

Leong, Y.; Karakurt Cevik, B.; Hernandez, C.; Griffin, R. J.; Taylor, N.; Matus, J.; Collins, D. R.

2013-12-01

Secondary organic aerosol (SOA) represents a large portion of sub-micron particulate matter on a global scale. The composition of SOA and its formation processes are heavily influenced by anthropogenic and biogenic activity. Volatile organic compounds (VOCs) that are emitted naturally from forests or from human activity serve as precursors to SOA formation. Biogenic SOA (BSOA) is formed from biogenic VOCs and is prevalent in forested regions like the Southeastern United States. The formation and enhancement of BSOA under anthropogenic influences such as nitrogen oxides (NOx), sulfur dioxide (SO2), and oxygen radicals are still not well understood. The lack of information on anthropogenic BSOA enhancement and the reversibility of SOA formation could explain the underprediction of SOA in current models. To address some of these gaps in knowledge, this study was conducted as part of the Southern Oxidant and Aerosol Study (SOAS) in Centreville, AL during the summer of 2013. SOA growth experiments were conducted in two Captive Aerosol Growth and Evolution (CAGE) outdoor chambers located at the SEARCH site. Ambient trace gas concentrations were maintained in these chambers using semi-permeable gas-exchange membranes, while studying the growth of injected monodisperse seed aerosol. The control chamber was operated under ambient conditions; the relative humidity and oxidant and NOx levels were perturbed in the second chamber. This design allows experiments to capture the natural BSOA formation processes in the southeastern atmosphere and to study the influence of anthropogenic activity on aerosol chemistry. Chamber experiments were periodically monitored with physical and chemical instrumentation including a scanning mobility particle sizer (SMPS), a cloud condensation nuclei counter (CCNC), a humidified tandem differential mobility analyzer (H-TDMA), and an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS). The CAGE experiments focused on SOA reversibility and the sensitivity of SOA reactions to oxidant or NOx enhancement and aerosol liquid water content. Available ambient trace gas concentrations include VOCs, NOx, SO2, ozone, peroxyaxyl nitrates, and ammonia. Chamber data will also be compared to ambient aerosol measurements collected by the instruments mentioned above as well as those from other research groups.

Improving Secondary Organic Aerosol (SOA) Models using Global Sensitivity Analysis and by Comparison to Chamber Data.

NASA Astrophysics Data System (ADS)

Miller, D. O.; Brune, W. H.

2017-12-01

Accurate estimates of secondary organic aerosol (SOA) from atmospheric models is a major research challenge due to the complexity of the chemical and physical processes involved in the SOA formation and continuous aging. The primary uncertainties of SOA models include those associated with the formation of gas-phase products, the conversion between gas phase and particle phase, the aging mechanisms of SOA, and other processes related to the heterogeneous and particle-phase reactions. To address this challenge, we us a modular modeling framework that combines both simple and near-explicit gas-phase reactions and a two-dimensional volatility basis set (2D-VBS) to simulate the formation and evolution of SOA. Global sensitivity analysis is used to assess the relative importance of the model input parameters. In addition, the model is compared to the measurements from the Focused Isoprene eXperiment at the California Institute of Technology (FIXCIT).

Updated aerosol module and its application to simulate secondary organic aerosols during IMPACT campaign May 2008

NASA Astrophysics Data System (ADS)

Li, Y. P.; Elbern, H.; Lu, K. D.; Friese, E.; Kiendler-Scharr, A.; Mentel, Th. F.; Wang, X. S.; Wahner, A.; Zhang, Y. H.

2013-03-01

The formation of Secondary organic aerosol (SOA) was simulated with the Secondary ORGanic Aerosol Model (SORGAM) by a classical gas-particle partitioning concept, using the two-product model approach, which is widely used in chemical transport models. In this study, we extensively updated SORGAM including three major modifications: firstly, we derived temperature dependence functions of the SOA yields for aromatics and biogenic VOCs, based on recent chamber studies within a sophisticated mathematic optimization framework; secondly, we implemented the SOA formation pathways from photo oxidation (OH initiated) of isoprene; thirdly, we implemented the SOA formation channel from NO3-initiated oxidation of reactive biogenic hydrocarbons (isoprene and monoterpenes). The temperature dependence functions of the SOA yields were validated against available chamber experiments. Moreover, the whole updated SORGAM module was validated against ambient SOA observations represented by the summed oxygenated organic aerosol (OOA) concentrations abstracted from Aerosol Mass Spectrometer (AMS) measurements at a rural site near Rotterdam, the Netherlands, performed during the IMPACT campaign in May 2008. In this case, we embedded both the original and the updated SORGAM module into the EURopean Air pollution and Dispersion-Inverse Model (EURAD-IM), which showed general good agreements with the observed meteorological parameters and several secondary products such as O3, sulfate and nitrate. With the updated SORGAM module, the EURAD-IM model also captured the observed SOA concentrations reasonably well especially those during nighttime. In contrast, the EURAD-IM model before update underestimated the observations by a factor of up to 5. The large improvements of the modeled SOA concentrations by updated SORGAM were attributed to the mentioned three modifications. Embedding the temperature dependence functions of the SOA yields, including the new pathways from isoprene photo oxidations, and switching on the SOA formation from NO3 initiated biogenic VOCs oxidations contributed to this enhancement by 10%, 22% and 47%, respectively. However, the EURAD-IM model with updated SORGAM still clearly underestimated the afternoon SOA observations up to a factor of two. More work such as to improve the simulated OH concentrations under high VOCs and low NOx concentrations, further including the SOA formation from semi-volatile organic compounds, the correct aging process of aerosols, oligomerization process and the influence on the biogenic SOA by the anthropogenic SOA, are still required to fill the gap.

SOA VOLATILITY EVOLUTION: FORMATION AND OXIDATION OVER THE LIFECYCLE OF PM2.5

EPA Science Inventory

Secondary Organic Aerosols are a major, possibly dominant, source of organic PM_2.5 that remain enigmatic. Enormous progress has been made in the past 15 years regarding SOA formation, starting with recognition that most SOA products are semivolatile, continuing to a...

Observational Constraints on Modeling Growth and Evaporation Kinetics of Isoprene SOA

NASA Astrophysics Data System (ADS)

Zaveri, R. A.; Shilling, J. E.; Zelenyuk, A.; Liu, J.; Wilson, J. M.; Laskin, A.; Wang, B.; Fast, J. D.; Easter, R. C.; Wang, J.; Kuang, C.; Thornton, J. A.; Setyan, A.; Zhang, Q.; Onasch, T. B.; Worsnop, D. R.

2014-12-01

Isoprene is thought to be a major contributor to the global secondary organic aerosol (SOA) budget, and therefore has the potential to exert a significant influence on earth's climate via aerosol direct and indirect radiative effects. Both aerosol optical and cloud condensation nuclei properties are quite sensitive to aerosol number size distribution, as opposed to the total aerosol mass concentration. Recent studies suggest that SOA particles can be highly viscous, which can affect the kinetics of SOA partitioning and size distribution evolution when the condensing organic vapors are semi-volatile. In this study, we examine the growth kinetics of SOA formed from isoprene photooxidation in the presence of pre-existing Aitken and accumulation mode aerosols in: (a) the ambient atmosphere during the CARES field campaign, and (b) the environmental chamber at PNNL. Each growth episode is analyzed and interpreted with the updated MOSAIC aerosol box model, which performs kinetic gas-particle partitioning of SOA and takes into account diffusion and chemical reaction within the particle phase. The model is initialized with the observed aerosol size distribution and composition at the beginning of the experiment, and the total amount of SOA formed in the model at any given time is constrained by the observed total amount of SOA formed. The variable model parameters include the number of condensing organic species, their gas-phase formation rates, their effective volatilities, and their bulk diffusivities in the Aitken and accumulation modes. The objective of the constrained modeling exercise is then to determine which model configuration is able to best reproduce the observed size distribution evolution, thus providing valuable insights into the possible mechanism of SOA formation. We also examine the evaporation kinetics of size-selected particles formed in the environmental chamber to provide additional constraints on the effective volatility and bulk diffusivity of the organic species. Our results suggest that SOA formed from isoprene photooxidation is semi-volatile, and the resulting size distribution evolution is highly sensitive to the phase state (bulk diffusivity) of the pre-existing aerosol. Implications of these findings on further SOA model development and evaluation strategy will be discussed.

Humidity influence on gas-particle phase partitioning of α-pinene + O3 secondary organic aerosol

NASA Astrophysics Data System (ADS)

Prisle, N. L.; Engelhart, G. J.; Bilde, M.; Donahue, N. M.

2010-01-01

Water vapor uptake to particles could potentially affect organic-aerosol mass in three ways: first, water in the organic phase could reduce organic (equilibrium) partial pressures according to Raoult's law; second, an aqueous phase could attract water soluble organics according to Henry's law; finally, deliquescence of inorganic particle cores could mix the organic and inorganic particle phases, significantly diluting the organics and again reducing organic partial pressures according to Raoult's law. We present experiments using initially dry α-pinene + ozone secondary organic aerosol (SOA) on ammonium sulfate (AS) seeds at atmospheric concentrations in a smog chamber. After SOA formation, the chamber relative humidity is increased steadily by addition of steam to near 100%. Little subsequent SOA mass growth is observed, suggesting that none of these potential effects play a strong role in this system.

Secondary organic aerosol formation from ozone-initiated reactions with nicotine and secondhand tobacco smoke

NASA Astrophysics Data System (ADS)

Sleiman, Mohamad; Destaillats, Hugo; Smith, Jared D.; Liu, Chen-Lin; Ahmed, Musahid; Wilson, Kevin R.; Gundel, Lara A.

2010-11-01

We used controlled laboratory experiments to evaluate the aerosol-forming potential of ozone reactions with nicotine and secondhand smoke. Special attention was devoted to real-time monitoring of the particle size distribution and chemical composition of SOA as they are believed to be key factors determining the toxicity of SOA. The experimental approach was based on using a vacuum ultraviolet photon ionization time-of-flight aerosol mass spectrometer (VUV-AMS), a scanning mobility particle sizer (SMPS) and off-line thermal desorption coupled to mass spectrometry (TD-GC-MS) for gas-phase byproducts analysis. Results showed that exposure of SHS to ozone induced the formation of ultrafine particles (<100 nm) that contained high molecular weight nitrogenated species ( m/ z 400-500), which can be due to accretion/acid-base reactions and formation of oligomers. In addition, nicotine was found to contribute significantly (with yields 4-9%) to the formation of secondary organic aerosol through reaction with ozone. The main constituents of the resulting SOA were tentatively identified and a reaction mechanism was proposed to elucidate their formation. These findings identify a new component of thirdhand smoke that is associated with the formation of ultrafine particles (UFP) through oxidative aging of secondhand smoke. The significance of this chemistry for indoor exposure and health effects is highlighted.

Organic aerosol formation in citronella candle plumes.

PubMed

Bothe, Melanie; Donahue, Neil McPherson

2010-09-01

Citronella candles are widely used as insect repellants, especially outdoors in the evening. Because these essential oils are unsaturated, they have a unique potential to form secondary organic aerosol (SOA) via reaction with ozone, which is also commonly elevated on summer evenings when the candles are often in use. We investigated this process, along with primary aerosol emissions, by briefly placing a citronella tealight candle in a smog chamber and then adding ozone to the chamber. In repeated experiments, we observed rapid and substantial SOA formation after ozone addition; this process must therefore be considered when assessing the risks and benefits of using citronella candle to repel insects.

Investigating the influences of SO2 and NH3 levels on isoprene-derived secondary organic aerosol formation using conditional sampling approaches

NASA Astrophysics Data System (ADS)

Lin, Y.-H.; Knipping, E. M.; Edgerton, E. S.; Shaw, S. L.; Surratt, J. D.

2013-08-01

Filter-based PM2.5 samples were chemically analyzed to investigate secondary organic aerosol (SOA) formation from isoprene in a rural atmosphere of the southeastern US influenced by both anthropogenic sulfur dioxide (SO2) and ammonia (NH3) emissions. Daytime PM2.5 samples were collected during summer 2010 using conditional sampling approaches based on pre-defined high and low SO2 or NH3 thresholds. Known molecular-level tracers for isoprene SOA formation, including 2-methylglyceric acid, 3-methyltetrahydrofuran-3,4-diols, 2-methyltetrols, C5-alkene triols, dimers, and organosulfate derivatives, were identified and quantified by gas chromatography coupled to electron ionization mass spectrometry (GC/EI-MS) and ultra performance liquid chromatography coupled to electrospray ionization high-resolution quadrupole time-of-flight mass spectrometry (UPLC/ESI-HR-Q-TOFMS). Mass concentrations of six isoprene low-NOx SOA tracers contributed to 12-19% of total organic matter (OM) in PM2.5 samples collected during the sampling period, indicating the importance of the hydroxyl radical (OH)-initiated oxidation (so-called photooxidation) of isoprene under low-NOx conditions that lead to SOA formation through reactive uptake of gaseous isoprene epoxydiols (IEPOX) in this region. The contribution of the IEPOX-derived SOA tracers to total organic matter was enhanced by 1.4% (p = 0.012) under high-SO2 sampling scenarios, although only weak associations between aerosol acidity and mass of IEPOX SOA tracers were observed. This suggests that IEPOX-derived SOA formation might be modulated by other factors simultaneously, rather than only aerosol acidity. No clear associations between isoprene SOA formation and high or low NH3 conditional samples were found. Positive correlations between sulfate aerosol loadings and IEPOX-derived SOA tracers for samples collected under all conditions indicates that sulfate aerosol could be a surrogate for surface accommodation in the uptake of IEPOX onto preexisting aerosols.

Examining the effects of anthropogenic emissions on isoprene-derived secondary organic aerosol formation during the 2013 Southern Oxidant and Aerosol Study (SOAS) at the Look Rock, Tennessee ground site

NASA Astrophysics Data System (ADS)

Budisulistiorini, S. H.; Li, X.; Bairai, S. T.; Renfro, J.; Liu, Y.; Liu, Y. J.; McKinney, K. A.; Martin, S. T.; McNeill, V. F.; Pye, H. O. T.; Nenes, A.; Neff, M. E.; Stone, E. A.; Mueller, S.; Knote, C.; Shaw, S. L.; Zhang, Z.; Gold, A.; Surratt, J. D.

2015-08-01

A suite of offline and real-time gas- and particle-phase measurements was deployed at Look Rock, Tennessee (TN), during the 2013 Southern Oxidant and Aerosol Study (SOAS) to examine the effects of anthropogenic emissions on isoprene-derived secondary organic aerosol (SOA) formation. High- and low-time-resolution PM2.5 samples were collected for analysis of known tracer compounds in isoprene-derived SOA by gas chromatography/electron ionization-mass spectrometry (GC/EI-MS) and ultra performance liquid chromatography/diode array detection-electrospray ionization-high-resolution quadrupole time-of-flight mass spectrometry (UPLC/DAD-ESI-HR-QTOFMS). Source apportionment of the organic aerosol (OA) was determined by positive matrix factorization (PMF) analysis of mass spectrometric data acquired on an Aerodyne Aerosol Chemical Speciation Monitor (ACSM). Campaign average mass concentrations of the sum of quantified isoprene-derived SOA tracers contributed to ~ 9 % (up to 28 %) of the total OA mass, with isoprene-epoxydiol (IEPOX) chemistry accounting for ~ 97 % of the quantified tracers. PMF analysis resolved a factor with a profile similar to the IEPOX-OA factor resolved in an Atlanta study and was therefore designated IEPOX-OA. This factor was strongly correlated (r2 > 0.7) with 2-methyltetrols, C5-alkene triols, IEPOX-derived organosulfates, and dimers of organosulfates, confirming the role of IEPOX chemistry as the source. On average, IEPOX-derived SOA tracer mass was ~ 26 % (up to 49 %) of the IEPOX-OA factor mass, which accounted for 32 % of the total OA. A low-volatility oxygenated organic aerosol (LV-OOA) and an oxidized factor with a profile similar to 91Fac observed in areas where emissions are biogenic-dominated were also resolved by PMF analysis, whereas no primary organic aerosol (POA) sources could be resolved. These findings were consistent with low levels of primary pollutants, such as nitric oxide (NO ~ 0.03 ppb), carbon monoxide (CO ~ 116 ppb), and black carbon (BC ~ 0.2 μg m-3). Particle-phase sulfate is fairly correlated (r2 ~ 0.3) with both methacrylic acid epoxide (MAE)/hydroxymethyl-methyl-α-lactone (HMML)- (henceforth called methacrolein (MACR)-derived SOA tracers) and IEPOX-derived SOA tracers, and more strongly correlated (r2 ~ 0.6) with the IEPOX-OA factor, in sum suggesting an important role of sulfate in isoprene SOA formation. Moderate correlation between the MACR-derived SOA tracer 2-methylglyceric acid with sum of reactive and reservoir nitrogen oxides (NOy; r2 = 0.38) and nitrate (r2 = 0.45) indicates the potential influence of anthropogenic emissions through long-range transport. Despite the lack of a clear association of IEPOX-OA with locally estimated aerosol acidity and liquid water content (LWC), box model calculations of IEPOX uptake using the simpleGAMMA model, accounting for the role of acidity and aerosol water, predicted the abundance of the IEPOX-derived SOA tracers 2-methyltetrols and the corresponding sulfates with good accuracy (r2 ~ 0.5 and ~ 0.7, respectively). The modeling and data combined suggest an anthropogenic influence on isoprene-derived SOA formation through acid-catalyzed heterogeneous chemistry of IEPOX in the southeastern US. However, it appears that this process was not limited by aerosol acidity or LWC at Look Rock during SOAS. Future studies should further explore the extent to which acidity and LWC as well as aerosol viscosity and morphology becomes a limiting factor of IEPOX-derived SOA, and their modulation by anthropogenic emissions.

Partitioning phase preference for secondary organic aerosol in an urban atmosphere.

PubMed

Chang, Wayne L; Griffin, Robert J; Dabdub, Donald

2010-04-13

Secondary organic aerosol (SOA) comprises a significant portion of atmospheric particular matter. The impact of particular matter on both human health and global climate has long been recognized. Despite its importance, there are still many unanswered questions regarding the formation and evolution of SOA in the atmosphere. This study uses a modeling approach to understand the preferred partitioning behavior of SOA species into aqueous or organic condensed phases. More specifically, this work uses statistical analyses of approximately 24,000 data values for each variable from a state of the art 3D airshed model. Spatial and temporal distributions of fractions of SOA residing in the aqueous phase (fAQ) in the South Coast Air Basin of California are presented. Typical values of fAQ within the basin near the surface range from 5 to 80%. Results show that the likelihood of large fAQ values is inversely proportional to the total SOA loading. Analysis of various meteorological parameters indicates that large fAQ values are predicted because modeled aqueous-phase SOA formation is less sensitive than that of organic-phase SOA to atmospheric conditions that are not conducive to SOA formation. There is a diurnal variation of fAQ near the surface: It tends to be larger during daytime hours than during nighttime hours. Results also indicate that the largest fAQ values are simulated in layers above ground level at night. In summary, one must consider SOA in both organic and aqueous phases for proper regional and global SOA budget estimation.

Limited Effect of Anthropogenic Nitrogen Oxides on Secondary Organic Aerosol Formation

NASA Astrophysics Data System (ADS)

Zheng, Y.; Unger, N.; Hodzic, A.; Knote, C. J.; Tilmes, S.; Emmons, L. K.; Lamarque, J. F.; Yu, P.

2014-12-01

Globally secondary organic aerosol (SOA) is mostly formed from biogenic vegetation emissions and as such is regarded as natural aerosol that cannot be reduced by emission control legislation. However, recent research implies that human activities facilitate SOA formation by affecting the amount of precursor emission, the chemical processing and the partitioning into the aerosol phase. Among the multiple human influences, nitrogen oxides (NO + NO2 = NOx) have been assumed to play a critical role in the chemical formation of low volatile compounds. The goal of this study is to improve the SOA scheme in the global NCAR Community Atmospheric Model version 4 with chemistry (CAM4-Chem) by implementing an updated 4-product Volatility Basis Set (VBS) scheme, and apply it to investigate the impact of anthropogenic NOx on SOA. We first compare three different SOA parameterizations: a 2-product model and the updated VBS model both with and without a SOA aging parameterization. Secondly we evaluate predicted organic aerosol amounts against surface measurement from the Interagency Monitoring of Protected Visual Environments (IMPROVE) network and Aerosol Mass Spectrometer (AMS) measurements from 13 aircraft-based field campaigns. We then perform sensitivity experiments to examine how the SOA loading responds to a 50% reduction in anthropogenic NOx in different regions. We find limited SOA reductions of -2.3%, -5.6% and -4.0% for global, southeastern U.S. and Amazon NOx perturbations, respectively. To investigate the chemical processes in more detail, we also use a simplified box model with the same gas-phase chemistry and gas-aerosol partitioning mechanism as in CAM4-Chem to examine the SOA yields dependence on initial precursor emissions and background NOx level. The fact that SOA formation is almost unaffected by changes in NOx can be largely attributed to buffering in chemical pathways (low- versus high-NOx pathways, OH versus NO3-initiated oxidation) and to offsetting tendencies in the biogenic versus anthropogenic SOA responses.

Synthesis and coherent vibrational laser spectroscopy of putative molecular constituents in isoprene-derived secondary organic aerosol particles

NASA Astrophysics Data System (ADS)

Ebben, C. J.; Strick, B. F.; Upshur, M. A.; Chase, H. M.; Achtyl, J. L.; Thomson, R. J.; Geiger, F. M.

2013-11-01

SOA particle formation ranks among the least understood processes in the atmosphere, rooted in part in (a) the limited knowledge about SOA chemical composition; (b) the availability of only little concrete evidence for chemical structures; and (c) little availability of reference compounds needed for benchmarking and chemical identification in pure and homogenous form. Here, we address these challenges by synthesizing and subjecting to physical and chemical analysis putative isoprene-derived SOA particle constituents. Our surface-selective spectroscopic analysis of these compounds is followed by comparison to synthetic SOA particles prepared at the Harvard Environmental Chamber (HEC) and to authentic SOA particles collected in a tropical forest environment, namely the Amazon Basin, where isoprene oxidation by OH radicals has been reported to dominate SOA particle formation (Martin et al., 2010b; Sun et al., 2003; Hudson et al., 2008; Yasmeen et al., 2010). We focus on the epoxides and tetraols that have been proposed to be present in the SOA particles. We characterize the compounds prepared here by a variety of physical measurements and polarization-resolved vibrational sum frequency generation (SFG), paying particular attention to the phase state (condensed vs. vapor) of four epoxides and two tetraols in contact with a fused silica window. We compare the spectral responses from the tetraol and epoxide model compounds with those obtained from the natural and synthetic SOA particle samples that were collected on filter substrates and pressed against a fused silica window and discuss a possible match for the SFG response of one of the epoxides with that of the synthetic SOA particle material. We conclude our work by discussing how the approach described here will allow for the study of the SOA particle formation pathways from first- and second-generation oxidation products by effectively "fast-forwarding" through the initial reaction steps of particle nucleation via a chemically resolved approach aimed at testing the underlying chemical mechanisms of SOA particle formation.

Molecular characterization of nitrogen and sulfur containing compounds in night-time SOA

NASA Astrophysics Data System (ADS)

Iinuma, Yoshiteru; Mutzel, Anke; Rodigast, Maria; Böge, Olaf; Herrmann, Hartmut

2014-05-01

The oxidation of volatile organic compounds (VOCs) leads to the formation of low volatile organic compounds that can form secondary organic aerosol (SOA). Studies in the past showed that laboratory generated and ambient SOA are made of polar molecules with O/C ratios generally greater than 0.5. More recent studies have shown that SOA compounds can contain heteroatoms mainly sulfur and nitrogen atoms. Offline chemical analysis with high-resolution mass spectrometers and fragmentation experiments has shown that sulphur containing compounds are mainly organosulfates and nitrogen containing species are aromatic heterocyclic compounds such as imidazole and nitrated aromatic compounds such as nitrophenols. In addition to these, SOA compounds containing both sulfur and nitrogen have been reported from the analysis of ambient organic aerosol, rainwater, fog and cloud samples. Based on the mass spectrometric evidence these compounds are attributed to nitrooxy-organosulfates originating from isoprene and monoterpenes. Although these compounds are ubiquitously detected in the ambient samples, reports about their detection in laboratory generated SOA are scares and their formation mechanisms are not well understood. In the present study, we investigated the formation of sulfur and nitrogen containing SOA species in the oxidation of biogenic VOCs. Photooxidation and night-time oxidation experiments were performed in a smog chamber to produce SOA samples. The laboratory generated SOA samples were analysed with UPLC-IMS-TOFMS (Ultra Performance Liquid Chromatography coupled to Ion Mobility Spectrometry and Time of Flight Mass Spectrometry). The presence of highly acidic sulphate seed particles (pH0) did not promote the formation of compounds with chemical formula of C10H17NO7S- and m/z value of 294.0653, indicating that the formation mechanisms of these compounds unlikely involve the ring opening reactions of epoxides and subsequent sulfation reactions. On the other hand, their formation was significantly enhanced when the night-time oxidation was performed in the presence of both neutral seed particle and gas-phase SO2, suggesting that the presence of gas-phase SO2 is a key for their formation.

Nighttime aqueous-phase secondary organic aerosols in Los Angeles and its implication for fine particulate matter composition and oxidative potential

NASA Astrophysics Data System (ADS)

Saffari, Arian; Hasheminassab, Sina; Shafer, Martin M.; Schauer, James J.; Chatila, Talal A.; Sioutas, Constantinos

2016-05-01

Recent investigations suggest that aqueous phase oxidation of hydrophilic organic compounds can be a significant source of secondary organic aerosols (SOA) in the atmosphere. Here we investigate the possibility of nighttime aqueous phase formation of SOA in Los Angeles during winter, through examination of trends in fine particulate matter (PM2.5) carbonaceous content during two contrasting seasons. Distinctive winter and summer trends were observed for the diurnal variation of organic carbon (OC) and secondary organic carbon (SOC), with elevated levels during the nighttime in winter, suggesting an enhanced formation of SOA during that period. The nighttime ratio of SOC to OC was positively associated with the relative humidity (RH) at high RH levels (above 70%), which is when the liquid water content of the ambient aerosol would be high and could facilitate dissolution of hydrophilic primary organic compounds into the aqueous phase. Time-integrated collection and analysis of wintertime particles at three time periods of the day (morning, 6:00 a.m.-9:00 a.m.; afternoon, 11:00 a.m.-3:00 p.m.; night, 8:00 p.m.-4:00 a.m.) revealed higher levels of water soluble organic carbon (WSOC) and organic acids during the night and afternoon periods compared to the morning period, indicating that the SOA formation in winter continues throughout the nighttime. Furthermore, diurnal trends in concentrations of semi-volatile organic compounds (SVOCs) from primary emissions showed that partitioning of SVOCs from the gas to the particle phase due to the decreased nighttime temperatures cannot explain the substantial OC and SOC increase at night. The oxidative potential of the collected particles (quantified using a biological macrophage-based reactive oxygen species assay, in addition to the dithiothreitol assay) was comparable during afternoon and nighttime periods, but higher (by at least ∼30%) compared to the morning period, suggesting that SOA formation processes possibly enhance the toxicity of the ambient particles compared to mobile-source dominated primary emissions in the Los Angeles area.

Primary emissions and secondary organic aerosol formation from the exhaust of a flex-fuel (ethanol) vehicle

NASA Astrophysics Data System (ADS)

Suarez-Bertoa, R.; Zardini, A. A.; Platt, S. M.; Hellebust, S.; Pieber, S. M.; El Haddad, I.; Temime-Roussel, B.; Baltensperger, U.; Marchand, N.; Prévôt, A. S. H.; Astorga, C.

2015-09-01

Incentives to use biofuels may result in increasing vehicular emissions of compounds detrimental to air quality. Therefore, regulated and unregulated emissions from a Euro 5a flex-fuel vehicle, tested using E85 and E75 blends (gasoline containing 85% and 75% of ethanol (vol/vol), respectively), were investigated at 22 and -7 °C over the New European Driving Cycle, at the Vehicle Emission Laboratory at the European Commission Joint Research Centre Ispra, Italy. Vehicle exhaust was comprehensively analyzed at the tailpipe and in a dilution tunnel. A fraction of the exhaust was injected into a mobile smog chamber to study the photochemical aging of the mixture. We found that emissions from a flex-fuel vehicle, fueled by E85 and E75, led to secondary organic aerosol (SOA) formation, despite the low aromatic content of these fuel blends. Emissions of regulated and unregulated compounds, as well as emissions of black carbon (BC) and primary organic aerosol (POA) and SOA formation were higher at -7 °C. The flex-fuel unregulated emissions, mainly composed of ethanol and acetaldehyde, resulted in very high ozone formation potential and SOA, especially at low temperature (860 mg O3 km-1 and up to 38 mg C kg-1). After an OH exposure of 10 × 106 cm-3 h, SOA mass was, on average, 3 times larger than total primary particle mass emissions (BC + POA) with a high O:C ratio (up to 0.7 and 0.5 at 22 and -7 °C, respectively) typical of highly oxidized mixtures. Furthermore, high resolution organic mass spectra showed high 44/43 ratios (ratio of the ions m/z 44 and m/z 43) characteristic of low-volatility oxygenated organic aerosol. We also hypothesize that SOA formation from vehicular emissions could be due to oxidation products of ethanol and acetaldehyde, both short-chain oxygenated VOCs, e.g. methylglyoxal and acetic acid, and not only from aromatic compounds.

Effect of high concentrations of inorganic seed aerosols on secondary organic aerosol formation in the m-xylene/NO x photooxidation system

NASA Astrophysics Data System (ADS)

Lu, Zifeng; Hao, Jiming; Takekawa, Hideto; Hu, Lanhua; Li, Junhua

High concentrations (>15 μm 3 cm -3) of CaSO 4, Ca(NO 3) 2 and (NH 4) 2SO 4 were selected as surrogates of dry neutral, aqueous neutral and dry acidic inorganic seed aerosols, respectively, to study the effects of inorganic seeds on secondary organic aerosol (SOA) formation in irradiated m-xylene/NO x photooxidation systems. The results indicate that neither ozone formation nor SOA formation is significantly affected by the presence of neutral aerosols (both dry CaSO 4 and aqueous Ca(NO 3) 2), even at elevated concentrations. The presence of high concentrations of (NH 4) 2SO 4 aerosols (dry acidic) has no obvious effect on ozone formation, but it does enhance SOA generation and increase SOA yields. In addition, the effect of dry (NH 4) 2SO 4 on SOA yield is found to be positively correlated with the (NH 4) 2SO 4 surface concentration, and the effect is pronounced only when the surface concentration reaches a threshold value. Further, it is proposed that the SOA generation enhancement is achieved by particle-phase heterogeneous reactions induced and catalyzed by the acidity of dry (NH 4) 2SO 4 seed aerosols.

SOA formation from partitioning and heterogeneous reactions: model study in the presence of inorganic species.

PubMed

Jang, Myoseon; Czoschke, Nadine M; Northcross, Amanda L; Cao, Gang; Shaof, David

2006-05-01

A predictive model for secondary organic aerosol (SOA) formation by both partitioning and heterogeneous reactions was developed for SOA created from ozonolysis of alpha-pinene in the presence of preexisting inorganic seed aerosols. SOA was created in a 2 m3 polytetrafluoroethylene film indoor chamber under darkness. Extensive sets of SOA experiments were conducted varying humidity, inorganic seed compositions comprising of ammonium sulfate and sulfuric acid, and amounts of inorganic seed mass. SOA mass was decoupled into partitioning (OM(P)) and heterogeneous aerosol production (OM(H)). The reaction rate constant for OM(H) production was subdivided into three categories (fast, medium, and slow) to consider different reactivity of organic products for the particle phase heterogeneous reactions. The influence of particle acidity on reaction rates was treated in a previous semiempirical model. Model OM(H) was developed with medium and strong acidic seed aerosols, and then extrapolated to OM(H) in weak acidic conditions, which are more relevant to atmospheric aerosols. To demonstrate the effects of preexisting glyoxal derivatives (e.g., glyoxal hydrate and dimer) on OM(H), SOA was created with a seed mixture comprising of aqueous glyoxal and inorganic species. Our results show that heterogeneous SOA formation was also influenced by preexisting reactive glyoxal derivatives.

Review of Urban Secondary Organic Aerosol Formation from Gasoline and Diesel Motor Vehicle Emissions.

PubMed

Gentner, Drew R; Jathar, Shantanu H; Gordon, Timothy D; Bahreini, Roya; Day, Douglas A; El Haddad, Imad; Hayes, Patrick L; Pieber, Simone M; Platt, Stephen M; de Gouw, Joost; Goldstein, Allen H; Harley, Robert A; Jimenez, Jose L; Prévôt, André S H; Robinson, Allen L

2017-02-07

Secondary organic aerosol (SOA) is formed from the atmospheric oxidation of gas-phase organic compounds leading to the formation of particle mass. Gasoline- and diesel-powered motor vehicles, both on/off-road, are important sources of SOA precursors. They emit complex mixtures of gas-phase organic compounds that vary in volatility and molecular structure-factors that influence their contributions to urban SOA. However, the relative importance of each vehicle type with respect to SOA formation remains unclear due to conflicting evidence from recent laboratory, field, and modeling studies. Both are likely important, with evolving contributions that vary with location and over short time scales. This review summarizes evidence, research needs, and discrepancies between top-down and bottom-up approaches used to estimate SOA from motor vehicles, focusing on inconsistencies between molecular-level understanding and regional observations. The effect of emission controls (e.g., exhaust aftertreatment technologies, fuel formulation) on SOA precursor emissions needs comprehensive evaluation, especially with international perspective given heterogeneity in regulations and technology penetration. Novel studies are needed to identify and quantify "missing" emissions that appear to contribute substantially to SOA production, especially in gasoline vehicles with the most advanced aftertreatment. Initial evidence suggests catalyzed diesel particulate filters greatly reduce emissions of SOA precursors along with primary aerosol.

Mechanisms leading to oligomers and SOA through aqueous photooxidation: insights from OH radical oxidation of acetic acid

NASA Astrophysics Data System (ADS)

Tan, Y.; Lim, Y. B.; Altieri, K. E.; Seitzinger, S. P.; Turpin, B. J.

2011-06-01

Previous experiments have demonstrated that the aqueous OH radical oxidation of methylglyoxal produces low volatility products including oxalate and oligomers. These products are found predominantly in the particle phase in the atmosphere, suggesting that methylglyoxal is a precursor of secondary organic aerosol (SOA). Acetic acid is an important intermediate in aqueous methylglyoxal oxidation and a ubiquitous product of gas phase photochemistry, making it a potential "aqueous" SOA precursor in its own right. Altieri et al. (2008) proposed that acetic acid was the precursor of oligoesters observed in methylglyoxal oxidation. However, the fate of acetic acid upon aqueous-phase oxidation is not well understood. In this research, acetic acid at concentrations relevant to atmospheric waters (20 μM-10 mM) was oxidized by OH radical. Products were analyzed by ion chromatography (IC), electrospray ionization mass spectrometry (ESI-MS), and IC-ESI-MS. The formation of glyoxylic, glycolic, and oxalic acids were observed. In contrast to methylglyoxal oxidation, succinic acid and oligomers were not detected. Using results from these and methylglyoxal + OH radical experiments, radical mechanisms responsible for oligomer formation from methylglyoxal oxidation in clouds and wet aerosols are proposed. The importance of acetic acid/acetate as an SOA precursor is also discussed. We hypothesize that this and similar chemistry is central to the daytime formation of oligomers in wet aerosols.

Modelling of Criegee Intermediates using the 3-D global model, STOCHEM-CRI and investigating their global impacts on Secondary Organic Aerosol formation

NASA Astrophysics Data System (ADS)

Khan, M. Anwar H.; Cooke, Michael; Utembe, Steve; Archibald, Alexander; Derwent, Richard; Jenkin, Mike; Lyons, Kyle; Kent, Adam; Percival, Carl; Shallcross, Dudley E.

2016-04-01

Gas phase reactions of ozone with unsaturated compounds form stabilized Criegee intermediates (sCI) which play an important role in controlling the budgets of many tropospheric species including OH, organic acids and secondary organic aerosols (SOA). Recently sCI has been proposed to play a significant role in atmospheric sulfate and nitrate chemistry by forming sulfuric acid (promoter of aerosol formation) and nitrate radical (a powerful oxidizing agent). sCI can also undergo association reactions with water, alcohols, and carboxylic acids to form hydroperoxides and with aldehydes and ketones to form secondary ozonides. The products from these reactions are low volatility compounds which can contribute to the formation of SOA. The importance of plant emitted alkenes (isoprene, monoterpenes, sesquiterpenes) in the production of SOA through sCI formation have already been investigated in laboratory studies. However, the SOA formation from these reactions are absent in current global models. Thus, the formation of SOA has been incorporated in the global model, STOCHEM-CRI, a 3-D global chemistry transport model and the role of CI chemistry in controlling atmospheric composition and climate, and the influence of water vapor has been discussed in the study.

Evaporation kinetics of laboratory-generated secondary organic aerosols at elevated relative humidity.

PubMed

Wilson, Jacqueline; Imre, Dan; Beránek, Josef; Shrivastava, Manish; Zelenyuk, Alla

2015-01-06

Secondary organic aerosols (SOA) dominate atmospheric organic aerosols that affect climate, air quality, and health. Recent studies indicate that, contrary to previously held assumptions, at low relative humidity (RH) these particles are semisolid and evaporate orders of magnitude slower than expected. Elevated relative humidity has the potential to affect significantly formation, properties, and atmospheric evolution of SOA particles. Here we present a study of the effect of RH on the room-temperature evaporation kinetics of SOA particles formed by ozonolysis of α-pinene and limonene. Experiments were carried out on α-pinene SOA particles generated, evaporated, and aged at <5%, 50 and 90% RH, and on limonene SOA particles at <5% and 90% RH. We find that in all cases evaporation begins with a relatively fast phase, during which 30-70% of the particle mass evaporates in 2 h, followed by a much slower evaporation rate. Evaporation kinetics at <5% and 50% RH are nearly the same, while at 90% RH a slightly larger fraction evaporates. In all cases, aging the particles prior to inducing evaporation reduces the evaporative losses; with aging at elevated RH leading to a more significant effect. In all cases, the observed SOA evaporation is nearly size-independent.

Modeling the formation and aging of secondary organic aerosols in Los Angeles during CalNex 2010

NASA Astrophysics Data System (ADS)

Hayes, P. L.; Carlton, A. G.; Baker, K. R.; Ahmadov, R.; Washenfelder, R. A.; Alvarez, S.; Rappenglück, B.; Gilman, J. B.; Kuster, W. C.; de Gouw, J. A.; Zotter, P.; Prévôt, A. S. H.; Szidat, S.; Kleindienst, T. E.; Offenberg, J. H.; Jimenez, J. L.

2014-12-01

Four different parameterizations for the formation and evolution of secondary organic aerosol (SOA) are evaluated using a 0-D box model representing the Los Angeles Metropolitan Region during the CalNex 2010 field campaign. We constrain the model predictions with measurements from several platforms and compare predictions with particle and gas-phase observations from the CalNex Pasadena ground site. That site provides a unique opportunity to study aerosol formation close to anthropogenic emission sources with limited recirculation. The model SOA formed only from the oxidation of VOCs (V-SOA) is insufficient to explain the observed SOA concentrations, even when using SOA parameterizations with multi-generation oxidation that produce much higher yields than have been observed in chamber experiments, or when increasing yields to their upper limit estimates accounting for recently reported losses of vapors to chamber walls. The Community Multiscale Air Quality (WRF-CMAQ) model (version 5.0.1) provides excellent predictions of secondary inorganic particle species but underestimates the observed SOA mass by a factor of 25 when an older VOC-only parameterization is used, which is consistent with many previous model-measurement comparisons for pre-2007 anthropogenic SOA modules in urban areas. Including SOA from primary semi-volatile and intermediate volatility organic compounds (P-S/IVOCs) following the parameterizations of Robinson et al. (2007), Grieshop et al. (2009), or Pye and Seinfeld (2010) improves model/measurement agreement for mass concentration. When comparing the three parameterizations, the Grieshop et al. (2009) parameterization more accurately reproduces both the SOA mass concentration and oxygen-to-carbon ratio inside the urban area. Our results strongly suggest that other precursors besides VOCs, such as P-S/IVOCs, are needed to explain the observed SOA concentrations in Pasadena. All the parameterizations over-predict urban SOA formation at long photochemical ages (≈ 3 days) compared to observations from multiple sites, which can lead to problems in regional and global modeling. Among the explicitly modeled VOCs, the precursor compounds that contribute the greatest SOA mass are methylbenzenes. Polycyclic aromatic hydrocarbons (PAHs) are less important precursors and contribute less than 4% of the SOA mass. The amounts of SOA mass from diesel vehicles, gasoline vehicles, and cooking emissions are estimated to be 16-27, 35-61, and 19-35%, respectively, depending on the parameterization used, which is consistent with the observed fossil fraction of urban SOA, 71 (±3) %. In-basin biogenic VOCs are predicted to contribute only a few percent to SOA. A regional SOA background of approximately 2.1 μg m-3 is also present due to the long distance transport of highly aged OA. The percentage of SOA from diesel vehicle emissions is the same, within the estimated uncertainty, as reported in previous work that analyzed the weekly cycles in OA concentrations (Bahreini et al., 2012; Hayes et al., 2013). However, the modeling work presented here suggests a strong anthropogenic source of modern carbon in SOA, due to cooking emissions, which was not accounted for in those previous studies. Lastly, this work adapts a simple two-parameter model to predict SOA concentration and O/C from urban emissions. This model successfully predicts SOA concentration, and the optimal parameter combination is very similar to that found for Mexico City. This approach provides a computationally inexpensive method for predicting urban SOA in global and climate models. We estimate pollution SOA to account for 26 Tg yr-1 of SOA globally, or 17% of global SOA, 1/3 of which is likely to be non-fossil.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Charnawskas, Joseph C.; Alpert, Peter A.; Lambe, Andrew

Anthropogenic and biogenic gas emissions contribute to the formation of secondary organic aerosol (SOA). When present, soot particles from fossil-fuel combustion can acquire a coating of SOA. We investigate SOA-soot biogenic-anthropogenic interactions and their impact on ice nucleation in relation to the particles’ organic phase state. SOA particles were generated from the OH oxidation of naphthalene, α-pinene, longifolene, or isoprene, with or without presence of sulfate or soot particles. Corresponding particle glass transition (T g) and full deliquescence relative humidity (FDRH) were estimated by a numerical diffusion model. Longifolene SOA particles are solid-like and all biogenic SOA sulfate mixtures exhibitmore » a core-shell configuration (i.e. a sulfate-rich core coated with SOA). Biogenic SOA with or without sulfate formed ice at conditions expected for homogeneous ice nucleation in agreement with respective T g and FDRH. α-pinene SOA coated soot particles nucleated ice above the homogeneous freezing temperature with soot acting as ice nuclei (IN). At lower temperatures the α-pinene SOA coating can be semisolid inducing ice nucleation. Naphthalene SOA coated soot particles acted as IN above and below the homogeneous freezing limit, which can be explained by the presence of a highly viscous SOA phase. Our results suggest that biogenic SOA does not play a significant role in mixed-phase cloud formation and the presence of sulfate further renders this even less likely. Furthermore, anthropogenic SOA may have an enhancing effect on cloud glaciation under mixed-phase and cirrus cloud conditions compared to biogenic SOA that dominate during preindustrial times or in pristine areas.« less

The SOA formation model combined with semiempirical quantum chemistry for predicting UV-Vis absorption of secondary organic aerosols.

PubMed

Zhong, Min; Jang, Myoseon; Oliferenko, Alexander; Pillai, Girinath G; Katritzky, Alan R

2012-07-07

A new model for predicting the UV-visible absorption spectra of secondary organic aerosols (SOA) has been developed. The model consists of two primary parts: a SOA formation model and a semiempirical quantum chemistry method. The mass of SOA is predicted using the PHRCSOA (Partitioning Heterogeneous Reaction Consortium Secondary Organic Aerosol) model developed by Cao and Jang [Environ. Sci. Technol., 2010, 44, 727]. The chemical composition is estimated using a combination of the kinetic model (MCM) and the PHRCSOA model. The absorption spectrum is obtained by taking the sum of the spectrum of each SOA product calculated using a semiempirical NDDO (Neglect of Diatomic Differential Overlap)-based method. SOA was generated from the photochemical reaction of toluene or α-pinene at different NO(x) levels (low NO(x): 24-26 ppm, middle NO(x): 49 ppb, high NO(x): 104-105 ppb) using a 2 m(3) indoor Teflon film chamber. The model simulation reasonably agrees with the measured absorption spectra of α-pinene SOA but underestimates toluene SOA under high and middle NO(x) conditions. The absorption spectrum of toluene SOA is moderately enhanced with increasing NO(x) concentrations, while that of α-pinene SOA is not affected. Both measured and calculated UV-visible spectra show that the light absorption of toluene SOA is much stronger than that of α-pinene SOA.

Examining the effects of anthropogenic emissions on isoprene-derived secondary organic aerosol formation during the 2013 Southern Oxidant and Aerosol Study (SOAS) at the Look Rock, Tennessee, ground site

NASA Astrophysics Data System (ADS)

Budisulistiorini, S. H.; Li, X.; Bairai, S. T.; Renfro, J.; Liu, Y.; Liu, Y. J.; McKinney, K. A.; Martin, S. T.; McNeill, V. F.; Pye, H. O. T.; Nenes, A.; Neff, M. E.; Stone, E. A.; Mueller, S.; Knote, C.; Shaw, S. L.; Zhang, Z.; Gold, A.; Surratt, J. D.

2015-03-01

A suite of offline and real-time gas- and particle-phase measurements was deployed at Look Rock, Tennessee (TN), during the 2013 Southern Oxidant and Aerosol Study (SOAS) to examine the effects of anthropogenic emissions on isoprene-derived secondary organic aerosol (SOA) formation. High- and low-time resolution PM2.5 samples were collected for analysis of known tracer compounds in isoprene-derived SOA by gas chromatography/electron ionization-mass spectrometry (GC/EI-MS) and ultra performance liquid chromatography/diode array detection-electrospray ionization-high-resolution quadrupole time-of-flight mass spectrometry (UPLC/DAD-ESI-HR-QTOFMS). Source apportionment of the organic aerosol (OA) was determined by positive matrix factorization (PMF) analysis of mass spectrometric data acquired on an Aerodyne Aerosol Chemical Speciation Monitor (ACSM). Campaign average mass concentrations of the sum of quantified isoprene-derived SOA tracers contributed to ~9% (up to 26%) of the total OA mass, with isoprene-epoxydiol (IEPOX) chemistry accounting for ~97% of the quantified tracers. PMF analysis resolved a factor with a profile similar to the IEPOX-OA factor resolved in an Atlanta study and was therefore designated IEPOX-OA. This factor was strongly correlated (r2>0.7) with 2-methyltetrols, C5-alkene triols, IEPOX-derived organosulfates, and dimers of organosulfates, confirming the role of IEPOX chemistry as the source. On average, IEPOX-derived SOA tracer mass was ~25% (up to 47%) of the IEPOX-OA factor mass, which accounted for 32% of the total OA. A low-volatility oxygenated organic aerosol (LV-OOA) and an oxidized factor with a profile similar to 91Fac observed in areas where emissions are biogenic-dominated were also resolved by PMF analysis, whereas no primary organic aerosol (POA) sources could be resolved. These findings were consistent with low levels of primary pollutants, such as nitric oxide (NO~0.03ppb), carbon monoxide (CO~116 ppb), and black carbon (BC~0.2 μg m-3). Particle-phase sulfate is fairly correlated (r2~0.3) with both MAE- and IEPOX-derived SOA tracers, and more strongly correlated (r2~0.6) with the IEPOX-OA factor, in sum suggesting an important role of sulfate in isoprene SOA formation. Moderate correlation between the methacrylic acid epoxide (MAE)-derived SOA tracer 2-methylglyceric acid with sum of reactive and reservoir nitrogen oxides (NOy; r2=0.38) and nitrate (r2=0.45) indicates the potential influence of anthropogenic emissions through long-range transport. Despite the lack of a~clear association of IEPOX-OA with locally estimated aerosol acidity and liquid water content (LWC), box model calculations of IEPOX uptake using the simpleGAMMA model, accounting for the role of acidity and aerosol water, predicted the abundance of the IEPOX-derived SOA tracers 2-methyltetrols and the corresponding sulfates with good accuracy (r2~0.5 and ~0.7, respectively). The modeling and data combined suggest an anthropogenic influence on isoprene-derived SOA formation through acid-catalyzed heterogeneous chemistry of IEPOX in the southeastern US. However, it appears that this process was not limited by aerosol acidity or LWC at Look Rock during SOAS. Future studies should further explore the extent to which acidity and LWC becomes a limiting factor of IEPOX-derived SOA, and their modulation by anthropogenic emissions.

Sources of secondary organic aerosols over North China Plain in winter

NASA Astrophysics Data System (ADS)

Xing, L.; Li, G.; Tie, X.; Junji, C.; Long, X.

2017-12-01

Organic aerosol (OA) concentrations are simulated over the North China Plain (NCP) from 10th to 26th January, 2014 using the Weather Research and Forecasting model coupled to chemistry (WRF-CHEM), with the goal of examining the impact of heterogeneous HONO sources on atmospheric oxidation capacity and consequently on SOA formation and SOA formation from different pathways in winter. Generally, the model well reproduced the spatial and temporal distribution of PM2.5, SO2, NO2, and O3 concentrations. The heterogeneous HONO formation contributed a major part of atmospheric HONO concentrations in Beijing. The heterogeneous HONO sources significantly increased the daily maximum OH concentrations by 260% on average in Beijing, which enhanced the atmospheric oxidation capacity and consequently SOA concentrations by 80% in Beijing on average. Under severe haze pollution on January 16th 2014, the regional average HONO concentration over NCP was 0.86 ppb, which increased SOA concentration by 68% on average. The average mass fractions of ASOA (SOA from oxidation of anthropogenic VOCs), BSOA (SOA from oxidation of biogenic VOCs), PSOA (SOA from oxidation of evaporated POA), and GSOA (SOA from irreversible uptake of glyoxal and methylglyoxal) during the simulation period over NCP were 24%, 5%, 26% and 45%, respectively. GSOA contributed most to the total SOA mass over NCP in winter. The model sensitivity simulation revealed that GSOA in winter was mainly from primary residential sources. The regional average of GSOA from primary residential sources constituted 87% of total GSOA mass.

Critical factors determining the variation in SOA yields from terpene ozonolysis: a combined experimental and computational study.

PubMed

Donahue, Neil M; Hartz, Kara E Huff; Chuong, Bao; Presto, Albert A; Stanier, Charles O; Rosenhørn, Thomas; Robinson, Allen L; Pandis, Spyros N

2005-01-01

A substantial fraction of the total ultrafine particulate mass is comprised of organic compounds. Of this fraction, a significant subfraction is secondary organic aerosol (SOA), meaning that the compounds are a by-product of chemistry in the atmosphere. However, our understanding of the kinetics and mechanisms leading to and following SOA formation is in its infancy. We lack a clear description of critical phenomena; we often don't know the key, rate limiting steps in SOA formation mechanisms. We know almost nothing about aerosol yields past the first generation of oxidation products. Most importantly, we know very little about the derivatives in these mechanisms; we do not understand how changing conditions, be they precursor levels, oxidant concentrations, co-reagent concentrations (i.e., the VOC/NOx ratio) or temperature will influence the yields of SOA. In this paper we explore the connections between fundamental details of physical chemistry and the multitude of steps associated with SOA formation, including the initial gas-phase reaction mechanisms leading to condensible products, the phase partitioning itself, and the continued oxidation of the condensed-phase organic products. We show that SOA yields in the alpha-pinene + ozone are highly sensitive to NOx, and that SOA yields from beta-caryophylene + ozone appear to increase with continued ozone exposure, even as aerosol hygroscopicity increases as well. We suggest that SOA yields are likely to increase substantially through several generations of oxidative processing of the semi-volatile products.

SOA Measurements vs. Models: a Status Report

NASA Astrophysics Data System (ADS)

Jimenez, J. L.; de Gouw, J. A.

2009-12-01

The advent of fast and more detailed organic aerosol (OA) and VOC measurements in the last decade has allowed clearer model-measurement comparisons for OA and secondary OA (SOA). Here we summarize the patterns emerging from studies to date.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Charnawskas, Joseph C.; Alpert, Peter A.; Lambe, Andrew T.

Anthropogenic and biogenic gas emissions contribute to the formation of secondary organic aerosol (SOA). When present, soot particles from fossil fuel combustion can acquire a coating of SOA. We investigate SOA–soot biogenic–anthropogenic interactions and their impact on ice nucleation in relation to the particles’ organic phase state. SOA particles were generated from the OH oxidation of naphthalene, α-pinene, longifolene, or isoprene, with or without the presence of sulfate or soot particles. Corresponding particle glass transition (T g) and full deliquescence relative humidity (FDRH) were estimated using a numerical diffusion model. Longifolene SOA particles are solid-like and all biogenic SOA sulfatemore » mixtures exhibit a core–shell configuration (i.e.a sulfate-rich core coated with SOA). Biogenic SOA with or without sulfate formed ice at conditions expected for homogeneous ice nucleation, in agreement with respectiveT gand FDRH. α-pinene SOA coated soot particles nucleated ice above the homogeneous freezing temperature with soot acting as ice nuclei (IN). At lower temperatures the α-pinene SOA coating can be semisolid, inducing ice nucleation. Naphthalene SOA coated soot particles acted as ice nuclei above and below the homogeneous freezing limit, which can be explained by the presence of a highly viscous SOA phase. Our results suggest that biogenic SOA does not play a significant role in mixed-phase cloud formation and the presence of sulfate renders this even less likely. However, anthropogenic SOA may have an enhancing effect on cloud glaciation under mixed-phase and cirrus cloud conditions compared to biogenic SOA that dominate during pre-industrial times or in pristine areas.« less

Photochemical Aging of α-pinene and β-pinene Secondary Organic Aerosol formed from Nitrate Radical Oxidation: New Insights into the Formation and Fates of Highly Oxygenated Gas- and Particle-phase Organic Nitrates

NASA Astrophysics Data System (ADS)

Nah, T.; Sanchez, J.; Boyd, C.; Ng, N. L.

2015-12-01

The nitrate radical (NO3), one of the most important oxidants in the nocturnal atmosphere, can react rapidly with a variety of biogenic volatile organic compounds (BVOCs) to form high mass concentrations of secondary organic aerosol (SOA) and organic nitrates (ON). Despite its critical importance in aerosol formation, the mechanisms and products from the NO3 oxidation of BVOCs have been largely unexplored, and the fates of their SOA and ON after formation are not well characterized. In this work, we studied the formation of SOA and ON from the NO3 oxidation of α-pinene and β-pinene and investigated for the first time how they evolve during dark and photochemical aging through a series of chamber experiments performed at the Georgia Tech Environmental Chamber (GTEC) facility. The α-pinene and β-pinene SOA are characterized using real-time gas- and particle-phase measurements, which are used to propose mechanisms for SOA and organic nitrate formation and aging. Highly oxygenated gas- and particle-phase ON (containing as many as 9 oxygen atoms) are detected during the NO3 reaction. In addition, the β-pinene SOA and α-pinene SOA exhibited drastically different behavior during photochemical aging. Our results indicate that nighttime ON formed by NO3+monoterpene chemistry can serve as either NOx reservoirs or sinks depending on the monoterpene precursor. Results from this study provide fundamental data for evaluating the contributions of NO3+monoterpene reactions to ambient OA measured in the Southeastern U.S.

Secondary Organic Aerosol Formation and Aging in a Flow Reactor in the Forested Southeast US during SOAS

NASA Astrophysics Data System (ADS)

Hu, W.; Palm, B. B.; Hacker, L.; Campuzano Jost, P.; Day, D. A.; de Sá, S. S.; Ayres, B. R.; Draper, D.; Fry, J.; Ortega, A. M.; Kiendler-Scharr, A.; Pajunoja, A.; Virtanen, A.; Krechmer, J.; Canagaratna, M. R.; Thompson, S.; Yatavelli, R. L. N.; Stark, H.; Worsnop, D. R.; Martin, S. T.; Farmer, D.; Brown, S. S.; Jimenez, J. L.

2015-12-01

A major field campaign (Southern Oxidant and Aerosol Study, SOAS) was conducted in summer 2013 in a forested area in Centreville Supersite, AL (SEARCH network) in the southeast U.S. To investigate secondary organic aerosol (SOA) formation from biogenic volatile organic compounds (BVOCs), 3 oxidation flow reactors (OFR) were used to expose ambient air to oxidants and their output was analyzed by state-of-the-art gas and aerosol instruments including a High-Resolution Aerosol Mass Spectrometer (HR-AMS), a HR Proton-Transfer Reaction Time-of-Flight Mass Spectrometer (PTR-TOFMS), and Two HR-TOF Chemical Ionization Mass Spectrometers (HRToF-CIMS). Ambient air was exposed 24/7 to variable concentrations of each of the 3 main atmospheric oxidants (OH, NO3 radicals and O3) to investigate the oxidation of BVOCs (including isoprene derived epoxydiols, IEPOX) and SOA formation and aging. Effective OH exposures up to 1×1013 molec cm-3 s were achieved, equivalent to over a month of aging in the atmosphere. Multiple oxidation products from isoprene and monoterpenes including small gas-phase acids were observed in OH OFR. High SOA formation of up to 12 μg m-3 above ambient concentrations of 5 μg m-3 was observed under intermediate OH exposures, while very high OH exposures led to destruction of ~30% of ambient OA, indicating shifting contributions of functionalization vs. fragmentation, consistent with results from urban and terpene-dominated environments. The highest SOA enhancements were 3-4 times higher than ambient OA. More SOA is typically formed during nighttime when terpenes are higher and photochemistry is absent, and less during daytime when isoprene is higher, although the IEPOX pathway is suppressed in the OFR. SOA is also observed after exposure of ambient air to O3 or NO3, although the amounts and oxidation levels were lower than for OH. Formation of organic nitrates in the NO3 reaction will also be discussed.A major field campaign (Southern Oxidant and Aerosol Study, SOAS) was conducted in summer 2013 in a forested area in Centreville Supersite, AL (SEARCH network) in the southeast U.S. To investigate secondary organic aerosol (SOA) formation from biogenic volatile organic compounds (BVOCs), 3 oxidation flow reactors (OFR) were used to expose ambient air to oxidants and their output was analyzed by state-of-the-art gas and aerosol instruments including a High-Resolution Aerosol Mass Spectrometer (HR-AMS), a HR Proton-Transfer Reaction Time-of-Flight Mass Spectrometer (PTR-TOFMS), and two HR-TOF Chemical Ionization Mass Spectrometers (HRToF-CIMS). Ambient air was exposed 24/7 to variable concentrations of each of the 3 main atmospheric oxidants (OH, NO3 radicals and O3) to investigate the oxidation of BVOCs (including ambient isoprene-derived epoxydiols, IEPOX) and SOA formation and aging. Effective OH exposures up to 1×1013 molec cm-3 s were achieved, equivalent to over a month of aging in the atmosphere. Multiple oxidation products from isoprene and monoterpenes including small gas-phase acids were observed in OH OFR. High SOA formation of up to 12 μg m-3 above ambient concentrations of 5 μg m-3 was observed under intermediate OH exposures, while very high OH exposures led to destruction of ~30% of ambient OA, indicating shifting contributions of functionalization vs. fragmentation, consistent with results from urban and terpene-dominated environments. The highest SOA enhancements were 3-4 times higher than ambient OA. More SOA is typically formed during nighttime when terpenes are higher and photochemistry is absent, and less during daytime when isoprene is higher, although the IEPOX pathway is suppressed in the OFR. SOA is also observed after exposure of ambient air to O3 or NO3, although the amounts and oxidation levels were lower than for OH. Formation of organic nitrates in the NO3 reaction will also be discussed.

VOC species and emission inventory from vehicles and their SOA formation potentials estimation in Shanghai, China

NASA Astrophysics Data System (ADS)

Huang, C.; Wang, H. L.; Li, L.; Wang, Q.; Lu, Q.; de Gouw, J. A.; Zhou, M.; Jing, S. A.; Lu, J.; Chen, C. H.

2015-03-01

VOC species from vehicle exhaust and gas evaporation were investigated by chassis dynamometer and on-road measurements of 9 gasoline vehicles, 7 diesel vehicles, 5 motorcycles, and 4 gas evaporation samples. The SOA mass yields of gasoline, diesel, motorcycle exhausts, and gas evaporation were calculated based on the mixing ratio of individual VOC species. The SOA mass yields of gasoline and motorcycle exhaust were similar to the results of the published smog chamber study with the exception of that of diesel exhaust was 20% lower than experimental data (Gordon et al., 2013, 2014a, b). This suggests the requirement for further research on SVOC or LVOC emissions. A vehicular emission inventory was compiled based on a local survey of vehicle mileage traveled and real-world measurements of vehicle emission factors. The inventory-based vehicular initial emission ratio of OA to CO was 15.6 μg m-3 ppmv-1. The OA production rate reached 22.3 and 42.7 μg m-3 ppmv-1 under high-NOx and low-NOx conditions, respectively. To determine the vehicular contribution to OA pollution, the inventory-based OA formation ratios for vehicles were calculated with a photochemical-age-based parameterization method and compared with the observation-based OA formation ratios in the urban atmosphere of Shanghai. The results indicated that VOC emissions from vehicle exhaust and gas evaporation only explained 15 and 22% of the total organic aerosols observed in summer and winter, respectively. SOA production only accounted for 25 and 18% of the total vehicular OA formation in summer and winter. VOC emissions from gasoline vehicles contribute 21-38% of vehicular OA formation after 6-24 h of photochemical aging. The results suggest that vehicle emissions are an important contributor to OA pollution in the urban atmosphere of Shanghai. However, a large number of OA mass in the atmosphere still cannot be explained in this study. SOA formation contributions from other sources (e.g. coal burning, biomass burning, cooking, dust, etc.) as well as IVOCs and SVOCs from the combustion sources need to be considered in future studies.

Modeling the formation and aging of secondary organic aerosols in the Los Angeles metropolitan region during the CalNex 2010 field campaign

NASA Astrophysics Data System (ADS)

Hayes, P. L.; Ma, P. K.; Jimenez, J. L.; Zhao, Y.; Robinson, A. L.; Carlton, A. M. G.; Baker, K. R.; Ahmadov, R.; Washenfelder, R. A.; Alvarez, S. L.; Rappenglück, B.; Gilman, J.; Kuster, W.; De Gouw, J. A.; Prevot, A. S.; Zotter, P.; Szidat, S.; Kleindienst, T. E.; Offenberg, J. H.

2015-12-01

Several different literature parameterizations for the formation and evolution of urban secondary organic aerosol (SOA) are evaluated using a box model representing the Los Angeles Region during CalNex. The model SOA formed only from the oxidation of VOCs (V-SOA) is insufficient to explain the observed SOA concentrations, even when using SOA parameterizations with multi-generation oxidation that produce much higher yields than have been observed in chamber experiments, or when increasing yields to their upper limit estimates accounting for recently reported losses of vapors to chamber walls. Including SOA from primary semi-volatile and intermediate volatility organic compounds (P-S/IVOCs) following the parameterizations of Robinson et al. (2007), Grieshop et al. (2009), or Pye and Seinfeld (2010) improves model/measurement agreement for mass concentration at shorter photochemical ages (0.5 days). Our results strongly suggest that other precursors besides VOCs are needed to explain the observed SOA concentrations. In contrast, all of the literature P-S/IVOC parameterizations over-predict urban SOA formation at long photochemical ages (3 days) compared to observations from multiple sites, which can lead to problems in regional and global modeling. Sensitivity studies that reduce the IVOC emissions by one-half in the model improve SOA predictions at these long ages. In addition, when IVOC emissions in the Robinson et al. parameterization are constrained using recently reported measurements of these species model/measurement agreement is achieved. The amounts of SOA mass from diesel vehicles, gasoline vehicles, and cooking emissions are estimated to be 16 - 27%, 35 - 61%, and 19 - 35%, respectively, depending on the parameterization used, which is consistent with the observed fossil fraction of urban SOA, 71(±3)%. The percentage of SOA from diesel vehicle emissions is the same, within the estimated uncertainty, as reported in previous work that analyzed the weekly cycles in SOA concentrations (Bahreini et al., 2012; Hayes et al., 2013). However, the modeling work presented here suggests a strong anthropogenic source of modern carbon in urban SOA, possibly cooking emissions, that was not accounted for in those previous studies, and which is higher on weekends.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Seinfeld, John H.

Organic material constitutes about 50% of global atmospheric aerosol mass, and the dominant source of organic aerosol is the oxidation of volatile hydrocarbons, to produce secondary organic aerosol (SOA). Understanding the formation of SOA is crucial to predicting present and future climate effects of atmospheric aerosols. The goal of this program is to significantly increase our understanding of secondary organic aerosol (SOA) formation in the atmosphere. Ambient measurements indicate that the amount of SOA in the atmosphere exceeds that predicted in current models based on existing laboratory chamber data. This would suggest that either the SOA yields measured in laboratorymore » chambers are understated or that all major organic precursors have not been identified. In this research program we are systematically exploring these possibilities.« less

Reprint of "How do components of real cloud water affect aqueous pyruvate oxidation?"

NASA Astrophysics Data System (ADS)

Boris, Alexandra J.; Desyaterik, Yury; Collett, Jeffrey L.

2015-01-01

Chemical oxidation of dissolved volatile or semi-volatile organic compounds within fog and cloud droplets in the atmosphere could be a major pathway for secondary organic aerosol (SOA) formation. This proposed pathway consists of: (1) dissolution of organic chemicals from the gas phase into a droplet; (2) reaction with an aqueous phase oxidant to yield low volatility products; and (3) formation of particle phase organic matter as the droplet evaporates. The common approach to simulating aqueous SOA (aqSOA) reactions is photo-oxidation of laboratory standards in pure water. Reactions leading to aqSOA formation should be studied within real cloud and fog water to determine whether additional competing processes might alter apparent rates of reaction as indicated by rates of reactant loss or product formation. To evaluate and identify the origin of any cloud water matrix effects on one example of observed aqSOA production, pyruvate oxidation experiments simulating aqSOA formation were monitored within pure water, real cloud water samples, and an aqueous solution of inorganic salts. Two analysis methods were used: online electrospray ionization high-resolution time-of-flight mass spectrometry (ESI-HR-ToF-MS), and offline anion exchange chromatography (IC) with quantitative conductivity and qualitative ESI-HR-ToF-MS detection. The apparent rate of oxidation of pyruvate was slowed in cloud water matrices: overall measured degradation rates of pyruvate were lower than in pure water. This can be at least partially accounted for by the observed formation of pyruvate from reactions of other cloud water components. Organic constituents of cloud water also compete for oxidants and/or UV light, contributing to the observed slowed degradation rates of pyruvate. The oxidation of pyruvate was not significantly affected by the presence of inorganic anions (nitrate and sulfate) at cloud-relevant concentrations. Future bulk studies of aqSOA formation reactions using simplified simulated cloud solutions and model estimates of generated aqSOA mass should take into account possible generation of, or competition for, oxidant molecules by organic components found in the complex matrices typically associated with real atmospheric water droplets. Additionally, it is likely that some components of real atmospheric waters have not yet been identified as aqSOA precursors, but could be distinguished through further simplified bulk oxidations of known atmospheric water components.

Optical Properties and Aging of Light Absorbing Secondary Organic Aerosol

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Jiumeng; Lin, Peng; Laskin, Alexander

2016-10-14

The light-absorbing organic aerosol (OA), commonly referred to as “brown carbon (BrC)”, has attracted considerable attention in recent years because of its potential to affect atmospheric radiation balance, especially in the ultraviolet region and thus impact photochemical processes. A growing amount of data has indicated that BrC is prevalent in the atmosphere, which has motivated numerous laboratory and field studies; however, our understanding of the relationship between the chemical composition and optical properties of BrC remains limited. We conducted chamber experiments to investigate the effect of various VOC precursors, NOx concentrations, photolysis time and relative humidity (RH) on the lightmore » absorption of selected secondary organic aerosols (SOA). Light absorption of chamber generated SOA samples, especially aromatic SOA, was found to increase with NOx concentration, at moderate RH, and for the shortest photolysis aging times. The highest mass absorption coefficients (MAC) value is observed from toluene SOA products formed under high NOx conditions at moderate RH, in which nitro-aromatics were previously identified as the major light absorbing compounds. BrC light absorption is observed to decrease with photolysis time, correlated with a decline of the organonitrate fraction of SOA. SOA formed from mixtures of aromatics and isoprene absorb less visible and UV light than SOA formed from aromatic precursors alone on a mass basis. However, the mixed-SOA absorption was underestimated when optical properties were predicted using a two-product SOA formation model, as done in many current climate models. Further investigation, including analysis on detailed mechanisms, are required to explain the discrepancy.« less

Effect of Pellet Boiler Exhaust on Secondary Organic Aerosol Formation from α-Pinene.

PubMed

Kari, Eetu; Hao, Liqing; Yli-Pirilä, Pasi; Leskinen, Ari; Kortelainen, Miika; Grigonyte, Julija; Worsnop, Douglas R; Jokiniemi, Jorma; Sippula, Olli; Faiola, Celia L; Virtanen, Annele

2017-02-07

Interactions between anthropogenic and biogenic emissions, and implications for aerosol production, have raised particular scientific interest. Despite active research in this area, real anthropogenic emission sources have not been exploited for anthropogenic-biogenic interaction studies until now. This work examines these interactions using α-pinene and pellet boiler emissions as a model test system. The impact of pellet boiler emissions on secondary organic aerosol (SOA) formation from α-pinene photo-oxidation was studied under atmospherically relevant conditions in an environmental chamber. The aim of this study was to identify which of the major pellet exhaust components (including high nitrogen oxide (NO x ), primary particles, or a combination of the two) affected SOA formation from α-pinene. Results demonstrated that high NO x concentrations emitted by the pellet boiler reduced SOA yields from α-pinene, whereas the chemical properties of the primary particles emitted by the pellet boiler had no effect on observed SOA yields. The maximum SOA yield of α-pinene in the presence of pellet boiler exhaust (under high-NO x conditions) was 18.7% and in the absence of pellet boiler exhaust (under low-NO x conditions) was 34.1%. The reduced SOA yield under high-NO x conditions was caused by changes in gas-phase chemistry that led to the formation of organonitrate compounds.

Aqueous oxidation of green leaf volatiles by hydroxyl radical as a source of SOA: Kinetics and SOA yields

NASA Astrophysics Data System (ADS)

Richards-Henderson, Nicole K.; Hansel, Amie K.; Valsaraj, Kalliat T.; Anastasio, Cort

2014-10-01

Green leaf volatiles (GLVs) are a class of oxygenated hydrocarbons released from vegetation, especially during mechanical stress or damage. The potential for GLVs to form secondary organic aerosol (SOA) via aqueous-phase reactions is not known. Fog events over vegetation will lead to the uptake of GLVs into water droplets, followed by aqueous-phase reactions with photooxidants such as the hydroxyl radical (OH). In order to determine if the aqueous oxidation of GLVs by OH can be a significant source of secondary organic aerosol, we studied the partitioning and reaction of five GLVs: cis-3-hexen-1-ol, cis-3-hexenyl acetate, methyl salicylate, methyl jasmonate, and 2-methyl-3-butene-2-ol. For each GLV we measured the kinetics of aqueous oxidation by OH, and the corresponding SOA mass yield. The second-order rate constants for GLVs with OH were all near diffusion controlled, (5.4-8.6) × 109 M-1 s-1 at 298 K, and showed a small temperature dependence, with an average activation energy of 9.3 kJ mol-1 Aqueous-phase SOA mass yields ranged from 10 to 88%, although some of the smaller values were not statistically different from zero. Methyl jasmonate was the most effective aqueous-phase SOA precursor due to its larger Henry's law constant and high SOA mass yield (68 ± 8%). While we calculate that the aqueous-phase SOA formation from the five GLVs is a minor source of aqueous-phase SOA, the availability of other GLVs, other oxidants, and interfacial reactions suggest that GLVs overall might be a significant source of SOA via aqueous reactions.

Secondary organic aerosol (SOA) derived from isoprene epoxydiols: Insights into formation, aging and distribution over the continental US from the DC3 and SEAC4RS campaigns

NASA Astrophysics Data System (ADS)

Campuzano Jost, P.; Palm, B. B.; Day, D. A.; Hu, W.; Ortega, A. M.; Jimenez, J. L.; Liao, J.; Froyd, K. D.; Pollack, I. B.; Peischl, J.; Ryerson, T. B.; St Clair, J. M.; Crounse, J.; Wennberg, P. O.; Mikoviny, T.; Wisthaler, A.; Ziemba, L. D.; Anderson, B. E.

2014-12-01

Isoprene-derived SOA formation has been studied extensively in the laboratory. However, it is still unclear to what extent isoprene contributes to the overall SOA burden over the southeastern US, an area with both strong isoprene emissions as well as large discrepancies between modeled and observed aerosol optical depth. For the low-NO isoprene oxidation pathway, the key gas-phase intermediate is believed to be isoprene epoxide (IEPOX), which can be incorporated into the aerosol phase by either sulfate ester formation (IEPOX sulfate) or direct hydrolysis. As first suggested by Robinson et al, the SOA formed by this mechanism (IEPOX-SOA) has a characteristic fragmentation pattern when analyzed by an Aerodyne Aerosol Mass Spectrometer (AMS) with enhanced relative abundances of the C5H6O+ ion (fC5H6O). Based on data from previous ground campaigns and chamber studies, we have developed a empirical method to quantify IEPOX-SOA and have applied it to the data from the DC3 and SEAC4RS aircraft campaigns that sampled the SE US during the Spring of 2012 and the Summer of 2013. We used Positive Matrix Factorization (PMF) to extract IEPOX-SOA factors that show good correlation with inside or downwind of high isoprene emitting areas and in general agree well with the IEPOX-SOA mass predicted by the empirical expression. According to this analysis, the empirical method performs well regardless of (at times very strong) BBOA or urban OA influences. On average 17% of SOA in the SE US boundary layer was IEPOX-SOA. Overall, the highest concentrations of IEPOX-SOA were typically found around 1-2 km AGL, several hours downwind of the isoprene source areas with high gas-phase IEPOX present. IEPOX-SOA was also detected up to altitudes of 6 km, with a clear trend towards more aged aerosol at altitude, likely a combination of chemical aging and physical airmass mixing. The unique instrument package aboard the NASA-DC8 allows us to examine the influence of multiple factors (aerosol acidity, aerosol water content, sulfate mass fraction, isoprene and terpene source strength) to the relative and absolute contribution of IEPOX-SOA to the total OA burden. In particular, the IEPOX-sulfate measurement from the PALMS instrument was used to estimate the relative contribution of the organosulfate channel to the IEPOX-SOA formation.

FORMATION OF SECONDARY ORGANIC AEROSOL

EPA Science Inventory

(1) Gas-phase chemistry. With the clear and profound effect of the VOC/NO_x ratio on SOA formation, we will augment gas-phase VOC oxidation mechanisms in atmospheric models to account for the effect of NO_x level on the mechanism of SOA formation; (2) Revis...

Influence of Aerosol Acidity on the Formation of Secondary Organic Aerosol from Biogenic Precursor Hydrocarbons

EPA Science Inventory

Secondary organic aerosol (SOA) formation and dynamics may be important factors for the role of aerosols in adverse health effects, visibility and climate change. Formation of SOA occurs when a parent volatile organic compound is oxidized to create products that form in a conden...

Urban stress-induced biogenic VOC emissions impact secondary aerosol formation in Beijing

NASA Astrophysics Data System (ADS)

Ghirardo, A.; Xie, J.; Zheng, X.; Wang, Y.; Grote, R.; Block, K.; Wildt, J.; Mentel, T.; Kiendler-Scharr, A.; Hallquist, M.; Butterbach-Bahl, K.; Schnitzler, J.-P.

2015-08-01

Trees can significantly impact the urban air chemistry by the uptake and emission of reactive biogenic volatile organic compounds (BVOCs), which are involved in ozone and particle formation. Here we present the emission potentials of "constitutive" (cBVOCs) and "stress-induced" BVOCs (sBVOCs) from the dominant broadleaf woody plant species in the megacity of Beijing. Based on an inventory of BVOC emissions and the tree census, we assessed the potential impact of BVOCs on secondary particulate matter formation in 2005 and 2010, i.e., before and after realizing the large tree-planting program for the 2008 Olympic Games. We found that sBVOCs, such as fatty acid derivatives, benzenoids and sesquiterpenes, constituted a significant fraction (∼ 15 %) of the total annual BVOC emissions, and we estimated that the overall annual BVOC budget may have doubled from ∼ 3.6 × 109 g C year-1 in 2005 to ∼ 7.1 × 109 g C year-1 in 2010 due to the increase in urban greens, while at the same time, the emission of anthropogenic VOCs (AVOCs) could be lowered by 24 %. Based on our BVOC emission assessment, we estimated the biological impact on SOA mass formation in Beijing. Compared to AVOCs, the contribution of biogenic precursors (2-5 %) for secondary particulate matter in Beijing was low. However, sBVOCs can significantly contribute (∼ 40 %) to the formation of total secondary organic aerosol (SOA) from biogenic sources; apparently, their annual emission increased from 1.05 μg m-3 in 2005 to 2.05 μg m-3 in 2010. This study demonstrates that biogenic and, in particular, sBVOC emissions contribute to SOA formation in megacities. However, the main problems regarding air quality in Beijing still originate from anthropogenic activities. Nevertheless, the present survey suggests that in urban plantation programs, the selection of plant species with low cBVOC and sBVOC emission potentials have some possible beneficial effects on urban air quality.

Environmental conditions regulate the impact of plants on cloud formation

PubMed Central

Zhao, D. F.; Buchholz, A.; Tillmann, R.; Kleist, E.; Wu, C.; Rubach, F.; Kiendler-Scharr, A.; Rudich, Y.; Wildt, J.; Mentel, Th. F.

2017-01-01

The terrestrial vegetation emits large amounts of volatile organic compounds (VOC) into the atmosphere, which on oxidation produce secondary organic aerosol (SOA). By acting as cloud condensation nuclei (CCN), SOA influences cloud formation and climate. In a warming climate, changes in environmental factors can cause stresses to plants, inducing changes of the emitted VOC. These can modify particle size and composition. Here we report how induced emissions eventually affect CCN activity of SOA, a key parameter in cloud formation. For boreal forest tree species, insect infestation by aphids causes additional VOC emissions which modifies SOA composition thus hygroscopicity and CCN activity. Moderate heat increases the total amount of constitutive VOC, which has a minor effect on hygroscopicity, but affects CCN activity by increasing the particles' size. The coupling of plant stresses, VOC composition and CCN activity points to an important impact of induced plant emissions on cloud formation and climate. PMID:28218253

Environmental conditions regulate the impact of plants on cloud formation.

PubMed

Zhao, D F; Buchholz, A; Tillmann, R; Kleist, E; Wu, C; Rubach, F; Kiendler-Scharr, A; Rudich, Y; Wildt, J; Mentel, Th F

2017-02-20

The terrestrial vegetation emits large amounts of volatile organic compounds (VOC) into the atmosphere, which on oxidation produce secondary organic aerosol (SOA). By acting as cloud condensation nuclei (CCN), SOA influences cloud formation and climate. In a warming climate, changes in environmental factors can cause stresses to plants, inducing changes of the emitted VOC. These can modify particle size and composition. Here we report how induced emissions eventually affect CCN activity of SOA, a key parameter in cloud formation. For boreal forest tree species, insect infestation by aphids causes additional VOC emissions which modifies SOA composition thus hygroscopicity and CCN activity. Moderate heat increases the total amount of constitutive VOC, which has a minor effect on hygroscopicity, but affects CCN activity by increasing the particles' size. The coupling of plant stresses, VOC composition and CCN activity points to an important impact of induced plant emissions on cloud formation and climate.

Biogenic-Anthropogenic Interactions in Secondary Organic Aerosol Formation and Health Effects of Atmospheric Organic Aerosol

NASA Astrophysics Data System (ADS)

Ye, Jianhuai

Secondary organic aerosol (SOA) formed from oxidation of volatile organic compounds (VOCs), comprises a major fraction of atmospheric submicron particulate matter, which is crucial for global climate change and human health. While biogenic VOCs are naturally emitted and cannot be directly controlled, field measurements and satellite observations have shown that biogenic SOA (BSOA) formation correlates well with anthropogenic pollutants and may be anthropogenically controlled. In this work, the formation of the "anthropogenically controllable BSOA" was examined. BSOA from alpha-pinene ozonolysis was investigated in the presence of laboratory-generated or ambient organic aerosol such as Toronto ambient particles. It is shown that SOA was not equally miscible with all organic species. Aerosol mixing thermodynamics in the atmosphere is composition dependent. Based on laboratory observations, an empirical framework using bulk elemental ratios was developed to predict atmospheric organic miscibility and SOA yield enhancements. Besides organic aerosol, interactions between BSOA formation and SO2 was also examined. Synergistic effects were observed between BSOA formation and SO2 oxidation through Criegee and peroxide chemistry under atmospherically relevant RH conditions. In addition to the physicochemical properties of SOA, health impacts of SOA were examined. An atmospheric simulation reactor (ASR) was developed to investigate the health effects of air pollutants by permitting controlled chronic in vivo exposure of mice to combine particulate and gaseous pollutants at 'real-life' concentrations. Results show that daily exposure to SOA from naphthalene photooxidation led to increased airway hyperresponsiveness (AHR) to methacholine in a dose-dependent manner. Multi-pollutant exposures with ozone and/or NO2 in conjunction with a sub-toxic concentration of SOA resulted in additive effects on AHR to methacholine. Inflammatory cell recruitment to the airways was not observed in any of the exposure conditions, indicating the increased AHR was not associated with airway inflammation and may occur through other mechanisms.

Gasoline emissions dominate over diesel in formation of secondary organic aerosol mass

NASA Astrophysics Data System (ADS)

Bahreini, R.; Middlebrook, A. M.; de Gouw, J. A.; Warneke, C.; Trainer, M.; Brock, C. A.; Stark, H.; Brown, S. S.; Dube, W. P.; Gilman, J. B.; Hall, K.; Holloway, J. S.; Kuster, W. C.; Perring, A. E.; Prevot, A. S. H.; Schwarz, J. P.; Spackman, J. R.; Szidat, S.; Wagner, N. L.; Weber, R. J.; Zotter, P.; Parrish, D. D.

2012-03-01

Although laboratory experiments have shown that organic compounds in both gasoline fuel and diesel engine exhaust can form secondary organic aerosol (SOA), the fractional contribution from gasoline and diesel exhaust emissions to ambient SOA in urban environments is poorly known. Here we use airborne and ground-based measurements of organic aerosol (OA) in the Los Angeles (LA) Basin, California made during May and June 2010 to assess the amount of SOA formed from diesel emissions. Diesel emissions in the LA Basin vary between weekdays and weekends, with 54% lower diesel emissions on weekends. Despite this difference in source contributions, in air masses with similar degrees of photochemical processing, formation of OA is the same on weekends and weekdays, within the measurement uncertainties. This result indicates that the contribution from diesel emissions to SOA formation is zero within our uncertainties. Therefore, substantial reductions of SOA mass on local to global scales will be achieved by reducing gasoline vehicle emissions.

The effect of particle acidity on secondary organic aerosol formation from α-pinene photooxidation under atmospherically relevant conditions

NASA Astrophysics Data System (ADS)

Han, Yuemei; Stroud, Craig A.; Liggio, John; Li, Shao-Meng

2016-11-01

Secondary organic aerosol (SOA) formation from photooxidation of α-pinene has been investigated in a photochemical reaction chamber under varied inorganic seed particle acidity levels at moderate relative humidity. The effect of particle acidity on SOA yield and chemical composition was examined under high- and low-NOx conditions. The SOA yield (4.2-7.6 %) increased nearly linearly with the increase in particle acidity under high-NOx conditions. In contrast, the SOA yield (28.6-36.3 %) was substantially higher under low-NOx conditions, but its dependency on particle acidity was insignificant. A relatively strong increase in SOA yield (up to 220 %) was observed in the first hour of α-pinene photooxidation under high-NOx conditions, suggesting that SOA formation was more effective for early α-pinene oxidation products in the presence of fresh acidic particles. The SOA yield decreased gradually with the increase in organic mass in the initial stage (approximately 0-1 h) under high-NOx conditions, which is likely due to the inaccessibility to the acidity over time with the coating of α-pinene SOA, assuming a slow particle-phase diffusion of organic molecules into the inorganic seeds. The formation of later-generation SOA was enhanced by particle acidity even under low-NOx conditions when introducing acidic seed particles after α-pinene photooxidation, suggesting a different acidity effect exists for α-pinene SOA derived from later oxidation stages. This effect could be important in the atmosphere under conditions where α-pinene oxidation products in the gas-phase originating in forested areas (with low NOx and SOx) are transported to regions abundant in acidic aerosols such as power plant plumes or urban regions. The fraction of oxygen-containing organic fragments (CxHyO1+ 33-35 % and CxHyO2+ 16-17 %) in the total organics and the O / C ratio (0.52-0.56) of α-pinene SOA were lower under high-NOx conditions than those under low-NOx conditions (39-40, 17-19, and 0.61-0.64 %), suggesting that α-pinene SOA was less oxygenated in the studied high-NOx conditions. The fraction of nitrogen-containing organic fragments (CxHyNz+ and CxHyOzNp+) in the total organics was enhanced with the increases in particle acidity under high-NOx conditions, indicating that organic nitrates may be formed heterogeneously through a mechanism catalyzed by particle acidity or that acidic conditions facilitate the partitioning of gas-phase organic nitrates into particle phase. The results of this study suggest that inorganic acidity has a significant role to play in determining various organic aerosol chemical properties such as mass yields, oxidation state, and organic nitrate content. The acidity effect being further dependent on the timescale of SOA formation is also an important parameter in the modeling of SOA.

A review of stereochemical implications in the generation of secondary organic aerosol from isoprene oxidation.

PubMed

Cash, James M; Heal, Mathew R; Langford, Ben; Drewer, Julia

2016-11-09

The atmospheric reactions leading to the generation of secondary organic aerosol (SOA) from the oxidation of isoprene are generally assumed to produce only racemic mixtures, but aspects of the chemical reactions suggest this may not be the case. In this review, the stereochemical outcomes of published isoprene-degradation mechanisms contributing to high amounts of SOA are evaluated. Despite evidence suggesting isoprene first-generation oxidation products do not contribute to SOA directly, this review suggests the stereochemistry of first-generation products may be important because their stereochemical configurations may be retained through to the second-generation products which form SOA. Specifically, due to the stereochemistry of epoxide ring-opening mechanisms, the outcome of the reactions involving epoxydiols of isoprene (IEPOX), methacrylic acid epoxide (MAE) and hydroxymethylmethyl-α-lactone (HMML) are, in principle, stereospecific which indicates the stereochemistry is predefined from first-generation precursors. The products from these three epoxide intermediates oligomerise to form macromolecules which are proposed to form chiral structures within the aerosol and are considered to be the largest contributors to SOA. If conditions in the atmosphere such as pH, aerosol water content, relative humidity, pre-existing aerosol, aerosol coatings and aerosol cation/anion content (and other) variables acting on the reactions leading to SOA affect the tacticity (arrangement of chiral centres) in the SOA then they may influence its physical properties, for example its hygroscopicity. Chamber studies of SOA formation from isoprene encompass particular sets of controlled conditions of these variables. It may therefore be important to consider stereochemistry when upscaling from chamber study data to predictions of SOA yields across the range of ambient atmospheric conditions. Experiments analysing the stereochemistry of the reactions under varying conditions of the above variables would help elucidate whether there is stereoselectivity in SOA formation from isoprene and if the rates of SOA formation are affected.

Partitioning phase preference for secondary organic aerosol in an urban atmosphere

NASA Astrophysics Data System (ADS)

Chang, Wayne Li-Wen

Secondary organic aerosol (SOA) comprises a significant portion of atmospheric particular matter (PM). The impact of PM on both human health and global climate has long been recognized. Despite its importance, there are still many unanswered questions regarding the formation and evolution of SOA in the atmosphere. This study uses a modeling approach to understand the preferred partitioning behavior of SOA species into aqueous or organic condensed phases. More specifically, this work uses statistical analyses of approximately 24,000 data values for each variable from a state-of-the-art 3-D airshed model. Spatial and temporal distributions of fractions of SOA residing in the aqueous phase (fAQ) in the South Coast Air Basin of California are presented. Typical values of fAQ within the basin near the surface range from 5 to 80%. Results show that the distribution of fAQ values is inversely proportional to the total SOA loading. Further analysis accounting for various meteorological parameters indicates that large fAQ values are the results of aqueous-phase SOA insensitivity to the ambient conditions; while organic-phase SOA concentrations are dramatically reduced under unfavorable SOA formation conditions, aqueous-phase SOA level remains relatively unchanged, thus increasing fAQ at low SOA loading. Diurnal variations of fAQ near the surface are also observed: it tends to be larger during daytime hours than nighttime hours. When examining the vertical gradient of fAQ, largest values are found at heights above the surface layer. In summary, one must consider SOA in both organic and aqueous phases for proper regional and global SOA budget estimation.

Simulation of semi-explicit mechanisms of SOA formation from glyoxal in a 3-D model

NASA Astrophysics Data System (ADS)

Knote, C.; Hodzic, A.; Jimenez, J. L.; Volkamer, R.; Orlando, J. J.; Baidar, S.; Brioude, J.; Fast, J.; Gentner, D. R.; Goldstein, A. H.; Hayes, P. L.; Knighton, W. B.; Oetjen, H.; Setyan, A.; Stark, H.; Thalman, R.; Tyndall, G.; Washenfelder, R.; Waxman, E.; Zhang, Q.

2013-10-01

New pathways to form secondary organic aerosols (SOA) have been postulated recently. Glyoxal, the smallest dicarbonyl, is one of the proposed precursors. It has both anthropogenic and biogenic sources, and readily partitions into the aqueous-phase of cloud droplets and deliquesced aerosols where it undergoes both reversible and irreversible chemistry. In this work we extend the regional scale chemistry transport model WRF-Chem to include a detailed gas-phase chemistry of glyoxal formation as well as a state-of-the-science module describing its partitioning and reactions in the aqueous-phase of aerosols. A comparison of several proposed mechanisms is performed to quantify the relative importance of different formation pathways and their regional variability. The CARES/CalNex campaigns over California in summer 2010 are used as case studies to evaluate the model against observations. In all simulations the LA basin was found to be the hotspot for SOA formation from glyoxal, which contributes between 1% and 15% of the model SOA depending on the mechanism used. Our results indicate that a mechanism based only on a simple uptake coefficient, as frequently employed in global modeling studies, leads to higher SOA contributions from glyoxal compared to a more detailed description that considers aerosol phase state and chemical composition. In the more detailed simulations, surface uptake is found to be the main contributor to SOA mass compared to a volume process and reversible formation. We find that contribution of the latter is limited by the availability of glyoxal in aerosol water, which is in turn controlled by an increase in the Henry's law constant depending on salt concentrations ("salting-in"). A kinetic limitation in this increase prevents substantial partitioning of glyoxal into aerosol water at high salt concentrations. If this limitation is removed, volume pathways contribute >20% of glyoxal SOA mass, and the total mass formed (5.8% of total SOA in the LA basin) is about a third of the simple uptake coefficient formulation without consideration of aerosol phase state and composition. All these model formulations are based on very limited and recent field or laboratory data and we conclude that the current uncertainty on glyoxal SOA formation spans a factor of 10 in this domain and time period.

Laboratory studies of monoterpene secondary organic aerosol formation and evolution

NASA Astrophysics Data System (ADS)

Thornton, J. A.; D'Ambro, E.; Zhao, Y.; Lee, B. H.; Pye, H. O. T.; Schobesberger, S.; Shilling, J.; Liu, J.

2017-12-01

We have conducted a series of chamber experiments to study the molecular composition and properties of secondary organic aerosol (SOA) formed from monoterpenes under a range of photochemical and dark conditions. We connect variations in the SOA mass yield to molecular composition and volatility, and use a detailed Master Chemical Mechanism (MCM) based chemical box model with dynamic gas-particle partitioning to examine the importance of various peroxy radical reaction mechanisms in setting the SOA yield and properties. We compare the volatility distribution predicted by the model to that inferred from isothermal room-temperature evaporation experiments using the FIGAERO-CIMS where SOA particles collected on a filter are allowed to evaporate under humidified pure nitrogen flow stream for up to 24 hours. We show that the combination of results requires prompt formation of low volatility SOA from predominantly gas-phase mechanisms, with important differences between monoterpenes (alpha-Pinene and delta-3-Carene) followed by slower non-radical particle phase chemistry that modulates both the chemical and physical properties of the SOA. Implications for the regional evolution of atmospheric monoterpene SOA are also discussed.

Secondary Organic Aerosol Formation from the Photooxidation of Naphthalene

NASA Astrophysics Data System (ADS)

Zhou, S.; Chen, Y.; Wenger, J.

2009-04-01

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous air pollutants that are released into the atmosphere as a by-product of combustion processes. The gas-phase PAHs can be chemically transformed via reaction with the hydroxyl radical to produce a range of oxidised organic compounds and other pollutants such as ozone and secondary organic aerosol (SOA). Epidemiological studies have established that exposure to this type of air pollution is associated with damaging effects on the respiratory and cardiovascular systems, and can lead to asthma, oxidative stress, health deterioration and even death. The major anthropogenic source of SOA in urban areas is believed to be aromatic hydrocarbons, which are present in automobile fuels and are used as solvents. As a result, research is currently being performed on the characterisation of SOA produced from aromatic hydrocarbons such as toluene, the xylenes and trimethylbenzenes. However, significant amounts of PAHs are also released into urban areas from automobile emissions and the combustion of fossil fuels for home heating. Naphthalene is regularly cited as the most abundant PAH in polluted urban air, with typical ambient air concentrations of 0.05 - 0.20 parts per billion (ppbV) in European cities, comparable to the xylenes. Since naphthalene reacts in an analogous manner to monocyclic aromatic compounds then it is also expected to make a significant contribution to ambient SOA. However, the yield and chemical composition of SOA produced from the atmospheric degradation of naphthalene is not well known. In this presentation, the effects of NOx level and relative humidity on the SOA formation from the phootooixdation of naphthalene will be presented. A series of experiments has been performed in a large atmospheric simulation chamber equipped with a gas chromatograph and analyzers for monitoring nitrogen oxides (NOx) and ozone. SOA formation from the photooxidation of naphthalene was measured using a scanning mobility particle sizer. The effect of NOx concentration on SOA formation was evaluated by varying the initial naphthalene and NOx concentrations. The results clearly show that a higher hydrocarbon to NOx ratio produces a higher yield of SOA. The SOA mass yields were also found to increase as the relative humidity was raised from 0 to 50%. A recently developed denuder-filter sampling technique was used to investigate the gas/particle partitioning behavior of the photooxidation products. This work is the first study of the formation of SOA from naphthalene and the results will be compared to those obtained from other aromatic compounds.

Organosulfate Formation in Biogenic Secondary Organic Aerosol

EPA Science Inventory

Organosulfates of isoprene, α-pinene, and β-pinene have recently been identified in both laboratory-generated and ambient secondary organic aerosol (SOA). In this study, the mechanism and ubiquity of organosulfate formation in biogenic SOA is investigated by a comprehensive seri...

Recent advances in understanding secondary organic aerosol: Implications for global climate forcing: Advances in Secondary Organic Aerosol

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shrivastava, Manish; Cappa, Christopher D.; Fan, Jiwen

Anthropogenic emissions and land use changes have modified atmospheric aerosol concentrations and size distributions over time. Understanding preindustrial conditions and changes in organic aerosol due to anthropogenic activities is important because these features (1) influence estimates of aerosol radiative forcing and (2) can confound estimates of the historical response of climate to increases in greenhouse gases. Secondary organic aerosol (SOA), formed in the atmosphere by oxidation of organic gases, represents a major fraction of global submicron-sized atmospheric organic aerosol. Over the past decade, significant advances in understanding SOA properties and formation mechanisms have occurred through measurements, yet current climate modelsmore » typically do not comprehensively include all important processes. Our review summarizes some of the important developments during the past decade in understanding SOA formation. We also highlight the importance of some processes that influence the growth of SOA particles to sizes relevant for clouds and radiative forcing, including formation of extremely low volatility organics in the gas phase, acid-catalyzed multiphase chemistry of isoprene epoxydiols, particle-phase oligomerization, and physical properties such as volatility and viscosity. Several SOA processes highlighted in this review are complex and interdependent and have nonlinear effects on the properties, formation, and evolution of SOA. Current global models neglect this complexity and nonlinearity and thus are less likely to accurately predict the climate forcing of SOA and project future climate sensitivity to greenhouse gases. Efforts are also needed to rank the most influential processes and nonlinear process-related interactions, so that these processes can be accurately represented in atmospheric chemistry-climate models.« less

Recent advances in understanding secondary organic aerosol: Implications for global climate forcing: Advances in Secondary Organic Aerosol

DOE PAGES

Shrivastava, Manish; Cappa, Christopher D.; Fan, Jiwen; ...

2017-06-15

Anthropogenic emissions and land use changes have modified atmospheric aerosol concentrations and size distributions over time. Understanding preindustrial conditions and changes in organic aerosol due to anthropogenic activities is important because these features (1) influence estimates of aerosol radiative forcing and (2) can confound estimates of the historical response of climate to increases in greenhouse gases. Secondary organic aerosol (SOA), formed in the atmosphere by oxidation of organic gases, represents a major fraction of global submicron-sized atmospheric organic aerosol. Over the past decade, significant advances in understanding SOA properties and formation mechanisms have occurred through measurements, yet current climate modelsmore » typically do not comprehensively include all important processes. Our review summarizes some of the important developments during the past decade in understanding SOA formation. We also highlight the importance of some processes that influence the growth of SOA particles to sizes relevant for clouds and radiative forcing, including formation of extremely low volatility organics in the gas phase, acid-catalyzed multiphase chemistry of isoprene epoxydiols, particle-phase oligomerization, and physical properties such as volatility and viscosity. Several SOA processes highlighted in this review are complex and interdependent and have nonlinear effects on the properties, formation, and evolution of SOA. Current global models neglect this complexity and nonlinearity and thus are less likely to accurately predict the climate forcing of SOA and project future climate sensitivity to greenhouse gases. Efforts are also needed to rank the most influential processes and nonlinear process-related interactions, so that these processes can be accurately represented in atmospheric chemistry-climate models.« less

Recent advances in understanding secondary organic aerosol: Implications for global climate forcing

NASA Astrophysics Data System (ADS)

Shrivastava, Manish; Cappa, Christopher D.; Fan, Jiwen; Goldstein, Allen H.; Guenther, Alex B.; Jimenez, Jose L.; Kuang, Chongai; Laskin, Alexander; Martin, Scot T.; Ng, Nga Lee; Petaja, Tuukka; Pierce, Jeffrey R.; Rasch, Philip J.; Roldin, Pontus; Seinfeld, John H.; Shilling, John; Smith, James N.; Thornton, Joel A.; Volkamer, Rainer; Wang, Jian; Worsnop, Douglas R.; Zaveri, Rahul A.; Zelenyuk, Alla; Zhang, Qi

2017-06-01

Anthropogenic emissions and land use changes have modified atmospheric aerosol concentrations and size distributions over time. Understanding preindustrial conditions and changes in organic aerosol due to anthropogenic activities is important because these features (1) influence estimates of aerosol radiative forcing and (2) can confound estimates of the historical response of climate to increases in greenhouse gases. Secondary organic aerosol (SOA), formed in the atmosphere by oxidation of organic gases, represents a major fraction of global submicron-sized atmospheric organic aerosol. Over the past decade, significant advances in understanding SOA properties and formation mechanisms have occurred through measurements, yet current climate models typically do not comprehensively include all important processes. This review summarizes some of the important developments during the past decade in understanding SOA formation. We highlight the importance of some processes that influence the growth of SOA particles to sizes relevant for clouds and radiative forcing, including formation of extremely low volatility organics in the gas phase, acid-catalyzed multiphase chemistry of isoprene epoxydiols, particle-phase oligomerization, and physical properties such as volatility and viscosity. Several SOA processes highlighted in this review are complex and interdependent and have nonlinear effects on the properties, formation, and evolution of SOA. Current global models neglect this complexity and nonlinearity and thus are less likely to accurately predict the climate forcing of SOA and project future climate sensitivity to greenhouse gases. Efforts are also needed to rank the most influential processes and nonlinear process-related interactions, so that these processes can be accurately represented in atmospheric chemistry-climate models.

Optical properties and aging of light-absorbing secondary organic aerosol

DOE PAGES

Liu, Jiumeng; Lin, Peng; Laskin, Alexander; ...

2016-10-14

The light-absorbing organic aerosol (OA) commonly referred to as “brown carbon” (BrC) has attracted considerable attention in recent years because of its potential to affect atmospheric radiation balance, especially in the ultraviolet region and thus impact photochemical processes. A growing amount of data has indicated that BrC is prevalent in the atmosphere, which has motivated numerous laboratory and field studies; however, our understanding of the relationship between the chemical composition and optical properties of BrC remains limited. We conducted chamber experiments to investigate the effect of various volatile organic carbon (VOC) precursors, NO x concentrations, photolysis time, and relative humidity (RH) on the lightmore » absorption of selected secondary organic aerosols (SOA). Light absorption of chamber-generated SOA samples, especially aromatic SOA, was found to increase with NO x concentration, at moderate RH, and for the shortest photolysis aging times. The highest mass absorption coefficient (MAC) value is observed from toluene SOA products formed under high-NO x conditions at moderate RH, in which nitro-aromatics were previously identified as the major light-absorbing compounds. BrC light absorption is observed to decrease with photolysis time, correlated with a decline of the organic nitrate fraction of SOA. SOA formed from mixtures of aromatics and isoprene absorb less visible (Vis) and ultraviolet (UV) light than SOA formed from aromatic precursors alone on a mass basis. However, the mixed SOA absorption was underestimated when optical properties were predicted using a two-product SOA formation model, as done in many current climate models. Further investigation, including analysis on detailed mechanisms, are required to explain the discrepancy.« less

Secondary Organic Aerosol Produced from Aqueous Reactions of Phenols in Fog Drops and Deliquesced Particles

NASA Astrophysics Data System (ADS)

Smith, J.; Anastasio, C.

2014-12-01

The formation and evolution of secondary organic aerosol (SOA) in atmospheric condensed phases (i.e., aqueous SOA) can proceed rapidly, but relatively little is known of the important aqueous SOA precursors or their reaction pathways. In our work we are studying the aqueous SOA formed from reactions of phenols (phenol, guaiacol, and syringol), benzene-diols (catechol, resorcinol, and hydroquinone), and phenolic carbonyls (e.g., vanillin and syringaldehyde). These species are potentially important aqueous SOA precursors because they are released in large quantities from biomass burning, have high Henry's Law constants (KH = 103 -109 M-1 atm-1) and are rapidly oxidized. To evaluate the importance of aqueous reactions of phenols as a source of SOA, we first quantified the kinetics and SOA mass yields for 11 phenols reacting via direct photodegradation, hydroxyl radical (•OH), and with an excited organic triplet state (3C*). In the second step, which is the focus of this work, we use these laboratory results in a simple model of fog chemistry using conditions during a previously reported heavy biomass burning event in Bakersfield, CA. Our calculations indicate that under aqueous aerosol conditions (i.e., a liquid water content of 100 μg m-3) the rate of aqueous SOA production (RSOA(aq)) from phenols is similar to the rate in the gas phase. In contrast, under fog/cloud conditions the aqueous RSOA from phenols is 10 times higher than the rate in the gas phase. In both of these cases aqueous RSOA is dominated by the oxidation of phenols by 3C*, followed by direct photodegradation of phenolic carbonyls, and then •OH oxidation. Our results suggest that aqueous oxidation of phenols is a significant source of SOA during fog events and also during times when deliquesced aerosols are present.

Secondary organic aerosol from atmospheric photooxidation of indole

NASA Astrophysics Data System (ADS)

Montoya-Aguilera, Julia; Horne, Jeremy R.; Hinks, Mallory L.; Fleming, Lauren T.; Perraud, Véronique; Lin, Peng; Laskin, Alexander; Laskin, Julia; Dabdub, Donald; Nizkorodov, Sergey A.

2017-09-01

Indole is a heterocyclic compound emitted by various plant species under stressed conditions or during flowering events. The formation, optical properties, and chemical composition of secondary organic aerosol (SOA) formed by low-NOx photooxidation of indole were investigated. The SOA yield (1. 3 ± 0. 3) was estimated from measuring the particle mass concentration with a scanning mobility particle sizer (SMPS) and correcting it for wall loss effects. The high value of the SOA mass yield suggests that most oxidized indole products eventually end up in the particle phase. The SOA particles were collected on filters and analysed offline with UV-vis spectrophotometry to measure the mass absorption coefficient (MAC) of the bulk sample. The samples were visibly brown and had MAC values of ˜ 2 m2 g-1 at λ = 300 nm and ˜ 0. 5 m2 g-1 at λ = 400 nm, comparable to strongly absorbing brown carbon emitted from biomass burning. The chemical composition of SOA was examined with several mass spectrometry methods. Direct analysis in real-time mass spectrometry (DART-MS) and nanospray desorption electrospray high-resolution mass spectrometry (nano-DESI-HRMS) were both used to provide information about the overall distribution of SOA compounds. High-performance liquid chromatography, coupled to photodiode array spectrophotometry and high-resolution mass spectrometry (HPLC-PDA-HRMS), was used to identify chromophoric compounds that are responsible for the brown colour of SOA. Indole derivatives, such as tryptanthrin, indirubin, indigo dye, and indoxyl red, were found to contribute significantly to the visible absorption spectrum of indole SOA. The potential effect of indole SOA on air quality was explored with an airshed model, which found elevated concentrations of indole SOA during the afternoon hours contributing considerably to the total organic aerosol under selected scenarios. Because of its high MAC values, indole SOA can contribute to decreased visibility and poor air quality.

Limited effect of anthropogenic nitrogen oxides on secondary organic aerosol formation

NASA Astrophysics Data System (ADS)

Zheng, Y.; Unger, N.; Hodzic, A.; Emmons, L.; Knote, C.; Tilmes, S.; Lamarque, J.-F.; Yu, P.

2015-12-01

Globally, secondary organic aerosol (SOA) is mostly formed from emissions of biogenic volatile organic compounds (VOCs) by vegetation, but it can be modified by human activities as demonstrated in recent research. Specifically, nitrogen oxides (NOx = NO + NO2) have been shown to play a critical role in the chemical formation of low volatility compounds. We have updated the SOA scheme in the global NCAR (National Center for Atmospheric Research) Community Atmospheric Model version 4 with chemistry (CAM4-chem) by implementing a 4-product volatility basis set (VBS) scheme, including NOx-dependent SOA yields and aging parameterizations. Small differences are found for the no-aging VBS and 2-product schemes; large increases in SOA production and the SOA-to-OA ratio are found for the aging scheme. The predicted organic aerosol amounts capture both the magnitude and distribution of US surface annual mean measurements from the Interagency Monitoring of Protected Visual Environments (IMPROVE) network by 50 %, and the simulated vertical profiles are within a factor of 2 compared to aerosol mass spectrometer (AMS) measurements from 13 aircraft-based field campaigns across different regions and seasons. We then perform sensitivity experiments to examine how the SOA loading responds to a 50 % reduction in anthropogenic nitric oxide (NO) emissions in different regions. We find limited SOA reductions of 0.9-5.6, 6.4-12.0 and 0.9-2.8 % for global, southeast US and Amazon NOx perturbations, respectively. The fact that SOA formation is almost unaffected by changes in NOx can be largely attributed to a limited shift in chemical regime, to buffering in chemical pathways (low- and high-NOx pathways, O3 versus NO3-initiated oxidation) and to offsetting tendencies in the biogenic versus anthropogenic SOA responses.

Secondary Organic Aerosol (SOA) from Nitrate Radical Oxidation of Monoterpenes: Effects of Temperature, Dilution, and Humidity on Aerosol Formation, Mixing, and Evaporation.

PubMed

Boyd, Christopher M; Nah, Theodora; Xu, Lu; Berkemeier, Thomas; Ng, Nga Lee

2017-07-18

Nitrate radical (NO 3 ) oxidation of biogenic volatile organic compounds (BVOC) is important for nighttime secondary organic aerosol (SOA) formation. SOA produced at night may evaporate the following morning due to increasing temperatures or dilution of semivolatile compounds. We isothermally dilute the oxidation products from the limonene+NO 3 reaction at 25 °C and observe negligible evaporation of organic aerosol via dilution. The SOA yields from limonene+NO 3 are approximately constant (∼174%) at 25 °C and range from 81 to 148% at 40 °C. Based on the difference in yields between the two temperatures, we calculated an effective enthalpy of vaporization of 117-237 kJ mol -1 . The aerosol yields at 40 °C can be as much as 50% lower compared to 25 °C. However, when aerosol formed at 25 °C is heated to 40 °C, only about 20% of the aerosol evaporates, which could indicate a resistance to aerosol evaporation. To better understand this, we probe the possibility that SOA from limonene+NO 3 and β-pinene+NO 3 reactions is highly viscous. We demonstrate that particle morphology and evaporation is dependent on whether SOA from limonene is formed before or during the formation of SOA from β-pinene. This difference in particle morphology is present even at high relative humidity (∼70%).

SOA Measurements vs. Models: A Status Report

NASA Astrophysics Data System (ADS)

Jimenez, Jose-Luis; de Gouw, Joost; Hodzic, Alma

2010-05-01

The advent of fast and chemically-resolved organic aerosol (OA) and VOC measurements in the last decade has allowed more detailed model-measurement comparisons for OA and secondary OA (SOA). Large model underpredictions have been reported for SOA at many locations, but this is not always the case. Here we summarize the patterns emerging from studies to date, focusing on studies that use highly time and/or chemically resolved OA measurements. The model-measurement comparisons exhibit clear patterns depending on the region of the atmosphere. • At least 8 studies have reported a large (x5-10) underestimation of SOA for polluted regions when using traditional models (those developed until ~2006) (Heald GRL05, Volkamer GRL06, Johnson ACP06, Kleinman ACP08, Matsui JGR09, Dzepina ACP09, Hodzic ACP09, Tsimpidi ACP09). This is especially obvious when models are evaluated with the ΔOA/ΔCO ratio. • Close to pollution sources, discrepancies of an order-of-magnitude in SOA lead to smaller discrepancies (often x2-3) for total OA due to the presence of primary OA (de Gouw EST09). Such OA discrepancies have been repeatedly observed (e.g. Vutukuru JGR06, McKeen JGR07&09, Heald JGR07, Fast ACP09, Hodzic ACP09). • The discrepancy is reduced when recently-updated yields for aromatics (Ng ACP07) and SOA from glyoxal (Volkamer GRL07) are used, and is eliminated when using SOA formation from S/IVOC (Robinson Sci07) although with an overprediction of SOA at long aging times (Dzepina ACP09; Hodzic ACP10), especially with the Grieshop (ACP09) update of the Robison mechanism (Hodzic10). It is not clear whether the urban discrepancy is removed for the right reasons. • 4 evaluations of biogenic SOA formed in unpolluted regions find reasonable agreement between SOA from traditional models and field measurements (Tunved Sci06; Hodzic ACP09; Chen GRL09; Slowik ACPD09). One evaluation reports a significant underprediction (Capes ACP09), although the amount of precursor reacted was difficult to ascertain for that case. The difference with the systematic underprediction observed for anthropogenic SOA may be due to the lack of primary S/IVOC in biogenic emissions, or to other reasons (NOx, SO2, POA, etc.). • Comparisons for biogenic SOA formed in polluted regions are more complex. Several studies have reported a lack of clear influence of biogenic VOCs in SOA formation in polluted regions (de Gouw JGR05, GRL09; Weber JGR07; Bahreini JGR09), but 14C studies suggest a large fraction of modern C (Weber JGR07). Synergistic effects of pollution and BVOCs appear likely (e.g. de Gouw JGR05; Weber JGR07; Goldstein PNAS09). • Net SOA formation (above the POA mass emission) from biomass burning appears very variable in the field (Capes JGR09; Yokelson ACP09; DeCarlo ACPD10) as well as in the laboratory (Ortega AGU09; Prevot AGU09; Hennigan in prep.), likely due flaming vs. smoldering fraction and biomass identity, and perhaps also to prompt SOA formation triggered by HONO photolysis. Several studies report significant SOA formation, given enough photochemical processing. Models based on traditional precursors appear to underpredict SOA from BB sources (Grieshop ACP09; Hodzic ACP09). • The very large SOA source in the free troposphere postulated by Heald (GRL05) has not been confirmed nor disproved by later studies. Dunlea (ACP09) did not find evidence of this source across the Pacific near North America, though precipitation removal precludes any strong conclusions. However Carlton (EST09) reported better comparisons after implementing in-cloud SOA formation. • Evaluation of models against measured total OA or OC or SOA levels is thoroughly unsufficient to model verification. OA measurements can be matched through a large number of mechanism permutations, but investigators need to push further to determine whether the agreement is for the right reasons. Future model evaluations should compare POA, SOA precursors, OVOCs, oxidants, and boundary conditions. Multiple OA measurements (WSOC, OC, AMS, molecular tracers, 14C, etc.) are necessary to overcome the limitations of any one method. Measurements of semivolatile species are critically needed to constrain models. These advanced diagnostics are needed in order to build confidence on SOA models, which is needed to predict the changes in SOA concentrations in response to precursor and climate changes.

Impact of Propene on Secondary Organic Aerosol Formation from m-Xylene

DOE Office of Scientific and Technical Information (OSTI.GOV)

Song, Chen; Na, Kwangsam; Warren, Bethany

2007-10-15

Propene is widely used in smog chamber experiments to increase the hydroxyl radical (OH) level based on the assumption that the formation of secondary organic aerosol (SOA) from parent hydrocarbon is unaffected. A series ofm-xylene/NOx photooxidation experiments were conducted in the presence of propene in the University of California CECERT atmospheric chamber facility. The experimental data are compared with previousm-xylene/NOx photooxidation work performed in the same chamber facility in the absence of propene (Song et al. Environ. Sci. Technol. 2005, 39, 3143-3149). The result shows that, for similar initial conditions, experiments with propene have lower reaction rates of m-xylene thanmore » those without propene, which indicates that propene reduces OH in the system. Furthermore, experiments with propene showed more than 15% reduction in SOA yield compared to experiments in the absence of propene. Additional experiments ofm-xylene/NOx with CO showed similar trends of suppressing OH and SOA formation. These results indicate that SOA from m-xylene/NOx photooxidation is strongly dependent on the OH level present, which provides evidence for the critical role of OH in SOA formation from aromatic hydrocarbons.« less

Understanding sources of organic aerosol during CalNex-2010 using the CMAQ-VBS

NASA Astrophysics Data System (ADS)

Woody, Matthew C.; Baker, Kirk R.; Hayes, Patrick L.; Jimenez, Jose L.; Koo, Bonyoung; Pye, Havala O. T.

2016-03-01

Community Multiscale Air Quality (CMAQ) model simulations utilizing the traditional organic aerosol (OA) treatment (CMAQ-AE6) and a volatility basis set (VBS) treatment for OA (CMAQ-VBS) were evaluated against measurements collected at routine monitoring networks (Chemical Speciation Network (CSN) and Interagency Monitoring of Protected Visual Environments (IMPROVE)) and those collected during the 2010 California at the Nexus of Air Quality and Climate Change (CalNex) field campaign to examine important sources of OA in southern California. Traditionally, CMAQ treats primary organic aerosol (POA) as nonvolatile and uses a two-product framework to represent secondary organic aerosol (SOA) formation. CMAQ-VBS instead treats POA as semivolatile and lumps OA using volatility bins spaced an order of magnitude apart. The CMAQ-VBS approach underpredicted organic carbon (OC) at IMPROVE and CSN sites to a greater degree than CMAQ-AE6 due to the semivolatile POA treatment. However, comparisons to aerosol mass spectrometer (AMS) measurements collected at Pasadena, CA, indicated that CMAQ-VBS better represented the diurnal profile and primary/secondary split of OA. CMAQ-VBS SOA underpredicted the average measured AMS oxygenated organic aerosol (OOA, a surrogate for SOA) concentration by a factor of 5.2, representing a considerable improvement to CMAQ-AE6 SOA predictions (factor of 24 lower than AMS). We use two new methods, one based on species ratios (SOA/ΔCO and SOA/Ox) and another on a simplified SOA parameterization, to apportion the SOA underprediction for CMAQ-VBS to slow photochemical oxidation (estimated as 1.5 × lower than observed at Pasadena using -log(NOx : NOy)), low intrinsic SOA formation efficiency (low by 1.6 to 2 × for Pasadena), and low emissions or excessive dispersion for the Pasadena site (estimated to be 1.6 to 2.3 × too low/excessive). The first and third factors are common to CMAQ-AE6, while the intrinsic SOA formation efficiency for that model is estimated to be too low by about 7 × . From source-apportioned model results, we found most of the CMAQ-VBS modeled POA at the Pasadena CalNex site was attributable to meat cooking emissions (48 %, consistent with a substantial fraction of cooking OA in the observations). This is compared to 18 % from gasoline vehicle emissions, 13 % from biomass burning (in the form of residential wood combustion), and 8 % from diesel vehicle emissions. All "other" inventoried emission sources (e.g., industrial, point, and area sources) comprised the final 13 %. The CMAQ-VBS semivolatile POA treatment underpredicted AMS hydrocarbon-like OA (HOA) + cooking-influenced OA (CIOA) at Pasadena by a factor of 1.8 compared to a factor of 1.4 overprediction of POA in CMAQ-AE6, but it did capture the AMS diurnal profile of HOA and CIOA well, with the exception of the midday peak. Overall, the CMAQ-VBS with its semivolatile treatment of POA, SOA from intermediate volatility organic compounds (IVOCs), and aging of SOA improves SOA model performance (though SOA formation efficiency is still 1.6-2 × too low). However, continued efforts are needed to better understand assumptions in the parameterization (e.g., SOA aging) and provide additional certainty to how best to apply existing emission inventories in a framework that treats POA as semivolatile, which currently degrades existing model performance at routine monitoring networks. The VBS and other approaches (e.g., AE6) require additional work to appropriately incorporate IVOC emissions and subsequent SOA formation.

Understanding sources of organic aerosol during CalNex-2010 using the CMAQ-VBS

DOE PAGES

Woody, Matthew C.; Baker, Kirk R.; Hayes, Patrick L.; ...

2016-03-29

In this paper, Community Multiscale Air Quality (CMAQ) model simulations utilizing the traditional organic aerosol (OA) treatment (CMAQ-AE6) and a volatility basis set (VBS) treatment for OA (CMAQ-VBS) were evaluated against measurements collected at routine monitoring networks (Chemical Speciation Network (CSN) and Interagency Monitoring of Protected Visual Environments (IMPROVE)) and those collected during the 2010 California at the Nexus of Air Quality and Climate Change (CalNex) field campaign to examine important sources of OA in southern California. Traditionally, CMAQ treats primary organic aerosol (POA) as nonvolatile and uses a two-product framework to represent secondary organic aerosol (SOA) formation. CMAQ-VBS insteadmore » treats POA as semivolatile and lumps OA using volatility bins spaced an order of magnitude apart. The CMAQ-VBS approach underpredicted organic carbon (OC) at IMPROVE and CSN sites to a greater degree than CMAQ-AE6 due to the semivolatile POA treatment. However, comparisons to aerosol mass spectrometer (AMS) measurements collected at Pasadena, CA, indicated that CMAQ-VBS better represented the diurnal profile and primary/secondary split of OA. CMAQ-VBS SOA underpredicted the average measured AMS oxygenated organic aerosol (OOA, a surrogate for SOA) concentration by a factor of 5.2, representing a considerable improvement to CMAQ-AE6 SOA predictions (factor of 24 lower than AMS). We use two new methods, one based on species ratios (SOA/ΔCO and SOA/O x) and another on a simplified SOA parameterization, to apportion the SOA underprediction for CMAQ-VBS to slow photochemical oxidation (estimated as 1.5 × lower than observed at Pasadena using -log(NO x:NO y)), low intrinsic SOA formation efficiency (low by 1.6 to 2 × for Pasadena), and low emissions or excessive dispersion for the Pasadena site (estimated to be 1.6 to 2.3 × too low/excessive). The first and third factors are common to CMAQ-AE6, while the intrinsic SOA formation efficiency for that model is estimated to be too low by about 7 ×. From source-apportioned model results, we found most of the CMAQ-VBS modeled POA at the Pasadena CalNex site was attributable to meat cooking emissions (48 %, consistent with a substantial fraction of cooking OA in the observations). This is compared to 18 % from gasoline vehicle emissions, 13 % from biomass burning (in the form of residential wood combustion), and 8 % from diesel vehicle emissions. All "other" inventoried emission sources (e.g., industrial, point, and area sources) comprised the final 13 %. The CMAQ-VBS semivolatile POA treatment underpredicted AMS hydrocarbon-like OA (HOA) + cooking-influenced OA (CIOA) at Pasadena by a factor of 1.8 compared to a factor of 1.4 overprediction of POA in CMAQ-AE6, but it did capture the AMS diurnal profile of HOA and CIOA well, with the exception of the midday peak. Overall, the CMAQ-VBS with its semivolatile treatment of POA, SOA from intermediate volatility organic compounds (IVOCs), and aging of SOA improves SOA model performance (though SOA formation efficiency is still 1.6–2 × too low). However, continued efforts are needed to better understand assumptions in the parameterization (e.g., SOA aging) and provide additional certainty to how best to apply existing emission inventories in a framework that treats POA as semivolatile, which currently degrades existing model performance at routine monitoring networks. Finally, the VBS and other approaches (e.g., AE6) require additional work to appropriately incorporate IVOC emissions and subsequent SOA formation.« less

A critical role for autoxidation in the alpha-pinene + OH aerosol system

EPA Science Inventory

Oxidation of monoterpenes results in efficient formation of secondary organic aerosol (SOA) and is included as an SOA source in most chemical transport models. However, current model parameterizations lack a mechanistic dependence of monoterpene SOA on NOx and oxidant identity (e...

Lessons Learned About Organic Aerosol Formation in the Southeast U.S. Using Observations and Modeling

EPA Science Inventory

Isoprene emitted by vegetation is an important precursor of secondary organic aerosol (SOA). In this work, modeling of isoprene SOA via heterogeneous uptake is explored and compared to observations from the Southern Oxidant and Aerosol Study (SOAS).

EVIDENCE FOR ORGANOSULFATES IN SECONDARY ORGANIC AEROSOL

EPA Science Inventory

Recent work has shown that particle-phase reactions contribute to the formation of secondary organic aerosol (SOA), with enhancements of SOA yields in the presence of acidic seed aerosol. In this study, the chemical composition of SOA from the photooxidations of α-pinene and isop...

Simulating the SOA formation of isoprene from partitioning and aerosol phase reactions in the presence of inorganics

NASA Astrophysics Data System (ADS)

Beardsley, Ross L.; Jang, Myoseon

2016-05-01

The secondary organic aerosol (SOA) produced by the photooxidation of isoprene with and without inorganic seed is simulated using the Unified Partitioning Aerosol Phase Reaction (UNIPAR) model. Recent work has found the SOA formation of isoprene to be sensitive to both aerosol acidity ([H+], mol L-1) and aerosol liquid water content (LWC) with the presence of either leading to significant aerosol phase organic mass generation and large growth in SOA yields (YSOA). Classical partitioning models alone are insufficient to predict isoprene SOA formation due to the high volatility of photooxidation products and sensitivity of their mass yields to variations in inorganic aerosol composition. UNIPAR utilizes the chemical structures provided by a near-explicit chemical mechanism to estimate the thermodynamic properties of the gas phase products, which are lumped based on their calculated vapor pressure (eight groups) and aerosol phase reactivity (six groups). UNIPAR then determines the SOA formation of each lumping group from both partitioning and aerosol phase reactions (oligomerization, acid-catalyzed reactions and organosulfate formation) assuming a single homogeneously mixed organic-inorganic phase as a function of inorganic composition and VOC / NOx (VOC - volatile organic compound). The model is validated using isoprene photooxidation experiments performed in the dual, outdoor University of Florida Atmospheric PHotochemical Outdoor Reactor (UF APHOR) chambers. UNIPAR is able to predict the experimental SOA formation of isoprene without seed, with H2SO4 seed gradually titrated by ammonia, and with the acidic seed generated by SO2 oxidation. Oligomeric mass is predicted to account for more than 65 % of the total organic mass formed in all cases and over 85 % in the presence of strongly acidic seed. The model is run to determine the sensitivity of YSOA to [H+], LWC and VOC / NOx, and it is determined that the SOA formation of isoprene is most strongly related to [H+] but is dynamically related to all three parameters. For VOC / NOx > 10, with increasing NOx both experimental and simulated YSOA increase and are found to be more sensitive to [H+] and LWC. For atmospherically relevant conditions, YSOA is found to be more than 150 % higher in partially titrated acidic seeds (NH4HSO4) than in effloresced inorganics or in isoprene only.

Effect of Ammonia on Glyoxal SOA in Inorganic Aqueous Seed Particles

NASA Astrophysics Data System (ADS)

Waxman, E.; Volkamer, R. M.; Laskin, A.; Laskin, J.; Koenig, T. K.; Baltensperger, U.; Dommen, J.; Prevot, A. S.; Slowik, J.; Maxut, A.; Noziere, B.; Wang, S.; Yu, J.

2014-12-01

Glyoxal (C2H2O2) is a ubiquitous small molecule that is observed in the terrestrial biogenic, urban, marine and arctic atmosphere. It forms secondary organic aerosol (SOA) as a result of multiphase chemical reactions in water. The rate of these reactions is controlled by the effective Henry's law partitioning coefficient (Heff) which is enhanced in the presence of inorganic salts by up to 3 orders of magnitude (Kampf et al., 2013, ES&T). Aerosol particles are among the most concentrated salt solutions on Earth and the SOA formation rate in aerosol water is strongly modified by this 'salting-in' mechanism. We have studied the effect of gas-phase ammonia on the rate of SOA formation in real particles composed of different inorganic salts (sulfate, nitrate, chloride). A series of simulation chamber experiments were conducted at the Paul Scherrer Institut in Switzerland during Summer 2013. The SOA formation rate in experiments with added gas-phase ammonia (NH3) was found to be greatly accelerated compared to experiments without added NH3. Product analysis of particles included online HR-ToF-AMS and offline nano-DESI and LC-MS. We find that imidazole-like oligomer compounds dominate the observed products, rather than high-O/C oligomers containing solely C, H, and O. We further employed isotopically labelled di-substituted 13C glyoxal experiments in order to unambiguously link product formation to glyoxal (and separate it from chamber wall contamination). We present a molecular perspective on the reaction pathways and evaluate the effect of environmental parameters (RH, particle pH, seed chemical composition) on the formation of these imidazole-like oligomer compounds. The implications for SOA formation from photosensitized oxidation chemistry is discussed.

Organosulfates as tracers for secondary organic aerosol (SOA) formation from 2-methyl-3-buten-2-ol (MBO) in the atmosphere.

PubMed

Zhang, Haofei; Worton, David R; Lewandowski, Michael; Ortega, John; Rubitschun, Caitlin L; Park, Jeong-Hoo; Kristensen, Kasper; Campuzano-Jost, Pedro; Day, Douglas A; Jimenez, Jose L; Jaoui, Mohammed; Offenberg, John H; Kleindienst, Tadeusz E; Gilman, Jessica; Kuster, William C; de Gouw, Joost; Park, Changhyoun; Schade, Gunnar W; Frossard, Amanda A; Russell, Lynn; Kaser, Lisa; Jud, Werner; Hansel, Armin; Cappellin, Luca; Karl, Thomas; Glasius, Marianne; Guenther, Alex; Goldstein, Allen H; Seinfeld, John H; Gold, Avram; Kamens, Richard M; Surratt, Jason D

2012-09-04

2-Methyl-3-buten-2-ol (MBO) is an important biogenic volatile organic compound (BVOC) emitted by pine trees and a potential precursor of atmospheric secondary organic aerosol (SOA) in forested regions. In the present study, hydroxyl radical (OH)-initiated oxidation of MBO was examined in smog chambers under varied initial nitric oxide (NO) and aerosol acidity levels. Results indicate measurable SOA from MBO under low-NO conditions. Moreover, increasing aerosol acidity was found to enhance MBO SOA. Chemical characterization of laboratory-generated MBO SOA reveals that an organosulfate species (C(5)H(12)O(6)S, MW 200) formed and was substantially enhanced with elevated aerosol acidity. Ambient fine aerosol (PM(2.5)) samples collected from the BEARPEX campaign during 2007 and 2009, as well as from the BEACHON-RoMBAS campaign during 2011, were also analyzed. The MBO-derived organosulfate characterized from laboratory-generated aerosol was observed in PM(2.5) collected from these campaigns, demonstrating that it is a molecular tracer for MBO-initiated SOA in the atmosphere. Furthermore, mass concentrations of the MBO-derived organosulfate are well correlated with MBO mixing ratio, temperature, and acidity in the field campaigns. Importantly, this compound accounted for an average of 0.25% and as high as 1% of the total organic aerosol mass during BEARPEX 2009. An epoxide intermediate generated under low-NO conditions is tentatively proposed to produce MBO SOA.

Modeling the formation and aging of secondary organic aerosols in Los Angeles during CalNex 2010

DOE PAGES

Hayes, P. L.; Carlton, A. G.; Baker, K. R.; ...

2015-05-26

Four different literature parameterizations for the formation and evolution of urban secondary organic aerosol (SOA) frequently used in 3-D models are evaluated using a 0-D box model representing the Los Angeles metropolitan region during the California Research at the Nexus of Air Quality and Climate Change (CalNex) 2010 campaign. We constrain the model predictions with measurements from several platforms and compare predictions with particle- and gas-phase observations from the CalNex Pasadena ground site. That site provides a unique opportunity to study aerosol formation close to anthropogenic emission sources with limited recirculation. The model SOA that formed only from the oxidationmore » of VOCs (V-SOA) is insufficient to explain the observed SOA concentrations, even when using SOA parameterizations with multi-generation oxidation that produce much higher yields than have been observed in chamber experiments, or when increasing yields to their upper limit estimates accounting for recently reported losses of vapors to chamber walls. The Community Multiscale Air Quality (WRF-CMAQ) model (version 5.0.1) provides excellent predictions of secondary inorganic particle species but underestimates the observed SOA mass by a factor of 25 when an older VOC-only parameterization is used, which is consistent with many previous model–measurement comparisons for pre-2007 anthropogenic SOA modules in urban areas. Including SOA from primary semi-volatile and intermediate-volatility organic compounds (P-S/IVOCs) following the parameterizations of Robinson et al. (2007), Grieshop et al. (2009), or Pye and Seinfeld (2010) improves model–measurement agreement for mass concentration. The results from the three parameterizations show large differences (e.g., a factor of 3 in SOA mass) and are not well constrained, underscoring the current uncertainties in this area. Our results strongly suggest that other precursors besides VOCs, such as P-S/IVOCs, are needed to explain the observed SOA concentrations in Pasadena. All the recent parameterizations overpredict urban SOA formation at long photochemical ages (≈ 3 days) compared to observations from multiple sites, which can lead to problems in regional and especially global modeling. However, reducing IVOC emissions by one-half in the model to better match recent IVOC measurements improves SOA predictions at these long photochemical ages. Among the explicitly modeled VOCs, the precursor compounds that contribute the greatest SOA mass are methylbenzenes. Measured polycyclic aromatic hydrocarbons (naphthalenes) contribute 0.7% of the modeled SOA mass. The amounts of SOA mass from diesel vehicles, gasoline vehicles, and cooking emissions are estimated to be 16–27, 35–61, and 19–35%, respectively, depending on the parameterization used, which is consistent with the observed fossil fraction of urban SOA, 71(±3) %. The relative contribution of each source is uncertain by almost a factor of 2 depending on the parameterization used. In-basin biogenic VOCs are predicted to contribute only a few percent to SOA. A regional SOA background of approximately 2.1 μg m −3 is also present due to the long-distance transport of highly aged OA, likely with a substantial contribution from regional biogenic SOA. The percentage of SOA from diesel vehicle emissions is the same, within the estimated uncertainty, as reported in previous work that analyzed the weekly cycles in OA concentrations (Bahreini et al., 2012; Hayes et al., 2013). However, the modeling work presented here suggests a strong anthropogenic source of modern carbon in SOA, due to cooking emissions, which was not accounted for in those previous studies and which is higher on weekends. Lastly, this work adapts a simple two-parameter model to predict SOA concentration and O/C from urban emissions. This model successfully predicts SOA concentration, and the optimal parameter combination is very similar to that found for Mexico City. This approach provides a computationally inexpensive method for predicting urban SOA in global and climate models. We estimate pollution SOA to account for 26 Tg yr −1 of SOA globally, or 17% of global SOA, one-third of which is likely to be non-fossil.« less

Modeling the formation and aging of secondary organic aerosols in Los Angeles during CalNex 2010

NASA Astrophysics Data System (ADS)

Hayes, P. L.; Carlton, A. G.; Baker, K. R.; Ahmadov, R.; Washenfelder, R. A.; Alvarez, S.; Rappengluck, B.; Gilman, J. B.; Kuster, W. C.; de Gouw, J. A.; Zotter, P.; Prevot, A. S. H.; Szidat, S.; Kleindienst, T. E.; Offenberg, J. H.; Ma, P. K.; Jimenez, J. L.

2015-05-01

Four different literature parameterizations for the formation and evolution of urban secondary organic aerosol (SOA) frequently used in 3-D models are evaluated using a 0-D box model representing the Los Angeles metropolitan region during the California Research at the Nexus of Air Quality and Climate Change (CalNex) 2010 campaign. We constrain the model predictions with measurements from several platforms and compare predictions with particle- and gas-phase observations from the CalNex Pasadena ground site. That site provides a unique opportunity to study aerosol formation close to anthropogenic emission sources with limited recirculation. The model SOA that formed only from the oxidation of VOCs (V-SOA) is insufficient to explain the observed SOA concentrations, even when using SOA parameterizations with multi-generation oxidation that produce much higher yields than have been observed in chamber experiments, or when increasing yields to their upper limit estimates accounting for recently reported losses of vapors to chamber walls. The Community Multiscale Air Quality (WRF-CMAQ) model (version 5.0.1) provides excellent predictions of secondary inorganic particle species but underestimates the observed SOA mass by a factor of 25 when an older VOC-only parameterization is used, which is consistent with many previous model-measurement comparisons for pre-2007 anthropogenic SOA modules in urban areas. Including SOA from primary semi-volatile and intermediate-volatility organic compounds (P-S/IVOCs) following the parameterizations of Robinson et al. (2007), Grieshop et al. (2009), or Pye and Seinfeld (2010) improves model-measurement agreement for mass concentration. The results from the three parameterizations show large differences (e.g., a factor of 3 in SOA mass) and are not well constrained, underscoring the current uncertainties in this area. Our results strongly suggest that other precursors besides VOCs, such as P-S/IVOCs, are needed to explain the observed SOA concentrations in Pasadena. All the recent parameterizations overpredict urban SOA formation at long photochemical ages (~ 3 days) compared to observations from multiple sites, which can lead to problems in regional and especially global modeling. However, reducing IVOC emissions by one-half in the model to better match recent IVOC measurements improves SOA predictions at these long photochemical ages. Among the explicitly modeled VOCs, the precursor compounds that contribute the greatest SOA mass are methylbenzenes. Measured polycyclic aromatic hydrocarbons (naphthalenes) contribute 0.7% of the modeled SOA mass. The amounts of SOA mass from diesel vehicles, gasoline vehicles, and cooking emissions are estimated to be 16-27, 35-61, and 19-35%, respectively, depending on the parameterization used, which is consistent with the observed fossil fraction of urban SOA, 71(±3) %. The relative contribution of each source is uncertain by almost a factor of 2 depending on the parameterization used. In-basin biogenic VOCs are predicted to contribute only a few percent to SOA. A regional SOA background of approximately 2.1 μg m-3 is also present due to the long-distance transport of highly aged OA, likely with a substantial contribution from regional biogenic SOA. The percentage of SOA from diesel vehicle emissions is the same, within the estimated uncertainty, as reported in previous work that analyzed the weekly cycles in OA concentrations (Bahreini et al., 2012; Hayes et al., 2013). However, the modeling work presented here suggests a strong anthropogenic source of modern carbon in SOA, due to cooking emissions, which was not accounted for in those previous studies and which is higher on weekends. Lastly, this work adapts a simple two-parameter model to predict SOA concentration and O/C from urban emissions. This model successfully predicts SOA concentration, and the optimal parameter combination is very similar to that found for Mexico City. This approach provides a computationally inexpensive method for predicting urban SOA in global and climate models. We estimate pollution SOA to account for 26 Tg yr-1 of SOA globally, or 17% of global SOA, one-third of which is likely to be non-fossil.

Intermediate Volatility Organic Compound Emissions from On-Road Diesel Vehicles: Chemical Composition, Emission Factors, and Estimated Secondary Organic Aerosol Production.

PubMed

Zhao, Yunliang; Nguyen, Ngoc T; Presto, Albert A; Hennigan, Christopher J; May, Andrew A; Robinson, Allen L

2015-10-06

Emissions of intermediate-volatility organic compounds (IVOCs) from five on-road diesel vehicles and one off-road diesel engine were characterized during dynamometer testing. The testing evaluated the effects of driving cycles, fuel composition and exhaust aftertreatment devices. On average, more than 90% of the IVOC emissions were not identified on a molecular basis, instead appearing as an unresolved complex mixture (UCM) during gas-chromatography mass-spectrometry analysis. Fuel-based emissions factors (EFs) of total IVOCs (speciated + unspeciated) depend strongly on aftertreatment technology and driving cycle. Total-IVOC emissions from vehicles equipped with catalyzed diesel particulate filters (DPF) are substantially lower (factor of 7 to 28, depending on driving cycle) than from vehicles without any exhaust aftertreatment. Total-IVOC emissions from creep and idle operations are substantially higher than emissions from high-speed operations. Although the magnitude of the total-IVOC emissions can vary widely, there is little variation in the IVOC composition across the set of tests. The new emissions data are combined with published yield data to investigate secondary organic aerosol (SOA) formation. SOA production from unspeciated IVOCs is estimated using surrogate compounds, which are assigned based on gas-chromatograph retention time and mass spectral signature of the IVOC UCM. IVOCs contribute the vast majority of the SOA formed from exhaust from on-road diesel vehicles. The estimated SOA production is greater than predictions by previous studies and substantially higher than primary organic aerosol. Catalyzed DPFs substantially reduce SOA formation potential of diesel exhaust, except at low speed operations.

EFFECT OF ACIDITY ON SECONDARY ORGANIC AEROSOL FORMATION FROM ISOPRENE

EPA Science Inventory

The effect of particle-phase acidity on secondary organic aerosol (SOA) formation from isoprene is investigated in a laboratory chamber study, in which the acidity of the inorganic seed aerosol was controlled systematically. The observed enhancement in SOA mass concentration is c...

Formation of secondary organic aerosol in the Paris pollution plume and its impact on surrounding regions

NASA Astrophysics Data System (ADS)

Zhang, Q. J.; Beekmann, M.; Freney, E.; Sellegri, K.; Pichon, J. M.; Schwarzenboeck, A.; Colomb, A.; Bourrianne, T.; Michoud, V.; Borbon, A.

2015-12-01

Secondary pollutants such as ozone, secondary inorganic aerosol, and secondary organic aerosol formed in the plumes of megacities can affect regional air quality. In the framework of the FP7/EU MEGAPOLI (Megacities: Emissions, urban, regional and Global Atmospheric POLlution and climate effects, and Integrated tools for assessment and mitigation) project, an intensive campaign was launched in the greater Paris region in July 2009. The major objective was to quantify different sources of organic aerosol (OA) within a megacity and in its plume. In this study, we use airborne measurements aboard the French ATR-42 aircraft to evaluate the regional chemistry-transport model CHIMERE within and downwind of the Paris region. Two mechanisms of secondary OA (SOA) formation are used, both including SOA formation from oxidation and chemical aging of primary semivolatile and intermediate volatility organic compounds (SI-SOA) in the volatility basis set (VBS) framework. As for SOA formed from traditional VOC (volatile organic compound) precursors (traditional SOA), one applies chemical aging in the VBS framework adopting different SOA yields for high- and low-NOx environments, while another applies a single-step oxidation scheme without chemical aging. Two emission inventories are used for discussion of emission uncertainties. The slopes of the airborne OA levels versus Ox (i.e., O3 + NO2) show SOA formation normalized with respect to photochemical activity and are used for specific evaluation of the OA scheme in the model. The simulated slopes were overestimated slightly by factors of 1.1, 1.7 and 1.3 with respect to those observed for the three airborne measurements, when the most realistic "high-NOx" yields for traditional SOA formation in the VBS scheme are used in the model. In addition, these slopes are relatively stable from one day to another, which suggests that they are characteristic for the given megacity plume environment. The configuration with increased primary organic aerosol (POA) emissions and with a single-step oxidation scheme of traditional SOA also agrees with the OA / Ox slopes (about ± 50 % with respect to the observed ones); however, it underestimates the background. Both configurations are coherent with observed OA plume buildup, but they show very different SI-SOA and traditional anthropogenic SOA (ASOA) contributions. It is hence concluded that available theoretical knowledge and available data in this study are not sufficient to discern the relative contributions of different types of anthropogenic SOA in the Paris pollution plume, while its sum is correctly simulated. Based on these simulations, for specific plumes, the anthropogenic OA buildup can reach between 8 and 10μg m-3. For the average of the month of July 2009, maximum OA increases due to emissions from the Paris agglomeration are noticed close to the agglomeration at various length scales: several tens (for primary OA) to hundreds (for SI-SOA and ASOA) of kilometers from the Paris agglomeration. In addition, BSOA (SOA formed from biogenic VOC precursors) is an important contributor to regional OA levels (inside and outside the Paris plume).

Organic photolysis reactions in tropospheric aerosols: effect on secondary organic aerosol formation and lifetime

NASA Astrophysics Data System (ADS)

Hodzic, A.; Madronich, S.; Kasibhatla, P. S.; Tyndall, G.; Aumont, B.; Jimenez, J. L.; Lee-Taylor, J.; Orlando, J.

2015-08-01

This study presents the first modeling estimates of the potential effect of gas- and particle-phase organic photolysis reactions on the formation and lifetime of secondary organic aerosols (SOAs). Typically only photolysis of smaller organic molecules (e.g., formaldehyde) for which explicit data exist is included in chemistry-climate models. Here, we specifically examine the photolysis of larger molecules that actively partition between the gas and particle phases. The chemical mechanism generator GECKO-A is used to explicitly model SOA formation from α-pinene, toluene, and C12 and C16 n-alkane reactions with OH at low and high NOx. Simulations are conducted for typical mid-latitude conditions and a solar zenith angle of 45° (permanent daylight). The results show that after 4 days of chemical aging under those conditions (equivalent to 8 days in the summer mid-latitudes), gas-phase photolysis leads to a moderate decrease in SOA yields, i.e., ~15 % (low NOx) to ~45 % (high NOx) for α-pinene, ~15 % for toluene, ~25 % for C12 n-alkane, and ~10 % for C16 n-alkane. The small effect of gas-phase photolysis on low-volatility n-alkanes such as C16 n-alkane is due to the rapid partitioning of early-generation products to the particle phase, where they are protected from gas-phase photolysis. Minor changes are found in the volatility distribution of organic products and in oxygen to carbon ratios. The decrease in SOA mass is increasingly more important after a day of chemical processing, suggesting that most laboratory experiments are likely too short to quantify the effect of gas-phase photolysis on SOA yields. Our results also suggest that many molecules containing chromophores are preferentially partitioned into the particle phase before they can be photolyzed in the gas phase. Given the growing experimental evidence that these molecules can undergo in-particle photolysis, we performed sensitivity simulations using an empirically estimated SOA photolysis rate of JSOA = 4 × 10-4 JNO2. Modeling results indicate that this photolytic loss rate would decrease SOA mass by 40-60 % for most species after 10 days of equivalent atmospheric aging at mid-latitudes in the summer. It should be noted that in our simulations we do not consider in-particle or aqueous-phase reactions which could modify the chemical composition of the particle and thus the quantity of photolabile species. The atmospheric implications of our results are significant for both the SOA global distribution and lifetime. GEOS-Chem global model results suggest that particle-phase photolytic reactions could be an important loss process for SOA in the atmosphere, removing aerosols from the troposphere on timescales of less than 7 days that are comparable to wet deposition.

Organic photolysis reactions in tropospheric aerosols: effect on secondary organic aerosol formation and lifetime

NASA Astrophysics Data System (ADS)

Hodzic, A.; Madronich, S.; Kasibhatla, P. S.; Tyndall, G.; Aumont, B.; Jimenez, J. L.; Lee-Taylor, J.; Orlando, J.

2015-03-01

This study presents the first modeling estimates of the potential effect of gas- and particle-phase organic photolysis reactions on the formation and lifetime of secondary organic aerosols (SOA). Typically only photolysis of smaller organic molecules (e.g. formaldehyde) for which explicit data exist is included in chemistry-climate models. Here, we specifically examine the photolysis of larger molecules that actively partition between the gas and particle phases. The chemical mechanism generator GECKO-A is used to explicitly model SOA formation from α-pinene, toluene, and C12 and C16 n-alkane reactions with OH at low- and high-NOx. Simulations are conducted for typical mid-latitude conditions and a solar zenith angle of 45° (permanent daylight). The results show that after four days of chemical aging under those conditions (equivalent to eight days in the summer mid-latitudes), gas-phase photolysis leads to a moderate decrease in SOA yields i.e ~15% (low-NOx) to ~45% (high-NOx) for α-pinene, ~15% for toluene, ~25% for C12-alkane, and ~10% for C16-alkane. The small effect on low volatility n-alkanes such as C16-alkane is due to the rapid partitioning of early-generation products to the particle phase where they are assumed to be protected from gas-phase photolysis. Minor changes are found in the volatility distribution of organic products and in oxygen to carbon ratios. The decrease in SOA mass seems increasingly more important after a day of chemical processing, suggesting that most laboratory experiments are likely too short to quantify the effect of gas-phase photolysis on SOA yields. Our results also suggest that many molecules containing chromophores are preferentially partitioned into the particle phase before they can be photolyzed in the gas-phase. Given the growing experimental evidence that these molecules can undergo in-particle photolysis, we performed sensitivity simulations using an estimated SOA photolysis rate of JSOA=4 x 10-4JNO2. Modeling results indicate that this photolytic loss rate would decrease SOA mass by 40-60% for most species after ten days of equivalent atmospheric aging at mid-latitudes in the summer. It should be noted that in our simulations we do not consider in-particle or aqueous-phase reactions which could modify the chemical composition of the particle, and thus the amount of photolabile species. The atmospheric implications of our results are significant for both the SOA global distribution and lifetime. GEOS-Chem global model results suggest that particle-phase photolytic reactions could be an important loss process for SOA in the atmosphere, removing aerosols from the troposphere on timescales (less than 7 days) that are comparable to wet deposition.

Efficient Isoprene Secondary Organic Aerosol Formation from a Non-IEPOX Pathway

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Jiumeng; D’Ambro, Emma L.; Lee, Ben H.

2016-09-20

With a large global emission rate and high reactivity, isoprene has a profound effect upon atmospheric chemistry and composition. The atmospheric pathways by which isoprene converts to secondary organic aerosol (SOA) and how anthropogenic pollutants such as nitrogen oxides and sulfur affect this process are a subject of intense research because particles affect Earth’s climate and local air quality. In the absence of both nitrogen oxides and reactive aqueous seed particles, we measure SOA mass yields from isoprene photochemical oxidation of up to 15%, which are factors of 2, or more, higher than those typically used in coupled chemistry-climate models.more » SOA yield is initially constant with the addition of increasing amounts of nitric oxide (NO) but then sharply decreases for input concentrations above 10 ppbv. Online measurements of aerosol molecular composition show that the fate of second-generation RO2 radicals is key to understanding the efficient SOA formation and the NOx dependent yields described here and in the literature. These insights allow for improved quantitative estimates of SOA formation in the pre-industrial atmosphere and in biogenic-rich regions with limited anthropogenic impacts and suggest a more complex representation of NOx dependent SOA yields may be important in models.« less

Evaluation of New and Proposed Organic Aerosol Sources and Mechanisms using the Aerosol Modeling Testbed. MILAGRO, CARES, CalNex, BEACHON, and GVAX

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hodzic, Alma; Jimenez, Jose L.

2015-04-09

This work investigated the formation and evolution of organic aerosols (OA) arising from anthropogenic and biogenic sources in a framework that combined state-of-the-science process and regional modeling, and their evaluation against advanced and emerging field measurements. Although OA are the dominant constituents of submicron particles, our understanding of their atmospheric lifecycle is limited, and current models fail to describe the observed amounts and properties of chemically formed secondary organic aerosols (SOA), leaving large uncertainties on the effects of SOA on climate. Our work has provided novel modeling constraints on sources, formation, aging and removal of SOA by investigating in particularmore » (i) the contribution of trash burning emissions to OA levels in a megacity, (ii) the contribution of glyoxal to SOA formation in aqueous particles in California during CARES/CalNex and over the continental U.S., (iii) SOA formation and regional growth over a pine forest in Colorado and its sensitivity to anthropogenic NOx levels during BEACHON, and the sensitivity of SOA to (iv) the sunlight exposure during its atmospheric lifetime, and to (v) changes in solubility and removal of organic vapors in the urban plume (MILAGRO, Mexico City), and over the continental U.S.. We have also developed a parameterization of water solubility for condensable organic gases produced from major anthropogenic and biogenic precursors based on explicit chemical modeling, and made it available to the wider community. This work used for the first time constraints from the explicit model GECKO-A to improve SOA representation in 3D regional models such as WRF-Chem.« less

Diurnally resolved particulate and VOC measurements at a rural site: indication of significant biogenic secondary organic aerosol formation

NASA Astrophysics Data System (ADS)

Sjostedt, S. J.; Slowik, J. G.; Brook, J. R.; Chang, R. Y.-W.; Mihele, C.; Stroud, C. A.; Vlasenko, A.; Abbatt, J. P. D.

2010-11-01

We report simultaneous measurements of volatile organic compound (VOC) mixing ratios including C6 to C8 aromatics, isoprene, monoterpenes, acetone and organic aerosol mass loadings at a rural location in Southwestern Ontario, Canada by Proton-Transfer-Reaction Mass Spectrometry (PTR-MS) and Aerosol Mass Spectrometry (AMS), respectively. During the three-week-long Border Air Quality and Meteorology Study in June-July 2007, air was sampled from a range of sources, including aged air from the polluted US Midwest, direct outflow from Detroit 50 km away, and clean air with higher biogenic input. After normalization to the diurnal profile of CO, a long-lived tracer, diurnal analyses show clear photochemical loss of reactive aromatics and production of oxygenated VOCs and secondary organic aerosol (SOA) during the daytime. Biogenic VOC mixing ratios increase during the daytime in accord with their light- and temperature-dependent sources. Long-lived species, such as hydrocarbon-like organic aerosol and benzene show little to no photochemical reactivity on this timescale. From the normalized diurnal profiles of VOCs, an estimate of OH concentrations during the daytime, measured O3 concentrations, and laboratory SOA yields, we calculate integrated organic aerosol production amounts associated with each measured SOA precursor. Depending on whether the SOA formation is occurring in a low- or high-NOx regime, we estimate that the biogenic gases contribute between 10 to 36 times as much SOA as do the aromatic precursors, making this a highly biogenically dominated region for SOA formation. The conclusion that biogenic SOA formation is of significance to air quality in this region is supported by detailed air quality modeling during this period (Stroud et al., 2010).

Organic photolysis reactions in tropospheric aerosols: effect on secondary organic aerosol formation and lifetime

DOE PAGES

Hodzic, A.; Madronich, S.; Kasibhatla, P. S.; ...

2015-08-20

This paper presents the first modeling estimates of the potential effect of gas- and particle-phase organic photolysis reactions on the formation and lifetime of secondary organic aerosols (SOAs). Typically only photolysis of smaller organic molecules (e.g., formaldehyde) for which explicit data exist is included in chemistry–climate models. Here, we specifically examine the photolysis of larger molecules that actively partition between the gas and particle phases. The chemical mechanism generator GECKO-A is used to explicitly model SOA formation from α-pinene, toluene, and C 12 and C 16 n-alkane reactions with OH at low and high NO x. Simulations are conducted formore » typical mid-latitude conditions and a solar zenith angle of 45° (permanent daylight). The results show that after 4 days of chemical aging under those conditions (equivalent to 8 days in the summer mid-latitudes), gas-phase photolysis leads to a moderate decrease in SOA yields, i.e., ~15 % (low NO x) to ~45 % (high NO x) for α-pinene, ~15 % for toluene, ~25 % for C 12 n-alkane, and ~10 % for C 16 n-alkane. The small effect of gas-phase photolysis on low-volatility n-alkanes such as C 16 n-alkane is due to the rapid partitioning of early-generation products to the particle phase, where they are protected from gas-phase photolysis. Minor changes are found in the volatility distribution of organic products and in oxygen to carbon ratios. The decrease in SOA mass is increasingly more important after a day of chemical processing, suggesting that most laboratory experiments are likely too short to quantify the effect of gas-phase photolysis on SOA yields. Our results also suggest that many molecules containing chromophores are preferentially partitioned into the particle phase before they can be photolyzed in the gas phase. Given the growing experimental evidence that these molecules can undergo in-particle photolysis, we performed sensitivity simulations using an empirically estimated SOA photolysis rate of J SOA = 4 × 10 −4 J NO2. Modeling results indicate that this photolytic loss rate would decrease SOA mass by 40–60 % for most species after 10 days of equivalent atmospheric aging at mid-latitudes in the summer. It should be noted that in our simulations we do not consider in-particle or aqueous-phase reactions which could modify the chemical composition of the particle and thus the quantity of photolabile species. The atmospheric implications of our results are significant for both the SOA global distribution and lifetime. GEOS-Chem global model results suggest that particle-phase photolytic reactions could be an important loss process for SOA in the atmosphere, removing aerosols from the troposphere on timescales of less than 7 days that are comparable to wet deposition.« less

Airborne observations of IEPOX-derived isoprene SOA in the Amazon during SAMBBA

NASA Astrophysics Data System (ADS)

Allan, J. D.; Morgan, W. T.; Darbyshire, E.; Flynn, M. J.; Williams, P. I.; Oram, D. E.; Artaxo, P.; Brito, J.; Lee, J. D.; Coe, H.

2014-10-01

Isoprene is a potentially highly significant but currently poorly quantified source of secondary organic aerosols (SOA). This is especially important in the tropics, where large rainforests act as significant sources of isoprene. Methylfuran, produced through thermal decomposition during analysis, has recently been suggested as a marker for isoprene SOA formation through the isoprene epoxydiol (IEPOX) route, which mostly occurs under low NOx conditions. This is manifested as a peak at m/z=82 in Aerodyne Aerosol Mass Spectrometer (AMS) data. Here we present a study of this marker measured during five flights over the Amazon rainforest on board the UK Facility for Airborne Atmospheric Measurement (FAAM) BAe-146 research aircraft during the South American Biomass Burning Analysis (SAMBBA) campaign. Cases where this marker is and is not present are contrasted and linked to the presence of acidic seed particles, lower NOx concentrations and higher humidities. There are also data to suggest a role of organic nitrogen in the particulate composition. Furthermore, an inspection of the vertical trends of the marker indicates that concentrations are highest at the top of the boundary layer (possibly due to semivolatile repartitioning) and that upwards through the free troposphere, the mass spectral profile evolves towards that of low volatility oxygenated aerosol. These observations offer insights into the behaviour of IEPOX-derived SOA formation above the Amazon rainforest and the suitability of methylfuran as a marker for this process.

Direct Measurements of Gas/Particle Partitioning and Mass Accommodation Coefficients in Environmental Chambers.

PubMed

Krechmer, Jordan E; Day, Douglas A; Ziemann, Paul J; Jimenez, Jose L

2017-10-17

Secondary organic aerosols (SOA) are a major contributor to fine particulate mass and wield substantial influences on the Earth's climate and human health. Despite extensive research in recent years, many of the fundamental processes of SOA formation and evolution remain poorly understood. Most atmospheric aerosol models use gas/particle equilibrium partitioning theory as a default treatment of gas-aerosol transfer, despite questions about potentially large kinetic effects. We have conducted fundamental SOA formation experiments in a Teflon environmental chamber using a novel method. A simple chemical system produces a very fast burst of low-volatility gas-phase products, which are competitively taken up by liquid organic seed particles and Teflon chamber walls. Clear changes in the species time evolution with differing amounts of seed allow us to quantify the particle uptake processes. We reproduce gas- and aerosol-phase observations using a kinetic box model, from which we quantify the aerosol mass accommodation coefficient (α) as 0.7 on average, with values near unity especially for low volatility species. α appears to decrease as volatility increases. α has historically been a very difficult parameter to measure with reported values varying over 3 orders of magnitude. We use the experimentally constrained model to evaluate the correction factor (Φ) needed for chamber SOA mass yields due to losses of vapors to walls as a function of species volatility and particle condensational sink. Φ ranges from 1-4.

Chemical characterization of organosulfates from the hydroxyl radical-initiated oxidation and ozonolysis of cis-3-hexen-1-ol

NASA Astrophysics Data System (ADS)

Barbosa, Thais S.; Riva, Matthieu; Chen, Yuzhi; da Silva, Cleyton M.; Ameida, Jose Claudino S.; Zhang, Zhenfa; Gold, Avram; Arbilla, Graciela; Bauerfeldt, Glauco F.; Surratt, Jason D.

2017-08-01

Cis-3-hexen-1-ol (cis-HXO) is a green leaf volatile emitted from plants under stress and belongs to an important class of biogenic volatile organic compounds. In this study, we have investigated the potential formation of organosulfates (OSs) from the hydroxyl radical (OH)-initiated oxidation and ozonolysis of cis-HXO using either non-acidified or acidified sulfate seed aerosols under different relative humidity (RH) conditions. For selected ozonolysis experiments, an OH scavenger was utilized. Ultra performance liquid chromatography interfaced to high-resolution quadrupole time-of-flight mass spectrometry with electrospray ionization (UPLC/ESI-HR-Q-TOFMS) was used to characterize cis-HXO-derived secondary organic aerosol (SOA) formation. Chemical characterization of cis-HXO-derived SOA products reveals that OSs were generated in significant quantity from multiphase chemistry of gas-phase oxidation products of cis-HXO. Ambient fine aerosol (PM2.5) samples collected from Rio de Janeiro, Brazil, were also analyzed. Seven cis-HXO-derived OSs identified in the lab study with molecular weights 154, 186, 170, 210, 212, 226 and 270 were also found in the PM2.5 samples collected in Brazil. This study provides direct evidence that the oxidation of cis-HXO by OH and O3 yields biogenic SOA through the formation of polar OSs.

Chemical and cellular oxidant production induced by naphthalene secondary organic aerosol (SOA): effect of redox-active metals and photochemical aging.

PubMed

Tuet, Wing Y; Chen, Yunle; Fok, Shierly; Gao, Dong; Weber, Rodney J; Champion, Julie A; Ng, Nga L

2017-11-09

Exposure to air pollution is a leading global health risk. Secondary organic aerosol (SOA) constitute a large portion of ambient particulate matter (PM). In this study, the water-soluble oxidative potential (OP) determined by dithiothreitol (DTT) consumption and intracellular reactive oxygen and nitrogen species (ROS/RNS) production was measured for SOA generated from the photooxidation of naphthalene in the presence of iron sulfate and ammonium sulfate seed particles. The measured intrinsic OP varied for aerosol formed using different initial naphthalene concentrations, however, no trends were observed between OP and bulk aerosol composition or seed type. For all experiments, aerosol generated in the presence of iron-containing seed induced higher ROS/RNS production compared to that formed in the presence of inorganic seed. This effect was primarily attributed to differences in aerosol carbon oxidation state [Formula: see text]. In the presence of iron, radical concentrations are elevated via iron redox cycling, resulting in more oxidized species. An exponential trend was also observed between ROS/RNS and [Formula: see text] for all naphthalene SOA, regardless of seed type or aerosol formation condition. This may have important implications as aerosol have an atmospheric lifetime of a week, over which [Formula: see text] increases due to continued photochemical aging, potentially resulting in more toxic aerosol.

Limited effect of anthropogenic nitrogen oxides on Secondary Organic Aerosol formation

NASA Astrophysics Data System (ADS)

Zheng, Y.; Unger, N.; Hodzic, A.; Emmons, L.; Knote, C.; Tilmes, S.; Lamarque, J.-F.; Yu, P.

2015-08-01

Globally, secondary organic aerosol (SOA) is mostly formed from emissions of biogenic volatile organic compounds (VOCs) by vegetation, but can be modified by human activities as demonstrated in recent research. Specifically, nitrogen oxides (NOx = NO + NO2) have been shown to play a critical role in the chemical formation of low volatility compounds. We have updated the SOA scheme in the global NCAR Community Atmospheric Model version 4 with chemistry (CAM4-chem) by implementing a 4-product Volatility Basis Set (VBS) scheme, including NOx-dependent SOA yields and aging parameterizations. The predicted organic aerosol amounts capture both the magnitude and distribution of US surface annual mean measurements from the Interagency Monitoring of Protected Visual Environments (IMPROVE) network by 50 %, and the simulated vertical profiles are within a factor of two compared to Aerosol Mass Spectrometer (AMS) measurements from 13 aircraft-based field campaigns across different region and seasons. We then perform sensitivity experiments to examine how the SOA loading responds to a 50 % reduction in anthropogenic nitric oxide (NO) emissions in different regions. We find limited SOA reductions of 0.9 to 5.6, 6.4 to 12.0 and 0.9 to 2.8 % for global, the southeast US and the Amazon NOx perturbations, respectively. The fact that SOA formation is almost unaffected by changes in NOx can be largely attributed to buffering in chemical pathways (low- and high-NOx pathways, O3 versus NO3-initiated oxidation) and to offsetting tendencies in the biogenic versus anthropogenic SOA responses.

Primary particulate emissions and secondary organic aerosol (SOA) formation from idling diesel vehicle exhaust in China.

PubMed

Deng, Wei; Hu, Qihou; Liu, Tengyu; Wang, Xinming; Zhang, Yanli; Song, Wei; Sun, Yele; Bi, Xinhui; Yu, Jianzhen; Yang, Weiqiang; Huang, Xinyu; Zhang, Zhou; Huang, Zhonghui; He, Quanfu; Mellouki, Abdelwahid; George, Christian

2017-09-01

In China diesel vehicles dominate the primary emission of particulate matters from on-road vehicles, and they might also contribute substantially to the formation of secondary organic aerosols (SOA). In this study tailpipe exhaust of three typical in-use diesel vehicles under warm idling conditions was introduced directly into an indoor smog chamber with a 30m 3 Teflon reactor to characterize primary emissions and SOA formation during photo-oxidation. The emission factors of primary organic aerosol (POA) and black carbon (BC) for the three types of Chinese diesel vehicles ranged 0.18-0.91 and 0.15-0.51gkg-fuel -1 , respectively; and the SOA production factors ranged 0.50-1.8gkg-fuel -1 and SOA/POA ratios ranged 0.7-3.7 with an average of 2.2. The fuel-based POA emission factors and SOA production factors from this study for idling diesel vehicle exhaust were 1-3 orders of magnitude higher than those reported in previous studies for idling gasoline vehicle exhaust. The emission factors for total particle numbers were 0.65-4.0×10 15 particleskg-fuel -1 , and particles with diameters less than 50nm dominated in total particle numbers. Traditional C 2 -C 12 precursor non-methane hydrocarbons (NMHCs) could only explain less than 3% of the SOA formed during aging and contribution from other precursors including intermediate volatile organic compounds (IVOC) needs further investigation. Copyright © 2017 Elsevier B.V. All rights reserved.

Oxidation flow reactors (OFRs): overview of recent field and modeling studies

NASA Astrophysics Data System (ADS)

Jimenez, Jose-Luis; Palm, Brett B.; Peng, Zhe; Hu, Weiwei; Ortega, Amber M.; Li, Rui; Campuzano-Jost, Pedro; Day, Douglas A.; Stark, Harald; Brune, William H.; de Gouw, Joost; Schroder, Jason

2016-04-01

Oxidation flow reactors (OFRs) are popular tools for studying SOA formation and aging in both laboratory and field experiments. In an OFR, the concentration of an oxidant (OH, O3, or NO3) can be increased, leading to hours-months of equivalent atmospheric oxidation during the several-minute OFR residence time. Using gas- and particle-phase measurements from several recent field campaigns, we demonstrate SOA formation after oxidation of ambient air in an OFR. Typically, more SOA formation is observed from nighttime air than daytime air. This indicates that the concentration of SOA-forming gases in ambient air is relatively higher at night. Measured ambient VOCs are not able to explain the magnitude of SOA formation in the OFR, suggesting that typically unmeasured S/IVOCs (possibly VOC oxidation products or direct emissions) play a substantial intermediary role in ambient SOA formation. We also present highlights from recent OFR oxidant chemistry modeling studies. HOx, Ox, and photolysis chemistry was modeled for two common OH production methods (utilizing 185+254 nm UV light, or 254 nm only). OH exposure (OHexp) can be estimated within a factor of ~2 using model-derived equations, and can be verified in situ using VOC decay measurements. OHexp is strongly dependent on external OH reactivity, which may cause significant OH suppression in some circumstances (e.g., lab/source studies with high precursor concentrations). UV light photolysis and reaction with oxygen atoms are typically not major reaction pathways. Modeling the fate of condensable low-volatility organic gases (LVOCs) formed in an OFR suggests that LVOC fate is dependent on particle condensational sink. E.g., for the range of particle condensational sink at a remote pine forest, anywhere from 20-80% of produced LVOCs were predicted to condense onto aerosols for an OHexp of ~1 day, with the remainder lost to OFR or sampling line walls. Similar to large chamber wall loss corrections, a correction is needed to relate OFR sampling to the atmosphere, where condensation onto aerosols is the dominant LVOC fate. At high OHexp (>20 days) in an OFR, LVOCs are predicted to be oxidized many times before they can condense onto particles, leading to formation of volatile fragmentation products that can no longer condense to form SOA. Changes to preexisting OA at high OHexp should be predominantly a result of heterogeneous oxidation. SOA yields specific to OFR oxidation were investigated using standard addition of individual VOCs into ambient air in an OFR. SOA yields in the OFR were consistent with laboratory large chamber yields.

Mapping gas-phase organic reactivity and concomitant secondary organic aerosol formation: chemometric dimension reduction techniques for the deconvolution of complex atmospheric data sets

NASA Astrophysics Data System (ADS)

Wyche, K. P.; Monks, P. S.; Smallbone, K. L.; Hamilton, J. F.; Alfarra, M. R.; Rickard, A. R.; McFiggans, G. B.; Jenkin, M. E.; Bloss, W. J.; Ryan, A. C.; Hewitt, C. N.; MacKenzie, A. R.

2015-07-01

Highly non-linear dynamical systems, such as those found in atmospheric chemistry, necessitate hierarchical approaches to both experiment and modelling in order to ultimately identify and achieve fundamental process-understanding in the full open system. Atmospheric simulation chambers comprise an intermediate in complexity, between a classical laboratory experiment and the full, ambient system. As such, they can generate large volumes of difficult-to-interpret data. Here we describe and implement a chemometric dimension reduction methodology for the deconvolution and interpretation of complex gas- and particle-phase composition spectra. The methodology comprises principal component analysis (PCA), hierarchical cluster analysis (HCA) and positive least-squares discriminant analysis (PLS-DA). These methods are, for the first time, applied to simultaneous gas- and particle-phase composition data obtained from a comprehensive series of environmental simulation chamber experiments focused on biogenic volatile organic compound (BVOC) photooxidation and associated secondary organic aerosol (SOA) formation. We primarily investigated the biogenic SOA precursors isoprene, α-pinene, limonene, myrcene, linalool and β-caryophyllene. The chemometric analysis is used to classify the oxidation systems and resultant SOA according to the controlling chemistry and the products formed. Results show that "model" biogenic oxidative systems can be successfully separated and classified according to their oxidation products. Furthermore, a holistic view of results obtained across both the gas- and particle-phases shows the different SOA formation chemistry, initiating in the gas-phase, proceeding to govern the differences between the various BVOC SOA compositions. The results obtained are used to describe the particle composition in the context of the oxidised gas-phase matrix. An extension of the technique, which incorporates into the statistical models data from anthropogenic (i.e. toluene) oxidation and "more realistic" plant mesocosm systems, demonstrates that such an ensemble of chemometric mapping has the potential to be used for the classification of more complex spectra of unknown origin. More specifically, the addition of mesocosm data from fig and birch tree experiments shows that isoprene and monoterpene emitting sources, respectively, can be mapped onto the statistical model structure and their positional vectors can provide insight into their biological sources and controlling oxidative chemistry. The potential to extend the methodology to the analysis of ambient air is discussed using results obtained from a zero-dimensional box model incorporating mechanistic data obtained from the Master Chemical Mechanism (MCMv3.2). Such an extension to analysing ambient air would prove a powerful asset in assisting with the identification of SOA sources and the elucidation of the underlying chemical mechanisms involved.

Secondary organic aerosol formation exceeds primary particulate matter emissions for light-duty gasoline vehicles

NASA Astrophysics Data System (ADS)

Gordon, T. D.; Presto, A. A.; May, A. A.; Nguyen, N. T.; Lipsky, E. M.; Donahue, N. M.; Gutierrez, A.; Zhang, M.; Maddox, C.; Rieger, P.; Chattopadhyay, S.; Maldonado, H.; Maricq, M. M.; Robinson, A. L.

2014-05-01

The effects of photochemical aging on emissions from 15 light-duty gasoline vehicles were investigated using a smog chamber to probe the critical link between the tailpipe and ambient atmosphere. The vehicles were recruited from the California in-use fleet; they represent a wide range of model years (1987 to 2011), vehicle types and emission control technologies. Each vehicle was tested on a chassis dynamometer using the unified cycle. Dilute emissions were sampled into a portable smog chamber and then photochemically aged under urban-like conditions. For every vehicle, substantial secondary organic aerosol (SOA) formation occurred during cold-start tests, with the emissions from some vehicles generating as much as 6 times the amount of SOA as primary particulate matter (PM) after 3 h of oxidation inside the chamber at typical atmospheric oxidant levels (and 5 times the amount of SOA as primary PM after 5 × 106 molecules cm-3 h of OH exposure). Therefore, the contribution of light-duty gasoline vehicle exhaust to ambient PM levels is likely dominated by secondary PM production (SOA and nitrate). Emissions from hot-start tests formed about a factor of 3-7 less SOA than cold-start tests. Therefore, catalyst warm-up appears to be an important factor in controlling SOA precursor emissions. The mass of SOA generated by photooxidizing exhaust from newer (LEV2) vehicles was a factor of 3 lower than that formed from exhaust emitted by older (pre-LEV) vehicles, despite much larger reductions (a factor of 11-15) in nonmethane organic gas emissions. These data suggest that a complex and nonlinear relationship exists between organic gas emissions and SOA formation, which is not surprising since SOA precursors are only one component of the exhaust. Except for the oldest (pre-LEV) vehicles, the SOA production could not be fully explained by the measured oxidation of speciated (traditional) SOA precursors. Over the timescale of these experiments, the mixture of organic vapors emitted by newer vehicles appears to be more efficient (higher yielding) in producing SOA than the emissions from older vehicles. About 30% of the nonmethane organic gas emissions from the newer (LEV1 and LEV2) vehicles could not be speciated, and the majority of the SOA formed from these vehicles appears to be associated with these unspeciated organics. By comparing this study with a companion study of diesel trucks, we conclude that both primary PM emissions and SOA production for light-duty gasoline vehicles are much greater than for late-model (2007 and later) on-road heavy-duty diesel trucks.

Global distribution of secondary organic aerosol particle phase state

NASA Astrophysics Data System (ADS)

Shiraiwa, M.; Li, Y., Sr.; Tsimpidi, A.; Karydis, V.; Berkemeier, T.; Pandis, S. N.; Lelieveld, J.; Koop, T.; Poeschl, U.

2016-12-01

Secondary organic aerosols (SOA) account for a large fraction of submicron particles in the atmosphere and play a key role in aerosol effects on climate, air quality and public health. The formation and aging of SOA proceed through multiple steps of chemical reaction and mass transport in the gas and particle phases, which is challenging for the interpretation of field measurements and laboratory experiments as well as accurate representation of SOA evolution in atmospheric aerosol models. SOA particles can adopt liquid, semi-solid and amorphous solid (glassy) phase states depending on chemical composition, relative humidity and temperature. The particle phase state is crucial for various atmospheric gas-particle interactions, including SOA formation, heterogeneous and multiphase reactions and ice nucleation. We found that organic compounds with a wide variety of functional groups fall into molecular corridors, characterized by a tight inverse correlation between molar mass and volatility. Based on the concept of molecular corridors, we develop a method to estimate glass transition temperatures based on the molar mass and molecular O:C ratio of SOA components, which is a key property for determination of particle phase state. We use the global chemistry climate model EMAC with the organic aerosol module ORACLE to predict the atmospheric SOA phase state. For the planetary boundary layer, global simulations indicate that SOA is mostly liquid in tropical and polar air with high relative humidity, semi-solid in the mid-latitudes, and solid over dry lands. We find that in the middle and upper troposphere (>500 hPa) SOA should be mostly in a glassy solid phase state. Thus, slow diffusion of water, oxidants, and organic molecules could kinetically limit gas-particle interactions of SOA in the free and upper troposphere, promote ice nucleation and facilitate long-range transport of reactive and toxic organic pollutants embedded within SOA.

ORGANIC AEROSOL FORMATION IN THE HUMID, PHOTOCHEMICALLY-ACTIVE SOUTHEASTERN US: SOAS EXPERIMENTS AND SIMULATIONS

EPA Science Inventory

A better understanding of SOA formation, properties and behavior in the humid eastern U.S. including dependence on anthropogenic emissions (RFA Q #1, 2). More accurate air quality prediction enabling more accurate air quality management (EPA Goal #1). Scientific insights co...

How will SOA change in the future?: SOA IN THE FUTURE

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lin, Guangxing; Penner, Joyce E.; Zhou, Cheng

2016-02-17

Secondary organic aerosol (SOA) plays a significant role in the Earth system by altering its radiative balance. Here we use an Earth system model coupled with an explicit SOA formation module to estimate the response of SOA concentrations to changes in climate, anthropogenic emissions, and human land use in the future. We find that climate change is the major driver for SOA change under the representative concentration pathways for the 8.5 future scenario. Climate change increases isoprene emission rate by 18% with the effect of temperature increases outweighing that of the CO2 inhibition effect. Annual mean global SOA mass ismore » increased by 25% as a result of climate change. However, anthropogenic emissions and land use change decrease SOA. The net effect is that future global SOA burden in 2100 is nearly the same as that of the present day. The SOA concentrations over the Northern Hemisphere are predicted to decline in the future due to the control of sulfur emissions.« less

Products and Mechanism of Aerosol Formation from the Reaction of β-Pinene with NO3 Radicals: Role of Oligomer Formation

NASA Astrophysics Data System (ADS)

Claflin, M. S.; Ziemann, P. J.

2017-12-01

Large amounts of organic nitrates have been reported in aerosol analyzed during field studies conducted around the world. Although organic nitrates can be formed in daytime from the oxidation of volatile organic compounds in the presence of NOx, it has recently been proposed that the nighttime reaction of monoterpenes with NO3 radicals may account for a substantial fraction of these compounds. While past studies have made progress quantifying the aerosol forming potential of these reactions, relatively little is known about the gas-phase oxidation mechanism, the identities of stable products, and their fate after they partition into aerosol. In an effort to better understand these reactions, we conducted environmental chamber experiments in which β-pinene was reacted with NO3 radicals and the secondary organic aerosol (SOA) that formed was analyzed online using a thermal desorption particle beam mass spectrometer and offline using a variety of methods. SOA was collected on filters, extracted, and analyzed using derivatization-spectrophotometric methods to quantify carbonyl, hydroxyl, carboxyl, nitrate, peroxide, and ester functional groups; and molecular products were identified and quantified by coupling high performance liquid chromatography with UV-Vis detection and mass spectrometry with electrospray ionization, electron ionization, and chemical ionization. We identified and quantified >98% of the products in the SOA and found that 95% were oligomers formed through hemiacetal and acetal reactions. This information was used to determine the yields of monomer building blocks, which in turn were combined with modeling to estimate branching ratios in the gas-phase oxidation reaction and timescales of oligomer formation within the aerosol. The results of this study highlight several key processes in the formation of SOA from reactions of monoterpenes with NO3 radicals: (1) alkoxy radical chemistry, including the role of ring opening through decomposition (2) particle-phase reactions and (3) formation of separate organic and aqueous phases within aerosol.

Identifying precursors and aqueous organic aerosol formation pathways during the SOAS campaign

NASA Astrophysics Data System (ADS)

Sareen, Neha; Carlton, Annmarie G.; Surratt, Jason D.; Gold, Avram; Lee, Ben; Lopez-Hilfiker, Felipe D.; Mohr, Claudia; Thornton, Joel A.; Zhang, Zhenfa; Lim, Yong B.; Turpin, Barbara J.

2016-11-01

Aqueous multiphase chemistry in the atmosphere can lead to rapid transformation of organic compounds, forming highly oxidized, low-volatility organic aerosol and, in some cases, light-absorbing (brown) carbon. Because liquid water is globally abundant, this chemistry could substantially impact climate, air quality, and health. Gas-phase precursors released from biogenic and anthropogenic sources are oxidized and fragmented, forming water-soluble gases that can undergo reactions in the aqueous phase (in clouds, fogs, and wet aerosols), leading to the formation of secondary organic aerosol (SOAAQ). Recent studies have highlighted the role of certain precursors like glyoxal, methylglyoxal, glycolaldehyde, acetic acid, acetone, and epoxides in the formation of SOAAQ. The goal of this work is to identify additional precursors and products that may be atmospherically important. In this study, ambient mixtures of water-soluble gases were scrubbed from the atmosphere into water at Brent, Alabama, during the 2013 Southern Oxidant and Aerosol Study (SOAS). Hydroxyl (OH⚫) radical oxidation experiments were conducted with the aqueous mixtures collected from SOAS to better understand the formation of SOA through gas-phase followed by aqueous-phase chemistry. Total aqueous-phase organic carbon concentrations for these mixtures ranged from 92 to 179 µM-C, relevant for cloud and fog waters. Aqueous OH-reactive compounds were primarily observed as odd ions in the positive ion mode by electrospray ionization mass spectrometry (ESI-MS). Ultra high-resolution Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) spectra and tandem MS (MS-MS) fragmentation of these ions were consistent with the presence of carbonyls and tetrols. Products were observed in the negative ion mode and included pyruvate and oxalate, which were confirmed by ion chromatography. Pyruvate and oxalate have been found in the particle phase in many locations (as salts and complexes). Thus, formation of pyruvate/oxalate suggests the potential for aqueous processing of these ambient mixtures to form SOAAQ.

Modeling organic aerosols in a megacity: potential contribution of semi-volatile and intermediate volatility primary organic compounds to secondary organic aerosol formation

NASA Astrophysics Data System (ADS)

Hodzic, A.; Jimenez, J. L.; Madronich, S.; Canagaratna, M. R.; Decarlo, P. F.; Kleinman, L.; Fast, J.

2010-06-01

It has been established that observed local and regional levels of secondary organic aerosols (SOA) in polluted areas cannot be explained by the oxidation and partitioning of anthropogenic and biogenic VOC precursors, at least using current mechanisms and parameterizations. In this study, the 3-D regional air quality model CHIMERE is applied to estimate the potential contribution to SOA formation of recently identified semi-volatile and intermediate volatility organic precursors (S/IVOC) in and around Mexico City for the MILAGRO field experiment during March 2006. The model has been updated to include explicitly the volatility distribution of primary organic aerosols (POA), their gas-particle partitioning and the gas-phase oxidation of the vapors. Two recently proposed parameterizations, those of Robinson et al. (2007) ("ROB") and Grieshop et al. (2009) ("GRI") are compared and evaluated against surface and aircraft measurements. The 3-D model results are assessed by comparing with the concentrations of OA components from Positive Matrix Factorization of Aerosol Mass Spectrometer (AMS) data, and for the first time also with oxygen-to-carbon ratios derived from high-resolution AMS measurements. The results show a substantial enhancement in predicted SOA concentrations (2-4 times) with respect to the previously published base case without S/IVOCs (Hodzic et al., 2009), both within and downwind of the city leading to much reduced discrepancies with the total OA measurements. Model improvements in OA predictions are associated with the better-captured SOA magnitude and diurnal variability. The predicted production from anthropogenic and biomass burning S/IVOC represents 40-60% of the total measured SOA at the surface during the day and is somewhat larger than that from commonly measured aromatic VOCs, especially at the T1 site at the edge of the city. The SOA production from the continued multi-generation S/IVOC oxidation products continues actively downwind. Similar to aircraft observations, the predicted OA/ΔCO ratio for the ROB case increases from 20-30 μg sm-3 ppm-1 up to 60-70 μg sm-3 ppm-1 between a fresh and 1-day aged air mass, while the GRI case produces a 30% higher OA growth than observed. The predicted average O/C ratio of total OA for the ROB case is 0.16 at T0, substantially below observed value of 0.5. A much better agreement for O/C ratios and temporal variability (R2=0.63) is achieved with the updated GRI treatment. Both treatments show a deficiency in regard to POA ageing with a tendency to over-evaporate POA upon dilution of the urban plume suggesting that atmospheric HOA may be less volatile than assumed in these parameterizations. This study highlights the important potential role of S/IVOC chemistry in the SOA budget in this region, and highlights the need for further improvements in available parameterizations. The agreement observed in this study is not sufficient evidence to conclude that S/IVOC are the major missing SOA source in megacity environments. The model is still very underconstrained, and other possible pathways such as formation from very volatile species like glyoxal may explain some of the mass and especially increase the O/C ratio.

High-NOx Photooxidation of n-Dodecane: Temperature Dependence of SOA Formation.

PubMed

Lamkaddam, Houssni; Gratien, Aline; Pangui, Edouard; Cazaunau, Mathieu; Picquet-Varrault, Bénédicte; Doussin, Jean-François

2017-01-03

The temperature and concentration dependence of secondary organic aerosol (SOA) yields has been investigated for the first time for the photooxidation of n-dodecane (C 12 H 26 ) in the presence of NO x in the CESAM chamber (French acronym for "Chamber for Atmospheric Multiphase Experimental Simulation"). Experiments were performed with and without seed aerosol between 283 and 304.5 K. In order to quantify the SOA yields, a new parametrization is proposed to account for organic vapor loss to the chamber walls. Deposition processes were found to impact the aerosol yields by a factor from 1.3 to 1.8 between the lowest and the highest value. As with other photooxidation systems, experiments performed without seed and at low concentration of oxidant showed a lower SOA yield than other seeded experiments. Temperature did not significantly influence SOA formation in this study. This unforeseen behavior indicates that the SOA is dominated by sufficiently low volatility products for which a change in their partitioning due to temperature would not significantly affect the condensed quantities.

An SOA model for toluene oxidation in the presence of inorganic aerosols.

PubMed

Cao, Gang; Jang, Myoseon

2010-01-15

A predictive model for secondary organic aerosol (SOA) formation including both partitioning and heterogeneous reactions is explored for the SOA produced from the oxidation of toluene in the presence of inorganic seed aerosols. The predictive SOA model comprises the explicit gas-phase chemistry of toluene, gas-particle partitioning, and heterogeneous chemistry. The resulting products from the explicit gas phase chemistry are lumped into several classes of chemical species based on their vapor pressure and reactivity for heterogeneous reactions. Both the gas-particle partitioning coefficient and the heterogeneous reaction rate constant of each lumped gas-phase product are theoretically determined using group contribution and molecular structure-reactivity. In the SOA model, the predictive SOA mass is decoupled into partitioning (OM(P)) and heterogeneous aerosol production (OM(H)). OM(P) is estimated from the SOA partitioning model developed by Schell et al. (J. Geophys. Res. 2001, 106, 28275-28293 ) that has been used in a regional air quality model (CMAQ 4.7). OM(H) is predicted from the heterogeneous SOA model developed by Jang et al. (Environ. Sci. Technol. 2006, 40, 3013-3022 ). The SOA model is evaluated using a number of the experimental SOA data that are generated in a 2 m(3) indoor Teflon film chamber under various experimental conditions (e.g., humidity, inorganic seed compositions, NO(x) concentrations). The SOA model reasonably predicts not only the gas-phase chemistry, such as the ozone formation, the conversion of NO to NO(2), and the toluene decay, but also the SOA production. The model predicted that the OM(H) fraction of the total toluene SOA mass increases as NO(x) concentrations decrease: 0.73-0.83 at low NO(x) levels and 0.17-0.47 at middle and high NO(x) levels for SOA experiments with high initial toluene concentrations. Our study also finds a significant increase in the OM(H) mass fraction in the SOA generated with low initial toluene concentrations, compared to those with high initial toluene concentrations. On average, more than a 1-fold increase in OM(H) fraction is observed when the comparison is made between SOA experiments with 40 ppb toluene to those with 630 ppb toluene. Such an observation implies that heterogeneous reactions of the second-generation products of toluene oxidation can contribute considerably to the total SOA mass under atmospheric relevant conditions.

Heterogeneous ice nucleation of viscous secondary organic aerosol produced from ozonolysis of α-pinene

NASA Astrophysics Data System (ADS)

Ignatius, Karoliina; Kristensen, Thomas B.; Järvinen, Emma; Nichman, Leonid; Fuchs, Claudia; Gordon, Hamish; Herenz, Paul; Hoyle, Christopher R.; Duplissy, Jonathan; Garimella, Sarvesh; Dias, Antonio; Frege, Carla; Höppel, Niko; Tröstl, Jasmin; Wagner, Robert; Yan, Chao; Amorim, Antonio; Baltensperger, Urs; Curtius, Joachim; Donahue, Neil M.; Gallagher, Martin W.; Kirkby, Jasper; Kulmala, Markku; Möhler, Ottmar; Saathoff, Harald; Schnaiter, Martin; Tomé, Antonio; Virtanen, Annele; Worsnop, Douglas; Stratmann, Frank

2016-05-01

There are strong indications that particles containing secondary organic aerosol (SOA) exhibit amorphous solid or semi-solid phase states in the atmosphere. This may facilitate heterogeneous ice nucleation and thus influence cloud properties. However, experimental ice nucleation studies of biogenic SOA are scarce. Here, we investigated the ice nucleation ability of viscous SOA particles. The SOA particles were produced from the ozone initiated oxidation of α-pinene in an aerosol chamber at temperatures in the range from -38 to -10 °C at 5-15 % relative humidity with respect to water to ensure their formation in a highly viscous phase state, i.e. semi-solid or glassy. The ice nucleation ability of SOA particles with different sizes was investigated with a new continuous flow diffusion chamber. For the first time, we observed heterogeneous ice nucleation of viscous α-pinene SOA for ice saturation ratios between 1.3 and 1.4 significantly below the homogeneous freezing limit. The maximum frozen fractions found at temperatures between -39.0 and -37.2 °C ranged from 6 to 20 % and did not depend on the particle surface area. Global modelling of monoterpene SOA particles suggests that viscous biogenic SOA particles are indeed present in regions where cirrus cloud formation takes place. Hence, they could make up an important contribution to the global ice nucleating particle budget.

Limited effect of anthropogenic nitrogen oxides on secondary organic aerosol formation

DOE PAGES

Zheng, Y.; Unger, N.; Hodzic, A.; ...

2015-12-08

Globally, secondary organic aerosol (SOA) is mostly formed from emissions of biogenic volatile organic compounds (VOCs) by vegetation, but it can be modified by human activities as demonstrated in recent research. Specifically, nitrogen oxides (NO x = NO + NO 2) have been shown to play a critical role in the chemical formation of low volatility compounds. We have updated the SOA scheme in the global NCAR (National Center for Atmospheric Research) Community Atmospheric Model version 4 with chemistry (CAM4-chem) by implementing a 4-product volatility basis set (VBS) scheme, including NO x-dependent SOA yields and aging parameterizations. Small differences aremore » found for the no-aging VBS and 2-product schemes; large increases in SOA production and the SOA-to-OA ratio are found for the aging scheme. The predicted organic aerosol amounts capture both the magnitude and distribution of US surface annual mean measurements from the Interagency Monitoring of Protected Visual Environments (IMPROVE) network by 50 %, and the simulated vertical profiles are within a factor of 2 compared to aerosol mass spectrometer (AMS) measurements from 13 aircraft-based field campaigns across different regions and seasons. We then perform sensitivity experiments to examine how the SOA loading responds to a 50 % reduction in anthropogenic nitric oxide (NO) emissions in different regions. We find limited SOA reductions of 0.9–5.6, 6.4–12.0 and 0.9–2.8 % for global, southeast US and Amazon NO x perturbations, respectively. The fact that SOA formation is almost unaffected by changes in NO x can be largely attributed to a limited shift in chemical regime, to buffering in chemical pathways (low- and high-NO x pathways, O 3 versus NO 3-initiated oxidation) and to offsetting tendencies in the biogenic versus anthropogenic SOA responses.« less

OH radical-initiated oxidation of (E)- and (Z)-β-ocimene in the presence of NOx: the role of light-dependent monoterpenes in organic nitrate and secondary organic aerosol formation in the above-canopy forest environment

NASA Astrophysics Data System (ADS)

Slade, J. H., Jr.; Jayarathne, T.; Morales, A. C.; Shepson, P. B.

2017-12-01

Biogenic volatile organic compound (BVOC) oxidation represents a significant pathway in the production of secondary organic aerosol (SOA). BVOC oxidation products, including organic nitrates (ON), impact both the SOA burden and the oxidative capacity of the atmosphere by sequestering NOx. A recent field study in the mixed deciduous/coniferous forest of northern Michigan showed that concentrations of multifunctional monoterpene-derived hydroxy nitrates (MTN) and SOA can be greater in the above-canopy environment during daytime, but the source of MTN is unclear as model simulations cannot replicate the higher concentrations above canopy. Light-dependent monoterpenes, including the polyolefinic species, trans-ocimene, may be one such contributor to the higher measured ON and SOA above canopy as this compound has been predicted to be an important source of monoterpene-derived ON during daytime in this environment. However, there are currently no measurements of the ON (and SOA yields) from trans-ocimene oxidation by OH in the presence of NOx, the dominant pathway for daytime ON production. Here we conduct photochemical reaction chamber studies of the OH radical-initiated oxidation of authentic (E)- and (Z)-β-ocimene isomers in the presence of NOx to examine the total (gas and particle) ON, hydroxy nitrate, and SOA yields. The effects of variable chamber relative humidity and seed particle acidity on the ON and SOA yields are examined to better understand the role of hydrolysis on SOA formation and the lifetime of ocimene-derived ON in the particles. This work underscores the importance of light-dependent monoterpenes on mediating the oxidative capacity of the near canopy forest environment and has important implications for understanding NOx cycling and the formation of SOA in forests, which are not currently included in atmospheric models.

Primary sources and secondary formation of organic aerosols in Beijing, China.

PubMed

Guo, Song; Hu, Min; Guo, Qingfeng; Zhang, Xin; Zheng, Mei; Zheng, Jun; Chang, Chih Chung; Schauer, James J; Zhang, Renyi

2012-09-18

Ambient aerosol samples were collected at an urban site and an upwind rural site of Beijing during the CAREBEIJING-2008 (Campaigns of Air quality REsearch in BEIJING and surrounding region) summer field campaign. Contributions of primary particles and secondary organic aerosols (SOA) were estimated by chemical mass balance (CMB) modeling and tracer-yield method. The apportioned primary and secondary sources explain 73.8% ± 9.7% and 79.6% ± 10.1% of the measured OC at the urban and rural sites, respectively. Secondary organic carbon (SOC) contributes to 32.5 ± 15.9% of the organic carbon (OC) at the urban site, with 17.4 ± 7.6% from toluene, 9.7 ± 5.4% from isoprene, 5.1 ± 2.0% from α-pinene, and 2.3 ± 1.7% from β-caryophyllene. At the rural site, the secondary sources are responsible for 38.4 ± 14.4% of the OC, with the contributions of 17.3 ± 6.9%, 13.9 ± 9.1%, 5.6 ± 1.9%, and 1.7 ± 1.0% from toluene, isoprene, α-pinene, and β-caryophyllene, respectively. Compared with other regions in the world, SOA in Beijing is less aged, but the concentrations are much higher; between the sites, SOA is more aged and affected by regional transport at the urban site. The high SOA loading in Beijing is probably attributed to the high regional SOC background (~2 μg m(-3)). The toluene SOC concentration is high and comparable at the two sites, implying that some anthropogenic components, at least toluene SOA, are widespread in Beijing and represents a major factor in affecting the regional air quality. The aerosol gaseous precursor concentrations and temperature correlate well with SOA, both affecting SOA formation. The significant SOA enhancement with increasing water uptake and acidification indicates that the aqueous-phase reactions are largely responsible SOA formation in Beijing.

Light-absorbing oligomer formation in secondary organic aerosol from reactive uptake of isoprene epoxydiols.

PubMed

Lin, Ying-Hsuan; Budisulistiorini, Sri Hapsari; Chu, Kevin; Siejack, Richard A; Zhang, Haofei; Riva, Matthieu; Zhang, Zhenfa; Gold, Avram; Kautzman, Kathryn E; Surratt, Jason D

2014-10-21

Secondary organic aerosol (SOA) produced from reactive uptake and multiphase chemistry of isoprene epoxydiols (IEPOX) has been found to contribute substantially (upward of 33%) to the fine organic aerosol mass over the Southeastern U.S. Brown carbon (BrC) in rural areas of this region has been linked to secondary sources in the summer when the influence of biomass burning is low. We demonstrate the formation of light-absorbing (290 < λ < 700 nm) SOA constituents from reactive uptake of trans-β-IEPOX onto preexisting sulfate aerosols as a potential source of secondary BrC. IEPOX-derived BrC generated in controlled chamber experiments under dry, acidic conditions has an average mass absorption coefficient of ∼ 300 cm(2) g(-1). Chemical analyses of SOA constituents using UV-visible spectroscopy and high-resolution mass spectrometry indicate the presence of highly unsaturated oligomeric species with molecular weights separated by mass units of 100 (C5H8O2) and 82 (C5H6O) coincident with the observations of enhanced light absorption, suggesting such oligomers as chromophores, and potentially explaining one source of humic-like substances (HULIS) ubiquitously present in atmospheric aerosol. Similar light-absorbing oligomers were identified in fine aerosol collected in the rural Southeastern U.S., supporting their atmospheric relevance and revealing a previously unrecognized source of oligomers derived from isoprene that contributes to ambient fine aerosol mass.

Quantifying Volatile Organic Compound Emissions from Solvents and their Impacts on Urban Air Quality

NASA Astrophysics Data System (ADS)

Mcdonald, B. C.; De Gouw, J. A.; Gilman, J.; Ahmadov, R.; Cappa, C. D.; Frost, G. J.; Goldstein, A. H.; Jathar, S.; Jimenez, J. L.; Kim, S. W.; McKeen, S. A.; Roberts, J. M.; Trainer, M.

2016-12-01

Solvents, which consist of personal care products, paints, degreasing agents, and other chemical products, are an important anthropogenic source of volatile organic compound (VOC) emissions. Yet there are many unresolved questions related to their emission rates, chemical composition, and relative importance on urban air quality problems. Using atmospheric measurements of speciated VOCs collected at a ground site located in the Los Angeles basin during the California Nexus (CalNex) Study in 2010, and utilizing data on the composition of solvent emissions from the California Air Resources Board (CARB), we are able to reconcile solvent emissions with ambient observations. Our analysis indicates that solvent emissions are underestimated by a factor of 2-3 in the CARB inventory. We then estimate the reactivity of solvent emissions with the hydroxyl (OH) radical, and also estimate the propensity of solvent emissions to form secondary organic aerosol (SOA). Solvents contain significant fractions of oxygenated compounds, including intermediate volatility compounds, which if released to the atmosphere are potentially reactive and can lead to the formation of SOA. Overall, our results suggest that in the Los Angeles basin, solvents are now the largest anthropogenic source of VOC emissions, OH reactivity, and SOA formation, and larger than the contribution from motor vehicles. This suggests that more research is needed in better constraining this potentially important source of urban VOC emissions.

Evaporation Kinetics of Laboratory Generated Secondary Organic Aerosols at Elevated Relative Humidity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wilson, Jacqueline M.; Imre, D.; Beranek, Josef

2015-01-06

Secondary organic aerosols (SOA) dominate atmospheric organic aerosols that affect climate, air quality, and health. Recent studies indicate that, contrary to previously held assumptions, at low relative humidity (RH) these particles are semi-solid and evaporate orders of magnitude slower than expected. Elevated relative humidity has the potential to affect significantly formation, properties, and atmospheric evolution of SOA particles. Here we present a study of the effect of RH on the room-temperature evaporation kinetics of SOA particles formed by ozonolysis of α-pinene and limonene. Experiments were carried out on SOA particles generated, evaporated, and aged at 0%, 50% and 90% RH.more » We find that in all cases evaporation begins with a relatively fast phase, during which 30% to 70% of the particle mass evaporates in 2 hours, followed by a much slower evaporation rate. Evaporation kinetics at 0% and 50% RH are nearly the same, while at 90% RH a slightly larger fraction evaporates. In all cases, aging the particles prior to inducing evaporation reduces the evaporative losses, with aging at elevated RH leading to more significant effect. In all cases, SOA evaporation is nearly size-independent, providing direct evidence that oligomers play a crucial role in determining the evaporation kinetics.« less

Molecular selectivity of brown carbon chromophores.

PubMed

Laskin, Julia; Laskin, Alexander; Nizkorodov, Sergey A; Roach, Patrick; Eckert, Peter; Gilles, Mary K; Wang, Bingbing; Lee, Hyun Ji Julie; Hu, Qichi

2014-10-21

Complementary methods of high-resolution mass spectrometry and microspectroscopy were utilized for molecular analysis of secondary organic aerosol (SOA) generated from ozonolysis of two structural monoterpene isomers: D-limonene SOA (LSOA) and α-pinene SOA (PSOA). The LSOA compounds readily formed adducts with Na(+) under electrospray ionization conditions, with only a small fraction of compounds detected in the protonated form. In contrast, a significant fraction of PSOA compounds appeared in the protonated form because of their increased molecular rigidity. Laboratory simulated aging of LSOA and PSOA, through conversion of carbonyls into imines mediated by NH3 vapors in humid air, resulted in selective browning of the LSOA sample, while the PSOA sample remained white. Comparative analysis of the reaction products in the aged LSOA and PSOA samples provided insights into chemistry relevant to formation of brown carbon chromophores. A significant fraction of carbonyl-imine conversion products with identical molecular formulas was detected in both samples. This reflects the high level of similarity in the molecular composition of these two closely related SOA materials. Several highly conjugated products were detected exclusively in the brown LSOA sample and were identified as potential chromophores responsible for the observed color change. The majority of the unique products in the aged LSOA sample with the highest number of double bonds contain two nitrogen atoms. We conclude that chromophores characteristic of the carbonyl-imine chemistry in LSOA are highly conjugated oligomers of secondary imines (Schiff bases) present at relatively low concentrations. Formation of this type of conjugated compounds in PSOA is hindered by the structural rigidity of the α-pinene oxidation products. Our results suggest that the overall light-absorbing properties of SOA may be determined by trace amounts of strong brown carbon chromophores.

Potential contribution of semi-volatile and intermediate volatility primary organic compounds to secondary organic aerosol in the Mexico City region

NASA Astrophysics Data System (ADS)

Hodzic, A.; Jimenez, J. L.; Madronich, S.; Canagaratna, M. R.; Decarlo, P. F.; Kleinman, L.; Fast, J.

2010-01-01

It has been established that observed local and regional levels of secondary organic aerosols (SOA) in polluted areas cannot be explained by the oxidation and partitioning of anthropogenic and biogenic VOC precursors, at least using current mechanisms and parameterizations. In this study, the 3-D regional air quality model CHIMERE is applied to quantify the contribution to SOA formation of recently identified semi-volatile and intermediate volatility organic vapors (S/IVOC) in and around Mexico City for the MILAGRO field experiment during March 2006. The model has been updated to include explicitly the volatility distribution of primary organic aerosols (POA), their gas-particle partitioning and the gas-phase oxidation of the vapors. Two recently proposed parameterizations, those of Robinson et al. (2007) ("ROB") and Grieshop et al. (2009) ("GRI") are compared and evaluated against surface and aircraft measurements. The 3-D model results are assessed by comparing with the concentrations of OA components from Positive Matrix Factorization of Aerosol Mass Spectrometer (AMS) data, and for the first time also with oxygen-to-carbon ratios derived from high-resolution AMS measurements. The results show a substantial enhancement in predicted SOA concentrations (3-6 times) with respect to the previously published base case without S/IVOCs (Hodzic et al., 2009), both within and downwind of the city leading to much reduced discrepancies with the total OA measurements. The predicted anthropogenic POA levels are found to agree within 20% with the observed HOA concentrations for both the ROB and GRI simulations, consistent with the interpretation of the emissions inventory by previous studies. The impact of biomass burning POA within the city is underestimated in comparison to the AMS BBOA, presumably due to insufficient nighttime smoldering emissions. Model improvements in OA predictions are associated with the better-captured SOA magnitude and diurnal variability. The predicted production from anthropogenic and biomass burning S/IVOC represents 40-60% of the total SOA at the surface during the day and is somewhat larger than that from aromatics, especially at the T1 site at the edge of the city. The SOA production from the continued multi-generation S/IVOC oxidation products continues actively downwind. Similar to aircraft observations, the predicted OA/ΔCO ratio for the ROB case increases from 20-30 μg sm-3 ppm-1 up to 60-70 μg sm-3 ppm-1 between a fresh and 1-day aged air mass, while the GRI case produces a 30-40% higher OA growth than observed. The predicted average O/C ratio of total OA for the ROB case is 0.16 at T0, substantially below observed value of 0.5. A much better agreement for O/C ratios and temporal variability (R2=0.63) is achieved with the updated GRI treatment. Both treatments show a deficiency in regard to POA evolution with a tendency to over-evaporate POA upon dilution of the urban plume suggesting that atmospheric HOA may be less volatile than assumed in these parameterizations. This study highlights the important potential role of S/IVOC chemistry in the SOA budget in this region, and highlights the need for improvements in current parameterizations. We note that our simulations did not include other proposed pathways of SOA formation such as formation from very volatile species like glyoxal, which can also contribute SOA mass and especially increase the O/C ratio.

Reactive intermediates revealed in secondary organic aerosol formation from isoprene

PubMed Central

Surratt, Jason D.; Chan, Arthur W. H.; Eddingsaas, Nathan C.; Chan, ManNin; Loza, Christine L.; Kwan, Alan J.; Hersey, Scott P.; Flagan, Richard C.; Wennberg, Paul O.; Seinfeld, John H.

2010-01-01

Isoprene is a significant source of atmospheric organic aerosol; however, the oxidation pathways that lead to secondary organic aerosol (SOA) have remained elusive. Here, we identify the role of two key reactive intermediates, epoxydiols of isoprene (IEPOX = β-IEPOX + δ-IEPOX) and methacryloylperoxynitrate (MPAN), which are formed during isoprene oxidation under low- and high-NOx conditions, respectively. Isoprene low-NOx SOA is enhanced in the presence of acidified sulfate seed aerosol (mass yield 28.6%) over that in the presence of neutral aerosol (mass yield 1.3%). Increased uptake of IEPOX by acid-catalyzed particle-phase reactions is shown to explain this enhancement. Under high-NOx conditions, isoprene SOA formation occurs through oxidation of its second-generation product, MPAN. The similarity of the composition of SOA formed from the photooxidation of MPAN to that formed from isoprene and methacrolein demonstrates the role of MPAN in the formation of isoprene high-NOx SOA. Reactions of IEPOX and MPAN in the presence of anthropogenic pollutants (i.e., acidic aerosol produced from the oxidation of SO2 and NO2, respectively) could be a substantial source of “missing urban SOA” not included in current atmospheric models. PMID:20080572

Organic Nitrate Contribution to New Particle Formation and Growth in Secondary Organic Aerosols from α-Pinene Ozonolysis.

PubMed

Berkemeier, Thomas; Ammann, Markus; Mentel, Thomas F; Pöschl, Ulrich; Shiraiwa, Manabu

2016-06-21

The chemical kinetics of organic nitrate production during new particle formation and growth of secondary organic aerosols (SOA) were investigated using the short-lived radioactive tracer (13)N in flow-reactor studies of α-pinene oxidation with ozone. Direct and quantitative measurements of the nitrogen content indicate that organic nitrates accounted for ∼40% of SOA mass during initial particle formation, decreasing to ∼15% upon particle growth to the accumulation-mode size range (>100 nm). Experiments with OH scavengers and kinetic model results suggest that organic peroxy radicals formed by α-pinene reacting with secondary OH from ozonolysis are key intermediates in the organic nitrate formation process. The direct reaction of α-pinene with NO3 was found to be less important for particle-phase organic nitrate formation. The nitrogen content of SOA particles decreased slightly upon increase of relative humidity up to 80%. The experiments show a tight correlation between organic nitrate content and SOA particle-number concentrations, implying that the condensing organic nitrates are among the extremely low volatility organic compounds (ELVOC) that may play an important role in the nucleation and growth of atmospheric nanoparticles.

On the mixing and evaporation of secondary organic aerosol components.

PubMed

Loza, Christine L; Coggon, Matthew M; Nguyen, Tran B; Zuend, Andreas; Flagan, Richard C; Seinfeld, John H

2013-06-18

The physical state and chemical composition of an organic aerosol affect its degree of mixing and its interactions with condensing species. We present here a laboratory chamber procedure for studying the effect of the mixing of organic aerosol components on particle evaporation. The procedure is applied to the formation of secondary organic aerosol (SOA) from α-pinene and toluene photooxidation. SOA evaporation is induced by heating the chamber aerosol from room temperature (25 °C) to 42 °C over 7 h and detected by a shift in the peak diameter of the SOA size distribution. With this protocol, α-pinene SOA is found to be more volatile than toluene SOA. When SOA is formed from the two precursors sequentially, the evaporation behavior of the SOA most closely resembles that of SOA from the second parent hydrocarbon, suggesting that the structure of the mixed SOA resembles a core of SOA from the initial precursor coated by a layer of SOA from the second precursor. Such a core-and-shell configuration of the organic aerosol phases implies limited mixing of the SOA from the two precursors on the time scale of the experiments, consistent with a high viscosity of at least one of the phases.

Secondary organic aerosol formation exceeds primary particulate matter emissions for light-duty gasoline vehicles

NASA Astrophysics Data System (ADS)

Gordon, T. D.; Presto, A. A.; May, A. A.; Nguyen, N. T.; Lipsky, E. M.; Donahue, N. M.; Gutierrez, A.; Zhang, M.; Maddox, C.; Rieger, P.; Chattopadhyay, S.; Maldonado, H.; Maricq, M. M.; Robinson, A. L.

2013-09-01

The effects of photochemical aging on emissions from 15 light-duty gasoline vehicles were investigated using a smog chamber to probe the critical link between the tailpipe and ambient atmosphere. The vehicles were recruited from the California in-use fleet; they represent a wide range of model years (1987 to 2011), vehicle types and emission control technologies. Each vehicle was tested on a chassis dynamometer using the unified cycle. Dilute emissions were sampled into a portable smog chamber and then photochemically aged under urban-like conditions. For every vehicle, substantial secondary organic aerosol (SOA) formation occurred during cold-start tests, with the emissions from some vehicles generating as much as 6 times the amount of SOA as primary particulate matter after three hours of oxidation inside the chamber at typical atmospheric oxidant levels. Therefore, the contribution of light duty gasoline vehicle exhaust to ambient PM levels is likely dominated by secondary PM production (SOA and nitrate). Emissions from hot-start tests formed about a factor of 3-7 less SOA than cold-start tests. Therefore, catalyst warm-up appears to be an important factor in controlling SOA precursor emissions. The mass of SOA generated by photo-oxidizing exhaust from newer (LEV1 and LEV2) vehicles was only modestly lower (38%) than that formed from exhaust emitted by older (pre-LEV) vehicles, despite much larger reductions in non-methane organic gas emissions. These data suggest that a complex and non-linear relationship exists between organic gas emissions and SOA formation, which is not surprising since SOA precursors are only one component of the exhaust. Except for the oldest (pre-LEV) vehicles, the SOA production could not be fully explained by the measured oxidation of speciated (traditional) SOA precursors. Over the time scale of these experiments, the mixture of organic vapors emitted by newer vehicles appear to be more efficient (higher yielding) in producing SOA than the emissions from older vehicles. About 30% of the non-methane organic gas emissions from the newer (LEV1 and LEV2) vehicles could not be speciated, and the majority of the SOA formed from these vehicles appears to be associated with these unspeciated organics. These results for light-duty gasoline vehicles contrast with the results from a companion study of on-road heavy-duty diesel trucks; in that study late model (2007 and later) diesel trucks equipped with catalyzed diesel particulate filters emitted very little primary PM, and the photo-oxidized emissions produced negligible amounts of SOA.

Model analysis of secondary organic aerosol formation by glyoxal in laboratory studies: the case for photoenhanced chemistry.

PubMed

Sumner, Andrew J; Woo, Joseph L; McNeill, V Faye

2014-10-21

The reactive uptake of glyoxal by atmospheric aerosols is believed to be a significant source of secondary organic aerosol (SOA). Several recent laboratory studies have been performed with the goal of characterizing this process, but questions remain regarding the effects of photochemistry on SOA growth. We applied GAMMA (McNeill et al. Environ. Sci. Technol. 2012, 46, 8075-8081), a photochemical box model with coupled gas-phase and detailed aqueous aerosol-phase chemistry, to simulate aerosol chamber studies of SOA formation by the uptake of glyoxal by wet aerosol under dark and irradiated conditions (Kroll et al. J. Geophys. Res. 2005, 110 (D23), 1-10; Volkamer et al. Atmos. Chem. Phys. 2009, 9, 1907-1928; Galloway et al. Atmos. Chem. Phys. 2009, 9, 3331- 306 3345 and Geophys. Res. Lett. 2011, 38, L17811). We find close agreement between simulated SOA growth and the results of experiments conducted under dark conditions using values of the effective Henry's Law constant of 1.3-5.5 × 10(7) M atm(-1). While irradiated conditions led to the production of some organic acids, organosulfates, and other oxidation products via well-established photochemical mechanisms, these additional product species contribute negligible aerosol mass compared to the dark uptake of glyoxal. Simulated results for irradiated experiments therefore fell short of the reported SOA mass yield by up to 92%. This suggests a significant light-dependent SOA formation mechanism that is not currently accounted for by known bulk photochemistry, consistent with recent laboratory observations of SOA production via photosensitizer chemistry.

Limited effect of anthropogenic nitrogen oxides on Secondary Organic Aerosol formation

DOE PAGES

Zheng, Y.; Unger, N.; Hodzic, A.; ...

2015-08-28

Globally, secondary organic aerosol (SOA) is mostly formed from emissions of biogenic volatile organic compounds (VOCs) by vegetation, but can be modified by human activities as demonstrated in recent research. Specifically, nitrogen oxides (NO x = NO + NO 2) have been shown to play a critical role in the chemical formation of low volatility compounds. We have updated the SOA scheme in the global NCAR Community Atmospheric Model version 4 with chemistry (CAM4-chem) by implementing a 4-product Volatility Basis Set (VBS) scheme, including NO x-dependent SOA yields and aging parameterizations. The predicted organic aerosol amounts capture both the magnitudemore » and distribution of US surface annual mean measurements from the Interagency Monitoring of Protected Visual Environments (IMPROVE) network by 50 %, and the simulated vertical profiles are within a factor of two compared to Aerosol Mass Spectrometer (AMS) measurements from 13 aircraft-based field campaigns across different region and seasons. We then perform sensitivity experiments to examine how the SOA loading responds to a 50 % reduction in anthropogenic nitric oxide (NO) emissions in different regions. We find limited SOA reductions of 0.9 to 5.6, 6.4 to 12.0 and 0.9 to 2.8 % for global, the southeast US and the Amazon NO x perturbations, respectively. The fact that SOA formation is almost unaffected by changes in NO x can be largely attributed to buffering in chemical pathways (low- and high-NO x pathways, O 3 versus NO 3-initiated oxidation) and to offsetting tendencies in the biogenic versus anthropogenic SOA responses.« less

Isoprene in poplar emissions: effects on new particle formation and OH concentrations

NASA Astrophysics Data System (ADS)

Kiendler-Scharr, A.; Andres, S.; Bachner, M.; Behnke, K.; Broch, S.; Hofzumahaus, A.; Holland, F.; Kleist, E.; Mentel, T. F.; Rubach, F.; Springer, M.; Steitz, B.; Tillmann, R.; Wahner, A.; Schnitzler, J.-P.; Wildt, J.

2012-01-01

Stress-induced volatile organic compound (VOC) emissions from transgenic Grey poplar modified in isoprene emission potential were used for the investigation of photochemical secondary organic aerosol (SOA) formation. In poplar, acute ozone stress induces the emission of a wide array of VOCs dominated by sesquiterpenes and aromatic VOCs. Constitutive light-dependent emission of isoprene ranged between 66 nmol m-2 s-1 in non-transgenic controls (wild type WT) and nearly zero (<0.5 nmol m-2 s-1) in isoprene emission-repressed plants (line RA22), respectively. Nucleation rates of up to 3600 cm-3 s-1 were observed in our experiments. In the presence of isoprene new particle formation was suppressed compared to non-isoprene containing VOC mixtures. Compared to isoprene/monoterpene systems emitted from other plants the suppression of nucleation by isoprene was less effective for the VOC mixture emitted from stressed poplar. This is explained by the observed high efficiency of new particle formation for emissions from stressed poplar. Direct measurements of OH in the reaction chamber revealed that the steady state concentration of OH is lower in the presence of isoprene than in the absence of isoprene, supporting the hypothesis that isoprenes' suppressing effect on nucleation is related to radical chemistry. In order to test whether isoprene contributes to SOA mass formation, fully deuterated isoprene (C5D8) was added to the stress-induced emission profile of an isoprene free poplar mutant. Mass spectral analysis showed that, despite the isoprene-induced suppression of particle formation, fractions of deuterated isoprene were incorporated into the SOA. A fractional mass yield of 2.3% of isoprene was observed. Future emission changes due to land use and climate change may therefore affect both gas phase oxidation capacity and new particle number formation.

Isoprene in poplar emissions: effects on new particle formation and OH concentrations

NASA Astrophysics Data System (ADS)

Kiendler-Scharr, A.; Andres, S.; Bachner, M.; Behnke, K.; Broch, S.; Hofzumahaus, A.; Holland, F.; Kleist, E.; Mentel, T. F.; Rubach, F.; Springer, M.; Steitz, B.; Tillmann, R.; Wahner, A.; Schnitzler, J.-P.; Wildt, J.

2011-08-01

Stress-induced volatile organic compound (VOC) emissions from transgenic Grey poplar, modified in isoprene emission potential were used for the investigation of photochemical secondary organic aerosol (SOA) formation. Nucleation rates of up to 3600 cm-3 s-1 were observed in our experiments. In poplar, acute ozone stress induces the emission of a wide array of VOCs dominated by sesquiterpenes and aromatic VOCs. Constitutive light-dependent emission of isoprene ranged between 66 nmol m-2 s-1 in non-transgenic controls (wild type WT) and nearly zero (<0.5 nmol m-2 s-1) in isoprene emission-repressed lines (line RA22), respectively. In the presence of isoprene new particle formation was suppressed compared to non-isoprene containing VOC mixtures. Compared to isoprene/monoterpene systems emitted from other plants the suppression of nucleation by isoprene was less effective for the VOC mixture emitted from stressed poplar. This is explained by the observed high efficiency of new particle formation for emissions from stressed poplar. Direct measurements of OH in the reaction chamber revealed that the steady state concentration of OH is lower in the presence of isoprene than in the absence of isoprene, supporting the hypothesis that isoprenes' suppressing effect on nucleation is related to radical chemistry. In order to test whether isoprene contributes to SOA mass formation, fully deuterated isoprene (C5D8) was added to the stress-induced emission profile of an isoprene free poplar mutant. Mass spectral analysis showed that, despite the isoprene-induced suppression of particle formation, fractions of deuterated isoprene were incorporated into the SOA. A fractional mass yield of 2.3 % of isoprene was observed. Future emission changes due to land use and climate change may therefore affect both gas phase oxidation capacity and new particle number formation.

Secondary organic aerosol formation from propylene irradiations in a chamber study

NASA Astrophysics Data System (ADS)

Ge, Shuangshuang; Xu, Yongfu; Jia, Long

2017-05-01

Some studies have shown that low-molecular-weight VOCs such as ethylene and acetylene can form SOA. However, so far propylene (C3H6) has not been studied. The current work systematically investigates irradiations of propylene in the presence of NOx (x = 1, 2) in a self-made indoor chamber. Only a small amount of secondary organic aerosols (SOA) was formed under 5% and 80% RH conditions without sodium chloride (NaCl) seed particles or in the presence of solid NaCl. When NaCl was in the form of droplets, liquid water content (LWC) increased from 34.5 to 169.8 μg m-3 under different initial NaCl concentrations, and correspondingly the amount of SOA linearly increased from 5.9 to 29.8 μg m-3 (SOA = 0.0164 × LWC+1.137, R2 = 0.97) at the C3H6/NOx ratio of 32.2-44.9 (ppbC/ppb). The initial C3H6/NOx concentration ratio considerably impacted the formation of SOA, in which the amount of SOA increased from 12.1 to 47.9 μg m-3 exponentially as the ratio decreased from 46.5 to 6.3 with an important point of the ratio value of 11. At the ratio of less than 11 in the regime under the control of C3H6, SOA concentrations decreased considerably with increasing ratio, whereas at the ratio value of larger than 11 in the NOx controlled regime, SOA slightly decreased with increasing ratio. From combination of the analysis of different functional groups of particles by IR spectra and ESI-Exactive-Orbitrap mass spectrometer, the constituents of SOA were identified to be hydroperoxides (e.g. HOCH2CCl(CH3)OOH), esters (e.g. CH2ClC(O)OCHClCHO), organic nitrates (e.g. HO2CH(CH2Cl)C(O)OCCl(CH2Cl)C(O)OCHClCH2ONO2), etc. Furthermore, a liquid-phase mechanism of SOA formation has been proposed in this study.

Effect of Organic Coatings, Humidity and Aerosol Acidity on Multiphase Chemistry of Isoprene Epoxydiols

DOE Office of Scientific and Technical Information (OSTI.GOV)

Riva, Matthieu; Bell, David M.; Hansen, Anne-Maria Kaldal

2016-06-07

Multiphase chemistry of isomeric isoprene epoxydiols (IEPOX) has been shown to be the dominant source of isoprene-derived secondary organic aerosol (SOA). Recent studies have reported particles composed of ammonium bisulfate (ABS) mixed with model organics exhibit slower rates of IEPOX uptake. In the present study, we investigate the effect of atmospherically-relevant organic coatings of α-pinene (AP) SOA on the reactive uptake of trans-β-IEPOX onto ABS particles under different conditions and coating thicknesses. Single particle mass spectrometry was used to characterize in real-time particle size, shape, density, and quantitative composition before and after reaction with IEPOX. We find that IEPOX uptakemore » by pure sulfate particles is a volume-controlled process, which results in particles with uniform concentration of IEPOX-derived SOA across a wide range of sizes. Aerosol acidity was shown to enhance IEPOX-derived SOA formation, consistent with recent studies. The presence of water has a weaker impact on IEPOX-derived SOA yield, but significantly enhanced formation of 2-methyltetrols, consistent with offline filter analysis. In contrast, IEPOX uptake by ABS particles coated by AP-derived SOA is strongly dependent on particle size and composition. IEPOX uptake occurred only when weight fraction of AP-derived SOA dropped below 50 %, effectively limiting IEPOX uptake to larger particles.« less

A Combined Kinetic and Volatility Basis Set Approach to Model Secondary Organic Aerosol from Toluene and Diesel Exhaust/Meat Cooking Mixtures

NASA Astrophysics Data System (ADS)

Parikh, H. M.; Carlton, A. G.; Zhang, H.; Kamens, R.; Vizuete, W.

2011-12-01

Secondary organic aerosol (SOA) is simulated for 6 outdoor smog chamber experiments using a SOA model based on a kinetic chemical mechanism in conjunction with a volatility basis set (VBS) approach. The experiments include toluene, a non-SOA-forming hydrocarbon mixture, diesel exhaust or meat cooking emissions and NOx, and are performed under varying conditions of relative humidity. SOA formation from toluene is modeled using a condensed kinetic aromatic mechanism that includes partitioning of lumped semi-volatile products in particle organic-phase and incorporates particle aqueous-phase chemistry to describe uptake of glyoxal and methylglyoxal. Modeling using the kinetic mechanism alone, along with primary organic aerosol (POA) from diesel exhaust (DE) /meat cooking (MC) fails to simulate the rapid SOA formation at the beginning hours of the experiments. Inclusion of a VBS approach with the kinetic mechanism to characterize the emissions and chemistry of complex mixture of intermediate volatility organic compounds (IVOCs) from DE/MC, substantially improves SOA predictions when compared with observed data. The VBS model includes photochemical aging of IVOCs and evaporation of POA after dilution. The relative contribution of SOA mass from DE/MC is as high as 95% in the morning, but substantially decreases after mid-afternoon. For high humidity experiments, aqueous-phase SOA fraction dominates the total SOA mass at the end of the day (approximately 50%). In summary, the combined kinetic and VBS approach provides a new and improved framework to semi-explicitly model SOA from VOC precursors in conjunction with a VBS approach that can be used on complex emission mixtures comprised with hundreds of individual chemical species.

Mixing of secondary organic aerosols versus relative humidity

PubMed Central

Ye, Qing; Robinson, Ellis Shipley; Ding, Xiang; Ye, Penglin

2016-01-01

Atmospheric aerosols exert a substantial influence on climate, ecosystems, visibility, and human health. Although secondary organic aerosols (SOA) dominate fine-particle mass, they comprise myriad compounds with uncertain sources, chemistry, and interactions. SOA formation involves absorption of vapors into particles, either because gas-phase chemistry produces low-volatility or semivolatile products that partition into particles or because more-volatile organics enter particles and react to form lower-volatility products. Thus, SOA formation involves both production of low-volatility compounds and their diffusion into particles. Most chemical transport models assume a single well-mixed phase of condensing organics and an instantaneous equilibrium between bulk gas and particle phases; however, direct observations constraining diffusion of semivolatile organics into particles containing SOA are scarce. Here we perform unique mixing experiments between SOA populations including semivolatile constituents using quantitative, single-particle mass spectrometry to probe any mass-transfer limitations in particles containing SOA. We show that, for several hours, particles containing SOA from toluene oxidation resist exchange of semivolatile constituents at low relative humidity (RH) but start to lose that resistance above 20% RH. Above 40% RH, the exchange of material remains constant up to 90% RH. We also show that dry particles containing SOA from α-pinene ozonolysis do not appear to resist exchange of semivolatile compounds. Our interpretation is that in-particle diffusion is not rate-limiting to mass transfer in these systems above 40% RH. To the extent that these systems are representative of ambient SOA, we conclude that diffusion limitations are likely not common under typical ambient boundary layer conditions. PMID:27791066

Mixing of secondary organic aerosols versus relative humidity.

PubMed

Ye, Qing; Robinson, Ellis Shipley; Ding, Xiang; Ye, Penglin; Sullivan, Ryan C; Donahue, Neil M

2016-10-24

Atmospheric aerosols exert a substantial influence on climate, ecosystems, visibility, and human health. Although secondary organic aerosols (SOA) dominate fine-particle mass, they comprise myriad compounds with uncertain sources, chemistry, and interactions. SOA formation involves absorption of vapors into particles, either because gas-phase chemistry produces low-volatility or semivolatile products that partition into particles or because more-volatile organics enter particles and react to form lower-volatility products. Thus, SOA formation involves both production of low-volatility compounds and their diffusion into particles. Most chemical transport models assume a single well-mixed phase of condensing organics and an instantaneous equilibrium between bulk gas and particle phases; however, direct observations constraining diffusion of semivolatile organics into particles containing SOA are scarce. Here we perform unique mixing experiments between SOA populations including semivolatile constituents using quantitative, single-particle mass spectrometry to probe any mass-transfer limitations in particles containing SOA. We show that, for several hours, particles containing SOA from toluene oxidation resist exchange of semivolatile constituents at low relative humidity (RH) but start to lose that resistance above 20% RH. Above 40% RH, the exchange of material remains constant up to 90% RH. We also show that dry particles containing SOA from α-pinene ozonolysis do not appear to resist exchange of semivolatile compounds. Our interpretation is that in-particle diffusion is not rate-limiting to mass transfer in these systems above 40% RH. To the extent that these systems are representative of ambient SOA, we conclude that diffusion limitations are likely not common under typical ambient boundary layer conditions.

The formation of SOA and chemical tracer compounds from the photooxidation of naphthalene and its methyl analogs in the presence and absence of nitrogen oxides

EPA Science Inventory

Laboratory smog chamber experiments have been carried out to investigate secondary organic aerosol (SOA)formation from the photooxidation of naphthalene and its methyl analogs, 1- and 2-methylnaphthalene (1-MN and 2- MN, respectively). Laboratory smog chamber irradiations were co...

Identification of significant precursor gases of secondary organic aerosols from residential wood combustion

PubMed Central

Bruns, Emily A.; El Haddad, Imad; Slowik, Jay G.; Kilic, Dogushan; Klein, Felix; Baltensperger, Urs; Prévôt, André S. H.

2016-01-01

Organic gases undergoing conversion to form secondary organic aerosol (SOA) during atmospheric aging are largely unidentified, particularly in regions influenced by anthropogenic emissions. SOA dominates the atmospheric organic aerosol burden and this knowledge gap contributes to uncertainties in aerosol effects on climate and human health. Here we characterize primary and aged emissions from residential wood combustion using high resolution mass spectrometry to identify SOA precursors. We determine that SOA precursors traditionally included in models account for only ~3–27% of the observed SOA, whereas for the first time we explain ~84–116% of the SOA by inclusion of non-traditional precursors. Although hundreds of organic gases are emitted during wood combustion, SOA is dominated by the aging products of only 22 compounds. In some cases, oxidation products of phenol, naphthalene and benzene alone comprise up to ~80% of the observed SOA. Identifying the main precursors responsible for SOA formation enables improved model parameterizations and SOA mitigation strategies in regions impacted by residential wood combustion, more productive targets for ambient monitoring programs and future laboratories studies, and links between direct emissions and SOA impacts on climate and health in these regions. PMID:27312480

Can scooter emissions dominate urban organic aerosol?

NASA Astrophysics Data System (ADS)

El Haddad, Imad; Platt, Stephen; Huang, Ru-Jin; Zardini, Alessandro; Clairotte, Micheal; Pieber, Simone; Pfaffenberger, Lisa; Fuller, Steve; Hellebust, Stig; Temime-Roussel, Brice; Slowik, Jay; Chirico, Roberto; Kalberer, Markus; Marchand, Nicolas; Dommen, Josef; Astorga, Covadonga; Baltensperger, Urs; Prevot, Andre

2014-05-01

In urban areas, where the health impact of pollutants increases due to higher population density, traffic is a major source of ambient organic aerosol (OA). A significant fraction of OA from traffic is secondary, produced via the reaction of exhaust volatile organic compounds (VOCs) with atmospheric oxidants. Secondary OA (SOA) has not been systematically assessed for different vehicles and driving conditions and thus its relative importance compared to directly emitted, primary OA (POA) is unknown, hindering the design of effective vehicle emissions regulations. 2-stroke (2S) scooters are inexpensive and convenient and as such a popular means of transportation globally, particularly in Asia. European regulations for scooters are less stringent than for other vehicles and thus primary particulate emissions and SOA precursor VOCs from 2S engines are estimated to be much higher. Assessing the effects of scooters on public health requires consideration of both POA, and SOA production. Here, we quantify POA emission factors and potential SOA EFs from 2S scooters, and the effect of using aromatic free fuel instead of standard gasoline thereon. During the tests, Euro 1 and Euro 2 2S scooters were run in idle or simulated low power conditions. Emissions from a Euro 2 2S scooter were also sampled during regulatory driving cycles on a chassis dynamometer. Vehicle exhaust was introduced into smog chambers, where POA emission and SOA production were quantified using a high-resolution time-of-flight aerosol mass spectrometer. A high resolution proton transfer time-of-flight mass spectrometer was used to investigate volatile organic compounds and a suite of instruments was utilized to quantify CO, CO2, O3, NOX and total hydrocarbons. We show that the oxidation of VOCs in the exhaust emissions of 2S scooters produce significant SOA, exceeding by up to an order of magnitude POA emissions. By monitoring the decay of VOC precursors, we show that SOA formation from 2S scooter emissions essentially stems from the condensation of aromatic oxidation products. Further, we demonstrate that replacing the standard gasoline with an aromatic-free fuel mitigates SOA production, underlining the major role of aromatic compounds from 2S exhaust on SOA production. POA and potential SOA EFs determined here from 2S scooters will be presented and compared with EF from other vehicles, including 4-stroke scooters, gasoline cars and diesel cars to assess the contributions of 2S scooters in urban atmospheres.

Mechanism of the hydroxyl radical oxidation of methacryloyl peroxynitrate (MPAN) and its pathway toward secondary organic aerosol formation in the atmosphere

DOE PAGES

Nguyen, Tran B.; Bates, Kelvin H.; Crounse, John D.; ...

2015-06-12

Methacryloyl peroxynitrate (MPAN), the acyl peroxynitrate of methacrolein, has been suggested to be an important secondary organic aerosol (SOA) precursor from isoprene oxidation. Yet, the mechanism by which MPAN produces SOA through reaction with the hydroxyl radical (OH) is unclear. We systematically evaluate three proposed mechanisms in controlled chamber experiments and provide the first experimental support for the theoretically-predicted lactone formation pathway from the MPAN + OH reaction, producing hydroxymethyl-methyl-α-lactone (HMML). The decomposition of the MPAN–OH adduct yields HMML + NO 3 (~75%) and hydroxyacetone + CO + NO 3 (~25%), out-competing its reaction with atmospheric oxygen. The production ofmore » other proposed SOA precursors, e.g., methacrylic acid epoxide (MAE), from MPAN and methacrolein are negligible (<2%). Furthermore, we show that the beta-alkenyl moiety of MPAN is critical for lactone formation. Alkyl radicals formed cold via H-abstraction by OH do not decompose to HMML, even if they are structurally identical to the MPAN–OH adduct. The SOA formation from HMML, from polyaddition of the lactone to organic compounds at the particle interface or in the condensed phase, is close to unity under dry conditions. However, the SOA yield is sensitive to particle liquid water and solvated ions. In hydrated inorganic particles, HMML reacts primarily with H 2O to produce the monomeric 2-methylglyceric acid (2MGA) or with aqueous sulfate and nitrate to produce the associated organosulfate and organonitrate, respectively. 2MGA, a tracer for isoprene SOA, is semivolatile and its accommodation in aerosol water decreases with decreasing pH. Conditions that enhance the production of neutral 2MGA suppress SOA mass from the HMML channel. In conclusion, considering the liquid water content and pH ranges of ambient particles, 2MGA will exist largely as a gaseous compound in some parts of the atmosphere.« less

CONTRIBUTIONS OF TOLUENE AND Α -PINENE TO SOA FORMED IN AN IRRADIATED TOLUENE/Α-PINENE/NOX/AIR MIXTURE: COMPARISON OF RESULTS USING 14C CONTENT AND SOA ORGANIC TRACER METHODS

EPA Science Inventory

An organic tracer method, recently proposed for estimating individual contributions of toluene and α-pinene to secondary organic aerosol (SOA) formation, was evaluated by conducting a laboratory study where a binary hydrocarbon mixture, containing the anthropogenic aromatic hydro...

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hayes, P. L.; Carlton, A. G.; Baker, K. R.

Four different literature parameterizations for the formation and evolution of urban secondary organic aerosol (SOA) frequently used in 3-D models are evaluated using a 0-D box model representing the Los Angeles metropolitan region during the California Research at the Nexus of Air Quality and Climate Change (CalNex) 2010 campaign. We constrain the model predictions with measurements from several platforms and compare predictions with particle- and gas-phase observations from the CalNex Pasadena ground site. That site provides a unique opportunity to study aerosol formation close to anthropogenic emission sources with limited recirculation. The model SOA that formed only from the oxidationmore » of VOCs (V-SOA) is insufficient to explain the observed SOA concentrations, even when using SOA parameterizations with multi-generation oxidation that produce much higher yields than have been observed in chamber experiments, or when increasing yields to their upper limit estimates accounting for recently reported losses of vapors to chamber walls. The Community Multiscale Air Quality (WRF-CMAQ) model (version 5.0.1) provides excellent predictions of secondary inorganic particle species but underestimates the observed SOA mass by a factor of 25 when an older VOC-only parameterization is used, which is consistent with many previous model–measurement comparisons for pre-2007 anthropogenic SOA modules in urban areas. Including SOA from primary semi-volatile and intermediate-volatility organic compounds (P-S/IVOCs) following the parameterizations of Robinson et al. (2007), Grieshop et al. (2009), or Pye and Seinfeld (2010) improves model–measurement agreement for mass concentration. The results from the three parameterizations show large differences (e.g., a factor of 3 in SOA mass) and are not well constrained, underscoring the current uncertainties in this area. Our results strongly suggest that other precursors besides VOCs, such as P-S/IVOCs, are needed to explain the observed SOA concentrations in Pasadena. All the recent parameterizations overpredict urban SOA formation at long photochemical ages (≈ 3 days) compared to observations from multiple sites, which can lead to problems in regional and especially global modeling. However, reducing IVOC emissions by one-half in the model to better match recent IVOC measurements improves SOA predictions at these long photochemical ages. Among the explicitly modeled VOCs, the precursor compounds that contribute the greatest SOA mass are methylbenzenes. Measured polycyclic aromatic hydrocarbons (naphthalenes) contribute 0.7% of the modeled SOA mass. The amounts of SOA mass from diesel vehicles, gasoline vehicles, and cooking emissions are estimated to be 16–27, 35–61, and 19–35%, respectively, depending on the parameterization used, which is consistent with the observed fossil fraction of urban SOA, 71(±3) %. The relative contribution of each source is uncertain by almost a factor of 2 depending on the parameterization used. In-basin biogenic VOCs are predicted to contribute only a few percent to SOA. A regional SOA background of approximately 2.1 μg m −3 is also present due to the long-distance transport of highly aged OA, likely with a substantial contribution from regional biogenic SOA. The percentage of SOA from diesel vehicle emissions is the same, within the estimated uncertainty, as reported in previous work that analyzed the weekly cycles in OA concentrations (Bahreini et al., 2012; Hayes et al., 2013). However, the modeling work presented here suggests a strong anthropogenic source of modern carbon in SOA, due to cooking emissions, which was not accounted for in those previous studies and which is higher on weekends. Lastly, this work adapts a simple two-parameter model to predict SOA concentration and O/C from urban emissions. This model successfully predicts SOA concentration, and the optimal parameter combination is very similar to that found for Mexico City. This approach provides a computationally inexpensive method for predicting urban SOA in global and climate models. We estimate pollution SOA to account for 26 Tg yr −1 of SOA globally, or 17% of global SOA, one-third of which is likely to be non-fossil.« less

On the Evaporation Kinetics and Phase of Laboratory and Ambient Secondary Organic Aerosol

NASA Astrophysics Data System (ADS)

Zelenyuk, A.; Vaden, T.; Imre, D. G.; Beránek, J.; Shrivastava, M.

2010-12-01

Field measurements of secondary organic aerosol (SOA) find significantly higher mass loads than predicted by models, sparking intense effort that is focused on finding additional SOA sources, but leaves many of the fundamental assumptions that are used by models unchallenged. Current air-quality models use absorptive partitioning theory assuming SOA particles are liquid droplets that form instantaneous reversible equilibrium with gas phase. Further, they ignore the effects of adsorption of spectator organic species during SOA formation on SOA properties and fate. Using an accurate and highly sensitive experimental approach for studying evaporation kinetics of size-selected single SOA particles, we characterized room-temperature evaporation kinetics of laboratory generated α-pinene SOA and ambient atmospheric SOA. The experimental setup was first tested by measuring the evaporation kinetics of single component organic particles of known vapor pressure. We show that, as expected for liquid droplets, smaller particles evaporate faster, and that these data yield the correct vapor pressure. We then study the evaporation kinetics of α-pinene SOA and find that evaporation proceeds in two stages: a fast stage, during which 50% of the particle volume evaporates in ~100 minutes, followed by a slower stage, when additional 25% evaporate in 1400 minutes, which is in sharp contrast to the ~10 minutes timescale predicted by current kinetic models. α-pinene SOA formed in the presence of “spectator” hydrophobic organic vapors like dioctyl phthalate, dioctyl sebacate, pyrene, or their mixture, were shown to adsorb noticeable amounts of these organics, forming what we term here ‘coated’ SOA particles. We show that these adsorbed coatings reduce evaporation rates of SOA particles. Moreover, aging of coated SOA particles dramatically reduces evaporation rates, and in some cases nearly stops it. For example, aging of SOA with adsorbed pyrene reduces evaporation rate to the point that only ~11% of the particle volume evaporates within 24 hrs. For all cases studied in this work, SOA evaporation behavior is size-independent and does not follow the evaporation kinetics of liquid droplets, which is in sharp contrast with model assumptions. To address the question of how closely the laboratory observations described above reflect reality in the atmosphere we characterized the evaporation kinetics of size-selected atmospheric SOA particles sampled in-situ during the recent Carbonaceous Aerosols and Radiative Effects Study (CARES) field campaign. We find that the evaporation of ambient SOA is very similar to that of coated and aged laboratory-generated α-pinene SOA. Ambient SOA particles in Sacramento, CA lose between 17% and 25% of their volume in 6 hours. Like laboratory SOA, their evaporation is size-independent and does not follow the kinetics of liquid droplets. The findings about SOA phase, evaporation rates, and the importance of spectator gases and aging - all indicate the need to reformulate the way SOA formation and evaporation are treated by models.

Dimer esters in α-pinene secondary organic aerosol: effect of hydroxyl radical, ozone, relative humidity and aerosol acidity

NASA Astrophysics Data System (ADS)

Kristensen, K.; Cui, T.; Zhang, H.; Gold, A.; Glasius, M.; Surratt, J. D.

2013-12-01

The formation of secondary organic aerosol (SOA) from both ozonolysis and hydroxyl radical (OH)-initiated oxidation of α-pinene under conditions of high nitric oxide (NO) concentrations with varying relative humidity (RH) and aerosol acidity was investigated in the University of North Carolina dual outdoor smog chamber facility. SOA formation from ozonolysis of α-pinene was enhanced relative to that from OH-initiated oxidation in the presence of initially high NO conditions. However, no effect of RH on SOA mass was evident. Ozone (O3)-initiated oxidation of α-pinene in the presence of ammonium sulfate (AS) seed coated with organic aerosol from OH-initiated oxidation of α-pinene showed reduced nucleation compared to ozonolysis in the presence of pure AS seed aerosol. The chemical composition of α-pinene SOA was investigated by ultra-performance liquid chromatography/electrospray ionization high-resolution quadrupole time-of-flight mass spectrometry (UPLC/ESI-HR-Q-TOFMS), with a focus on the formation of carboxylic acids and high-molecular weight dimer esters. A total of eight carboxylic acids and four dimer esters were identified, constituting between 8 and 12% of the total α-pinene SOA mass. OH-initiated oxidation of α-pinene in the presence of nitrogen oxides (NOx) resulted in the formation of highly oxidized carboxylic acids, such as 3-methyl-1,2,3-butanetricarboxylic acid (MBTCA) and diaterpenylic acid acetate (DTAA). The formation of dimer esters was observed only in SOA produced from the ozonolysis of α-pinene in the absence of NOx, with increased concentrations by a~factor of two at higher RH (50-90%) relative to lower RH (30-50%). The increased formation of dimer esters correlates with an observed increase in new particle formation at higher RH due to nucleation. Increased aerosol acidity was found to have a negligible effect on the formation of the dimer esters. SOA mass yield did not influence the chemical composition of SOA formed from α-pinene ozonolysis with respect to carboxylic acids and dimer esters. The results support the formation of the high-molecular weight dimer esters through gas-phase reactions of the stabilized Criegee Intermediate (sCI) formed from the ozonolysis of α-pinene. The high molecular weight and polar nature of dimer esters formed in the gas-phase may explain increased particle number concentration as a~result of homogenous nucleation. Since three of these dimer esters (i.e., pinyl-diaterpenyl ester (MW 358), pinyl-diaterebyl ester (MW 344) and pinonyl-pinyl ester (MW 368)) have been observed in both laboratory-generated and ambient fine organic aerosol samples, we conclude that the dimer esters observed in this study can be used as tracers for the O3-initiated oxidation of α-pinene, and are therefore indicative of enhanced anthropogenic activities, and that the high molecular weight and low volatility esters result in homogenous nucleation under laboratory conditions, increasing the particle number concentration.

Dimers in α-pinene secondary organic aerosol: effect of hydroxyl radical, ozone, relative humidity and aerosol acidity

NASA Astrophysics Data System (ADS)

Kristensen, K.; Cui, T.; Zhang, H.; Gold, A.; Glasius, M.; Surratt, J. D.

2014-04-01

The formation of secondary organic aerosol (SOA) from both ozonolysis and hydroxyl radical (OH)-initiated oxidation of α-pinene under conditions of high nitric oxide (NO) concentrations with varying relative humidity (RH) and aerosol acidity was investigated in the University of North Carolina dual outdoor smog chamber facility. SOA formation from ozonolysis of α-pinene was enhanced relative to that from OH-initiated oxidation in the presence of initially high-NO conditions. However, no effect of RH on SOA mass was evident. Ozone (O3)-initiated oxidation of α-pinene in the presence of ammonium sulfate (AS) seed coated with organic aerosol from OH-initiated oxidation of α-pinene showed reduced nucleation compared to ozonolysis in the presence of pure AS seed aerosol. The chemical composition of α-pinene SOA was investigated by ultra-performance liquid chromatography/electrospray ionization high-resolution quadrupole time-of-flight mass spectrometry (UPLC/ESI-HR-Q-TOFMS), with a focus on the formation of carboxylic acids and high-molecular weight dimers. A total of eight carboxylic acids and four dimers were identified, constituting between 8 and 12% of the total α-pinene SOA mass. OH-initiated oxidation of α-pinene in the presence of nitrogen oxides (NOx) resulted in the formation of highly oxidized carboxylic acids, such as 3-methyl-1,2,3-butanetricarboxylic acid (MBTCA) and diaterpenylic acid acetate (DTAA). The formation of dimers was observed only in SOA produced from the ozonolysis of α-pinene in the absence of NOx, with increased concentrations by a factor of two at higher RH (50-90%) relative to lower RH (30-50%). The increased formation of dimers correlates with an observed increase in new particle formation at higher RH due to nucleation. Increased aerosol acidity was found to have a negligible effect on the formation of the dimers. SOA mass yield did not influence the chemical composition of SOA formed from α-pinene ozonolysis with respect to carboxylic acids and dimers. The results support the formation of the high-molecular weight dimers through gas-phase reactions of the stabilized Criegee Intermediate (sCI) formed from the ozonolysis of α-pinene. The high molecular weight and polar nature of dimers formed in the gas phase may explain increased particle number concentration as a result of homogenous nucleation. Since three of these dimers (i.e. pinyl-diaterpenyl dimer (MW 358), pinyl-diaterebyl dimer (MW 344) and pinonyl-pinyl dimer (MW 368)) have been observed in both laboratory-generated and ambient fine organic aerosol samples, we conclude that the dimers observed in this study can be used as tracers for the O3-initiated oxidation of α-pinene, and are therefore indicative of enhanced anthropogenic activities, and that the high molecular weight and low volatility dimers result in homogenous nucleation under laboratory conditions, increasing the particle number concentration.

Secondary organic aerosol formation from hydroxyl radical oxidation and ozonolysis of monoterpenes

NASA Astrophysics Data System (ADS)

Zhao, D. F.; Kaminski, M.; Schlag, P.; Fuchs, H.; Acir, I.-H.; Bohn, B.; Häseler, R.; Kiendler-Scharr, A.; Rohrer, F.; Tillmann, R.; Wang, M. J.; Wegener, R.; Wildt, J.; Wahner, A.; Mentel, Th. F.

2015-01-01

Oxidation by hydroxyl radical (OH) and ozonolysis are the two major pathways of daytime biogenic volatile organic compound (BVOC) oxidation and secondary organic aerosol (SOA) formation. In this study, we investigated the particle formation of several common monoterpenes (α-pinene, β-pinene and limonene) by OH-dominated oxidation, which has seldom been investigated. OH oxidation experiments were carried out in the SAPHIR (Simulation of Atmospheric PHotochemistry In a large Reaction) chamber in Jülich, Germany, at low NOx (0.01 ~ 1 ppbV) and low ozone (O3) concentration (< 20 ppbV). OH concentration and total OH reactivity (kOH) were measured directly, and through this the overall reaction rate of total organics with OH in each reaction system was quantified. Multi-generation reaction process, particle growth, new particle formation (NPF), particle yield and chemical composition were analyzed and compared with that of monoterpene ozonolysis. Multi-generation products were found to be important in OH-dominated SOA formation. The relative role of functionalization and fragmentation in the reaction process of OH oxidation was analyzed by examining the particle mass and the particle size as a function of OH dose. We developed a novel method which quantitatively links particle growth to the reaction rate of OH with total organics in a reaction system. This method was also used to analyze the evolution of functionalization and fragmentation of organics in the particle formation by OH oxidation. It shows that functionalization of organics was dominant in the beginning of the reaction (within two lifetimes of the monoterpene) and fragmentation started to play an important role after that. We compared particle formation from OH oxidation with that from pure ozonolysis. In individual experiments, growth rates of the particle size did not necessarily correlate with the reaction rate of monoterpene with OH and O3. Comparing the size growth rates at the similar reaction rates of monoterpene with OH or O3 indicates that, generally, OH oxidation and ozonolysis had similar efficiency in particle growth. The SOA yield of α-pinene and limonene by ozonolysis was higher than that of OH oxidation. Aerosol mass spectrometry (AMS) shows SOA elemental composition from OH oxidation follows a slope shallower than -1 in the O / C vs. H / C diagram, also known as Van Krevelen diagram, indicating that oxidation proceeds without significant loss of hydrogen. SOA from OH oxidation had higher H / C ratios than SOA from ozonolysis. In ozonolysis, a process with significant hydrogen loss seemed to play an important role in SOA formation.

A comparison of secondary organic aerosol (SOA) yields and composition from ozonolysis of monoterpenes at varying concentrations of NO2

NASA Astrophysics Data System (ADS)

Draper, D. C.; Farmer, D. K.; Desyaterik, Y.; Fry, J. L.

2015-05-01

The effect of NO2 on secondary organic aerosol (SOA) formation from ozonolysis of α-pinene, β-pinene, Δ3-carene, and limonene was investigated using a dark flow-through reaction chamber. SOA mass yields were calculated for each monoterpene from ozonolysis with varying NO2 concentrations. Kinetics modeling of the first generation gas-phase chemistry suggests that differences in observed aerosol yields for different NO2 concentrations are consistent with NO3 formation and subsequent competition between O3 and NO3 to oxidize each monoterpene. α-pinene was the only monoterpene studied that showed a systematic decrease in both aerosol number concentration and mass concentration with increasing [NO2]. β-pinene and Δ3-carene produced fewer particles at higher [NO2], but both retained moderate mass yields. Limonene exhibited both higher number concentrations and greater mass concentrations at higher [NO2]. SOA from each experiment was collected and analyzed by HPLC-ESI-MS, enabling comparisons between product distributions for each system. In general, the systems influenced by NO3 oxidation contained more high molecular weight products (MW >400 amu), suggesting the importance of oligomerization mechanisms in NO3-initiated SOA formation. α-pinene, which showed anomalously low aerosol mass yields in the presence of NO2, showed no increase in these oligomer peaks, suggesting that lack of oligomer formation is a likely cause of α-pinene's near 0% yields with NO3. Through direct comparisons of mixed-oxidant systems, this work suggests that NO3 is likely to dominate nighttime oxidation pathways in most regions with both biogenic and anthropogenic influences. Therefore, accurately constraining SOA yields from NO3 oxidation, which vary substantially with the VOC precursor, is essential in predicting nighttime aerosol production.

Considering the future of anthropogenic gas-phase organic compound emissions and the increasing influence of non-combustion sources on urban air quality

NASA Astrophysics Data System (ADS)

Khare, Peeyush; Gentner, Drew R.

2018-04-01

Decades of policy in developed regions has successfully reduced total anthropogenic emissions of gas-phase organic compounds, especially volatile organic compounds (VOCs), with an intentional, sustained focus on motor vehicles and other combustion-related sources. We examine potential secondary organic aerosol (SOA) and ozone formation in our case study megacity (Los Angeles) and demonstrate that non-combustion-related sources now contribute a major fraction of SOA and ozone precursors. Thus, they warrant greater attention beyond indoor environments to resolve large uncertainties in their emissions, oxidation chemistry, and outdoor air quality impacts in cities worldwide. We constrain the magnitude and chemical composition of emissions via several bottom-up approaches using chemical analyses of products, emissions inventory assessments, theoretical calculations of emission timescales, and a survey of consumer product material safety datasheets. We demonstrate that the chemical composition of emissions from consumer products as well as commercial and industrial products, processes, and materials is diverse across and within source subcategories. This leads to wide ranges of SOA and ozone formation potentials that rival other prominent sources, such as motor vehicles. With emission timescales from minutes to years, emission rates and source profiles need to be included, updated, and/or validated in emissions inventories with expected regional and national variability. In particular, intermediate-volatility and semi-volatile organic compounds (IVOCs and SVOCs) are key precursors to SOA, but are excluded or poorly represented in emissions inventories and exempt from emissions targets. We present an expanded framework for classifying VOC, IVOC, and SVOC emissions from this diverse array of sources that emphasizes a life cycle approach over longer timescales and three emission pathways that extend beyond the short-term evaporation of VOCs: (1) solvent evaporation, (2) solute off-gassing, and (3) volatilization of degradation by-products. Furthermore, we find that ambient SOA formed from these non-combustion-related emissions could be misattributed to fossil fuel combustion due to the isotopic signature of their petroleum-based feedstocks.

Formation of secondary aerosols from gasoline vehicle exhausts when mixing with SO2

NASA Astrophysics Data System (ADS)

Liu, T.; Wang, X.; Hu, Q.; Deng, W.; Zhang, Y.; Ding, X.; Fu, X.; Bernard, F.; Zhang, Z.; Lü, S.; He, Q.; Bi, X.; Chen, J.; Sun, Y.; Yu, J.; Peng, P.; Sheng, G.; Fu, J.

2015-09-01

Sulfur dioxide (SO2) can enhance the formation of secondary aerosols from biogenic volatile organic compounds (VOCs), but its influence on secondary aerosol formation from anthropogenic VOCs, particularly complex mixtures like vehicle exhausts, is still poorly understood. Here we directly co-introduced gasoline vehicles exhausts (GVE) and SO2, a typical pollutant from coal burning, into a smog chamber to investigate the formation of secondary organic aerosols (SOA) and sulfate aerosols through photooxidation. In the presence of high concentration of SO2, new particle formation was enhanced while substantial sulfate was formed through the oxidation of SO2. The homogenous oxidation by OH radicals contributed a negligible fraction to the conversion of SO2 to sulfate, and instead the oxidation by stabilized Criegee intermediates (sCIs), formed from alkenes in the exhaust reacting with ozone, dominated the conversion of SO2. After 5 h of photochemical aging, GVE's SOA production factor revealed an increase by 60-200 % in the presence of high concentration of SO2. This increase could largely be attributed to acid-catalyzed SOA formation, which was evidenced by the strong positive linear correlation (R2 = 0.97) between the SOA production factor and in-situ particle acidity calculated by AIM-II model. A high-resolution time-of-flight aerosol mass spectrometer (HR-TOF-AMS) resolved OA's relatively lower oxygen-to-carbon (O : C) and higher hydrogen-to-carbon (H : C) molar ratios for the GVE/SO2 mixture, with a much lower estimated average carbon oxidation state (OSc) of -0.51 ± 0.06 than that of -0.19 ± 0.08 for GVE alone. The relative higher mass loading of OA in the experiments with SO2 might be the major reason for the lower oxidation degree of SOA.

Is the gas-particle partitioning in alpha-pinene secondary organic aerosol reversible?

NASA Astrophysics Data System (ADS)

Grieshop, Andrew P.; Donahue, Neil M.; Robinson, Allen L.

2007-07-01

This paper discusses the reversibility of gas-particle partitioning in secondary organic aerosol (SOA) formed from α-pinene ozonolysis in a smog chamber. Previously, phase partitioning has been studied quantitatively via SOA production experiments and qualitatively by perturbing temperature and observing particle evaporation. In this work, two methods were used to isothermally dilute the SOA: an external dilution sampler and an in-chamber technique. Dilution caused some evaporation of SOA, but repartitioning took place on a time scale of tens of minutes to hours-consistent with an uptake coefficient on the order of 0.001-0.01. However, given sufficient time, α-pinene SOA repartitions reversibly based on comparisons with data from conventional SOA yield experiments. Further, aerosol mass spectrometer (AMS) data indicate that the composition of SOA varies with partitioning. These results suggest that oligomerization observed in high-concentration laboratory experiments may be a reversible process and underscore the complexity of the kinetics of formation and evaporation of SOA.

The influences of ammonia on aerosol formation in the ozonolysis of styrene: roles of Criegee intermediate reactions

PubMed Central

Ma, Qiao; Lin, Xiaoxiao; Yang, Chengqiang; Long, Bo; Zhang, Weijun

2018-01-01

The influences of ammonia (NH3) on secondary organic aerosol (SOA) formation from ozonolysis of styrene have been investigated using chamber experiments and quantum chemical calculations. With the value of [O3]0/[styrene]0 ratios between 2 and 4, chamber experiments were carried out without NH3 or under different [NH3]/[styrene]0 ratios. The chamber experiments reveal that the addition of NH3 led to significant decrease of SOA yield. The overall SOA yield decreased with the [NH3]0/[styrene]0 increasing. In addition, the addition of NH3 at the beginning of the reaction or several hours after the reaction occurs had obviously different influence on the yield of SOA. Gas phase reactions of Criegee intermediates (CIs) with aldehydes and NH3 were studied in detail by theoretical methods to probe into the mechanisms behind these phenomena. The calculated results showed that 3,5-diphenyl-1,2,4-trioxolane, a secondary ozonide formed through the reactions of C6H5ĊHOO· with C6H5CHO, could make important contribution to the aerosol composition. The addition of excess NH3 may compete with aldehydes, decreasing the secondary ozonide yield to some extent and thus affect the SOA formation. PMID:29892406

Examining the Effects of Anthropogenic Emissions on Isoprene-Derived Secondary Organic Aerosol Formation During the 2013 Southern Oxidant and Aerosol Study (SOAS) at the Look Rock, Tennessee, Ground Site

EPA Science Inventory

A suite of offline and real-time gas- and particle-phase measurements was deployed atLook Rock, Tennessee (TN), during the 2013 Southern Oxidant and Aerosol Study (SOAS) to examine the effects of anthropogenic emissions on isoprene-derived secondary organic aerosol (SOA) formatio...

Oil Sands Operations in Alberta, Canada: A large source of secondary organic aerosol

NASA Astrophysics Data System (ADS)

Liggio, J.; Li, S. M.; Hayden, K.; Taha, Y. M.; Stroud, C.; Darlington, A. L.; Drollette, B.; Gordon, M.; Lee, P.; Liu, P.; Leithead, A.; Moussa, S.; Wang, D.; O'Brien, J.; Mittermeier, R. L.; Brook, J.; Lu, G.; Staebler, R. M.; Han, Y.; Tokarek, T. W.; Osthoff, H. D.; Makar, P.; Zhang, J.; Plata, D.; Gentner, D. R.

2015-12-01

Little is known of the reaction products of emissions to the atmosphere from extraction of oil from unconventional sources in the oil sands (OS) region of Alberta, Canada. This study examines these reaction products, and in particular, the extent to which they form secondary organic aerosol (SOA), which can significantly contribute to regional particulate matter formation. An aircraft measurement campaign was conducted over the Athabasca oil sands region between August 13 and September 7, 2013. A broad suite of measurements were made during 22 flights, including organic aerosol mass and composition with a High Resolution Time of Flight Aerosol Mass Spectrometer (HR-ToF-AMS) and organic aerosol gas-phase precursors by Proton Transfer Reaction (PTR) and off-line gas chromatography mass spectrometry. Large concentrations of organic aerosol were measured downwind of the OS region, which we show to be entirely secondary in nature. Laboratory experiments demonstrated that bitumen (the mined product) contains semi-volatile vapours in the C12-C18 range that will be emitted at ambient temperatures. When oxidized, these vapours form SOA with highly similar HR-ToF-AMS spectra to the SOA measured in the flights. Box modelling of the OS plume evolution indicated that the measured levels of traditional volatile organic compounds (VOCs) are not capable of accounting for the amount of SOA formed in OS plumes. This discrepancy is only reconciled in the model by including bitumen vapours along with their oxidation and condensation into the model. The concentration of bitumen vapours required to produce SOA matching observations is similar to that of traditional VOC precursors of SOA. It was further estimated that the cumulative SOA mass formation approximately 100 km downwind of the OS during these flights, and under these meteorological conditions was up to 82 tonnes/day. The combination of airborne measurements, laboratory experiments and box modelling indicated that semi-volatile organic compounds (SVOC) are emitted from OS operations which accounted for >85% of the formed SOA mass in these plumes. Implications of this SOA formation will be discussed.

Photosensitized Formation of Secondary Organic Aerosols above the Air/Water Interface

PubMed Central

2016-01-01

In this study, we evaluated photosensitized chemistry at the air–sea interface as a source of secondary organic aerosols (SOA). Our results show that, in addition to biogenic emissions, abiotic processes could also be important in the marine boundary layer. Photosensitized production of marine secondary organic aerosol was studied in a custom-built multiphase atmospheric simulation chamber. The experimental chamber contained water, humic acid (1–10 mg L–1) as a proxy for dissolved organic matter, and nonanoic acid (0.1–10 mM), a fatty acid proxy which formed an organic film at the air–water interface. Dark secondary reaction with ozone after illumination resulted in SOA particle concentrations in excess of 1000 cm–3, illustrating the production of unsaturated compounds by chemical reactions at the air–water interface. SOA numbers via photosensitization alone and in the absence of ozone did not exceed background levels. From these results, we derived a dependence of SOA numbers on nonanoic acid surface coverage and dissolved organic matter concentration. We present a discussion on the potential role of the air–sea interface in the production of atmospheric organic aerosol from photosensitized origins. PMID:27434860

Aqueous-Phase Mechanism for Secondary Organic Aerosol Formation from Isoprene: Application to the Southeast United States and Co-Benefit of SO2 Emission Controls

NASA Technical Reports Server (NTRS)

Marais, E. A.; Jacob, D. J.; Jimenez, J. L.; Campuzano-Jost, P.; Day, D. A.; Hu, W.; Krechmer, J.; Zhu, L.; Kim, P. S.; Miller, C. C.;

Molecular formula composition of β-caryophyllene ozonolysis SOA formed in humid and dry conditions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kundu, Shuvashish; Fisseha, Rebeka; Putman, Annie L.

Here, we studied the molecular formula composition of six β-caryophyllene SOA samples using ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry under various reaction conditions. The SOA samples were generated in dry or low relative humidity (RH) chamber conditions with or without cyclohexane. All of the studied SOA mass spectra have three distinct clusters of hundreds of negative ions referred to as Group I (100 < m/z < 400), Group II (400 < m/z < 700) and Group III (700 < m/z < 1 000) compounds. C 14-16H 22-28O 2-11, C 28-29H 42-48O 6-16 and C 42-43H 68-70O 14-16more » were observed as highly abundant organic compounds in the compound class of Group I, II and III, respectively. The relative intensities of most analytes were higher in humid conditions compared to those in dry conditions, indicating the importance of water-dependent reactions and the catalytic role of water both in the presence and absence of cyclohexane. In addition, molecular formulas with higher average carbon numbers were observed in humid SOA than in dry SOA in the absence of cyclohexane, suggesting a decrease of cleavage reactions in humid condition. This study characterizes β-caryophyllene ozonolysis SOA based on ultrahigh mass resolution and demonstrates the significance of humidity in terms of the molecular distributions and relative abundances of the analytes. We also discuss the possible mechanism for the formation of Group I-III compounds based on the current understanding of SOA formation in the atmosphere.« less

Molecular formula composition of β-caryophyllene ozonolysis SOA formed in humid and dry conditions

DOE PAGES

Kundu, Shuvashish; Fisseha, Rebeka; Putman, Annie L.; ...

2016-12-22

Here, we studied the molecular formula composition of six β-caryophyllene SOA samples using ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry under various reaction conditions. The SOA samples were generated in dry or low relative humidity (RH) chamber conditions with or without cyclohexane. All of the studied SOA mass spectra have three distinct clusters of hundreds of negative ions referred to as Group I (100 < m/z < 400), Group II (400 < m/z < 700) and Group III (700 < m/z < 1 000) compounds. C 14-16H 22-28O 2-11, C 28-29H 42-48O 6-16 and C 42-43H 68-70O 14-16more » were observed as highly abundant organic compounds in the compound class of Group I, II and III, respectively. The relative intensities of most analytes were higher in humid conditions compared to those in dry conditions, indicating the importance of water-dependent reactions and the catalytic role of water both in the presence and absence of cyclohexane. In addition, molecular formulas with higher average carbon numbers were observed in humid SOA than in dry SOA in the absence of cyclohexane, suggesting a decrease of cleavage reactions in humid condition. This study characterizes β-caryophyllene ozonolysis SOA based on ultrahigh mass resolution and demonstrates the significance of humidity in terms of the molecular distributions and relative abundances of the analytes. We also discuss the possible mechanism for the formation of Group I-III compounds based on the current understanding of SOA formation in the atmosphere.« less

SOA precursors at the T0 site during the 2010 CARES campaign

NASA Astrophysics Data System (ADS)

Wallace, H. W.; Jobson, B. T.; Erickson, M. H.

2010-12-01

Continuous measurements of C5 to C12 Volatile Organic Compounds (VOC) have been made using the Washington State University Mobile Atmospheric Chemistry Laboratory (MACL), at the T0 site during the month of June 2010 Carbonaceous Aerosol Carbonaceous Aerosols and Radiative Effects Study (CARES). These measurements were made to better understand aerosol formation and growth in Sacramento, CA and the surrounding areas. Using a sorbent based preconcentration sampling technique for our quadrupole ion trap gas chromatography mass spectrometer (GCMS), we have measured anthropogenic and biogenic secondary organic aerosol (SOA) precursors. Major biogenic VOCs identified include: α-pinene, limonene, isoprene, phellanderene and β-pinene. Diurnal profiles of the concentrations will be presented. Monoterpenes were highest in the mornings while isoprene was highest in the afternoon. In addition to understanding the diurnal profiles the SOA precursors at the T0 site, the relative contributions of biogenic and anthropogenic compounds to SOA formation will be presented.

Contributions of toluene and alpha-pinene to SOA formed in an irradiated toluene/alpha-pinene/NO(x)/ air mixture: comparison of results using 14C content and SOA organic tracer methods.

PubMed

Offenberg, John H; Lewis, Charles W; Lewandowski, Michael; Jaoui, Mohammed; Kleindienst, Tadeusz E; Edney, Edward O

2007-06-01

An organic tracer method, recently proposed for estimating individual contributions of toluene and alpha-pinene to secondary organic aerosol (SOA) formation, was evaluated by conducting a laboratory study where a binary hydrocarbon mixture, containing the anthropogenic aromatic hydrocarbon, toluene, and the biogenic monoterpene, alpha-pinene, was irradiated in air in the presence of NO(x) to form SOA. The contributions of toluene and alpha-pinene to the total SOA concentration, calculated using the organic tracer method, were compared with those obtained with a more direct 14C content method. In the study, SOA to SOC ratios of 2.07 +/- 0.08 and 1.41 +/- 0.04 were measured for toluene and (alpha-pinene SOA, respectively. The individual tracer-based SOA contributions of 156 microg m(-3) for toluene and 198 microg m(-)3 for alpha-pinene, which together accounted for 82% of the gravimetrically determined total SOA concentration, compared well with the 14C values of 182 and 230 microg m(-3) measured for the respective SOA precursors. While there are uncertainties associated with the organic tracer method, largely due to the chemical complexity of SOA forming chemical mechanisms, the results of this study suggest the organic tracer method may serve as a useful tool for determining whether a precursor hydrocarbon is a major SOA contributor.

Primary and secondary organic aerosols in summer 2016 in Beijing

NASA Astrophysics Data System (ADS)

Tang, Rongzhi; Wu, Zepeng; Li, Xiao; Wang, Yujue; Shang, Dongjie; Xiao, Yao; Li, Mengren; Zeng, Limin; Wu, Zhijun; Hallquist, Mattias; Hu, Min; Guo, Song

2018-03-01

To improve air quality, the Beijing government has employed several air pollution control measures since the 2008 Olympics. In order to investigate organic aerosol sources after the implementation of these measures, ambient fine particulate matter was collected at a regional site in Changping (CP) and an urban site at the Peking University Atmosphere Environment Monitoring Station (PKUERS) during the Photochemical Smog in China field campaign in summer 2016. Chemical mass balance (CMB) modeling and the tracer yield method were used to apportion primary and secondary organic sources. Our results showed that the particle concentration decreased significantly during the last few years. The apportioned primary and secondary sources explained 62.8 ± 18.3 and 80.9 ± 27.2 % of the measured OC at CP and PKUERS, respectively. Vehicular emissions served as the dominant source. Except for gasoline engine emissions, the contributions of all the other primary sources decreased. In addition, the anthropogenic SOC, i.e., toluene SOC, also decreased, implying that deducting primary emissions can reduce anthropogenic SOA. In contrast to the SOA from other regions in the world where biogenic SOA was dominant, anthropogenic SOA was the major contributor to SOA, implying that deducting anthropogenic VOC emissions is an efficient way to reduce SOA in Beijing. Back-trajectory cluster analysis results showed that high mass concentrations of OC were observed when the air mass was from the south. However, the contributions of different primary organic sources were similar, suggesting regional particle pollution. The ozone concentration and temperature correlated well with the SOA concentration. Different correlations between day and night samples suggested different SOA formation pathways. Significant enhancement of SOA with increasing particle water content and acidity was observed in our study, suggesting that aqueous-phase acid-catalyzed reactions may be the important SOA formation mechanism in summer in Beijing.

SOA Formation from the Atmospheric Oxidation of 2-Methyl-3-Buten-2-ol and Its Implications for PM2.5

EPA Science Inventory

The formation of secondary organic aerosol (SOA) generated by irradiating 2-methyl-3-buten-2-01 (MBO) in the presence and/or absence of NO_x H₂O2, and/or SO₂ was examined. Experiments were conducted. in smog chambers operated either in dyna....

Isoprene derived secondary organic aerosol in a global aerosol chemistry climate model

NASA Astrophysics Data System (ADS)

Stadtler, Scarlet; Kühn, Thomas; Taraborrelli, Domenico; Kokkola, Harri; Schultz, Martin

2017-04-01

Secondary organic aerosol (SOA) impacts earth's climate and human health. Since its precursor chemistry and its formation are not fully understood, climate models cannot catch its direct and indirect effects. Global isoprene emissions are higher than any other non-methane hydrocarbons. Therefore, SOA from isoprene-derived, low volatile species (iSOA) is simulated using a global aerosol chemistry climate model ECHAM6-HAM-SALSA-MOZ. Isoprene oxidation in the chemistry model MOZ is following a novel semi-explicit scheme, embedded in a detailed atmospheric chemical mechanism. For iSOA formation four low volatile isoprene oxidation products were identified. The group method by Nanoonlal et al. 2008 was used to estimate their evaporation enthalpies ΔHvap. To calculate the saturation concentration C∗(T) the sectional aerosol model SALSA uses the gas phase concentrations simulated by MOZ and their corresponding ΔHvap to obtain the saturation vapor pressure p∗(T) from the Clausius Clapeyron equation. Subsequently, the saturation concentration is used to calculate the explicit kinetic partitioning of these compounds forming iSOA. Furthermore, the irreversible heterogeneous reactions of IEPOX and glyoxal from isoprene were included. The possibility of reversible heterogeneous uptake was ignored at this stage, leading to an upper estimate of the contribution of glyoxal to iSOA mass.

Modeling study of secondary organic aerosol in winter in China using NAQPMS

NASA Astrophysics Data System (ADS)

Yang, W.; Li, J.

2017-12-01

The concentration of organic aerosol (OA) in the central and eastern China is much higher than that in Europe and America. Compared with the observation, the current numerical modeling studies largely underestimated the concentration of OA, especially the secondary component. Based on the volatility basis set framework, a secondary organic aerosol (SOA) module was developed, which considering the multi-generation oxidation of volatile organic compounds (VOCs), semi-volatile POA and intermediate volatility organic compounds (IVOCs). The newly developed SOA module was coupled into the NAQPMS, and the performance of the simulation was validated by the observation with high temporal resolution. In wintertime, the OA concentration in the central and eastern China was maintained above 15-20 μg·m-3, and SOA accounted for 50-65% of OA concentration. The OA concentration even reached 40 μg·m-3 in the provinces emitting most pollutants (such as Hunan, Hubei, Henan, Anhui, Jiangsu, Shandong and Hubei province). IVOCs were important precursors of SOA in China, and could reduce the great discrepancy between simulation and observation. In wintertime, the contribution from IVOCs accounted for 60-80% of SOA formation. The aging of semi-volatile POA had less impact on the SOA formation, which maintained only 2-8% over central and eastern China.

Secondary organic aerosol production from pinanediol, a semi-volatile surrogate for first-generation oxidation products of monoterpenes

NASA Astrophysics Data System (ADS)

Ye, Penglin; Zhao, Yunliang; Chuang, Wayne K.; Robinson, Allen L.; Donahue, Neil M.

2018-05-01

We have investigated the production of secondary organic aerosol (SOA) from pinanediol (PD), a precursor chosen as a semi-volatile surrogate for first-generation oxidation products of monoterpenes. Observations at the CLOUD facility at CERN have shown that oxidation of organic compounds such as PD can be an important contributor to new-particle formation. Here we focus on SOA mass yields and chemical composition from PD photo-oxidation in the CMU smog chamber. To determine the SOA mass yields from this semi-volatile precursor, we had to address partitioning of both the PD and its oxidation products to the chamber walls. After correcting for these losses, we found OA loading dependent SOA mass yields from PD oxidation that ranged between 0.1 and 0.9 for SOA concentrations between 0.02 and 20 µg m-3, these mass yields are 2-3 times larger than typical of much more volatile monoterpenes. The average carbon oxidation state measured with an aerosol mass spectrometer was around -0.7. We modeled the chamber data using a dynamical two-dimensional volatility basis set and found that a significant fraction of the SOA comprises low-volatility organic compounds that could drive new-particle formation and growth, which is consistent with the CLOUD observations.

VOCs composition and reactivity during the combined pollution process at a comprehensive site in Guangzhou, China

NASA Astrophysics Data System (ADS)

Zou, Yu

2017-04-01

Guangzhou, one of China's megacities, is beset with frequent occurrence of high-concentration ozone and haze events. Volatile Organic Compounds(VOCs) were continuously monitor by online instrument at GPACS(the Guangzhou Panyu Atmospheric Composition Station) of the China Meteorological Administration during the two combined pollution processes from September 2th,2011 to September 5th,2011(P1) and from June 12th,2012 to June 15th ,2012(P2) to determine the VOCs composition and reactivity of ozone formation and secondary organic aerosol(SOA) formation. The results showed that during P1 and P2, alkanes occupied the largest proportion accounting for 57 and 57% of the VOC concentration, respectively, followed by aromatics (24 and 31%, respectively) and lastly alkenes (19 and 12%, respectively). As can be seen from the MIR-weighted concentrations, the alkenes and aromatics were dominant, accounting for 28 and 54% (P1), respectively, as well as 22 and 61% (P2), respectively. In terms of SOA formation potential by FAC estimation, alkanes, alkenes and aromatics were accounting for 13.2%, 21.4%, 65.4% (P1), respectively, and 4.6%, 13.8%, 81.6% (P2),respectively. Toluene, isoprene, ethylbenzene and m,p-Xylene had a high reactivity to the ozone and SOA formation during P1 and P2. It should be noted that the concentration of isoprene was not high, but it had a very high reactivity. Therefore, the isoprene emissions need to be considered with respect to the control of ozone and PM in Guangzhou.

Products and mechanism of secondary organic aerosol formation from reactions of n-alkanes with OH radicals in the presence of NOx.

PubMed

Lim, Yong Bin; Ziemann, Paul J

2005-12-01

Secondary organic aerosol (SOA) formation from reactions of n-alkanes with OH radicals in the presence of NOx was investigated in an environmental chamber using a thermal desorption particle beam mass spectrometer for particle analysis. SOA consisted of both first- and higher-generation products, all of which were nitrates. Major first-generation products were sigma-hydroxynitrates, while higher-generation products consisted of dinitrates, hydroxydinitrates, and substituted tetrahydrofurans containing nitrooxy, hydroxyl, and carbonyl groups. The substituted tetrahydrofurans are formed by a series of reactions in which sigma-hydroxycarbonyls isomerize to cyclic hemiacetals, which then dehydrate to form substituted dihydrofurans (unsaturated compounds) that quickly react with OH radicals to form lower volatility products. SOA yields ranged from approximately 0.5% for C8 to approximately 53% for C15, with a sharp increase from approximately 8% for C11 to approximately 50% for C13. This was probably due to an increase in the contribution of first-generation products, as well as other factors. For example, SOA formed from the C10 reaction contained no first-generation products, while for the C15 reaction SOA was approximately 40% first-generation and approximately 60% higher-generation products, respectively. First-generation sigma-hydroxycarbonyls are especially important in SOA formation, since their subsequent reactions can rapidly form low volatility compounds. In the atmosphere, substituted dihydrofurans created from sigma-hydroxycarbonyls will primarily react with O3 or NO3 radicals, thereby opening reaction pathways not normally accessible to saturated compounds.

Correlations between water-soluble organic aerosol and water vapor: a synergistic effect from biogenic emissions?

PubMed

Hennigan, Christopher J; Bergin, Michael H; Weber, Rodney J

2008-12-15

Ground-based measurements of meteorological parameters and water-soluble organic carbon in the gas(WSOCg) and particle (WSOCp) phases were carried out in Atlanta, Georgia, from May to September 2007. Fourteen separate events were observed throughout the summer in which WSOCp and water vapor concentrations were highly correlated (average WSOCp-water vapor r = 0.92); however, for the entire summer, no well-defined relationship existed between the two. The correlation events, which lasted on average 19 h, were characterized by a wide range of WSOCp and water vapor concentrations. Several hypotheses for the correlation are explored, including heterogeneous liquid phase SOA formation and the co-emission of biogenic VOCs and water vapor. The data provide supporting evidence for contributions from both and suggest the possibility of a synergistic effect between the co-emission of water vapor and VOCs from biogenic sources on SOA formation. Median WSOCp concentrations were also correlated with elemental carbon (EC), although this correlation extended over the entire summer. Despite the emission of water vapor from anthropogenic mobile sources and the WSOCp-EC correlation, mobile sources were not considered a potential cause for the WSOCp-water vapor correlations because of their low contribution to the water vapor budget. Meteorology could perhaps have influenced the WSOCp-EC correlation, but other factors are implicated as well. Overall, the results suggest that the temperature-dependent co-emission of water vapor through evapotranspiration and SOA precursor-VOCs by vegetation may be an important process contributing to SOA in some environments.

Formation of nitrogen- and sulfur-containing light-absorbing compounds accelerated by evaporation of water from secondary organic aerosols

NASA Astrophysics Data System (ADS)

Nguyen, Tran B.; Lee, Paula B.; Updyke, Katelyn M.; Bones, David L.; Laskin, Julia; Laskin, Alexander; Nizkorodov, Sergey A.

2012-01-01

Aqueous extracts of secondary organic aerosols (SOA) generated from the ozonolysis of d-limonene were subjected to dissolution, evaporation, and re-dissolution in the presence and absence of ammonium sulfate (AS). Evaporation with AS at pH 4-9 produced chromophores that were stable with respect to hydrolysis and had a distinctive absorption band at 500 nm. Evaporation accelerated the rate of chromophore formation by at least three orders of magnitude compared to the reaction in aqueous solution, which produced similar compounds. Absorption spectroscopy and high-resolution nanospray desorption electrospray ionization (nano-DESI) mass spectrometry experiments suggested that the molar fraction of the chromophores was small (<2%), and that they contained nitrogen atoms. Although the colored products represented only a small fraction of SOA, their large extinction coefficients (>105 L mol-1 cm-1 at 500 nm) increased the effective mass absorption coefficient of the residual organics in excess of 103 cm2 g-1 - a dramatic effect on the optical properties from minor constituents. Evaporation of SOA extracts in the absence of AS resulted in the production of colored compounds only when the SOA extract was acidified to pH ˜ 2 with sulfuric acid. These chromophores were produced by acid-catalyzed aldol condensation, followed by a conversion into organosulfates. The presence of organosulfates was confirmed by high resolution mass spectrometry experiments. Results of this study suggest that evaporation of cloud or fog droplets containing dissolved organics leads to significant modification of the molecular composition and serves as a potentially important source of light-absorbing compounds.

Impact of primary and secondary organic sources on the oxidative potential of quasi-ultrafine particles (PM0.25) at three contrasting locations in the Los Angeles Basin

NASA Astrophysics Data System (ADS)

Saffari, Arian; Hasheminassab, Sina; Wang, Dongbin; Shafer, Martin M.; Schauer, James J.; Sioutas, Constantinos

2015-11-01

To investigate the changing contribution of primary and secondary sources on the oxidative potential of particulate matter (PM) in a real-world urban atmosphere, 7 sets of quasi-ultrafine particles (PM0.25) were collected at three contrasting locations in the Los Angeles Basin, California, USA. Samples were collected in the coastal area of Long Beach during the morning rush hour period, representing fresh primary emissions from nearby freeways and the LA port; in central Los Angeles during midday, representing a mixture of fresh primary emissions and early products of photochemical secondary organic aerosol (SOA) formation; and at a downwind site (Upland) during afternoon, when the impacts of photochemically aged secondary PM are significant. Chemical composition showed distinctive trends, with the lowest fraction of water soluble organic carbon (WSOC) and other organic tracers of SOA formation (e.g. organic acids) at Long Beach, and the lowest abundance of organic tracers of primary vehicular emissions (such as polycyclic aromatic hydrocarbons and hopanes) at Upland. A molecular marker-based chemical mass balance (MM-CMB) model indicated that 72% of the total organic carbon at Long Beach was comprised of primary vehicular sources (combined heavy duty and light duty vehicles), while the vehicular fraction was found to be 50% and 39% at Los Angeles and Upland, respectively. Regression analysis suggested that at Long Beach, the variation in oxidative potential of PM0.25 (quantified using a macrophage-based reactive oxygen species (ROS) assay) was mainly driven by mobile vehicular emissions and the water-insoluble fraction of the organic carbon. In contrast, at Upland, where photochemical processing and secondary aerosol formation was the highest, WSOC and secondary organics were the major drivers of the oxidative potential variation. The multivariate regression analysis also indicated that as much as 58% of the overall spatial and temporal variation in the oxidative potential of PM0.25 at these three locations can be explained by mobile emissions and SOA.

Pollution data analysis and characteristics of volatile organic compounds in the environment

NASA Astrophysics Data System (ADS)

Wang, Qi; Wang, Chěn; Hou, Lujian; Lv, Bo; WANG, Chén

2018-06-01

Volatile organic compounds (VOCs) have a wide range of sources and have a significant impact on the ecological environment and human health, which have attracted wide attention of many researchers. In this paper, the pollution characteristics of VOCs, the role of VOCs in atmospheric chemistry including OH reaction reactivity (LOH), Ozone Formation Potential (OFP) and SOA generation potential (SOAP), VOCs source apportionment were discussed and reviewed.

Novel insight on photochemistry at interfaces: potential impact on Seconday Aerosol Formation?

NASA Astrophysics Data System (ADS)

Rossignol, S.; George, C.; Aregahegn, K.

2014-12-01

Traditionally, the driving forces for SOA growth is believed to be the partitioning onto aerosol seeds of condensable gases, either emitted primarily or resulting from the gas phase oxidation of organic gases. However, even the most up-to-date models based on such mechanisms cannot account for the SOA mass observed in the atmosphere, suggesting the existence of other, yet unknown formation processes. The present study shows experimental evidence that particulate phase chemistry produces photo-sensitizers that lead to photo-induced formation and growth of secondary organic aerosol in the near UV and the presence of volatile organic compounds (VOC) such as terpenes. By means of an aerosol flow tube reactor equipped with Scanning Mobility Particle Sizer (SMPS), Differential Mobility Analyzer (DMA) and Condensation Particle Sizer (CPC), we identified that traces in the aerosol phase of glyoxal chemistry products, namely imidazole-2-carboxaldehyde (IC) are strong photo-sensitizers when irradiated with near-UV. In the presence of volatile organic compounds such as terpenes, this chemistry leads to a fast aerosol growth. Given the potential importance of this new photosensitized growth pathway for ambient OA, the related reaction mechanism was investigated at a molecular level. Bulk and flow tube experiments were performed to identify major products of the reaction of limonene with the triplet state of IC by direct (+/-)ESI-HRMS and UPLC/(+/-)HESI-HRMS analysis. Detection of recombination products of IC with limonene or with itself, in bulk and flow tube experiment ts, showed that IC is able to initiate a radical chemistry in the aerosol phase under realistic irradiation conditions. Furthermore, highly oxygenated limonene reaction products were detected, clearly explaining the observed OA growth. The chemistry of peroxy radicals derived from limonene upon addition of oxygen explains the formation of such low-volatile compounds without any traditional gas phase oxidant. These results demonstrate that, upon ageing, organic aerosols can produce photo-sensitizers which auto-photo-catalyse their SOA growth.

Chemical characterization of secondary organic aerosol constituents from isoprene ozonolysis in the presence of acidic aerosol

NASA Astrophysics Data System (ADS)

Riva, Matthieu; Budisulistiorini, Sri Hapsari; Zhang, Zhenfa; Gold, Avram; Surratt, Jason D.

2016-04-01

Isoprene is the most abundant non-methane hydrocarbon emitted into Earth's atmosphere and is predominantly derived from terrestrial vegetation. Prior studies have focused largely on the hydroxyl (OH) radical-initiated oxidation of isoprene and have demonstrated that highly oxidized compounds, such as isoprene-derived epoxides, enhance the formation of secondary organic aerosol (SOA) through heterogeneous (multiphase) reactions on acidified sulfate aerosol. However, studies on the impact of acidified sulfate aerosol on SOA formation from isoprene ozonolysis are lacking and the current work systematically examines this reaction. SOA was generated in an indoor smog chamber from isoprene ozonolysis under dark conditions in the presence of non-acidified or acidified sulfate seed aerosol. The effect of OH radicals on SOA chemical composition was investigated using diethyl ether as an OH radical scavenger. Aerosols were collected and chemically characterized by ultra performance liquid chromatography/electrospray ionization high-resolution quadrupole time-of-flight mass spectrometry (UPLC/ESI-HR-QTOFMS) and gas chromatography/electron impact ionization-mass spectrometry (GC/EI-MS). Analysis revealed the formation of highly oxidized compounds, including organosulfates (OSs) and 2-methylterols, which were significantly enhanced in the presence of acidified sulfate seed aerosol. OSs identified in the chamber experiments were also observed and quantified in summertime fine aerosol collected from two rural locations in the southeastern United States during the 2013 Southern Oxidant and Aerosol Study (SOAS).

Ammonia Partitioning into the Condensed Phase in Winter Time Conditions

NASA Astrophysics Data System (ADS)

Green, J. R.; Bililign, S.; Fiddler, M. N.; Leen, J. B.; Holloway, J. S.; Fibiger, D. L.; McDuffie, E. E.; Thornton, J. A.; Brown, S. S.

2015-12-01

Secondary aerosol (SOA) formation has been linked to health problems and environmental damage in regions impacted by the emission of gaseous NH3 and SO2. SOA formation, (NH4)2SO4 and NH4NO3, in the presence of NO NO2, is favored under high relative humidity and low temperature and low temperature conditions. In the East and Mid Atlantic regions of the United States humidity is low in wintertime. Utilizing ambient concentration data of gaseous NO, NO2, SO2 and NH3 collected aboard a survey aircraft we examined the partitioning of gaseous NH3 towards aerosol products. The calculated mixing ratio of gaseous SO2/NH3 correlated with relative humidity will give an indication of the potential SOA formation when the mixing ratio of other reactants is small in the region of interest. The data obtained originates from a series of night and day survey flights on a C-130 aircraft that occurred from February 3 to March 13, 2015 over the Eastern coastal region of the United States extending from New York to Florida. NOx was obtained from the Airborne Ring-down Nitrogen Oxide Laser Detector (ARNOLD) instrument (NOAA) and Thermal Dissociation-Laser Induced Fluorescence (TD-LIF) (UC Berkley). SO2 measurements were done using the TECO 43C SO2 analyzer and for NH3 measurements the an Ammonia Analyzer - Trace (NH3) (Los Gatos Research). Estimates of aerosol dry deposition fluxes are presented.

[Numerical modeling analysis of secondary organic aerosol (SOA) combined with the ground-based measurements in the Pearl River Delta region].

PubMed

Guo, Xiao-Shuang; Situ, Shu-Ping; Wang, Xue-Mei; Ding, Xiang; Wang, Xin-Ming; Yan, Cai-Qing; Li, Xiao-Ying; Zheng, Mei

2014-05-01

Two simulations were conducted with different secondary organic aerosol (SOA) methods-VBS (volatile basis set) approach and SORGAM (secondary organic aerosol model) , which have been coupled in the WRF/Chem (weather research and forecasting model with chemistry) model. Ground-based observation data from 18th to 25th November 2008 were used to examine the model performance of SOA in the Pearl River Delta(PRD)region. The results showed that VBS approach could better reproduce the temporal variation and magnitude of SOA compared with SORGAM, and the mean absolute deviation and correlation coefficient between the observed and the simulated data using VBS approach were -4.88 microg m-3 and 0.91, respectively, while they were -5.32 microg.m-3 and 0. 18 with SORGAM. This is mainly because the VBS approach considers SOA precursors with a wider volatility range and the process of chemical aging in SOA formation. Spatiotemporal distribution of SOA in the PRD from the VBS simulation was also analyzed. The results indicated that the SOA has a significant diurnal variation, and the maximal SOA concentration occurred at noon and in the early afternoon. Because of the transport and the considerable spatial distribution of O3 , the SOA concentrations were different in different PRD cities, and the highest concentration of SOA was observed in the downwind area, including Zhongshan, Zhuhai and Jiangmen.

SOA from BVOCs in the Southeastern United States

EPA Science Inventory

Biogenic hydrocarbons contribute to organic aerosol in the southeast United States. In this work, we represent aerosol formation from the oxidation of isoprene and monoterpenes in CMAQ and compare to data from the Southeast Oxidants and Aerosol Study (SOAS). Sensitivity simulatio...

Relating hygroscopicity and optical properties to chemical composition and structure of secondary organic aerosol particles generated from the ozonolysis of α-pinene

NASA Astrophysics Data System (ADS)

Denjean, C.; Formenti, P.; Picquet-Varrault, B.; Pangui, E.; Zapf, P.; Katrib, Y.; Giorio, C.; Tapparo, A.; Monod, A.; Temime-Roussel, B.; Decorse, P.; Mangeney, C.; Doussin, J. F.

2014-04-01

Secondary Organic Aerosol (SOA) were generated from the ozonolysis of α-pinene in the CESAM simulation chamber. The formation and ageing of the SOA were studied by following their optical, hygroscopic and chemical properties. The optical properties investigated by determining the particle Complex Refractive Index (CRI). The hygroscopicity was quantified by measuring the effect of RH on particle size (Growth Factor, GF) and scattering coefficient (f(RH)). The oxygen to carbon (O : C) atomic ratio of the particle surface and bulk were used as a sensitive parameter to correlate the changes in hygroscopic and optical properties of the SOA composition in CESAM. The real CRI at 525 nm wavelength decreased from 1.43-1.60 (±0.02) to 1.32-1.38 (±0.02) during the SOA formation. The decrease in real CRI correlates with a decrease in the O : C ratio of SOA from 0.68 (±0.20) to 0.55 (±0.16). In contrast, the GF stayed roughly constant over the reaction time, with values of 1.02-1.07 (±0.02) at 90% (±4.2) RH. Simultaneous measurements of O : C ratio of the particle surface revealed that the SOA was not composed of a homogeneous mixture, but with less oxidised species at the surface which would limit the water adsorption onto particle. In addition, an apparent change of both mobility diameter and scattering coefficient with increasing RH from 0 to 30% was observed for SOA after 16 h reaction. We postulate that this change could be due to a change in the viscosity of the SOA from a predominantly glassy state to a predominantly liquid state.

Heating-Induced Evaporation of Nine Different Secondary Organic Aerosol Types

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kolesar, Katheryn R.; Li, Ziyue; Wilson, Kevin R.

The volatility of the compounds comprising organic aerosol (OA) determines their distribution between the gas and particle phases. However, there is a disconnect between volatility distributions as typically derived from secondary OA (SOA) growth experiments and the effective particle volatility as probed in evaporation experiments. Specifically, the evaporation experiments indicate an overall much less volatile SOA. This raises questions regarding the use of traditional volatility distributions in the simulation and prediction of atmospheric SOA concentrations. Here, we present results from measurements of thermally induced evaporation of SOA for nine different SOA types (i.e., distinct volatile organic compound and oxidant pairs)more » encompassing both anthropogenic and biogenic compounds and O 3 and OH to examine the extent to which the low effective volatility of SOA is a general phenomenon or specific to a subset of SOA types. The observed extents of evaporation with temperature were similar for all the SOA types and indicative of a low effective volatility. Furthermore, minimal variations in the composition of all the SOA types upon heating-induced evaporation were observed. These results suggest that oligomer decomposition likely plays a major role in controlling SOA evaporation, and since the SOA formation time scale in these measurements was less than a minute, the oligomer-forming reactions must be similarly rapid. Overall, these results emphasize the importance of accounting for the role of condensed phase reactions in altering the composition of SOA when assessing particle volatility.« less

Heating-Induced Evaporation of Nine Different Secondary Organic Aerosol Types

DOE PAGES

Kolesar, Katheryn R.; Li, Ziyue; Wilson, Kevin R.; ...

2015-09-22

The volatility of the compounds comprising organic aerosol (OA) determines their distribution between the gas and particle phases. However, there is a disconnect between volatility distributions as typically derived from secondary OA (SOA) growth experiments and the effective particle volatility as probed in evaporation experiments. Specifically, the evaporation experiments indicate an overall much less volatile SOA. This raises questions regarding the use of traditional volatility distributions in the simulation and prediction of atmospheric SOA concentrations. Here, we present results from measurements of thermally induced evaporation of SOA for nine different SOA types (i.e., distinct volatile organic compound and oxidant pairs)more » encompassing both anthropogenic and biogenic compounds and O 3 and OH to examine the extent to which the low effective volatility of SOA is a general phenomenon or specific to a subset of SOA types. The observed extents of evaporation with temperature were similar for all the SOA types and indicative of a low effective volatility. Furthermore, minimal variations in the composition of all the SOA types upon heating-induced evaporation were observed. These results suggest that oligomer decomposition likely plays a major role in controlling SOA evaporation, and since the SOA formation time scale in these measurements was less than a minute, the oligomer-forming reactions must be similarly rapid. Overall, these results emphasize the importance of accounting for the role of condensed phase reactions in altering the composition of SOA when assessing particle volatility.« less

Long-term particulate matter modeling for health effect studies in California - Part 2: Concentrations and sources of ultrafine organic aerosols

NASA Astrophysics Data System (ADS)

Hu, Jianlin; Jathar, Shantanu; Zhang, Hongliang; Ying, Qi; Chen, Shu-Hua; Cappa, Christopher D.; Kleeman, Michael J.

2017-04-01

Organic aerosol (OA) is a major constituent of ultrafine particulate matter (PM0. 1). Recent epidemiological studies have identified associations between PM0. 1 OA and premature mortality and low birth weight. In this study, the source-oriented UCD/CIT model was used to simulate the concentrations and sources of primary organic aerosols (POA) and secondary organic aerosols (SOA) in PM0. 1 in California for a 9-year (2000-2008) modeling period with 4 km horizontal resolution to provide more insights about PM0. 1 OA for health effect studies. As a related quality control, predicted monthly average concentrations of fine particulate matter (PM2. 5) total organic carbon at six major urban sites had mean fractional bias of -0.31 to 0.19 and mean fractional errors of 0.4 to 0.59. The predicted ratio of PM2. 5 SOA / OA was lower than estimates derived from chemical mass balance (CMB) calculations by a factor of 2-3, which suggests the potential effects of processes such as POA volatility, additional SOA formation mechanism, and missing sources. OA in PM0. 1, the focus size fraction of this study, is dominated by POA. Wood smoke is found to be the single biggest source of PM0. 1 OA in winter in California, while meat cooking, mobile emissions (gasoline and diesel engines), and other anthropogenic sources (mainly solvent usage and waste disposal) are the most important sources in summer. Biogenic emissions are predicted to be the largest PM0. 1 SOA source, followed by mobile sources and other anthropogenic sources, but these rankings are sensitive to the SOA model used in the calculation. Air pollution control programs aiming to reduce the PM0. 1 OA concentrations should consider controlling solvent usage, waste disposal, and mobile emissions in California, but these findings should be revisited after the latest science is incorporated into the SOA exposure calculations. The spatial distributions of SOA associated with different sources are not sensitive to the choice of SOA model, although the absolute amount of SOA can change significantly. Therefore, the spatial distributions of PM0. 1 POA and SOA over the 9-year study period provide useful information for epidemiological studies to further investigate the associations with health outcomes.

Relating hygroscopicity and optical properties to chemical composition and structure of secondary organic aerosol particles generated from the ozonolysis of α-pinene

NASA Astrophysics Data System (ADS)

Denjean, C.; Formenti, P.; Picquet-Varrault, B.; Pangui, E.; Zapf, P.; Katrib, Y.; Giorio, C.; Tapparo, A.; Monod, A.; Temime-Roussel, B.; Decorse, P.; Mangeney, C.; Doussin, J. F.

2015-03-01

Secondary organic aerosol (SOA) were generated from the ozonolysis of α-pinene in the CESAM (French acronym for Experimental Multiphasic Atmospheric Simulation Chamber) simulation chamber. The SOA formation and aging were studied by following their optical, hygroscopic and chemical properties. The optical properties were investigated by determining the particle complex refractive index (CRI). The hygroscopicity was quantified by measuring the effect of relative humidity (RH) on the particle size (size growth factor, GF) and on the scattering coefficient (scattering growth factor, f(RH)). The oxygen to carbon atomic ratios (O : C) of the particle surface and bulk were used as a sensitive parameter to correlate the changes in hygroscopic and optical properties of the SOA composition during their formation and aging in CESAM. The real CRI at 525 nm wavelength decreased from 1.43-1.60 (±0.02) to 1.32-1.38 (±0.02) during the SOA formation. The decrease in the real CRI correlated to the O : C decrease from 0.68 (±0.20) to 0.55 (±0.16). In contrast, the GF remained roughly constant over the reaction time, with values of 1.02-1.07 (±0.02) at 90% (±4.2%) RH. Simultaneous measurements of O : C of the particle surface revealed that the SOA was not composed of a homogeneous mixture, but contained less oxidised species at the surface which may limit water absorption. In addition, an apparent change in both mobility diameter and scattering coefficient with increasing RH from 0 to 30% was observed for SOA after 14 h of reaction. We postulate that this change could be due to a change in the viscosity of the SOA from a predominantly glassy state to a predominantly liquid state.

Aging of plumes from emission sources based on chamber simulation

NASA Astrophysics Data System (ADS)

Wang, X.; Deng, W.; Fang, Z.; Bernard, F.; Zhang, Y.; Yu, J.; Mellouki, A.; George, C.

2017-12-01

Study on atmospheric aging of plumes from emission sources is essential to understand their contribution to both secondary and primary pollutants occurring in the ambient air. Here we directly introduced vehicle exhaust, biomass burning plume, industrial solvents and cooking plumes into a smog chamber with 30 m3 fluorinated ethylene propylene (FEP) Teflon film reactor housed in a temperature-controlled enclosure, for characterizing primarily emitted air pollutants and for investigating secondarily formed products during photo-oxidation. Moreover, we also initiated study on the formation of secondary aerosols when gasoline vehicle exhaust is mixed with typical coal combustion pollutant SO2 or typical agricultural-related pollutant NH3. Formation of secondary organic aerosols (SOA) from typical solvent toluene was also investigated in ambient air matrix in comparison with purified air matrix. Main findings include: 1) Except for exhaust from idling gasoline vehicles, traditional precursor volatile organic compounds could only explain a very small fraction of SOA formed from vehicle exhaust, biomass burning or cooking plumes, suggesting knowledge gap in SOA precursors; 2) There is the need to re-think vehicle emission standards with a combined primary and/or secondary contribution of vehicle exhaust to PM2.5 or other secondary pollutants such as ozone; 3) When mixed with SO2, the gasoline vehicle exhaust revealed an increase of SOA production factor by 60-200% and meanwhile SO2 oxidation rates increased about a factor of 2.7; when the aged gasoline vehicle exhaust were mixing with NH3, both particle number and mass concentrations were increasing explosively. These phenomenons implied the complex interaction during aging of co-existing source emissions. 4) For typical combination of "tolune+SO2+NOx", when compared to chamber simulation with purified air as matrix, both SOA formation and SO2 oxidation were greatly enhanced under ambient air matrix, and the enhancement of SO2 oxidation was found be largely heterogonous and the enhancement of SOA formation seemed to be acid-catalyzed.

Characterization of secondary organic aerosol from photo-oxidation of gasoline exhaust and specific sources of major components.

PubMed

Ma, Pengkun; Zhang, Peng; Shu, Jinian; Yang, Bo; Zhang, Haixu

2018-01-01

To further explore the composition and distribution of secondary organic aerosol (SOA) components from the photo-oxidation of light aromatic precursors (toluene, m-xylene, and 1,3,5-trimethylbenzene (1,3,5-TMB)) and idling gasoline exhaust, a vacuum ultraviolet photoionization mass spectrometer (VUV-PIMS) was employed. Peaks of the molecular ions of the SOA components with minimum molecular fragmentation were clearly observed from the mass spectra of SOA, through the application of soft ionization methods in VUV-PIMS. The experiments comparing the exhaust-SOA and light aromatic mixture-SOA showed that the observed distributions of almost all the predominant cluster ions in the exhaust-SOA were similar to that of the mixture-SOA. Based on the characterization experiments of SOA formed from individual light aromatic precursors, the SOA components with molecular weights of 98 and 110 amu observed in the exhaust-SOA resulted from the photo-oxidation of toluene and m-xylene; the components with a molecular weight of 124 amu were derived mainly from m-xylene; and the components with molecular weights of 100, 112, 128, 138, and 156 amu were mainly derived from 1,3,5-TMB. These results suggest that C 7 -C 9 light aromatic hydrocarbons are significant SOA precursors and that major SOA components originate from gasoline exhaust. Additionally, some new light aromatic hydrocarbon-SOA components were observed for the first time using VUV-PIMS. The corresponding reaction mechanisms were also proposed in this study to enrich the knowledge base of the formation mechanisms of light aromatic hydrocarbon-SOA compounds. Copyright © 2017 Elsevier Ltd. All rights reserved.

Formation of secondary aerosols from gasoline vehicle exhaust when mixing with SO2

NASA Astrophysics Data System (ADS)

Liu, T.; Wang, X.; Hu, Q.; Deng, W.; Zhang, Y.; Ding, X.; Fu, X.; Bernard, F.; Zhang, Z.; Lü, S.; He, Q.; Bi, X.; Chen, J.; Sun, Y.; Yu, J.; Peng, P.; Sheng, G.; Fu, J.

2016-01-01

Sulfur dioxide (SO2) can enhance the formation of secondary aerosols from biogenic volatile organic compounds (VOCs), but its influence on secondary aerosol formation from anthropogenic VOCs, particularly complex mixtures like vehicle exhaust, remains uncertain. Gasoline vehicle exhaust (GVE) and SO2, a typical pollutant from coal burning, are directly co-introduced into a smog chamber, in this study, to investigate the formation of secondary organic aerosols (SOA) and sulfate aerosols through photooxidation. New particle formation was enhanced, while substantial sulfate was formed through the oxidation of SO2 in the presence of high concentration of SO2. Homogenous oxidation by OH radicals contributed a negligible fraction to the conversion of SO2 to sulfate, and instead the oxidation by stabilized Criegee intermediates (sCIs), formed from alkenes in the exhaust reacting with ozone, dominated the conversion of SO2. After 5 h of photochemical aging, GVE's SOA production factor revealed an increase by 60-200 % in the presence of high concentration of SO2. The increase could principally be attributed to acid-catalyzed SOA formation as evidenced by the strong positive linear correlation (R2 = 0.97) between the SOA production factor and in situ particle acidity calculated by the AIM-II model. A high-resolution time-of-flight aerosol mass spectrometer (HR-TOF-AMS) resolved OA's relatively lower oxygen-to-carbon (O : C) (0.44 ± 0.02) and higher hydrogen-to-carbon (H : C) (1.40 ± 0.03) molar ratios for the GVE / SO2 mixture, with a significantly lower estimated average carbon oxidation state (OSc) of -0.51 ± 0.06 than -0.19 ± 0.08 for GVE alone. The relative higher mass loading of OA in the experiments with SO2 might be a significant explanation for the lower SOA oxidation degree.

Observational insights into aerosol formation from isoprene.

PubMed

Worton, David R; Surratt, Jason D; Lafranchi, Brian W; Chan, Arthur W H; Zhao, Yunliang; Weber, Robin J; Park, Jeong-Hoo; Gilman, Jessica B; de Gouw, Joost; Park, Changhyoun; Schade, Gunnar; Beaver, Melinda; Clair, Jason M St; Crounse, John; Wennberg, Paul; Wolfe, Glenn M; Harrold, Sara; Thornton, Joel A; Farmer, Delphine K; Docherty, Kenneth S; Cubison, Michael J; Jimenez, Jose-Luis; Frossard, Amanda A; Russell, Lynn M; Kristensen, Kasper; Glasius, Marianne; Mao, Jingqiu; Ren, Xinrong; Brune, William; Browne, Eleanor C; Pusede, Sally E; Cohen, Ronald C; Seinfeld, John H; Goldstein, Allen H

2013-10-15

Atmospheric photooxidation of isoprene is an important source of secondary organic aerosol (SOA) and there is increasing evidence that anthropogenic oxidant emissions can enhance this SOA formation. In this work, we use ambient observations of organosulfates formed from isoprene epoxydiols (IEPOX) and methacrylic acid epoxide (MAE) and a broad suite of chemical measurements to investigate the relative importance of nitrogen oxide (NO/NO2) and hydroperoxyl (HO2) SOA formation pathways from isoprene at a forested site in California. In contrast to IEPOX, the calculated production rate of MAE was observed to be independent of temperature. This is the result of the very fast thermolysis of MPAN at high temperatures that affects the distribution of the MPAN reservoir (MPAN / MPA radical) reducing the fraction that can react with OH to form MAE and subsequently SOA (F(MAE formation)). The strong temperature dependence of F(MAE formation) helps to explain our observations of similar concentrations of IEPOX-derived organosulfates (IEPOX-OS; ~1 ng m(-3)) and MAE-derived organosulfates (MAE-OS; ~1 ng m(-3)) under cooler conditions (lower isoprene concentrations) and much higher IEPOX-OS (~20 ng m(-3)) relative to MAE-OS (<0.0005 ng m(-3)) at higher temperatures (higher isoprene concentrations). A kinetic model of IEPOX and MAE loss showed that MAE forms 10-100 times more ring-opening products than IEPOX and that both are strongly dependent on aerosol water content when aerosol pH is constant. However, the higher fraction of MAE ring opening products does not compensate for the lower MAE production under warmer conditions (higher isoprene concentrations) resulting in lower formation of MAE-derived products relative to IEPOX at the surface. In regions of high NOx, high isoprene emissions and strong vertical mixing the slower MPAN thermolysis rate aloft could increase the fraction of MPAN that forms MAE resulting in a vertically varying isoprene SOA source.

Aqueous Oxidation of Green Leaf Volatiles as a Source of Secondary Organic Aerosol

NASA Astrophysics Data System (ADS)

Richards-Henderson, N. K.; Hansel, A.; Pham, A. T.; Vempati, H. S.; Valsaraj, K. T.; Anastasio, C.

2013-12-01

Vegetation emits volatile oxygenated hydrocarbons - the green leaf volatiles (GLVs) - which are formed from the biochemical conversion of linoleic and linolenic acids within plant cells. Stress or damage to vegetation can significantly elevate emission fluxes of these compounds, some of which are fairly water soluble. Aqueous-phase reactions of the GLVs with photochemically generated oxidants - such as hydroxyl radical (OH), singlet oxygen (1O2) and excited triplet states of organic compounds (3C*) _ might then form low-volatility products that can act as secondary organic aerosol (SOA). In order to determine if GLVs can be a significant source of secondary organic carbon in fogwater, studies of GLVs in laboratory solutions are needed to elucidate the oxidation kinetics and the corresponding SOA mass yields. In this study we are determining the second-order rate constants, and SOA mass yields, for five GLVs (cis-3-hexen-1-ol, cis-3-hexenylacetate, methyl salicylate, methyl jasmonate, and 2-methyl-3-butene-2-ol) reacting with OH,1O2 and 3C*. Experiments are performed at relevant fog water pHs, temperatures, and oxidant concentrations. Rate constants are determined using a relative rate approach in which the decay of GLVs and reference compounds are monitored as function of time by HPLC. The capacity of GLVs to form aqueous SOA was determined by following the formation of their decomposition products with HPLC-UV/DAD and HPLC-ESI/MS. SOA mass yields are measured gravimetrically from laboratory solutions containing atmospherically relevant concentrations of photooxidants and GLVs, and irradiated with simulated sunlight. We will use our results to assess the potential contribution of aqueous GLV reactions as a source of SOA in cloudy or foggy atmospheres.

Nitrate radical oxidation of γ-terpinene: hydroxy nitrate, total organic nitrate, and secondary organic aerosol yields

NASA Astrophysics Data System (ADS)

Slade, Jonathan H.; de Perre, Chloé; Lee, Linda; Shepson, Paul B.

2017-07-01

Polyolefinic monoterpenes represent a potentially important but understudied source of organic nitrates (ONs) and secondary organic aerosol (SOA) following oxidation due to their high reactivity and propensity for multi-stage chemistry. Recent modeling work suggests that the oxidation of polyolefinic γ-terpinene can be the dominant source of nighttime ON in a mixed forest environment. However, the ON yields, aerosol partitioning behavior, and SOA yields from γ-terpinene oxidation by the nitrate radical (NO3), an important nighttime oxidant, have not been determined experimentally. In this work, we present a comprehensive experimental investigation of the total (gas + particle) ON, hydroxy nitrate, and SOA yields following γ-terpinene oxidation by NO3. Under dry conditions, the hydroxy nitrate yield = 4(+1/-3) %, total ON yield = 14(+3/-2) %, and SOA yield ≤ 10 % under atmospherically relevant particle mass loadings, similar to those for α-pinene + NO3. Using a chemical box model, we show that the measured concentrations of NO2 and γ-terpinene hydroxy nitrates can be reliably simulated from α-pinene + NO3 chemistry. This suggests that NO3 addition to either of the two internal double bonds of γ-terpinene primarily decomposes forming a relatively volatile keto-aldehyde, reconciling the small SOA yield observed here and for other internal olefinic terpenes. Based on aerosol partitioning analysis and identification of speciated particle-phase ON applying high-resolution liquid chromatography-mass spectrometry, we estimate that a significant fraction of the particle-phase ON has the hydroxy nitrate moiety. This work greatly contributes to our understanding of ON and SOA formation from polyolefin monoterpene oxidation, which could be important in the northern continental US and the Midwest, where polyolefinic monoterpene emissions are greatest.

Modeling the Transition From Predominantly Gas- to Predominantly Aerosol-Phase Products From OH Reactions With the Homologous Series of C10 to C15 n- Alkanes

NASA Astrophysics Data System (ADS)

Jordan, C. E.; Ziemann, P. J.; Griffin, R. J.; Lim, Y. B.; Atkinson, R.; Arey, J.

2006-12-01

Recent laboratory studies have shown significant formation of secondary organic aerosol (SOA) from OH reactions with a homologous series of n-alkanes. SOA mass yields of 56% were observed for pentadecane (C15), while only 0.5% yield was observed from octane (C8, the smallest alkane in the series). A rapid transition in SOA yield is observed from C10 to C13, with SOA yields increasing from 4% to 49%. In standard gas-aerosol partitioning theory, the vapor pressure controls the amount of material that can condense into the particle phase. However, the rapid transition observed here suggests there may also be a shift in the predominant reaction pathways for longer chain alkanes, leading to greater production of lower vapor pressure products. Here we present an investigation of the role of vapor pressure versus the role of shifting branching ratios to test the influence of each of these on SOA mass yields. We have added each of the alkanes in this series to the Caltech Atmospheric Chemistry Mechanism (CACM). This mechanism was developed in part to predict explicitly concentrations of secondary and tertiary semivolatile oxidation products that potentially form SOA. Although it is has been developed to lump similar compounds together for computational efficiency, it is nonetheless easily adapted and ideally suited for a detailed zero-dimensional modeling study of this kind. This gas-phase mechanism is linked to the aerosol partitioning module MPMPO (Model to Predict the Multi- phase Partitioning of Organics). MPMPO is a fully coupled module that allows the simultaneous partitioning of semi-volatile species to both an aqueous and an organic aerosol phase.

Inflammatory responses to secondary organic aerosols (SOA) generated from biogenic and anthropogenic precursors

NASA Astrophysics Data System (ADS)

Tuet, Wing Y.; Chen, Yunle; Fok, Shierly; Champion, Julie A.; Ng, Nga L.

2017-09-01

Cardiopulmonary health implications resulting from exposure to secondary organic aerosols (SOA), which comprise a significant fraction of ambient particulate matter (PM), have received increasing interest in recent years. In this study, alveolar macrophages were exposed to SOA generated from the photooxidation of biogenic and anthropogenic precursors (isoprene, α-pinene, β-caryophyllene, pentadecane, m-xylene, and naphthalene) under different formation conditions (RO2 + HO2 vs. RO2 + NO dominant, dry vs. humid). Various cellular responses were measured, including reactive oxygen and nitrogen species (ROS/RNS) production and secreted levels of cytokines, tumor necrosis factor-α (TNF-α) and interleukin-6 (IL-6). SOA precursor identity and formation condition affected all measured responses in a hydrocarbon-specific manner. With the exception of naphthalene SOA, cellular responses followed a trend where TNF-α levels reached a plateau with increasing IL-6 levels. ROS/RNS levels were consistent with relative levels of TNF-α and IL-6, due to their respective inflammatory and anti-inflammatory effects. Exposure to naphthalene SOA, whose aromatic-ring-containing products may trigger different cellular pathways, induced higher levels of TNF-α and ROS/RNS than suggested by the trend. Distinct cellular response patterns were identified for hydrocarbons whose photooxidation products shared similar chemical functionalities and structures, which suggests that the chemical structure (carbon chain length and functionalities) of photooxidation products may be important for determining cellular effects. A positive nonlinear correlation was also detected between ROS/RNS levels and previously measured DTT (dithiothreitol) activities for SOA samples. In the context of ambient samples collected during summer and winter in the greater Atlanta area, all laboratory-generated SOA produced similar or higher levels of ROS/RNS and DTT activities. These results suggest that the health effects of SOA are important considerations for understanding the health implications of ambient aerosols.

Reactive oxygen species formed in aqueous mixtures of secondary organic aerosols and mineral dust influencing cloud chemistry and public health in the Anthropocene.

PubMed

Tong, Haijie; Lakey, Pascale S J; Arangio, Andrea M; Socorro, Joanna; Kampf, Christopher J; Berkemeier, Thomas; Brune, William H; Pöschl, Ulrich; Shiraiwa, Manabu

2017-08-24

Mineral dust and secondary organic aerosols (SOA) account for a major fraction of atmospheric particulate matter, affecting climate, air quality and public health. How mineral dust interacts with SOA to influence cloud chemistry and public health, however, is not well understood. Here, we investigated the formation of reactive oxygen species (ROS), which are key species of atmospheric and physiological chemistry, in aqueous mixtures of SOA and mineral dust by applying electron paramagnetic resonance (EPR) spectrometry in combination with a spin-trapping technique, liquid chromatography-tandem mass spectrometry (LC-MS/MS), and a kinetic model. We found that substantial amounts of ROS including OH, superoxide as well as carbon- and oxygen-centred organic radicals can be formed in aqueous mixtures of isoprene, α-pinene, naphthalene SOA and various kinds of mineral dust (ripidolite, montmorillonite, kaolinite, palygorskite, and Saharan dust). The molar yields of total radicals were ∼0.02-0.5% at 295 K, which showed higher values at 310 K, upon 254 nm UV exposure, and under low pH (<3) conditions. ROS formation can be explained by the decomposition of organic hydroperoxides, which are a prominent fraction of SOA, through interactions with water and Fenton-like reactions with dissolved transition metal ions. Our findings imply that the chemical reactivity and aging of SOA particles can be enhanced upon interaction with mineral dust in deliquesced particles or cloud/fog droplets. SOA decomposition could be comparably important to the classical Fenton reaction of H 2 O 2 with Fe 2+ and that SOA can be the main source of OH radicals in aqueous droplets at low concentrations of H 2 O 2 and Fe 2+ . In the human respiratory tract, the inhalation and deposition of SOA and mineral dust can also lead to the release of ROS, which may contribute to oxidative stress and play an important role in the adverse health effects of atmospheric aerosols in the Anthropocene.

Observations of speciated monoterpenes above a Southeastern United States Forest and comparison with a 0-D model

NASA Astrophysics Data System (ADS)

Mcavey, K. M.; Groff, C. J.; Harkins, A. D.; Bertman, S. B.; Starn, T.; Seeley, J. S.; Shepson, P. B.

2013-12-01

Biogenic emissions of monoterpenes play a role in the formation of secondary organic aerosols (SOA) and tropospheric ozone, as well as impacting the fate of nitrogen through production of organic nitrates. Monoterpene emissions can interact with anthropgenic emissions (e.g. sulfate aerosol) to produce a variety of SOA components, such as organosulfates. Concentrations of several monoterpenes, including some combination of α-pinene, β-pinene, camphene, limonene, terpinolene, γ-terpinene, myrcene, and ρ-cymene (depending on chromatographic resolution) were quantified in a forested site in rural Alabama using an automated solid sorbent sampler/2D-GC, as part of the Southern Oxidant and Aerosol Study (SOAS). Monoterpene concentrations were relatively large in this mixed coniferous/deciduous forest, with individual terpenes maximizing at concentrations as high as 1 ppb or more, making them important OH sinks, as well as organic nitrate precursors. α-pinene was the dominant terpene measured. Diurnal patterns show a clear increase in observed monoterpene concentrations occurring in the later evening hours. In this presentation we will compare the observed terpene distribution with that from a simple landcover survey and emissions model, and discuss the relative role of isoprene and the terpenes as OH sinks, and precursors to organic nitrates, which are themselves potentially important SOA components.

A microphysical parameterization of aqSOA and sulfate formation in clouds

NASA Astrophysics Data System (ADS)

McVay, Renee; Ervens, Barbara

2017-07-01

Sulfate and secondary organic aerosol (cloud aqSOA) can be chemically formed in cloud water. Model implementation of these processes represents a computational burden due to the large number of microphysical and chemical parameters. Chemical mechanisms have been condensed by reducing the number of chemical parameters. Here an alternative is presented to reduce the number of microphysical parameters (number of cloud droplet size classes). In-cloud mass formation is surface and volume dependent due to surface-limited oxidant uptake and/or size-dependent pH. Box and parcel model simulations show that using the effective cloud droplet diameter (proportional to total volume-to-surface ratio) reproduces sulfate and aqSOA formation rates within ≤30% as compared to full droplet distributions; other single diameters lead to much greater deviations. This single-class approach reduces computing time significantly and can be included in models when total liquid water content and effective diameter are available.

Multifunctional switching unit for add/drop, wavelength conversion, format conversion, and WDM multicast based on bidirectional LCoS and SOA-loop architecture.

PubMed

Wang, Danshi; Zhang, Min; Qin, Jun; Lu, Guo-Wei; Wang, Hongxiang; Huang, Shanguo

2014-09-08

We propose a multifunctional optical switching unit based on the bidirectional liquid crystal on silicon (LCoS) and semiconductor optical amplifier (SOA) architecture. Add/drop, wavelength conversion, format conversion, and WDM multicast are experimentally demonstrated. Due to the bidirectional characteristic, the LCoS device cannot only multiplex the input signals, but also de-multiplex the converted signals. Dual-channel wavelength conversion and format conversion from 2 × 25Gbps differential quadrature phase-shift-keying (DQPSK) to 2 × 12.5Gbps differential phase-shift-keying (DPSK) based on four-wave mixing (FWM) in SOA is obtained with only one pump. One-to-six WDM multicast of 25Gbps DQPSK signals with two pumps is also achieved. All of the multicast channels are with a power penalty less than 1.1 dB at FEC threshold of 3.8 × 10⁻³.

High-bandwidth generation of duobinary and alternate-mark-inversion modulation formats using SOA-based signal processing.

PubMed

Dailey, James M; Power, Mark J; Webb, Roderick P; Manning, Robert J

2011-12-19

We report on the novel all-optical generation of duobinary (DB) and alternate-mark-inversion (AMI) modulation formats at 42.6 Gb/s from an input on-off keyed signal. The modulation converter consists of two semiconductor optical amplifier (SOA)-based Mach-Zehnder interferometer gates. A detailed SOA model numerically confirms the operational principles and experimental data shows successful AMI and DB conversion at 42.6 Gb/s. We also predict that the operational bandwidth can be extended beyond 40 Gb/s by utilizing a new pattern-effect suppression scheme, and demonstrate dramatic reductions in patterning up to 160 Gb/s. We show an increasing trade-off between pattern-effect reduction and mean output power with increasing bitrate.

Significant Contributions of Isoprene to Summertime Secondary Organic Aerosol in Eastern United States.

PubMed

Ying, Qi; Li, Jingyi; Kota, Sri Harsha

2015-07-07

A modified SAPRC-11 (S11) photochemical mechanism with more detailed treatment of isoprene oxidation chemistry and additional secondary organic aerosol (SOA) formation through surface-controlled reactive uptake of dicarbonyls, isoprene epoxydiol and methacrylic acid epoxide was incorporated in the Community Multiscale Air Quality Model (CMAQ) to quantitatively determine contributions of isoprene to summertime ambient SOA concentrations in the eastern United States. The modified model utilizes a precursor-origin resolved approach to determine secondary glyoxal and methylglyoxal produced by oxidation of isoprene and other major volatile organic compounds (VOCs). Predicted OC concentrations show good agreement with field measurements without significant bias (MFB ∼ 0.07 and MFE ∼ 0.50), and predicted SOA reproduces observed day-to-day and diurnal variation of Oxygenated Organic Aerosol (OOA) determined by an aerosol mass spectrometer (AMS) at two locations in Houston, Texas. On average, isoprene SOA accounts for 55.5% of total predicted near-surface SOA in the eastern U.S., followed by aromatic compounds (13.2%), sesquiterpenes (13.0%) and monoterpenes (10.9%). Aerosol surface uptake of isoprene-generated glyoxal, methylglyoxal and epoxydiol accounts for approximately 83% of total isoprene SOA or more than 45% of total SOA. A domain wide reduction of NOx emissions by 40% leads to a slight decrease of domain average SOA by 3.6% and isoprene SOA by approximately 2.6%. Although most of the isoprene SOA component concentrations are decreased, SOA from isoprene epoxydiol is increased by ∼16%.

Unspeciated organic emissions from combustion sources and their influence on the secondary organic aerosol budget in the United States

PubMed Central

Jathar, Shantanu H.; Gordon, Timothy D.; Hennigan, Christopher J.; Pye, Havala O. T.; Pouliot, George; Adams, Peter J.; Donahue, Neil M.; Robinson, Allen L.

2014-01-01

Secondary organic aerosol (SOA) formed from the atmospheric oxidation of nonmethane organic gases (NMOG) is a major contributor to atmospheric aerosol mass. Emissions and smog chamber experiments were performed to investigate SOA formation from gasoline vehicles, diesel vehicles, and biomass burning. About 10–20% of NMOG emissions from these major combustion sources are not routinely speciated and therefore are currently misclassified in emission inventories and chemical transport models. The smog chamber data demonstrate that this misclassification biases model predictions of SOA production low because the unspeciated NMOG produce more SOA per unit mass than the speciated NMOG. We present new source-specific SOA yield parameterizations for these unspeciated emissions. These parameterizations and associated source profiles are designed for implementation in chemical transport models. Box model calculations using these new parameterizations predict that NMOG emissions from the top six combustion sources form 0.7 Tg y−1 of first-generation SOA in the United States, almost 90% of which is from biomass burning and gasoline vehicles. About 85% of this SOA comes from unspeciated NMOG, demonstrating that chemical transport models need improved treatment of combustion emissions to accurately predict ambient SOA concentrations. PMID:25002466

Analysis of Glyoxal and Methylglyoxal in atmospheric particulate matter - Qualification and Quantification using a derivatisation method for HPLC-ESI-MS

NASA Astrophysics Data System (ADS)

Kampf, Christopher; Hoffmann, Thorsten

2010-05-01

In recent years much effort has been put into the analysis of so called secondary organic aerosols (SOA). SOA is produced through gas phase oxidation of volatile organic compounds (VOC's) by atmospheric oxidants like OH- or NO3-radicals or ozone with subsequent gas-particle partitioning of the low volatility products. VOC's are emitted by both biogenic and anthropogenic sources in large amounts into the atmosphere. However, it is found that gas to particle partitioning alone cannot explain the complete amount of SOA produced in the atmosphere. It is therefore proposed that heterogeneous reactions on the particle surface or in the particles themselves could lead to the formation of additional SOA mass from semi-volatile compounds such as the reactive dialdehydes glyoxal and methylglyoxal[1]. Global glyoxal and methylglyoxal emissions are estimated to be 45 Tg a-1 and 140 Tg a-1, respectively. The oxidation of biogenic isoprene contributes to about 47% of the total glyoxal mass formed and even to about 79% for methylglyoxal[2]. Due to their high solubility in water (hydration of aldehyde functions), glyoxal and methylglyoxal have a high potential to form SOA via heterogeneous reactions in the particle phase although their volatility is relatively high. Several studies propose oligomerisation or formation of imidazole derivatives as potential reaction pathways to reduce their volatility[1,3,4,5]. Here we present a method for the qualification and quantification of both glyoxal and methylglyoxal in atmospheric PM2.5 filter samples via derivatisation with phenylhydrazine. Reproducibility, recovery and limits of detection and quantification are given. The method is found to be easily suitable for measurements at atmospheric concentration levels for both substances. First results of a measurement campaign in Mainz, Germany in August 2009 are shown for a proof of principle. Initial problems of the method development due to the chemical nature of the analytes und future enhancements of the sampling procedure are discussed. References 1. Kalberer, M., et al. (2004). Science, 303(5664), 1659-1662 2. Fu, T.-M., et al. (2008). Journal of Geophysical Research, 113, D15303 3. Iinuma, Y., et al. (2004). Atmospheric Environment, 38(5), 761-773 4. Galloway, M. M., et al. (2009), Atmos. Chem. Phys., 9, 3331-3345 5. Nozière, B., et al. (2009), J. Phys. Chem. A, 113, 231-237

Constraining the Volatility Distributions and Possible Diffusion Limitations of Secondary Organic Aerosols Using Laboratory Dilution Experiments

NASA Astrophysics Data System (ADS)

Ye, Q.; Robinson, E. S.; Mahfouz, N.; Sullivan, R. C.; Donahue, N. M.

2016-12-01

Secondary organic aerosols (SOA) dominate the mass of fine particles in the atmosphere. Their formation involves both oxidation of volatile organics from various sources that produce products with uncertain volatilities, and diffusion of these products into the condensed phase. Therefore, constraining volatility distribution and diffusion timescales of the constituents in SOA are important in predicting size, concentration and composition of SOA, as well as how these properties of SOA evolve in the atmosphere. In this work, we demonstrate how carefully designed laboratory isothermal dilution experiments in smog chambers can shed light into the volatility distribution and any diffusion barriers of common types of SOA over time scales relevant to atmospheric transport and diurnal cycling. We choose SOA made from mono-terpenes (alpha-pinene and limonene) and toluene to represent biogenic and anthropogenic SOA. We look into how moisture content can alter any evaporation behaviors of SOA by varying relative humidity during SOA generation and during dilution process. This provides insight into whether diffusion in the condensed phase is rate limiting in reaching gas/particle equilibrium of semi-volatile organic compounds. Our preliminary results show that SOA from alpha-pinene evaporates continuously over several hours of experiments, and there is no substantial discernible differences over wide ranges of the chamber humidity. SOA from toluene oxidation shows slower evaporation. We fit these experimental data using absorptive partitioning theory and a particle dynamic model to obtain volatility distributions and to predict particle size evolution. This in the end will help us to improve representation of SOA in large scale chemical transport models.

Influence of metal-mediated aerosol-phase oxidation on secondary organic aerosol formation from the ozonolysis and OH-oxidation of α-pinene

PubMed Central

Chu, Biwu; Liggio, John; Liu, Yongchun; He, Hong; Takekawa, Hideto; Li, Shao-Meng; Hao, Jiming

2017-01-01

The organic component is the most abundant fraction of atmospheric submicron particles, while the formation mechanisms of secondary organic aerosol (SOA) are not fully understood. The effects of sulfate seed aerosols on SOA formation were investigated with a series of experiments carried out using a 9 m3 smog chamber. The presence of FeSO4 or Fe2(SO4)3 seed aerosols decreased SOA yields and increased oxidation levels in both ozonolysis and OH-oxidation of α-pinene compared to that in the presence of ZnSO4 or (NH4)2SO4. These findings were explained by metal-mediated aerosol-phase oxidation of organics: reactive radicals were generated on FeSO4 or Fe2(SO4)3 seed aerosols and reacted further with the organic mass. This effect would help to explain the high O/C ratios of organics in ambient particles that thus far cannot be reproduced in laboratory and model studies. In addition, the gap in the SOA yields between experiments with different seed aerosols was more significant in OH-oxidation experiments compared to ozonolysis experiments, while the gap in estimated O/C ratios was less obvious. This may have resulted from the different chemical compositions and oxidation levels of the SOA generated in the two systems, which affect the branching ratio of functionalization and fragmentation during aerosol oxidation. PMID:28059151

Influence of metal-mediated aerosol-phase oxidation on secondary organic aerosol formation from the ozonolysis and OH-oxidation of α-pinene.

PubMed

Chu, Biwu; Liggio, John; Liu, Yongchun; He, Hong; Takekawa, Hideto; Li, Shao-Meng; Hao, Jiming

2017-01-06

The organic component is the most abundant fraction of atmospheric submicron particles, while the formation mechanisms of secondary organic aerosol (SOA) are not fully understood. The effects of sulfate seed aerosols on SOA formation were investigated with a series of experiments carried out using a 9 m 3 smog chamber. The presence of FeSO 4 or Fe 2 (SO 4 ) 3 seed aerosols decreased SOA yields and increased oxidation levels in both ozonolysis and OH-oxidation of α-pinene compared to that in the presence of ZnSO 4 or (NH 4 ) 2 SO 4 . These findings were explained by metal-mediated aerosol-phase oxidation of organics: reactive radicals were generated on FeSO 4 or Fe 2 (SO 4 ) 3 seed aerosols and reacted further with the organic mass. This effect would help to explain the high O/C ratios of organics in ambient particles that thus far cannot be reproduced in laboratory and model studies. In addition, the gap in the SOA yields between experiments with different seed aerosols was more significant in OH-oxidation experiments compared to ozonolysis experiments, while the gap in estimated O/C ratios was less obvious. This may have resulted from the different chemical compositions and oxidation levels of the SOA generated in the two systems, which affect the branching ratio of functionalization and fragmentation during aerosol oxidation.

Secondary organic aerosol formation from isoprene photooxidation

NASA Astrophysics Data System (ADS)

Kroll, J. H.; Ng, N. L.; Murphy, S. M.; Flagan, R. C.; Seinfeld, J. H.

2005-12-01

We report chamber studies of the formation of secondary organic aerosol (SOA) from the oxidation of isoprene (2-methyl-1,3-butadiene). Isoprene is the most abundant non-methane hydrocarbon emitted into the troposphere (source strength of ~500 Tg/year), so even small SOA yields may have a large impact on global SOA production. Reactions are carried out in Caltech's dual 28 m3 Teflon chambers, and aerosol growth is monitored by a differential mobility analyzer (DMA) and an Aerodyne time-of-flight aerosol mass spectrometer (AMS). Isoprene oxidation is initiated by the UV irradiation of isoprene in the presence of hydrogen peroxide, with NO added for high-NOx experiments. These conditions ensure that isoprene oxidation is initiated by reaction with the OH radical, with negligible interference from other oxidants (ozone, nitrate radicals, and O atoms). Aerosol growth is observed under both high-NOx and low-NOx conditions, at isoprene concentrations lower than measured in previous studies (down to 8 ppb). SOA yields are found to be in the range of 1-2%. Yields exhibit a complex dependence on NOx concentration, likely a result of changes in the chemistry of organic peroxy radicals. It is shown that condensable compounds are formed from further reactions of first-generation isoprene oxidation products; the rates and products of such gas-phase reactions are at present poorly understood. Additionally, measurements of SOA composition indicate that these products undergo reactions in the aerosol phase, leading to the formation of low-volatility oligomeric products.

The effect of sub-zero temperature on the formation and composition of secondary organic aerosol from ozonolysis of alpha-pinene.

PubMed

Kristensen, K; Jensen, L N; Glasius, M; Bilde, M

2017-10-18

This study presents a newly constructed temperature controlled cold-room smog chamber at Aarhus University, Denmark. The chamber is herein utilized to study the effect of sub-zero temperature on the formation and chemical composition of secondary organic aerosol (SOA) from ozone initiated oxidation of α-pinene. The chemical composition of α-pinene SOA formed from dark ozonolysis of α-pinene at 293 K and 258 K was investigated using High-Resolution Time-of-Flight Aerosol Mass Spectrometry (HR-ToF-AMS) and Ultra-High Performance Liquid Chromatography/Electrospray Ionization Quadrupole Time-of-Flight Mass Spectrometry (UHPLC/ESI-qToF-MS). For comparison, an OH-initiated oxidation experiment was performed at 293 K. In ozonolysis experiments it was found that oxygen-to-carbon (O : C) ratios were higher in the particles formed at 293 K compared to 258 K. A total of 16 different organic acids and 30 dimers esters were quantified in the collected particles composing up to 34% of the total α-pinene SOA mass with increased mass fraction of carboxylic acids in particles from α-pinene ozonolysis at 258 K compared to 293 K. In contrast, dimer esters showed suppressed formation at the sub-zero reaction temperature, thus contributing 3% to SOA mass at 258 K while contributing 9% at 293 K. SOA formed in the OH-initiated oxidation of α-pinene at 293 K resulted in low concentrations of dimer esters supporting Criegee intermediates as a possible pathway to dimer ester formation. Vapour pressure estimates of the identified carboxylic acids and dimer esters are presented and show how otherwise semi-volatile carboxylic acids at sufficiently low temperatures may classify as low or even extremely low volatile organic compounds (ELVOC), thus may add to an enhanced particle formation observed at the sub-zero temperature through gas-to-particle conversion. The change in chemical composition of the SOA particles with temperature is ascribed to a combination of effects: the decreased vapour pressures and hence increased condensation of carboxylic acids from the gas phase to the particle phase along with suppressed formation of the high molecular weight dimer esters and different gas and particle phase chemistry results in particles of different chemical composition as a consequence of low reaction temperatures.

Implications of Low Volatility SOA and Gas-Phase Fragmentation Reactions on SOA Loadings and their Spatial and Temporal Evolution in the Atmosphere

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shrivastava, ManishKumar B.; Zelenyuk, Alla; Imre, Dan

2013-04-27

Recent laboratory and field measurements by a number of groups show that secondary organic aerosol (SOA) evaporates orders of magnitude slower than traditional models assume. In addition, chemical transport models using volatility basis set (VBS) SOA schemes neglect gas-phase fragmentation reactions, which are known to be extremely important. In this work, we present modeling studies to investigate the implications of non-evaporating SOA and gas-phase fragmentation reactions. Using the 3-D chemical transport model, WRF-Chem, we show that previous parameterizations, which neglect fragmentation during multi-generational gas-phase chemistry of semi-volatile/inter-mediate volatility organics ("aging SIVOC"), significantly over-predict SOA as compared to aircraft measurements downwindmore » of Mexico City. In sharp contrast, the revised models, which include gas-phase fragmentation, show much better agreement with measurements downwind of Mexico City. We also demonstrate complex differences in spatial SOA distributions when we transform SOA to non-volatile secondary organic aerosol (NVSOA) to account for experimental observations. Using a simple box model, we show that for same amount of SOA precursors, earlier models that do not employ multi-generation gas-phase chemistry of precursors ("non-aging SIVOC"), produce orders of magnitude lower SOA than "aging SIVOC" parameterizations both with and without fragmentation. In addition, traditional absorptive partitioning models predict almost complete SOA evaporation at farther downwind locations for both "non-aging SIVOC" and "aging SIVOC" with fragmentation. In contrast, in our revised approach, SOA transformed to NVSOA implies significantly higher background concentrations as it remains in particle phase even under highly dilute conditions. This work has significant implications on understanding the role of multi-generational chemistry and NVSOA formation on SOA evolution in the atmosphere.« less

Ozone and OH-induced oxidation of monoterpenes: Changes in the thermal properties of secondary organic aerosol (SOA)

NASA Astrophysics Data System (ADS)

Watne, Ågot K.; Westerlund, Jonathan; Hallquist, Åsa M.; Brune, William H.; Hallquist, Mattias

2017-12-01

The behaviour of secondary organic aerosols (SOA) in the atmosphere is highly dependent on their thermal properties. Here we investigate the volatility of SOA formed from alpha-pinene, beta-pinene and limonene upon ozone- and OH-induced oxidation, and the effect of OH-induced ageing on the initially produced SOA. For all three terpenes, the ozone-induced SOA was less volatile than the OH-induced SOA. The thermal properties of the SOA were described using three parameters extracted from the volatility measurements: the temperature at which 50 per cent of the volume has evaporated (TVFR0.5), which is used as a general volatility indicator; a slope factor (SVFR), which describes the volatility distribution; and TVFR0.1, which measures the volatility of the least volatile particle fraction. Limonene-derived SOA generally had higher TVFR0.5 values and shallower slopes than SOA derived from alpha- and beta-pinene. This was especially true for the ozone-induced SOA, partially because the ozonolysis of limonene has a strong tendency to cause SOA formation and to produce extremely low volatility VOCs (ELVOCs). Ageing by OH exposure did not reduce TVFR0.5 for any of the studied terpenes but did increase the breadth of the volatility distribution by increasing the aerosols heterogeneity and contents of substances with different vapour pressures, also leading to increases in TVFR0.1. This stands in contrast to previously reported results from smog chamber experiments, in which TVFR0.5 always increased with ageing. These results demonstrate that there are two opposing processes that influence the evolution of SOAs thermal properties as they age, and that results from both flow reactors and static chambers are needed to fully understand the temporal evolution of atmospheric SOA thermal properties.

Characterization of organic nitrate constituents of secondary organic aerosol (SOA) from nitrate-radical-initiated oxidation of limonene using high-resolution chemical ionization mass spectrometry

NASA Astrophysics Data System (ADS)

Faxon, Cameron; Hammes, Julia; Le Breton, Michael; Kant Pathak, Ravi; Hallquist, Mattias

2018-04-01

The gas-phase nitrate radical (NO3⚫) initiated oxidation of limonene can produce organic nitrate species with varying physical properties. Low-volatility products can contribute to secondary organic aerosol (SOA) formation and organic nitrates may serve as a NOx reservoir, which could be especially important in regions with high biogenic emissions. This work presents the measurement results from flow reactor studies on the reaction of NO3⚫ with limonene using a High-Resolution Time-of-Flight Chemical Ionization Mass Spectrometer (HR-ToF-CIMS) combined with a Filter Inlet for Gases and AEROsols (FIGAERO). Major condensed-phase species were compared to those in the Master Chemical Mechanism (MCM) limonene mechanism, and many non-listed species were identified. The volatility properties of the most prevalent organic nitrates in the produced SOA were determined. Analysis of multiple experiments resulted in the identification of several dominant species (including C10H15NO6, C10H17NO6, C8H11NO6, C10H17NO7, and C9H13NO7) that occurred in the SOA under all conditions considered. Additionally, the formation of dimers was consistently observed and these species resided almost completely in the particle phase. The identities of these species are discussed, and formation mechanisms are proposed. Cluster analysis of the desorption temperatures corresponding to the analyzed particle-phase species yielded at least five distinct groupings based on a combination of molecular weight and desorption profile. Overall, the results indicate that the oxidation of limonene by NO3⚫ produces a complex mixture of highly oxygenated monomer and dimer products that contribute to SOA formation.

A qualitative comparison of secondary organic aerosol yields and composition from ozonolysis of monoterpenes at varying concentrations of NO2

NASA Astrophysics Data System (ADS)

Draper, D. C.; Farmer, D. K.; Desyaterik, Y.; Fry, J. L.

2015-11-01

The effect of NO2 on secondary organic aerosol (SOA) formation from ozonolysis of α-pinene, β-pinene, Δ3-carene, and limonene was investigated using a dark flow-through reaction chamber. SOA mass yields were calculated for each monoterpene from ozonolysis with varying NO2 concentrations. Kinetics modeling of the first-generation gas-phase chemistry suggests that differences in observed aerosol yields for different NO2 concentrations are consistent with NO3 formation and subsequent competition between O3 and NO3 to oxidize each monoterpene. α-Pinene was the only monoterpene studied that showed a systematic decrease in both aerosol number concentration and mass concentration with increasing [NO2]. β-Pinene and Δ3-carene produced fewer particles at higher [NO2], but both retained moderate mass yields. Limonene exhibited both higher number concentrations and greater mass concentrations at higher [NO2]. SOA from each experiment was collected and analyzed by HPLC-ESI-MS, enabling comparisons between product distributions for each system. In general, the systems influenced by NO3 oxidation contained more high molecular weight products (MW > 400 amu), suggesting the importance of oligomerization mechanisms in NO3-initiated SOA formation. α-Pinene, which showed anomalously low aerosol mass yields in the presence of NO2, showed no increase in these oligomer peaks, suggesting that lack of oligomer formation is a likely cause of α-pinene's near 0 % yields with NO3. Through direct comparisons of mixed-oxidant systems, this work suggests that NO3 is likely to dominate nighttime oxidation pathways in most regions with both biogenic and anthropogenic influences. Therefore, accurately constraining SOA yields from NO3 oxidation, which vary substantially with the volatile organic compound precursor, is essential in predicting nighttime aerosol production.

Formation of secondary organic aerosol coating on black carbon particles near vehicular emissions

NASA Astrophysics Data System (ADS)

Lee, Alex K. Y.; Chen, Chia-Li; Liu, Jun; Price, Derek J.; Betha, Raghu; Russell, Lynn M.; Zhang, Xiaolu; Cappa, Christopher D.

2017-12-01

Black carbon (BC) emitted from incomplete combustion can result in significant impacts on air quality and climate. Understanding the mixing state of ambient BC and the chemical characteristics of its associated coatings is particularly important to evaluate BC fate and environmental impacts. In this study, we investigate the formation of organic coatings on BC particles in an urban environment (Fontana, California) under hot and dry conditions using a soot-particle aerosol mass spectrometer (SP-AMS). The SP-AMS was operated in a configuration that can exclusively detect refractory BC (rBC) particles and their coatings. Using the -log(NOx / NOy) ratio as a proxy for photochemical age of air masses, substantial formation of secondary organic aerosol (SOA) coatings on rBC particles was observed due to active photochemistry in the afternoon, whereas primary organic aerosol (POA) components were strongly associated with rBC from fresh vehicular emissions in the morning rush hours. There is also evidence that cooking-related organic aerosols were externally mixed from rBC. Positive matrix factorization and elemental analysis illustrate that most of the observed SOA coatings were freshly formed, providing an opportunity to examine SOA coating formation on rBCs near vehicular emissions. Approximately 7-20 wt % of secondary organic and inorganic species were estimated to be internally mixed with rBC on average, implying that rBC is unlikely the major condensation sink of SOA in this study. Comparison of our results to a co-located standard high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) measurement suggests that at least a portion of SOA materials condensed on rBC surfaces were chemically different from oxygenated organic aerosol (OOA) particles that were externally mixed with rBC, although they could both be generated from local photochemistry.

Direct Observations of Isoprene Secondary Organic Aerosol Formation in Ambient Cloud Droplets

NASA Astrophysics Data System (ADS)

Zelenyuk, A.; Bell, D.; Thornton, J. A.; Fast, J. D.; Shrivastava, M. B.; Berg, L. K.; Imre, D. G.; Mei, F.; Shilling, J.; Suski, K. J.; Liu, J.; Tomlinson, J. M.; Wang, J.

2017-12-01

Multiphase chemistry of isoprene photooxidation products has been shown to be one of the major sources of secondary organic aerosol (SOA) in the atmosphere. A number of recent studies indicate that aqueous aerosol phase provides a medium for reactive uptake of isoprene photooxidation products, and in particular, isomeric isoprene epoxydiols (IEPOX), with reaction rates and yields being dependent on aerosol acidity, water content, sulfate concentration, and organic coatings. However, very few studies focused on chemistry occurring within actual cloud droplets. We will present data acquired during recent Holistic Interactions of Shallow Clouds, Aerosols, and Land Ecosystems (HI-SCALE) Campaign, which provide direct evidence for IEPOX-SOA formation in cloud droplets. Single particle mass spectrometer, miniSPLAT, and a high-resolution, time-of-flight aerosol mass spectrometer were used to characterize the composition of aerosol particles and cloud droplet residuals, while a high-resolution, time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS) was used to characterize gas-phase compounds. We find that the composition of cloud droplet residuals was markedly different than that of aerosol particles sampled outside the cloud. Cloud droplet residuals were comprised of individual particles with high relative fractions of sulfate and nitrate and significant fraction of particles with mass spectra that are nearly identical to those of laboratory-generated IEPOX-SOA particles. The observed cloud-induced formation of IEPOX-SOA was accompanied by simultaneous decrease in measured concentrations of IEPOX and other gas-phase isoprene photooxidation products. Ultimately, the combined cloud, aerosol, and gas-phase measurements conducted during HI-SCALE will be used to develop and evaluate model treatments of aqueous-phase isoprene SOA formation.

Kinetics, Mechanism, and Secondary Organic Aerosol Yield of Aqueous Phase Photo-oxidation of α-Pinene Oxidation Products.

PubMed

Aljawhary, Dana; Zhao, Ran; Lee, Alex K Y; Wang, Chen; Abbatt, Jonathan P D

2016-03-10

Formation of secondary organic aerosol (SOA) involves atmospheric oxidation of volatile organic compounds (VOCs), the majority of which are emitted from biogenic sources. Oxidation can occur not only in the gas-phase but also in atmospheric aqueous phases such as cloudwater and aerosol liquid water. This study explores for the first time the aqueous-phase OH oxidation chemistry of oxidation products of α-pinene, a major biogenic VOC species emitted to the atmosphere. The kinetics, reaction mechanisms, and formation of SOA compounds in the aqueous phase of two model compounds, cis-pinonic acid (PIN) and tricarballylic acid (TCA), were investigated in the laboratory; TCA was used as a surrogate for 3-methyl-1,2,3-butanetricarboxylic acid (MBTCA), a known α-pinene oxidation product. Aerosol time-of-flight chemical ionization mass spectrometry (Aerosol-ToF-CIMS) was used to follow the kinetics and reaction mechanisms at the molecular level. Room-temperature second-order rate constants of PIN and TCA were determined to be 3.3 (± 0.5) × 10(9) and 3.1 (± 0.2) × 10(8) M(-1) s(-1), respectively, from which were estimated their condensed-phase atmospheric lifetimes. Aerosol-ToF-CIMS detected a large number of products leading to detailed reaction mechanisms for PIN and MBTCA. By monitoring the particle size distribution after drying, the amount of SOA material remaining in the particle phase was determined. An aqueous SOA yield of 40 to 60% was determined for PIN OH oxidation. Although recent laboratory studies have focused primarily on aqueous-phase processing of isoprene-related compounds, we demonstrate that aqueous formation of SOA materials also occurs from monoterpene oxidation products, thus representing an additional source of biogenically driven aerosol formation.

Modeling the Role of Alkanes, Polycyclic Aromatic Hydrocarbons, and Their Oligomers in Secondary Organic Aerosol Formation

EPA Science Inventory

A computationally efficient method to treat secondary organic aerosol (SOA) from various length and structure alkanes as well as SOA from polycyclic aromatic hydrocarbons (PAHs) is implemented in the Community Multiscale Air Quality (CMAQ) model to predict aerosol concentrations ...

EVALUATION OF SECONDARY ORGANIC AEROSOL FORMATION IN WINTER. (R823514)

EPA Science Inventory

Three different methods are used to predict secondary organic aerosol (SOA)
concentrations in the San Joaquin Valley of California during the winter of 1995-1996 [Integrated
Monitoring Study, (IMS95)]. The first of these methods estimates SOA by using elemental carbon as

Improving the representation of secondary organic aerosol (SOA) in the MOZART-4 global chemical transport model

NASA Astrophysics Data System (ADS)

Mahmud, A.; Barsanti, K.

2013-07-01

The secondary organic aerosol (SOA) module in the Model for Ozone and Related Chemical Tracers, version 4 (MOZART-4) was updated by replacing existing two-product (2p) parameters with those obtained from two-product volatility basis set (2p-VBS) fits (MZ4-C1), and by treating SOA formation from the following additional volatile organic compounds (VOCs): isoprene, propene and lumped alkenes (MZ4-C2). Strong seasonal and spatial variations in global SOA distributions were demonstrated, with significant differences in the predicted concentrations between the base case and updated model simulations. Updates to the model resulted in significant increases in annual average SOA mass concentrations, particularly for the MZ4-C2 simulation in which the additional SOA precursor VOCs were treated. Annual average SOA concentrations predicted by the MZ4-C2 simulation were 1.00 ± 1.04 μg m-3 in South America, 1.57 ± 1.88 μg m-3 in Indonesia, 0.37 ± 0.27 μg m-3 in the USA, and 0.47 ± 0.29 μg m-3 in Europe with corresponding increases of 178, 406, 311 and 292% over the base-case simulation, respectively, primarily due to inclusion of isoprene. The increases in predicted SOA mass concentrations resulted in corresponding increases in SOA contributions to annual average total aerosol optical depth (AOD) by ~ 1-6%. Estimated global SOA production was 5.8, 6.6 and 19.1 Tg yr-1 with corresponding burdens of 0.22, 0.24 and 0.59 Tg for the base-case, MZ4-C1 and MZ4-C2 simulations, respectively. The predicted SOA budgets fell well within reported ranges for comparable modeling studies, 6.7 to 96 Tg yr-1, but were lower than recently reported observationally constrained values, 50 to 380 Tg yr-1. For MZ4-C2, simulated SOA concentrations at the surface also were in reasonable agreement with comparable modeling studies and observations. Total organic aerosol (OA) mass concentrations at the surface, however, were slightly over-predicted in Europe, Amazonian regions and Malaysian Borneo (Southeast Asia) during certain months of the year, and under-predicted in most sites in Asia; relative to those regions, the model performed better for sites in North America. Overall, with the inclusion of additional SOA precursors (MZ4-C2), namely isoprene, MOZART-4 showed consistently better skill (NMB (normalized mean bias) of -11 vs. -26%) in predicting total OA levels and spatial distributions of SOA as compared with unmodified MOZART-4. Treatment of SOA formation by these known precursors (isoprene, propene and lumped alkenes) may be particularly important when MOZART-4 output is used to generate boundary conditions for regional air quality simulations that require more accurate representation of SOA concentrations and distributions.

FORMATION OF 2-METHYL TETROLS AND 2-METHYLGLYCERIC ACID IN SECONDARY ORGANIC AEROSOL FROM LABORATORY IRRADIATED ISOPRENE/NO X/SO 2/AIR MIXTURES AND THEIR DETECTION IN AMBIENT PM 2.5 SAMPLES COLLECTED IN THE EASTERN UNITED STATES

EPA Science Inventory

A series of isoprene/NOx/air irradiation experiments, carried out in both the absence and presence of SO2, were conducted to assess whether isoprene contributes to secondary organic aerosol (SOA) formation. In the absence of SO2 , the SOA yield of 0.002 was low. However, in th...

Characterization of secondary organic aerosol generated from ozonolysis of α-pinene mixtures

NASA Astrophysics Data System (ADS)

Amin, Hardik S.; Hatfield, Meagan L.; Huff Hartz, Kara E.

2013-03-01

In the atmosphere, multiple volatile organic compounds (VOCs) co-exist, and they can be oxidized concurrently and generate secondary organic aerosol (SOA). In this work, SOA is formed by the oxidation (in presence of excess ozone) of mixtures containing α-pinene and other VOCs. The VOC mixtures were made so their composition approached a commercially-available α-pinene-based essential oil, Siberian fir needle oil. The SOA products were sampled using filters, solvent extracted and analyzed by gas chromatography/mass spectrometry with trimethylsilyl derivatization. The individual product yields for SOA generated from α-pinene changed upon the addition of other VOCs. An increase in concentration of non-reactive VOCs (bornyl acetate, camphene, and borneol) lead to a decrease in individual product yields of characteristic α-pinene SOA products. Although these experiments were carried out under higher VOC and ozone concentrations in comparison to the atmosphere, this work suggests that the role of non-reactive VOCs should be explored in SOA products formation.

Epoxide as a Precursor to Secondary Organic Aerosol Formation from Isoprene Photooxidation in the Presence of Nitrogen Oxides

EPA Science Inventory

Isoprene is a substantial contributor to the global secondary organic aerosol (SOA) burden, with implications for public health and the climate system. The mechanism by which isoprene-derived SOA is formed and the influence of environmental conditions, however, remain unclear...

Unspeciated organic emissions from combustion sources and their influence on the secondary organic aerosol budget in the United States

EPA Science Inventory

Secondary organic aerosol (SOA) formed from the atmospheric oxidation of nonmethane organic gases (NMOG) is a major contributor to atmospheric aerosol mass. Emissions and smog chamber experiments were performed to investigate SOA formation from gasoline vehicles, diesel vehicles,...

Formation of Organic Tracers for Isoprene SOA under Acidic Conditions

EPA Science Inventory

The chemical compositions of a series of secondary organic aerosol (SOA) samples, formed by irradiating mixtures of isoprene and NO in a smog chamber in the absence or presence of acidic aerosols, were analyzed using derivatization-based GC-MS methods. In addition to the known is...

Semivolatile POA and parameterized total combustion SOA in CMAQv5.2: impacts on source strength and partitioning

DOE PAGES

Murphy, Benjamin N.; Woody, Matthew C.; Jimenez, Jose L.; ...

2017-09-20

Mounting evidence from field and laboratory observations coupled with atmospheric model analyses shows that primary combustion emissions of organic compounds dynamically partition between the vapor and particulate phases, especially as near-source emissions dilute and cool to ambient conditions. The most recent version of the Community Multiscale Air Quality model version 5.2 (CMAQv5.2) accounts for the semivolatile partitioning and gas-phase aging of these primary organic aerosol (POA) compounds consistent with experimentally derived parameterizations. We also include a new surrogate species, potential secondary organic aerosol from combustion emissions (pcSOA), which provides a representation of the secondary organic aerosol (SOA) from anthropogenic combustionmore » sources that could be missing from current chemical transport model predictions. The reasons for this missing mass likely include the following: (1) unspeciated semivolatile and intermediate volatility organic compound (SVOC and IVOC, respectively) emissions missing from current inventories, (2) multigenerational aging of organic vapor products from known SOA precursors (e.g., toluene, alkanes), (3) underestimation of SOA yields due to vapor wall losses in smog chamber experiments, and (4) reversible organic compounds–water interactions and/or aqueous-phase processing of known organic vapor emissions. CMAQ predicts the spatially averaged contribution of pcSOA to OA surface concentrations in the continental United States to be 38.6 and 23.6 % in the 2011 winter and summer, respectively. Whereas many past modeling studies focused on a particular measurement campaign, season, location, or model configuration, we endeavor to evaluate the model and important uncertain parameters with a comprehensive set of United States-based model runs using multiple horizontal scales (4 and 12 km), gas-phase chemical mechanisms, and seasons and years. The model with representation of semivolatile POA improves predictions of hourly OA observations over the traditional nonvolatile model at sites during field campaigns in southern California (CalNex, May–June 2010), northern California (CARES, June 2010), the southeast US (SOAS, June 2013; SEARCH, January and July, 2011). Model improvements manifest better correlations (e.g., the correlation coefficient at Pasadena at night increases from 0.38 to 0.62) and reductions in underprediction during the photochemically active afternoon period (e.g., bias at Pasadena from -5.62 to -2.42 µg m -3). Daily averaged predictions of observations at routine-monitoring networks from simulations over the continental US (CONUS) in 2011 show modest improvement during winter, with mean biases reducing from 1.14 to 0.73 µg m -3, but less change in the summer when the decreases from POA evaporation were similar to the magnitude of added SOA mass. Because the model-performance improvement realized by including the relatively simple pcSOA approach is similar to that of more-complicated parameterizations of OA formation and aging, we recommend caution when applying these more-complicated approaches as they currently rely on numerous uncertain parameters. The pcSOA parameters optimized for performance at the southern and northern California sites lead to higher OA formation than is observed in the CONUS evaluation. This may be due to any of the following: variations in real pcSOA in different regions or time periods, too-high concentrations of other OA sources in the model that are important over the larger domain, or other model issues such as loss processes. This discrepancy is likely regionally and temporally dependent and driven by interferences from factors like varying emissions and chemical regimes.« less

Semivolatile POA and parameterized total combustion SOA in CMAQv5.2: impacts on source strength and partitioning

DOE Office of Scientific and Technical Information (OSTI.GOV)

Murphy, Benjamin N.; Woody, Matthew C.; Jimenez, Jose L.

Mounting evidence from field and laboratory observations coupled with atmospheric model analyses shows that primary combustion emissions of organic compounds dynamically partition between the vapor and particulate phases, especially as near-source emissions dilute and cool to ambient conditions. The most recent version of the Community Multiscale Air Quality model version 5.2 (CMAQv5.2) accounts for the semivolatile partitioning and gas-phase aging of these primary organic aerosol (POA) compounds consistent with experimentally derived parameterizations. We also include a new surrogate species, potential secondary organic aerosol from combustion emissions (pcSOA), which provides a representation of the secondary organic aerosol (SOA) from anthropogenic combustionmore » sources that could be missing from current chemical transport model predictions. The reasons for this missing mass likely include the following: (1) unspeciated semivolatile and intermediate volatility organic compound (SVOC and IVOC, respectively) emissions missing from current inventories, (2) multigenerational aging of organic vapor products from known SOA precursors (e.g., toluene, alkanes), (3) underestimation of SOA yields due to vapor wall losses in smog chamber experiments, and (4) reversible organic compounds–water interactions and/or aqueous-phase processing of known organic vapor emissions. CMAQ predicts the spatially averaged contribution of pcSOA to OA surface concentrations in the continental United States to be 38.6 and 23.6 % in the 2011 winter and summer, respectively. Whereas many past modeling studies focused on a particular measurement campaign, season, location, or model configuration, we endeavor to evaluate the model and important uncertain parameters with a comprehensive set of United States-based model runs using multiple horizontal scales (4 and 12 km), gas-phase chemical mechanisms, and seasons and years. The model with representation of semivolatile POA improves predictions of hourly OA observations over the traditional nonvolatile model at sites during field campaigns in southern California (CalNex, May–June 2010), northern California (CARES, June 2010), the southeast US (SOAS, June 2013; SEARCH, January and July, 2011). Model improvements manifest better correlations (e.g., the correlation coefficient at Pasadena at night increases from 0.38 to 0.62) and reductions in underprediction during the photochemically active afternoon period (e.g., bias at Pasadena from -5.62 to -2.42 µg m -3). Daily averaged predictions of observations at routine-monitoring networks from simulations over the continental US (CONUS) in 2011 show modest improvement during winter, with mean biases reducing from 1.14 to 0.73 µg m -3, but less change in the summer when the decreases from POA evaporation were similar to the magnitude of added SOA mass. Because the model-performance improvement realized by including the relatively simple pcSOA approach is similar to that of more-complicated parameterizations of OA formation and aging, we recommend caution when applying these more-complicated approaches as they currently rely on numerous uncertain parameters. The pcSOA parameters optimized for performance at the southern and northern California sites lead to higher OA formation than is observed in the CONUS evaluation. This may be due to any of the following: variations in real pcSOA in different regions or time periods, too-high concentrations of other OA sources in the model that are important over the larger domain, or other model issues such as loss processes. This discrepancy is likely regionally and temporally dependent and driven by interferences from factors like varying emissions and chemical regimes.« less

Semivolatile POA and parameterized total combustion SOA in CMAQv5.2: impacts on source strength and partitioning

NASA Astrophysics Data System (ADS)

Murphy, Benjamin N.; Woody, Matthew C.; Jimenez, Jose L.; Carlton, Ann Marie G.; Hayes, Patrick L.; Liu, Shang; Ng, Nga L.; Russell, Lynn M.; Setyan, Ari; Xu, Lu; Young, Jeff; Zaveri, Rahul A.; Zhang, Qi; Pye, Havala O. T.

2017-09-01

Mounting evidence from field and laboratory observations coupled with atmospheric model analyses shows that primary combustion emissions of organic compounds dynamically partition between the vapor and particulate phases, especially as near-source emissions dilute and cool to ambient conditions. The most recent version of the Community Multiscale Air Quality model version 5.2 (CMAQv5.2) accounts for the semivolatile partitioning and gas-phase aging of these primary organic aerosol (POA) compounds consistent with experimentally derived parameterizations. We also include a new surrogate species, potential secondary organic aerosol from combustion emissions (pcSOA), which provides a representation of the secondary organic aerosol (SOA) from anthropogenic combustion sources that could be missing from current chemical transport model predictions. The reasons for this missing mass likely include the following: (1) unspeciated semivolatile and intermediate volatility organic compound (SVOC and IVOC, respectively) emissions missing from current inventories, (2) multigenerational aging of organic vapor products from known SOA precursors (e.g., toluene, alkanes), (3) underestimation of SOA yields due to vapor wall losses in smog chamber experiments, and (4) reversible organic compounds-water interactions and/or aqueous-phase processing of known organic vapor emissions. CMAQ predicts the spatially averaged contribution of pcSOA to OA surface concentrations in the continental United States to be 38.6 and 23.6 % in the 2011 winter and summer, respectively. Whereas many past modeling studies focused on a particular measurement campaign, season, location, or model configuration, we endeavor to evaluate the model and important uncertain parameters with a comprehensive set of United States-based model runs using multiple horizontal scales (4 and 12 km), gas-phase chemical mechanisms, and seasons and years. The model with representation of semivolatile POA improves predictions of hourly OA observations over the traditional nonvolatile model at sites during field campaigns in southern California (CalNex, May-June 2010), northern California (CARES, June 2010), the southeast US (SOAS, June 2013; SEARCH, January and July, 2011). Model improvements manifest better correlations (e.g., the correlation coefficient at Pasadena at night increases from 0.38 to 0.62) and reductions in underprediction during the photochemically active afternoon period (e.g., bias at Pasadena from -5.62 to -2.42 µg m-3). Daily averaged predictions of observations at routine-monitoring networks from simulations over the continental US (CONUS) in 2011 show modest improvement during winter, with mean biases reducing from 1.14 to 0.73 µg m-3, but less change in the summer when the decreases from POA evaporation were similar to the magnitude of added SOA mass. Because the model-performance improvement realized by including the relatively simple pcSOA approach is similar to that of more-complicated parameterizations of OA formation and aging, we recommend caution when applying these more-complicated approaches as they currently rely on numerous uncertain parameters. The pcSOA parameters optimized for performance at the southern and northern California sites lead to higher OA formation than is observed in the CONUS evaluation. This may be due to any of the following: variations in real pcSOA in different regions or time periods, too-high concentrations of other OA sources in the model that are important over the larger domain, or other model issues such as loss processes. This discrepancy is likely regionally and temporally dependent and driven by interferences from factors like varying emissions and chemical regimes.

A perspective on SOA generated in aerosol water from glyoxal and methylglyoxal and its impacts on climate-relevant aerosol properties

NASA Astrophysics Data System (ADS)

Sareen, N.; McNeill, V. F.

2011-12-01

In recent years, glyoxal and methylglyoxal have emerged to be potentially important SOA precursors with significant implications for climate-related aerosol properties. Here we will discuss how the chemistry of these and similar organic compounds in aerosol water can affect the aerosol optical and cloud formation properties. Aqueous-phase SOA production from glyoxal and methylglyoxal is a potential source of strongly light-absorbing organics, or "brown carbon". We characterized the kinetics of brown carbon formation from these precursors in mixtures of ammonium sulfate and water using UV-Vis spectrophotometry. This mechanism has been incorporated into a photochemical box model with coupled gas phase-aqueous aerosol chemistry. Methylglyoxal and related compounds also may impact an aerosol's ability to act as a cloud condensation nucleus. We recently showed via pendant drop tensiometry and aerosol chamber studies that uptake of methylglyoxal from the gas phase driven by aqueous-phase oligomerization chemistry is a potentially significant, previously unidentified source of surface-active organic material in aerosols. Results from pendant drop tensiometry showed significantly depressed surface tension in methylglyoxal-ammonium sulfate solutions. We further found that ammonium sulfate particles exposed to gas-phase methylglyoxal in a 3.5 m3 aerosol reaction chamber activate into cloud droplets at sizes up to 15% lower at a given supersaturation than do pure ammonium sulfate particles. The observed enhancement exceeds that predicted based on Henry's Law and our measurements of surface tension depression in bulk solutions, suggesting that surface adsorption of methylglyoxal plays a role in determining CCN activity. Methylglyoxal and similar gas-phase surfactants may be an important and overlooked source of enhanced CCN activity in the atmosphere. To characterize the SOA products formed in these solutions, an Aerosol Chemical Ionization Mass Spectrometer (CIMS) was used. These compounds included (hemi)acetals, aldol condensation products, and oligomeric species up to 759 amu. Since these products are vulnerable to oxidants such as O3 and OH in the atmosphere, kinetic studies were conducted to study their affect upon exposure to O3 and OH. Custom-designed flow tube reactors were coupled with the Aerosol-CIMS to monitor aerosol composition, and consequently this data was used to determine reactive uptake coefficients (γO3~10-8 and γOH~ 10-6). Additionally, the lifetime of these SOA species in the atmosphere can be estimated and if these time scales are sufficiently long, they may affect aerosol optical properties. The effect of oxidation on the optical properties is also currently being tested by collecting aerosol particles before and after oxidation on a quartz window and testing changes in absorption using the UV-Vis spectrophotometer. The results of all these studies will be integrated to understand the role of methylglyoxal as a SOA precursor and the effect on various aerosol properties, and this will be used as a model system to predict the fate of similar organics in the atmosphere.

Effect of SO2 and Photolysis on Photooxidized Diesel Fuel Secondary Organic Aerosol Composition

NASA Astrophysics Data System (ADS)

MacMillan, A. C.; Blair, S. L.; Lin, P.; Laskin, A.; Laskin, J.; Nizkorodov, S.

2014-12-01

Diesel fuel (DSL) and sulfur dioxide (SO2) are important precursors to secondary organic aerosol (SOA) formation. DSL is often co-emitted with SO2 and NO2, thus it is important to understand the possible effects of SO2 on DSL SOA composition. Additionally, DSL SOA composition can be affected by photochemical aging processes such as photolysis. In this study, DSL SOA was first prepared under dry, high-NOx conditions with various concentrations of SO2 by photooxidation in a smog chamber. The SOA was then stripped of excess oxidants and gaseous organics with a denuder train and the resulting particles were photolyzed at various photolysis times in a quartz flow tube. The SOA composition, photochemical aging, properties, and mass concentration, before and after direct photolysis in the flow tube, were examined using several techniques. High-resolution mass spectrometry (HR-MS) was performed on DSL SOA samples to investigate the effect of SO2 on molecular level composition. SOA composition as a function of photolysis time was measured with an aerosol mass spectrometer (AMS). HR-MS results show that organosulfates are produced in DSL SOA. Both AMS and HR-MS results show that photolysis also has an effect on composition; though, this is more apparent in the HR-MS results than in the AMS results. In summary, both the presence of SO2 and solar radiation has an effect on DSL SOA composition.

Formation of brown carbon via reactions of ammonia with secondary organic aerosols from biogenic and anthropogenic precursors

NASA Astrophysics Data System (ADS)

Updyke, Katelyn M.; Nguyen, Tran B.; Nizkorodov, Sergey A.

2012-12-01

Filter samples of secondary organic aerosols (SOA) generated from the ozone (O3)- and hydroxyl radical (OH)-initiated oxidation of various biogenic (isoprene, α-pinene, limonene, α-cedrene, α-humulene, farnesene, pine leaf essential oils, cedar leaf essential oils) and anthropogenic (tetradecane, 1,3,5-trimethylbenzene, naphthalene) precursors were exposed to humid air containing approximately 100 ppb of gaseous ammonia (NH3). Reactions of SOA compounds with NH3 resulted in production of light-absorbing "brown carbon" compounds, with the extent of browning ranging from no observable change (isoprene SOA) to visible change in color (limonene SOA). The aqueous phase reactions with dissolved ammonium (NH4+) salts, such as ammonium sulfate, were equally efficient in producing brown carbon. Wavelength-dependent mass absorption coefficients (MAC) of the aged SOA were quantified by extracting known amounts of SOA material in methanol and recording its UV/Vis absorption spectra. For a given precursor, the OH-generated SOA had systematically lower MAC compared to the O3-generated SOA. The highest MAC values, for brown carbon from SOA resulting from O3 oxidation of limonene and sesquiterpenes, were comparable to MAC values for biomass burning particles but considerably smaller than MAC values for black carbon aerosols. The NH3/NH4+ + SOA brown carbon aerosol may contribute to aerosol optical density in regions with elevated concentrations of NH3 or ammonium sulfate and high photochemical activity.

Aqueous Photochemistry of Secondary Organic Aerosol of α-Pinene and α-Humulene Oxidized with Ozone, Hydroxyl Radical, and Nitrate Radical

DOE Office of Scientific and Technical Information (OSTI.GOV)

Romonosky, Dian E.; Li, Ying; Shiraiwa, Manabu

Formation of secondary organic aerosols (SOA) from biogenic volatile organic compounds 13 (BVOC) occurs via O 3 - and OH-initiated reactions during the day and reactions with NO 3 during the 14 night. We explored the effect of these three oxidation conditions on the molecular composition and 15 aqueous photochemistry of model SOA prepared from two common BVOC. A common monoterpene, α- 16 pinene, and sesquiterpene, α-humulene, were used to form SOA in a smog chamber via BVOC + O3, 17 BVOC + NO3, and BVOC + OH + NOx oxidation. Samples of SOA were collected, extracted in water,more » 18 and photolyzed in an aqueous solution in order to simulate the photochemical cloud processing of SOA. 19 The extent of change in the molecular level composition of SOA over 4 hours of photolysis (roughly 20 equivalent to 64 hours of photolysis under ambient conditions) was assessed with high-resolution 21 electrospray ionization mass spectrometry. The analysis revealed significant differences in the molecular 22 composition between monoterpene and sesquiterpene SOA formed by the different oxidation pathways. 23 The composition further evolved during photolysis with the most notable change corresponding to the 24 nearly-complete removal of nitrogen-containing organic compounds. Hydrolysis of SOA compounds also 25 occurred in parallel with photolysis. The preferential loss of larger SOA compounds during photolysis 26 and hydrolysis made the SOA compounds more volatile on average. This study suggests that cloud- and 27 fog-processing may under certain conditions lead to a reduction in the SOA loading as opposed to an 28 increase in SOA loading commonly assumed in the literature.« less

Flow Reactor for studying Physicochemical and aging properties of SOA

NASA Astrophysics Data System (ADS)

Babar, Z. B.

2016-12-01

Secondary organic aerosols (SOA) have importance in environmental processes such as affecting earth's radiative balance and cloud formation processes. For studying SOA formation large scale environmental batch reactors and laboratory scale flow reactors have been used. In this study application of flow reactor to study physicochemical properties of SOA is also investigated after its characterization. The flow reactor is of cylindrical design (ID 15 cm x L 70 cm) equipped with UV lamps. It is coupled with various instruments such as scanning mobility particle sizer, NOx analyzer, ozone analyzer, VOC analyzer, hygrometer, and temperature sensors for gas and particle phase measurements. OH radicals were generated by custom build ozone generator and relative humidity. The following characterizations were performed: (1) residence time distribution (RTD) measurements, (2) RH and temperature control, (3) OH radical exposure range (atmospheric aging time), (4) gas phase oxidation of SOA precursors such as α-pinene by OH radical. The flow reactor yielded narrow RTDs. In particular, RH and temperature can be controlled effectively between 0-60% and 22-43oC, respectively. OH radical exposure ranges from 6.49x1010 to 3.68x1011 molecules/cm3s (0.49 to 4.91 days). Our initial efforts on OH radical generation using hydrogen peroxide and its quantification by using flourescenet technique will be also be presented.

Primary Emission and the Potential of Secondary Aerosol Formation from Chinese Gasoline Engine Exhaust

NASA Astrophysics Data System (ADS)

Hu, Min; Peng, Jianfei; Qin, Yanhong; Du, Zhuofei; Li, Mengjin; Zheng, Rong; Zheng, Jing; Shang, Dongjie; Lu, Sihua; Wu, Yusheng; Zeng, Limin; Guo, Song; Shao, Min; Wang, Yinhui; Shuai, Shijin

2017-04-01

Along with the urbanization and economic growth, vehicle population in China reached 269 million, ranked the second in the world in 2015. Gasoline vehicle is identified to be the main source for urban PM2.5 in China, accounting for 15%-31%. In this study the impact of fuel components on PM2.5 and volatile organic compounds (VOCs) emissions from a gasoline port fuel injection (PFI) engine and a gasoline direct injection (GDI) engine are discussed. Results show that, higher proportion of aromatics, alkenes or sulfur in gasoline fuel will lead to higher PM emissions. The PM from the PFI engine mainly consists of OC and a small amount of EC and inorganic ions, while the PM discharge from the GDI engine mainly consists of EC, OM and a small amount of inorganic ions. Since the GDI engines can reduce fuel consumption and CO2 emissions, and it would become more and more popular in the near future. The characteristics of POM component, emission factors and source profile were investigated from GDI engine, particularly focused on the effect of engine speed, load and the catalyst, which will be very much helpful for source identification as source indicators. Chamber experiments were conducted to quantify the potential of secondary aerosol formation from exhaust of a PFI gasoline engine and China V gasoline fuel. During 4-5 h simulation, equivalent to10 days of atmospheric photo-oxidation in Beijing, the extreme SOA production was 426 ± 85 mg/kg fuel, with high precursors and OH exposure. 14% of SOA measured in the chamber experiments could be explained through the oxidation of speciated single-ring aromatics. Unspeciated precursors, such as intermediate-volatility organic compounds and semi-volatility organic compounds, might be significant for SOA formation from gasoline VOCs. We concluded that reduction of emissions of aerosol precursor gases from vehicles is essential to mediate pollution in China.

Modeling SOA production from the oxidation of intermediate volatility alkanes

NASA Astrophysics Data System (ADS)

Aumont, B.; Mouchel-Vallon, C.; Camredon, M.; Lee-Taylor, J.; Madronich, S.

2012-12-01

Secondary Organic Aerosols (SOA) production and ageing is a multigenerational oxidation process involving the formation of successive organic compounds with higher oxidation degree and lower vapour pressure. This process was investigated using the explicit oxidation model GECKO-A (Generator for Explicit Chemistry and Kinetics of Organics in the Atmosphere). Results for the C8-C24 n-alkane series show the expected trends, i.e. (i) SOA yield grows with the carbon backbone of the parent hydrocarbon, (ii) SOA yields decreases with the decreasing pre-existing organic aerosol concentration, (iii) the number of generations required to describe SOA production increases when the pre-existing organic aerosol concentration decreases. Most SOA contributors were found to be not oxidized enough to be categorized as highly oxygenated organic aerosols (OOA) but reduced enough to be categorized as hydrocarbon like organic aerosols (HOA). Branched alkanes are more prone to fragment in the early stage of the oxidation than their corresponding linear analogues. Fragmentation is expected to alter both the yield and the mean oxidation state of the SOA. Here, GECKO-A is applied to generate highly detailed oxidation schemes for various series of branched and cyclised alkanes. Branching and cyclisation effects on SOA yields and oxidation states will be examined.

Novel methods for predicting gas-particle partitioning during the formation of secondary organic aerosol

NASA Astrophysics Data System (ADS)

Wania, F.; Lei, Y. D.; Wang, C.; Abbatt, J. P. D.; Goss, K.-U.

2014-12-01

Several methods have been presented in the literature to predict an organic chemical's equilibrium partitioning between the water insoluble organic matter (WIOM) component of aerosol and the gas phase, Ki,WIOM, as a function of temperature. They include (i) polyparameter linear free energy relationships calibrated with empirical aerosol sorption data, as well as (ii) the solvation models implemented in SPARC and (iii) the quantum-chemical software COSMOtherm, which predict solvation equilibria from molecular structure alone. We demonstrate that these methods can be used to predict Ki,WIOM for large numbers of individual molecules implicated in secondary organic aerosol (SOA) formation, including those with multiple functional groups. Although very different in their theoretical foundations, these methods give remarkably consistent results for the products of the reaction of normal alkanes with OH, i.e. their partition coefficients Ki,WIOM generally agree within one order of magnitude over a range of more than ten orders of magnitude. This level of agreement is much better than that achieved by different vapour pressure estimation methods that are more commonly used in the SOA community. Also, in contrast to the agreement between vapour pressure estimates, the agreement between the Ki,WIOM estimates does not deteriorate with increasing number of functional groups. Furthermore, these partitioning coefficients Ki,WIOM predicted SOA mass yields in agreement with those measured in chamber experiments of the oxidation of normal alkanes. If a Ki,WIOM prediction method was based on one or more surrogate molecules representing the solvation properties of the mixed OM phase of SOA, the choice of those molecule(s) was found to have a relatively minor effect on the predicted Ki,WIOM, as long as the molecule(s) are not very polar. This suggests that a single surrogate molecule, such as 1-octanol or a hypothetical SOA structure proposed by Kalberer et al. (2004), may often be sufficient to represent the WIOM component of the SOA phase, greatly simplifying the prediction. The presented methods could substitute for vapour-pressure-based methods in studies such as the explicit modelling of SOA formation from single precursor molecules in chamber experiments.

Dithiothreitol activity by particulate oxidizers of SOA produced from photooxidation of hydrocarbons under varied NOx levels

NASA Astrophysics Data System (ADS)

Jiang, Huanhuan; Jang, Myoseon; Yu, Zechen

2017-08-01

When hydrocarbons (HCs) are atmospherically oxidized, they form particulate oxidizers, including quinones, organic hydroperoxides, and peroxyacyl nitrates (PANs). These particulate oxidizers can modify cellular materials (e.g., proteins and enzymes) and adversely modulate cell functions. In this study, the contribution of particulate oxidizers in secondary organic aerosols (SOAs) to the oxidative potential was investigated. SOAs were generated from the photooxidation of toluene, 1,3,5-trimethylbenzene, isoprene, and α-pinene under varied NOx levels. Oxidative potential was determined from the typical mass-normalized consumption rate (reaction time t = 30 min) of dithiothreitol (DTTt), a surrogate for biological reducing agents. Under high-NOx conditions, the DTTt of toluene SOA was 2-5 times higher than that of the other types of SOA. Isoprene DTTt significantly decreased with increasing NOx (up to 69 % reduction by changing the HC / NOx ratio from 30 to 5). The DTTt of 1,3,5-trimethylbenzene and α-pinene SOA was insensitive to NOx under the experimental conditions of this study. The significance of quinones to the oxidative potential of SOA was tested through the enhancement of DTT consumption in the presence of 2,4-dimethylimidazole, a co-catalyst for the redox cycling of quinones; however, no significant effect of 2,4-dimethylimidazole on modulation of DTT consumption was observed for all SOA, suggesting that a negligible amount of quinones was present in the SOA of this study. For toluene and isoprene, mass-normalized DTT consumption (DTTm) was determined over an extended period of reaction time (t = 2 h) to quantify their maximum capacity to consume DTT. The total quantities of PANs and organic hydroperoxides in toluene SOA and isoprene SOA were also measured using the Griess assay and the 4-nitrophenylboronic acid assay, respectively. Under the NOx conditions (HC / NOx ratio: 5-36 ppbC ppb-1) applied in this study, the amount of organic hydroperoxides was substantial, while PANs were found to be insignificant for both SOAs. Isoprene DTTm was almost exclusively attributable to organic hydroperoxides, while toluene DTTm was partially attributable to organic hydroperoxides. The DTT assay results of the model compound study suggested that electron-deficient alkenes, which are abundant in toluene SOA, could also modulate DTTm.

High Molecular Weight Dimer Esters in α-Pinene Secondary Organic Aerosol

NASA Astrophysics Data System (ADS)

Kristensen, Kasper; Cui, Tianqu; Zhang, Haofei; Gold, Avram; Glasius, Marianne; Surratt, Jason D.

2014-05-01

Monoterpenes, such as α-pinene, constitute an important group of biogenic volatile organic compounds (BVOC). Once emitted into the atmosphere α-pinene is removed by oxidization by the hydroxyl radical (OH), reactions with ozone (O3), and with nitrate radicals (NO3) resulting in the formation of first-generation oxidation products, such as semi-volatile carboxylic acids. In addition, higher molecular weight dimer esters originating from the oxidation of α-pinene have been observed in both laboratory-generated and ambient secondary organic aerosols (SOA). While recent studies suggest that the dimers are formed through esterification between carboxylic acids in the particle phase, the formation mechanism of the dimer esters is still ambiguous. In this work, we present the results of a series of smog chamber experiments to assess the formation of dimer esters formed from the oxidation of α-pinene. Experiments were conducted in the University of North Carolina (UNC) dual outdoor smog chamber facility to investigate the effect of oxidant species (OH versus O3), relative humidity (RH), and seed aerosol acidity in order to obtain a better understanding of the conditions leading to the formation of the dimer esters and how these parameters may affect the formation and chemical composition of SOA. The chemical composition of α-pinene SOA was investigated by ultra-performance liquid chromatography/electrospray ionization high-resolution quadrupole time-of-flight mass spectrometry (UPLC/ESI-HR-Q-TOFMS), and a total of eight carboxylic acids and four dimer esters were identified, constituting between 8 and 12 % of the total α-pinene SOA mass.

Aerosol composition and the contribution of SOA formation over Mediterranean forests

NASA Astrophysics Data System (ADS)

Freney, Evelyn; Sellegri, Karine; Chrit, Mounir; Adachi, Kouji; Brito, Joel; Waked, Antoine; Borbon, Agnès; Colomb, Aurélie; Dupuy, Régis; Pichon, Jean-Marc; Bouvier, Laetitia; Delon, Claire; Jambert, Corinne; Durand, Pierre; Bourianne, Thierry; Gaimoz, Cécile; Triquet, Sylvain; Féron, Anaïs; Beekmann, Matthias; Dulac, François; Sartelet, Karine

2018-05-01

As part of the Chemistry-Aerosol Mediterranean Experiment (ChArMEx), a series of aerosol and gas-phase measurements were deployed aboard the SAFIRE ATR42 research aircraft in summer 2014. The present study focuses on the four flights performed in late June early July over two forested regions in the south of France. We combine in situ observations and model simulations to aid in the understanding of secondary organic aerosol (SOA) formation over these forested areas in the Mediterranean and to highlight the role of different gas-phase precursors. The non-refractory particulate species measured by a compact aerosol time-of-flight mass spectrometer (cToF-AMS) were dominated by organics (60 to 72 %) followed by a combined contribution of 25 % by ammonia and sulfate aerosols. The contribution from nitrate and black carbon (BC) particles was less than 5 % of the total PM1 mass concentration. Measurements of non-refractory species from off-line transmission electron microscopy (TEM) showed that particles have different mixing states and that large fractions (35 %) of the measured particles were organic aerosol containing C, O, and S but without inclusions of crystalline sulfate particles. The organic aerosol measured using the cToF-AMS contained only evidence of oxidized organic aerosol (OOA), without a contribution of fresh primary organic aerosol. Positive matrix factorization (PMF) on the combined organic-inorganic matrices separated the oxidized organic aerosol into a more-oxidized organic aerosol (MOOA), and a less-oxidized organic aerosol (LOOA). The MOOA component is associated with inorganic species and had higher contributions of m/z 44 than the LOOA factor. The LOOA factor is not associated with inorganic species and correlates well with biogenic volatile organic species measured with a proton-transfer-reaction mass spectrometer, such as isoprene and its oxidation products (methyl vinyl ketone, MVK; methacroleine, MACR; and isoprene hydroxyhydroperoxides, ISOPOOH). Despite a significantly high mixing ratio of isoprene (0.4 to 1.2 ppbV) and its oxidation products (0.2 and 0.8 ppbV), the contribution of specific signatures for isoprene epoxydiols SOA (IEPOX-SOA) within the aerosol organic mass spectrum (m/z 53 and m/z 82) were very weak, suggesting that the presence of isoprene-derived SOA was either too low to be detected by the cToF-AMS, or that SOA was not formed through IEPOX. This was corroborated through simulations performed with the Polyphemus model showing that although 60 to 80 % of SOA originated from biogenic precursors, only about 15 to 32 % was related to isoprene (non-IEPOX) SOA; the remainder was 10 % sesquiterpene SOA and 35 to 40 % monoterpene SOA. The model results show that despite the zone of sampling being far from industrial or urban sources, a total contribution of 20 to 34 % of the SOA was attributed to purely anthropogenic precursors (aromatics and intermediate or semi-volatile compounds). The measurements obtained during this study allow us to evaluate how biogenic emissions contribute to increasing SOA concentrations over Mediterranean forested areas. Directly comparing these measurements with the Polyphemus model provides insight into the SOA formation pathways that are prevailing in these forested areas as well as processes that need to be implemented in future simulations.

UNDERSTANDING REGIONAL OXIDATION CAPACITY BY COMPREHENSIVE OBSERVATIONS TO CONSTRAIN HYDROXYL RADICAL SOURCES AND SINKS DURING THE SOUTHERN OXIDANT AEROSOL STUDY (SOAS)

EPA Science Inventory

The proposed field measurements and data analysis will provide an important constraint to understand oxidation capacity in the Southeastern U.S. that determines SOA and photochemical ozone formation. Unexpectedly high levels of OH determining oxidation capacity have been co...

Formation and aging of secondary organic aerosol from toluene: Changes in chemical composition, volatility, and hygroscopicity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hildebrandt Ruiz, L.; Paciga, A. L.; Cerully, K. M.

Secondary organic aerosol (SOA) is transformed after its initial formation, but this chemical aging of SOA is poorly understood. Experiments were conducted in the Carnegie Mellon environmental chamber to form secondary organic aerosol (SOA) from the photo-oxidation of toluene and other small aromatic volatile organic compounds (VOCs) in the presence of NO x under different oxidizing conditions. The effects of the oxidizing condition on organic aerosol (OA) composition, mass yield, volatility, and hygroscopicity were explored. Higher exposure to the hydroxyl radical resulted in different OA composition, average carbon oxidation state (OS c), and mass yield. The OA oxidation state generallymore » increased during photo-oxidation, and the final OA OS c ranged from –0.29 to 0.16 in the performed experiments. The volatility of OA formed in these different experiments varied by as much as a factor of 30, demonstrating that the OA formed under different oxidizing conditions can have a significantly different saturation concentration. In conclusion, there was no clear correlation between hygroscopicity and oxidation state for this relatively hygroscopic SOA.« less

Formation and aging of secondary organic aerosol from toluene: Changes in chemical composition, volatility, and hygroscopicity

DOE PAGES

Hildebrandt Ruiz, L.; Paciga, A. L.; Cerully, K. M.; ...

2015-07-24

Secondary organic aerosol (SOA) is transformed after its initial formation, but this chemical aging of SOA is poorly understood. Experiments were conducted in the Carnegie Mellon environmental chamber to form secondary organic aerosol (SOA) from the photo-oxidation of toluene and other small aromatic volatile organic compounds (VOCs) in the presence of NO x under different oxidizing conditions. The effects of the oxidizing condition on organic aerosol (OA) composition, mass yield, volatility, and hygroscopicity were explored. Higher exposure to the hydroxyl radical resulted in different OA composition, average carbon oxidation state (OS c), and mass yield. The OA oxidation state generallymore » increased during photo-oxidation, and the final OA OS c ranged from –0.29 to 0.16 in the performed experiments. The volatility of OA formed in these different experiments varied by as much as a factor of 30, demonstrating that the OA formed under different oxidizing conditions can have a significantly different saturation concentration. In conclusion, there was no clear correlation between hygroscopicity and oxidation state for this relatively hygroscopic SOA.« less

Multi-generation chemical aging of α-pinene ozonolysis products by reactions with OH

NASA Astrophysics Data System (ADS)

Wang, Ningxin; Kostenidou, Evangelia; Donahue, Neil M.; Pandis, Spyros N.

2018-03-01

Secondary organic aerosol (SOA) formation from volatile organic compounds (VOCs) in the atmosphere can be thought of as a succession of oxidation steps. The production of later-generation SOA via continued oxidation of the first-generation products is defined as chemical aging. This study investigates aging in the α-pinene ozonolysis system with hydroxyl radicals (OH) through smog chamber experiments. The first-generation α-pinene ozonolysis products were allowed to react further with OH formed via HONO photolysis. After an equivalent of 2-4 days of typical atmospheric oxidation conditions, homogeneous OH oxidation of the α-pinene ozonolysis products resulted in a 20-40 % net increase in the SOA for the experimental conditions used in this work. A more oxygenated product distribution was observed after aging based on the increase in aerosol atomic oxygen-to-carbon ratio (O : C) by up to 0.04. Experiments performed at intermediate relative humidity (RH) of 50 % showed no significant difference in additional SOA formation during aging compared to those performed at a low RH of less than 20 %.

"Do You Feel in Control?": Towards Novel Approaches to Characterise, Manipulate and Measure the Sense of Agency in Virtual Environments.

PubMed

Jeunet, Camille; Albert, Louis; Argelaguet, Ferran; Lecuyer, Anatole

2018-04-01

While the Sense of Agency (SoA) has so far been predominantly characterised in VR as a component of the Sense of Embodiment, other communities (e.g., in psychology or neurosciences) have investigated the SoA from a different perspective proposing complementary theories. Yet, despite the acknowledged potential benefits of catching up with these theories a gap remains. This paper first aims to contribute to fill this gap by introducing a theory according to which the SoA can be divided into two components, the feeling and the judgment of agency, and relies on three principles, namely the principles of priority, exclusivity and consistency. We argue that this theory could provide insights on the factors influencing the SoA in VR systems. Second, we propose novel approaches to manipulate the SoA in controlled VR experiments (based on these three principles) as well as to measure the SoA, and more specifically its two components based on neurophysiological markers, using ElectroEncephaloGraphy (EEG). We claim that these approaches would enable us to deepen our understanding of the SoA in VR contexts. Finally, we validate these approaches in an experiment. Our results (N=24) suggest that our approach was successful in manipulating the SoA as the modulation of each of the three principles induced significant decreases of the SoA (measured using questionnaires). In addition, we recorded participants' EEG signals during the VR experiment, and neurophysiological markers of the SoA, potentially reflecting the feeling and judgment of agency specifically, were revealed. Our results also suggest that users' profile, more precisely their Locus of Control (LoC), influences their level of immersion and SoA.

Is there an aerosol signature of aqueous processing?

NASA Astrophysics Data System (ADS)

Ervens, B.; Sorooshian, A.

2017-12-01

The formation of aerosol mass in cloud water has been recognized as a substantial source of atmospheric aerosol mass. While sulfate formation can be relatively well constrained, the formation of secondary organic aerosol mass in the aqueous phase (aqSOA) is much more complex due to the multitude of precursors and variety in chemical processes. Aqueous phase processing adds aerosol mass to the droplet mode, which is formed due to mass addition to activated particles in clouds. In addition, it has been shown that aqSOA mass has specific characteristics in terms of oxidation state and hygroscopicity that might help to distinguish it from other SOA sources. Many models do not include detailed chemical mechanisms of sulfate and aqSOA formation and also lack details on the mass distribution of newly formed mass. Mass addition inside and outside clouds modifies different parts of an aerosol population and consequently affects predictions of properties and lifetime of particles. Using a combination of field data analysis and model studies for a variety of air masses, we will show which chemical and physical aerosol properties can be used, in order to identify an `aqueous phase signature' in processed aerosol populations. We will discuss differences in this signature in clean (e.g., background), moderately polluted (e.g., urban) and highly polluted (e.g., biomass burning) air masses and suggest air-mass-specific chemical and/or physical properties that will help to quantify the aqueous-phase derived aerosol mass.

Development of an aerosol microphysical module: Aerosol Two-dimensional bin module for foRmation and Aging Simulation (ATRAS)

NASA Astrophysics Data System (ADS)

Matsui, H.; Koike, M.; Kondo, Y.; Fast, J. D.; Takigawa, M.

2014-09-01

Number concentrations, size distributions, and mixing states of aerosols are essential parameters for accurate estimations of aerosol direct and indirect effects. In this study, we develop an aerosol module, designated the Aerosol Two-dimensional bin module for foRmation and Aging Simulation (ATRAS), that can explicitly represent these parameters by considering new particle formation (NPF), black carbon (BC) aging, and secondary organic aerosol (SOA) processes. A two-dimensional bin representation is used for particles with dry diameters from 40 nm to 10 μm to resolve both aerosol sizes (12 bins) and BC mixing states (10 bins) for a total of 120 bins. The particles with diameters between 1 and 40 nm are resolved using additional eight size bins to calculate NPF. The ATRAS module is implemented in the WRF-Chem model and applied to examine the sensitivity of simulated mass, number, size distributions, and optical and radiative parameters of aerosols to NPF, BC aging, and SOA processes over East Asia during the spring of 2009. The BC absorption enhancement by coating materials is about 50% over East Asia during the spring, and the contribution of SOA processes to the absorption enhancement is estimated to be 10-20% over northern East Asia and 20-35% over southern East Asia. A clear north-south contrast is also found between the impacts of NPF and SOA processes on cloud condensation nuclei (CCN) concentrations: NPF increases CCN concentrations at higher supersaturations (smaller particles) over northern East Asia, whereas SOA increases CCN concentrations at lower supersaturations (larger particles) over southern East Asia. The application of ATRAS in East Asia also shows that the impact of each process on each optical and radiative parameter depends strongly on the process and the parameter in question. The module can be used in the future as a benchmark model to evaluate the accuracy of simpler aerosol models and examine interactions between NPF, BC aging, and SOA processes under different meteorological conditions and emissions.

Chemical characterization of SOA formed from aqueous-phase reactions of phenols with the triplet excited state of carbonyl and hydroxyl radical

DOE PAGES

Yu, L.; Smith, J.; Laskin, A.; ...

2014-12-23

Phenolic compounds, which are emitted in significant amounts from biomass burning, can undergo fast reactions in atmospheric aqueous phases to form secondary organic aerosol (aqSOA). In this study, we investigate the reactions of phenol (compound with formula C 6H 5OH)), guaiacol (2-methoxyphenol), and syringol (2,6-dimethoxyphenol) with two major aqueous-phase oxidants – the triplet excited states of an aromatic carbonyl ( 3C *) and hydroxyl radical (· OH). We thoroughly characterize the low-volatility species produced from these reactions and interpret their formation mechanisms using aerosol mass spectrometry (AMS), nanospray desorption electrospray ionization mass spectrometry (nano-DESI MS), and ion chromatography (IC). Amore » large number of oxygenated molecules are identified, including oligomers containing up to six monomer units, functionalized monomer and oligomers with carbonyl, carboxyl, and hydroxyl groups, and small organic acid anions (e.g., formate, acetate, oxalate, and malate). The average atomic oxygen-to-carbon (O / C) ratios of phenolic aqSOA are in the range of 0.85–1.23, similar to those of low-volatility oxygenated organic aerosol (LV-OOA) observed in ambient air. The aqSOA compositions are overall similar for the same precursor, but the reactions mediated by 3C * are faster than · OH-mediated reactions and produce more oligomers and hydroxylated species at the point when 50% of the phenolic compound has reacted. Profiles determined using a thermodenuder indicate that the volatility of phenolic aqSOA is influenced by both oligomer content and O / C ratio. In addition, the aqSOA shows enhanced light absorption in the UV–visible region, suggesting that aqueous-phase reactions of phenols may contribute to formation of secondary brown carbon in the atmosphere, especially in regions influenced by biomass burning.« less

Assessment of the impacts of aromatic VOC emissions and yields of SOA on SOA concentrations with the air quality model RAMS-CMAQ

NASA Astrophysics Data System (ADS)

Li, Jialin; Zhang, Meigen; Wu, Fangkun; Sun, Yele; Tang, Guiqian

2017-06-01

The secondary organic aerosol (SOA) concentration is generally underestimated by models. Recent studies suggest that the underprediction is related to underestimations of aromatic volatile organic compound (VOC) emissions and SOA yields in current models. Here, the impacts of these two factors in China were investigated with the regional air quality modeling system RAMS-CMAQ, referring to field observations during the episode from October 14 to November 14, 2014. Comparisons between the observed and modeled SOA of four sensitivity simulation cases indicated the significant impacts of the two underestimated factors on the SOA output. By considering these two aspects, the simulated mean SOA concentrations significantly increased by nearly 4 times with a good representation of the intensively temporal variations of concentrations, which were largely controlled by photochemical processes rather than meteorological conditions. The improvement in SOA compensated for the underestimations by approximately 23.5% and contributed to the mean fraction of SOA to organic aerosol (OA) by increasing the fraction from less than 7% to more than 25%, which was closer to the observed result. These results suggested a more reasonable and more realistic representation of SOA formation in the model after allowing for the two factors. Due to the better simulation of SOA, predictions of OA were correspondingly improved when the correlation coefficient increased from 0.57 to 0.73 and other bias parameters were reduced, which indicated the improved ability of our model to trace the temporal variations of OA. Based on the improved simulation throughout the episode, the mean SOA concentration was obviously higher in eastern China than in the west. The highest concentration appeared in the Sichuan Basin and Pearl River Delta (PRD) areas, with values of 6-11 μg/m3 and 8-17 μg/m3, respectively. Over the wide regions of central and eastern China, the dominant component in SOA was formed from anthropogenic sources (ASOA), generally accounting for more than 60%.

SOA Formation Potential of Emissions from Soil and Leaf Litter

NASA Astrophysics Data System (ADS)

Faiola, C. L.; Vanderschelden, G. S.; Wen, M.; Cobos, D. R.; Jobson, B. T.; VanReken, T. M.

2013-12-01

In the United States, emissions of volatile organic compounds (VOCs) from natural sources exceed all anthropogenic sources combined. VOCs participate in oxidative chemistry in the atmosphere and impact the concentrations of ozone and particulate material. The formation of secondary organic aerosol (SOA) is particularly complex and is frequently underestimated using state-of-the-art modeling techniques. We present findings that suggest emissions of important SOA precursors from soil and leaf litter are higher than current inventories would suggest, particularly under conditions typical of Fall and Spring. Soil and leaf litter samples were collected at Big Meadow Creek from the University of Idaho Experimental Forest. The dominant tree species in this area of the forest are ponderosa pine, Douglas-fir, and western larch. Samples were transported to the laboratory and housed within a 0.9 cubic meter Teflon dynamic chamber where VOC emissions were continuously monitored with a GC-FID-MS and PTR-MS. Aerosol was generated from soil and leaf litter emissions by pumping the emissions into a 7 cubic meter Teflon aerosol growth chamber where they were oxidized with ozone in the absence of light. The evolution of particle microphysical and chemical characteristics was monitored over the following eight hours. Particle size distribution and chemical composition were measured with a SMPS and HR-ToF-AMS respectively. Monoterpenes dominated the emission profile with emission rates up to 283 micrograms carbon per meter squared per hour. The dominant monoterpenes emitted were beta-pinene, alpha-pinene, and delta-3-carene in descending order. The composition of the SOA produced was similar to biogenic SOA formed from oxidation of ponderosa pine emissions and alpha-pinene. Measured soil/litter monoterpene emission rates were compared with modeled canopy emissions. Results suggest that during fall and spring when tree emissions are lower, monoterpene emissions within forests may be dominated by soil/litter emissions--soil/litter monoterpene emissions in spring could contribute up to 63% of total forest emissions. If this is the case, a significant portion of total forest monoterpene emission rates would be controlled by factors that affect soil/litter emissions rather than factors that affect plant emissions.

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

NASA Astrophysics Data System (ADS)

Chirico, R.; Decarlo, P. F.; Heringa, M. F.; Tritscher, T.; Richter, R.; Prévôt, A. S. H.; Dommen, J.; Weingartner, E.; Wehrle, G.; Gysel, M.; Laborde, M.; Baltensperger, U.

2010-12-01

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 third 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, 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 0.10 to 0.19. Five hours of oxidation led to a more oxidized OA with an O/C range of 0.21 to 0.37.

Formation and chemical aging of secondary organic aerosol during the β-caryophyllene oxidation

NASA Astrophysics Data System (ADS)

Tasoglou, A.; Pandis, S. N.

2015-06-01

The secondary organic aerosol (SOA) production during the oxidation of β-caryophyllene by ozone (O3) and hydroxyl radicals (OH) and the subsequent chemical aging of the products during reactions with OH were investigated. Experiments were conducted with ozone and with hydroxyl radicals at low NOx (zero added NOx) and at high NOx (hundreds of parts per billion). The SOA mass yield at 10 μg m-3 of organic aerosol was 27% for the ozonolysis, 20% for the reaction with OH at low NOx, and 38% at high NOx under dry conditions, 20 °C, and ozone excess. Parameterizations of the fresh SOA yields have been developed. The average fresh SOA atomic O : C ratio varied from 0.24 to 0.34 depending on the oxidant and the NOx level, while the H : C ratio was close to 1.5 for all systems examined. An average density of 1.06 ± 0.1 μg m-3 of the β-caryophyllene SOA was estimated. The exposure to UV light had no effect on the β-caryophyllene SOA concentration and aerosol mass spectrometer (AMS) measurements. The chemical aging of the β-caryophyllene SOA produced was studied by exposing the fresh SOA to high concentrations (107 molecules cm-3) of OH for several hours. These additional reactions increased the SOA concentration by 15-40% and O : C by approximately 25%. A limited number of experiments suggested that there was a significant impact of the relative humidity on the chemical aging of the SOA. The evaporation rates of β-caryophyllene SOA were quantified by using a thermodenuder allowing us to estimate the corresponding volatility distributions and effective vaporization enthalpies.

Hydroxyhydroperoxide (HHP) Formation From H2O2 Addition to Carbonyls in the Aqueous Phase and Its Environmental Implications

NASA Astrophysics Data System (ADS)

Zhao, R.; Soong, R.; Simpson, A. J.; Abbatt, J.

2012-12-01

Organic peroxides are major components of secondary organic aerosol (SOA), affecting the toxicity of SOA and its oxidative capacity. Hydroxyhydroperoxide (HHP) is a class of organic peroxide observed in ambient air, rain water, and cloud water. However, the formation pathway of HHPs remains under debate, with one potential path via reaction of water with Criegee Intermediates. The current study focuses on a formation mechanism involving reversible nucleophilic addition of H2O2 to aldehydes. This formation pathway of HHPs has been known for decades, but has long been considered as a minor reaction. This is because HHPs were observed to decompose rapidly into H2O2 and the corresponding aldehydes in dilute aqueous solutions. In the current study, proton transfer reaction mass spectrometry (PTR-MS) and proton nuclear magnetic resonance (1H NMR) spectrometry were employed to determine the equilibrium constants (Keq) of H2O2 addition to a variety of atmospherically relevant carbonyls in the aqueous phase. HHP formation was insignificant from ketones and methacrolein, but was significant from formaldehyde, acetaldehyde and propionaldehyde. The Keq values ranged from 80 to 150 M-1 at 25 °C. Based on these values, the environmental implications of HHP formation via this pathway suggest that HHP formation is unlikely to be significant in cloud water. However, in aerosol liquid water, where the concentrations of aldehydes and H2O2 can be at the mM level, this pathway may be significant.

Formation of halogen-induced secondary organic aerosol (XOA)

NASA Astrophysics Data System (ADS)

Kamilli, Katharina; Ofner, Johannes; Zetzsch, Cornelius; Held, Andreas

2013-04-01

Reactive halogen species (RHS) are very important due to their potential of stratospheric ozone depletion and surface ozone destruction. RHS seem to interact with precursors of secondary organic aerosol (SOA) similarly to common atmospheric oxidants like OH radicals and ozone. The potential interaction of RHS with preformed SOA has recently been studied (Ofner et al., 2012). Although aerosol formation from reaction of RHS with typical SOA precursors was previously studied (e.g. Cai et al., 2006), no data are available on bromine-induced aerosol formation from organic precursors yet. An aerosol smog-chamber was used to examine the halogen-induced secondary organic aerosol (XOA) formation under atmospheric conditions using simulated sunlight. With a concentration of 10 ppb for the organic precursor, 2 ppb for molecular chlorine, and 10 ppb for molecular bromine, the experimental setup is close to ambient conditions. By combined measurements of the aerosol size distribution, ozone and NOx mixing ratios, as well as the decay of the organic precursor, aerosol yields and aerosol growth rates were determined. The decay of the organic precursor was analyzed by capillary gas chromatography coupled with flame-ionization detection (GC-FID) and the aerosol size distribution was measured using a Scanning Mobility Particle Sizer (SMPS). Additionally, with the decay rate of the precursor and the calculated photolysis rates of molecular halogen species, based on the well-known spectrum of the solar simulator, mechanistic details on the XOA formation pathways can be determined. We observed XOA formation even at very low precursor and RHS concentrations with a diameter mode at 10-20 nm and a number concentration up to 1000000 particles cm-3. While the XOA formation from chlorine is very rapid, the interaction of bromine with the organic precursors is about five times slower. The aerosol yield reached maximum values of 0.01 for the reaction of chlorine with α-pinene and 0.0004 for bromine with α-pinene. This work was funded by German Research Foundation (DFG) under grants HE 5214/5-1 and ZE792/5-2. References: Cai, X., and Griffin, R. J.: Secondary aerosol formation from the oxidation of biogenic hydrocarbons by chlorine atoms, J. Geophys. Res., 111, D14206/14201-D14206/14214, 2006. Ofner, J. Balzer, N., Buxmann, J., Grothe, H., Schmitt-Kopplin, Ph., Platt, U., and Zetzsch, C., Halogenation processes of secondary organic aerosol and implications on halogen release mechanisms, Atmos. Chem. Phys. Discuss. 12, 2975-3017, 2012.

Neural correlates of cross-domain affective priming.

PubMed

Zhang, Qin; Li, Xiaohua; Gold, Brian T; Jiang, Yang

2010-05-06

The affective priming effect has mostly been studied using reaction time (RT) measures; however, the neural bases of affective priming are not well established. To understand the neural correlates of cross-domain emotional stimuli presented rapidly, we obtained event-related potential (ERP) measures during an affective priming task using short SOA (stimulus onset asynchrony) conditions. Two sets of 480 picture-word pairs were presented at SOAs of either 150ms or 250ms between prime and target stimuli. Participants decided whether the valence of each target word was pleasant or unpleasant. Behavioral results from both SOA conditions were consistent with previous reports of affective priming, with longer RTs for incongruent than congruent pairs at SOAs of 150ms (771 vs. 738ms) and 250ms (765 vs. 720ms). ERP results revealed that the N400 effect (associated with incongruent pairs in affective processing) occurred at anterior scalp regions at an SOA of 150ms, and this effect was only observed for negative target words across the scalp at an SOA of 250ms. In contrast, late positive potentials (LPPs) (associated with attentional resource allocation) occurred across the scalp at an SOA of 250ms. LPPs were only observed for positive target words at posterior parts of the brain at an SOA of 150ms. Our finding of ERP signatures at very short SOAs provides the first neural evidence that affective pictures can exert an automatic influence on the evaluation of affective target words. Copyright 2010 Elsevier B.V. All rights reserved.

Towards the identification of molecular constituents associated with the surfaces of isoprene-derived secondary organic aerosol (SOA) particles

NASA Astrophysics Data System (ADS)

Ebben, C. J.; Strick, B. F.; Upshur, M. A.; Chase, H. M.; Achtyl, J. L.; Thomson, R. J.; Geiger, F. M.

2014-03-01

Secondary organic aerosol (SOA) particle formation ranks among the least understood chemical processes in the atmosphere, rooted in part in the lack of knowledge about chemical composition and structure at the particle surface, and little availability of reference compounds needed for benchmarking and chemical identification in pure and homogenous form. Here, we synthesize and characterize SOA particle constituents consisting of the isoprene oxidation products α-, δ-, and cis- and trans-β-IEPOX (isoprene epoxide), as well as syn- and anti-2-methyltetraol. Paying particular attention to their phase state (condensed vs. vapor), we carry out a surface-specific and orientationally selective chemical analysis by vibrational sum frequency generation (SFG) spectroscopy of these compounds in contact with a fused silica window. Comparison to the vibrational SFG spectra of synthetic isoprene-derived SOA particle material prepared at the Harvard Environmental Chamber yields a plausible match with trans-β-IEPOX, suggesting it is an abundant species on their surfaces, while the other species studied here, if present, appear to be SFG inactive and thus likely to be localized in a centrosymmetric environment, e.g., the particle bulk. No match is found for authentic SOA particle material collected at the site of the Amazonian Aerosol Characterization Experiment (AMAZE-08) with the surface SFG spectra of the compounds surveyed here, yet we cannot rule out this mismatch being attributable to differences in molecular orientation. The implications of our findings for SOA formation are discussed in the context of condensational particle growth and reactivity.

[Social Cognition and the Sense of Agency in Autism: From Action to Interaction].

PubMed

Lafleur, Alexis; Soulières, Isabelle; Forgeot d'Arc, Baudoin

The sense of agency (SoA) refers to the ability for one to detect that she is the cause of an action (Gallagher, 2000). The SoA is linked to motor control but also to self-awareness and could play an important role in social interactions. Autism spectrum disorder (ASD) is characterized by an alteration of social interactions and communication (DSM-5; APA, 2013) and is often seen as a primary deficit of functions specific to social cognition. However, motor control is also altered in ASD. We hypothesize that motor symptoms and social impairments could both arise from the same alteration of SoA. We first introduce theoretical models of implicit and explicit SoA (Synofzik et al., 2008) and present their neurofunctional basis. Then, we assess the clinical expressions of a disrupted SoA in different neuropsychiatric disorders such as schizophrenia. In ASD, the atypical formation of internal models of action during motor acquisition (Haswell et al., 2009) could be at the source of an altered implicit SoA. A lack of fidelity of sensorimotor agency cues (Zalla et al., 2015) could also entail an alteration of explicit SoA. We discuss the main clinical expressions of ASD that may ensue from a disrupted SoA (difficulties in theory of mind and imitation, deficits in motor coordination and praxis, etc.).

Characterizing oxidative flow reactor SOA production and OH radical exposure from laboratory experiments of complex mixtures (engine exhaust) and simple precursors (monoterpenes)

NASA Astrophysics Data System (ADS)

Michael Link, M. L.; Friedman, B.; Ortega, J. V.; Son, J.; Kim, J.; Park, G.; Park, T.; Kim, K.; Lee, T.; Farmer, D.

2016-12-01

Recent commercialization of the Oxidative Flow Reactor (OFR, occasionally described in the literature as a "Potential Aerosol Mass") has created the opportunity for many researchers to explore the mechanisms behind OH-driven aerosol formation on a wide range of oxidative timescales (hours to weeks) in both laboratory and field measurements. These experiments have been conducted in both laboratory and field settings, including simple (i.e. single component) and complex (multi-component) precursors. Standard practices for performing OFR experiments, and interpreting data from the measurements, are still being developed. Measurement of gas and particle phase chemistry, from oxidation products generated in the OFR, through laboratory studies on single precursors and the measurement of SOA from vehicle emissions on short atmospheric timescales represent two very different experiments in which careful experimental design is essential for exploring reaction mechanisms and SOA yields. Two parameters essential in experimental design are (1) the role of seed aerosol in controlling gas-particle partitioning and SOA yields, and (2) the accurate determination of OH exposure during any one experiment. We investigated the role of seed aerosol surface area in controlling the observed SOA yields and gas/particle composition from the OH-initiated oxidation of four monoterpenes using an aerosol chemical ionization time-of-flight mass spectrometer and scanning mobility particle sizer. While the OH exposure during laboratory experiments is simple to constrain, complex mixtures such as diesel exhaust have high estimated OH reactivity values, and thus require careful consideration. We developed methods for constraining OH radical exposure in the OFR during vehicle exhaust oxidation experiments. We observe changes in O/C ratios and highly functionalized species over the temperature gradient employed in the aerosol-CIMS measurement. We relate this observed, speciated chemistry to the volatility of the aerosol, and compare observed SOA yields to other OFR and smog chamber SOA generation methods. Additionally, estimates of OH radical exposure in the OFR during different vehicle experiments of varying fuel type and speed were observed to vary as determined from a high-NOx and variable humidity calibration set.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Laskin, Julia; Laskin, Alexander; Nizkorodov, Sergey

Complementary methods of high-resolution mass spectrometry and micro-spectroscopy were utilized for molecular analysis of secondary organic aerosol (SOA) generated from ozonolysis of two structural monoterpene isomers: D-limonene (LSOA) and a-pinene (PSOA). Laboratory simulated aging of LSOA and PSOA, through conversion of carbonyls into imines mediated by NH3 vapors in humid air, resulted in selective browning of the LSOA sample, while the PSOA sample remained white. Comparative analysis of the reaction products in the aged LSOA and PSOA samples provided insights into chemistry relevant to formation of brown carbon chromophores. A significant fraction of carbonyl-imine conversion products with identical molecular formulasmore » were detected in both samples. This reflects the high level of similarity in the molecular composition of these two closely related SOA materials. Several highly conjugated products were detected exclusively in the brown LSOA sample and were identified as potential chromophores responsible for the observed color change. The majority of the unique products in the aged LSOA sample with the highest number of double bonds contain two nitrogen atoms. We conclude that chromophores characteristic of the carbonyl- imine chemistry in LSOA are highly conjugated oligomers of secondary imines (Schiff bases) present at relatively low concentrations. Formation of this type of conjugated compounds in PSOA is hindered by the structural rigidity of the a-pinene oxidation products. Our results suggest that the overall light-absorbing properties of SOA may be determined by trace amounts of strong brown carbon chromophores.« less

Secondary organic aerosol formation by limonene ozonolysis: Parameterizing multi-generational chemistry in ozone- and residence time-limited indoor environments

NASA Astrophysics Data System (ADS)

Waring, Michael S.

2016-11-01

Terpene ozonolysis reactions can be a strong source of secondary organic aerosol (SOA) indoors. SOA formation can be parameterized and predicted using the aerosol mass fraction (AMF), also known as the SOA yield, which quantifies the mass ratio of generated SOA to oxidized terpene. Limonene is a monoterpene that is at sufficient concentrations such that it reacts meaningfully with ozone indoors. It has two unsaturated bonds, and the magnitude of the limonene ozonolysis AMF varies by a factor of ∼4 depending on whether one or both of its unsaturated bonds are ozonated, which depends on whether ozone is in excess compared to limonene as well as the available time for reactions indoors. Hence, this study developed a framework to predict the limonene AMF as a function of the ozone [O3] and limonene [lim] concentrations and the air exchange rate (AER, h-1), which is the inverse of the residence time. Empirical AMF data were used to calculate a mixing coefficient, β, that would yield a 'resultant AMF' as the combination of the AMFs due to ozonolysis of one or both of limonene's unsaturated bonds, within the volatility basis set (VBS) organic aerosol framework. Then, β was regressed against predictors of log10([O3]/[lim]) and AER (R2 = 0.74). The β increased as the log10([O3]/[lim]) increased and as AER decreased, having the physical meaning of driving the resultant AMF to the upper AMF condition when both unsaturated bonds of limonene are ozonated. Modeling demonstrates that using the correct resultant AMF to simulate SOA formation owing to limonene ozonolysis is crucial for accurate indoor prediction.

Formation of secondary organic aerosol in the Paris pollution plume and its impact on surrounding regions

NASA Astrophysics Data System (ADS)

Zhang, Q. J.; Beekmann, M.; Freney, E.; Sellegri, K.; Pichon, J. M.; Schwarzenboeck, A.; Colomb, A.; Bourrianne, T.; Michoud, V.; Borbon, A.

2015-03-01

Secondary pollutants such as ozone, secondary inorganic aerosol, and secondary organic aerosol formed in the plume of megacities can affect regional air quality. In the framework of the FP7/EU MEGAPOLI project, an intensive campaign was launched in the Greater Paris Region in July 2009. The major objective was to quantify different sources of organic aerosol (OA) within a megacity and in its plume. In this study, we use airborne measurements aboard the French ATR-42 aircraft to evaluate the regional chemistry-transport model CHIMERE within and downwind the Paris region. Slopes of the plume OA levels vs. Ox (= O3 + NO2) show secondary OA (SOA) formation normalized with respect to photochemical activity and are used for specific evaluation of the OA scheme in the model. Simulated and observed slopes are in good agreement, when the most realistic "high-NOx" yields are used in the Volatility-Basis-Set scheme implemented into the model. In addition, these slopes are relatively stable from one day to another, which suggest that they are characteristic for the given megacity plume environment. Since OA within the plume is mainly formed from anthropogenic precursors (VOC and primary OA, POA), this work allows a specific evaluation of anthropogenic SOA and SOA formed from primary semi-volatile and intermediate volatile VOCs (SI-SOA) formation scheme in a model. For specific plumes, this anthropogenic OA build-up can reach about 10 μg m-3. For the average of the month of July 2009, maximum increases occur close to the agglomeration for primary OA are noticed at several tens (for POA) to hundred (for SI-SOA) kilometers of distance from the Paris agglomeration.

Organic aerosol composition and sources in Pasadena, California, during the 2010 CalNex campaign

NASA Astrophysics Data System (ADS)

Hayes, P. L.; Ortega, A. M.; Cubison, M. J.; Froyd, K. D.; Zhao, Y.; Cliff, S. S.; Hu, W. W.; Toohey, D. W.; Flynn, J. H.; Lefer, B. L.; Grossberg, N.; Alvarez, S.; Rappenglück, B.; Taylor, J. W.; Allan, J. D.; Holloway, J. S.; Gilman, J. B.; Kuster, W. C.; de Gouw, J. A.; Massoli, P.; Zhang, X.; Liu, J.; Weber, R. J.; Corrigan, A. L.; Russell, L. M.; Isaacman, G.; Worton, D. R.; Kreisberg, N. M.; Goldstein, A. H.; Thalman, R.; Waxman, E. M.; Volkamer, R.; Lin, Y. H.; Surratt, J. D.; Kleindienst, T. E.; Offenberg, J. H.; Dusanter, S.; Griffith, S.; Stevens, P. S.; Brioude, J.; Angevine, W. M.; Jimenez, J. L.

2013-08-01

Organic aerosols (OA) in Pasadena are characterized using multiple measurements from the California Research at the Nexus of Air Quality and Climate Change (CalNex) campaign. Five OA components are identified using positive matrix factorization including hydrocarbon-like OA (HOA) and two types of oxygenated OA (OOA). The Pasadena OA elemental composition when plotted as H : C versus O : C follows a line less steep than that observed for Riverside, CA. The OOA components from both locations follow a common line, however, indicating similar secondary organic aerosol (SOA) oxidation chemistry at the two sites such as fragmentation reactions leading to acid formation. In addition to the similar evolution of elemental composition, the dependence of SOA concentration on photochemical age displays quantitatively the same trends across several North American urban sites. First, the OA/ΔCO values for Pasadena increase with photochemical age exhibiting a slope identical to or slightly higher than those for Mexico City and the northeastern United States. Second, the ratios of OOA to odd-oxygen (a photochemical oxidation marker) for Pasadena, Mexico City, and Riverside are similar, suggesting a proportional relationship between SOA and odd-oxygen formation rates. Weekly cycles of the OA components are examined as well. HOA exhibits lower concentrations on Sundays versus weekdays, and the decrease in HOA matches that predicted for primary vehicle emissions using fuel sales data, traffic counts, and vehicle emission ratios. OOA does not display a weekly cycle—after accounting for differences in photochemical aging —which suggests the dominance of gasoline emissions in SOA formation under the assumption that most urban SOA precursors are from motor vehicles.

Assessment of the GECKO-A modeling tool using chamber observations for C12 alkanes

NASA Astrophysics Data System (ADS)

Aumont, B.; La, S.; Ouzebidour, F.; Valorso, R.; Mouchel-Vallon, C.; Camredon, M.; Lee-Taylor, J. M.; Hodzic, A.; Madronich, S.; Yee, L. D.; Loza, C. L.; Craven, J. S.; Zhang, X.; Seinfeld, J.

2013-12-01

Secondary Organic Aerosol (SOA) production and ageing is the result of atmospheric oxidation processes leading to the progressive formation of organic species with higher oxidation state and lower volatility. Explicit chemical mechanisms reflect our understanding of these multigenerational oxidation steps. Major uncertainties remain concerning the processes leading to SOA formation and the development, assessment and improvement of such explicit schemes is therefore a key issue. The development of explicit mechanism to describe the oxidation of long chain hydrocarbons is however a challenge. Indeed, explicit oxidation schemes involve a large number of reactions and secondary organic species, far exceeding the size of chemical schemes that can be written manually. The chemical mechanism generator GECKO-A (Generator for Explicit Chemistry and Kinetics of Organics in the Atmosphere) is a computer program designed to overcome this difficulty. GECKO-A generates gas phase oxidation schemes according to a prescribed protocol assigning reaction pathways and kinetics data on the basis of experimental data and structure-activity relationships. In this study, we examine the ability of the generated schemes to explain SOA formation observed in the Caltech Environmental Chambers from various C12 alkane isomers and under high NOx and low NOx conditions. First results show that the model overestimates both the SOA yields and the O/C ratios. Various sensitivity tests are performed to explore processes that might be responsible for these disagreements.

AN INITIAL ASSESSMENT OF THE CLIMATE IMPACT OF SECONDARY ORGANIC AEROSOLS

NASA Astrophysics Data System (ADS)

O'Donnell, D.; Feichter, J.

2009-12-01

Atmospheric aerosols influence the Earth’s climate by absorbing and scattering solar radiation (the direct effect) and by altering the properties of clouds (indirect effects). Measurements have shown that a substantial fraction of the tropospheric aerosol burden consists of organic compounds. Hundreds of different organic species have been identified. While progress has been made in the understanding of the role of certain aerosol types in the climate system, that of organic aerosols remains poorly understood and the climate influences resulting from their presence poorly constrained. Organic aerosols are emitted directly from the surface (primary organic aerosols, POA) and are also formed in the atmosphere from gaseous precursors by oxidation reactions (secondary organic aerosols, SOA). Both biogenic and anthropogenic precursors have been identified. Biogenic emissions of aerosol precursors are known to be climate-dependent. Thus, a bi-directional dependency exists between the biosphere and the atmosphere, whereby aerosols of biogenic origin influence the climate system, which in turn affects biogenic aerosol precursor production. This study builds upon the global aerosol-climate model ECHAM5/HAM and adds techniques to model SOA as well as the necessary global emission inventories. Emission of biogenic precursors is calculated online. Formation of SOA is modeled by the well-known two-product model of SOA formation. SOA is subject to the same aerosol microphysics and sink processes as other modeled species (sulphate, black carbon, primary organic carbon, sea salt and dust). The aerosol radiative effects are calculated on a size resolved basis, and the aerosol scheme is coupled to the model cloud microphysics, permitting estimation of both direct and indirect aerosol effects. The following results will be discussed: (i) Estimation of the direct and indirect effects of biogenic and anthropogenic SOA, (ii) Estimation of the sign and magnitude of the biospheric feedback (through biogenic aerosol precursor emission) on the climate system, and (iii) Identification of physical processes and aerosol physical properties that need further experimental investigation in order to improve our understanding of the climate impact of SOA

Reactive oxygen species from secondary organic aerosols decomposition in water and surrogate lung lining fluid

NASA Astrophysics Data System (ADS)

Tong, H.; Shen, F.; Lakey, P. S. J.; Arangio, A. M.; Socorro, J.; Brune, W. H.; Lucas, K.; Poeschl, U.; Shiraiwa, M.

2016-12-01

Reactive oxygen species (ROS) play a significant role in climate and adverse health effects of air pollutants (Anglada, J. M. et al., 2015; Pöschl and Shiraiwa, 2015). Secondary organic aerosols (SOA) account for a major fraction of fine particles (Jimenez et al., 2009; Huang et al., 2014). Thus, studies on ROS production ability of SOA are important for comprehensive evaluation of the impacts of air particulate matter on climate change and public health. In this study, we have investigated ROS formation by laboratory-generated SOA particles using a variety of different experimental techniques including electron paramagnetic resonance spectrometry, dithiothreitol and fluorometric hydrogen peroxide assays, and LC-MS/MS spectrometry, we found substantial amounts of ROS species such as •OH, O2•-, RO•, R• and H2O2 were generated by isoprene, β-pinene, and naphthalene SOA upon interaction with water and surrogate lung lining fluid. Antioxidants contained in surrogate lung lining fluid scavenge •OH and O2•-efficiently, but not organic radicals. LC-MS/MS analysis and kinetic modeling suggest that organic hydroperoxides, which account for a major fraction of SOA particles (Docherty et al., 2005; Ehn et al., 2014) play a critical role in ROS formation (Tong et al., 2016). We also found the cellular responses of human alveolar basal epithelial (A549) and macrophage cells (THP-1) to SOA could be explained by the ROS yields, indicating a key role of ROS on the cytotoxicity of SOA. Anglada, J. M. et al., Acc. Chem. Res. 48, 575-583, 2015. Docherty, K. S. eta al. Environ. Sci. Technol. 39, 4049-4059, 2005. Ehn, M. et al., Nature 506, 476-479, 2014. Huang, R.-J. et al., Nature 514, 218-222, 2014. Jimenez, J. L. et al., Science 326, 1525-1529, 2009. Pöschl, U., and Shiraiwa, M. Chem. Rev., 115, 4440-4475, 2015. Tong, H. et al., Atmos. Chem. Phys. 16, 1761-1771, 2016.

Recent advances in understanding secondary organic aerosols: implications for global climate forcing

NASA Astrophysics Data System (ADS)

Shrivastava, Manish

2017-04-01

Anthropogenic emissions and land-use changes have modified atmospheric aerosol concentrations and size distributions over time. Understanding pre-industrial conditions and changes in organic aerosol due to anthropogenic activities is important because these features 1) influence estimates of aerosol radiative forcing and 2) can confound estimates of the historical response of climate to increases in greenhouse gases (e.g. the 'climate sensitivity'). Secondary organic aerosol (SOA), formed in the atmosphere by oxidation of organic gases, often represents a major fraction of global submicron-sized atmospheric organic aerosol. Over the past decade, significant advances in understanding SOA properties and formation mechanisms have occurred through measurements, yet current climate models typically do not comprehensively include all important processes. This presentation is based on a US Department of Energy Atmospheric Systems Research sponsored workshop, which highlighted key SOA processes overlooked in climate models that could greatly affect climate forcing estimates. We will highlight the importance of processes that influence the growth of SOA particles to sizes relevant for clouds and radiative forcing, including: formation of extremely low-volatility organics in the gas-phase; isoprene epoxydiols (IEPOX) multi-phase chemistry; particle-phase oligomerization; and physical properties such as viscosity. We also highlight some of the recently discovered important processes that involve interactions between natural biogenic emissions and anthropogenic emissions such as effects of sulfur and NOx emissions on SOA. We will present examples of integrated model-measurement studies that relate the observed evolution of organic aerosol mass and number with knowledge of particle properties such as volatility and viscosity. We will also highlight the importance of continuing efforts to rank the most influential SOA processes that affect climate forcing, but are often missing in climate models. Ultimately, gas- and particle-phase chemistry processes that capture the dynamic evolution of number and mass concentrations of SOA particles need to be accurately and efficiently represented in regional and global atmospheric chemistry-climate models.

Transitions from functionalization to fragmentation reactions of laboratory secondary organic aerosol (SOA) generated from the OH oxidation of alkane precursors.

PubMed

Lambe, Andrew T; Onasch, Timothy B; Croasdale, David R; Wright, Justin P; Martin, Alexander T; Franklin, Jonathan P; Massoli, Paola; Kroll, Jesse H; Canagaratna, Manjula R; Brune, William H; Worsnop, Douglas R; Davidovits, Paul

2012-05-15

Functionalization (oxygen addition) and fragmentation (carbon loss) reactions governing secondary organic aerosol (SOA) formation from the OH oxidation of alkane precursors were studied in a flow reactor in the absence of NO(x). SOA precursors were n-decane (n-C10), n-pentadecane (n-C15), n-heptadecane (n-C17), tricyclo[5.2.1.0(2,6)]decane (JP-10), and vapors of diesel fuel and Southern Louisiana crude oil. Aerosol mass spectra were measured with a high-resolution time-of-flight aerosol mass spectrometer, from which normalized SOA yields, hydrogen-to-carbon (H/C) and oxygen-to-carbon (O/C) ratios, and C(x)H(y)+, C(x)H(y)O+, and C(x)H(y)O(2)+ ion abundances were extracted as a function of OH exposure. Normalized SOA yield curves exhibited an increase followed by a decrease as a function of OH exposure, with maximum yields at O/C ratios ranging from 0.29 to 0.74. The decrease in SOA yield correlates with an increase in oxygen content and decrease in carbon content, consistent with transitions from functionalization to fragmentation. For a subset of alkane precursors (n-C10, n-C15, and JP-10), maximum SOA yields were estimated to be 0.39, 0.69, and 1.1. In addition, maximum SOA yields correspond with a maximum in the C(x)H(y)O+ relative abundance. Measured correlations between OH exposure, O/C ratio, and H/C ratio may enable identification of alkane precursor contributions to ambient SOA.

The Optical Properties of Limonene Secondary Organic Aerosols: The Role of NO3, OH, and O3 in the Oxidation Processes

NASA Astrophysics Data System (ADS)

Peng, Chao; Wang, Weigang; Li, Kun; Li, Junling; Zhou, Li; Wang, Lingshu; Ge, Maofa

2018-03-01

Limonene, a typical proxy of monoterpenes emitted from biogenic sources, plays an important role in secondary organic aerosol (SOA) formation. However, the optical properties of SOA generated from limonene under various oxidation pathways remain poorly understood. In this study, we investigate the refractive index (RI) of limonene SOA produced from four oxidation conditions with cavity ring-down spectrometer (CRDS) and photoacoustic extinctiometer operated at 532 and 375 nm. Our results show that there is a significant difference in RI values of SOA produced from NO3 oxidation compared to other oxidation pathways. The mean values of RI of SOA produced from NO3 oxidation, NOx oxidation, OH oxidation with NOx-free, and O3 oxidation experiments are 1.578, 1.469, 1.495, and 1.494 at 532 nm; and 1.591, 1.527, 1.513, and 1.537 at 375 nm, respectively, while no detectable absorption is found in all oxidation conditions. We attribute the high RI values of SOA by NO3 oxidation to two factors: a large proportion of organic nitrates and high-molecular-weight dimers/oligomers in the SOA. Our study results indicate that the nighttime chemistry may significantly influence the optical properties of limonene oxidation products. The RI values of limonene SOA generated under various oxidation conditions at different wavelengths retrieved in our laboratory experiments could help improve the model predictions for evaluating the effect of biogenic SOA on the global radiative forcing as well as climate change.

Simulating secondary organic aerosol in a regional air quality model using the statistical oxidation model - Part 1: Assessing the influence of constrained multi-generational ageing

NASA Astrophysics Data System (ADS)

Jathar, S. H.; Cappa, C. D.; Wexler, A. S.; Seinfeld, J. H.; Kleeman, M. J.

2015-09-01

Multi-generational oxidation of volatile organic compound (VOC) oxidation products can significantly alter the mass, chemical composition and properties of secondary organic aerosol (SOA) compared to calculations that consider only the first few generations of oxidation reactions. However, the most commonly used state-of-the-science schemes in 3-D regional or global models that account for multi-generational oxidation (1) consider only functionalization reactions but do not consider fragmentation reactions, (2) have not been constrained to experimental data; and (3) are added on top of existing parameterizations. The incomplete description of multi-generational oxidation in these models has the potential to bias source apportionment and control calculations for SOA. In this work, we used the Statistical Oxidation Model (SOM) of Cappa and Wilson (2012), constrained by experimental laboratory chamber data, to evaluate the regional implications of multi-generational oxidation considering both functionalization and fragmentation reactions. SOM was implemented into the regional UCD/CIT air quality model and applied to air quality episodes in California and the eastern US. The mass, composition and properties of SOA predicted using SOM are compared to SOA predictions generated by a traditional "two-product" model to fully investigate the impact of explicit and self-consistent accounting of multi-generational oxidation. Results show that SOA mass concentrations predicted by the UCD/CIT-SOM model are very similar to those predicted by a two-product model when both models use parameters that are derived from the same chamber data. Since the two-product model does not explicitly resolve multi-generational oxidation reactions, this finding suggests that the chamber data used to parameterize the models captures the majority of the SOA mass formation from multi-generational oxidation under the conditions tested. Consequently, the use of low and high NOx yields perturbs SOA concentrations by a factor of two and are probably a much stronger determinant in 3-D models than constrained multi-generational oxidation. While total predicted SOA mass is similar for the SOM and two-product models, the SOM model predicts increased SOA contributions from anthropogenic (alkane, aromatic) and sesquiterpenes and decreased SOA contributions from isoprene and monoterpene relative to the two-product model calculations. The SOA predicted by SOM has a much lower volatility than that predicted by the traditional model resulting in better qualitative agreement with volatility measurements of ambient OA. On account of its lower-volatility, the SOA mass produced by SOM does not appear to be as strongly influenced by the inclusion of oligomerization reactions, whereas the two-product model relies heavily on oligomerization to form low volatility SOA products. Finally, an unconstrained contemporary hybrid scheme to model multi-generational oxidation within the framework of a two-product model in which "ageing" reactions are added on top of the existing two-product parameterization is considered. This hybrid scheme formed at least three times more SOA than the SOM during regional simulations as a result of excessive transformation of semi-volatile vapors into lower volatility material that strongly partitions to the particle phase. This finding suggests that these "hybrid" multi-generational schemes should be used with great caution in regional models.

Simulating secondary organic aerosol in a regional air quality model using the statistical oxidation model - Part 1: Assessing the influence of constrained multi-generational ageing

NASA Astrophysics Data System (ADS)

Jathar, S. H.; Cappa, C. D.; Wexler, A. S.; Seinfeld, J. H.; Kleeman, M. J.

2016-02-01

Multi-generational oxidation of volatile organic compound (VOC) oxidation products can significantly alter the mass, chemical composition and properties of secondary organic aerosol (SOA) compared to calculations that consider only the first few generations of oxidation reactions. However, the most commonly used state-of-the-science schemes in 3-D regional or global models that account for multi-generational oxidation (1) consider only functionalization reactions but do not consider fragmentation reactions, (2) have not been constrained to experimental data and (3) are added on top of existing parameterizations. The incomplete description of multi-generational oxidation in these models has the potential to bias source apportionment and control calculations for SOA. In this work, we used the statistical oxidation model (SOM) of Cappa and Wilson (2012), constrained by experimental laboratory chamber data, to evaluate the regional implications of multi-generational oxidation considering both functionalization and fragmentation reactions. SOM was implemented into the regional University of California at Davis / California Institute of Technology (UCD/CIT) air quality model and applied to air quality episodes in California and the eastern USA. The mass, composition and properties of SOA predicted using SOM were compared to SOA predictions generated by a traditional two-product model to fully investigate the impact of explicit and self-consistent accounting of multi-generational oxidation.Results show that SOA mass concentrations predicted by the UCD/CIT-SOM model are very similar to those predicted by a two-product model when both models use parameters that are derived from the same chamber data. Since the two-product model does not explicitly resolve multi-generational oxidation reactions, this finding suggests that the chamber data used to parameterize the models captures the majority of the SOA mass formation from multi-generational oxidation under the conditions tested. Consequently, the use of low and high NOx yields perturbs SOA concentrations by a factor of two and are probably a much stronger determinant in 3-D models than multi-generational oxidation. While total predicted SOA mass is similar for the SOM and two-product models, the SOM model predicts increased SOA contributions from anthropogenic (alkane, aromatic) and sesquiterpenes and decreased SOA contributions from isoprene and monoterpene relative to the two-product model calculations. The SOA predicted by SOM has a much lower volatility than that predicted by the traditional model, resulting in better qualitative agreement with volatility measurements of ambient OA. On account of its lower-volatility, the SOA mass produced by SOM does not appear to be as strongly influenced by the inclusion of oligomerization reactions, whereas the two-product model relies heavily on oligomerization to form low-volatility SOA products. Finally, an unconstrained contemporary hybrid scheme to model multi-generational oxidation within the framework of a two-product model in which ageing reactions are added on top of the existing two-product parameterization is considered. This hybrid scheme formed at least 3 times more SOA than the SOM during regional simulations as a result of excessive transformation of semi-volatile vapors into lower volatility material that strongly partitions to the particle phase. This finding suggests that these hybrid multi-generational schemes should be used with great caution in regional models.

Heterogeneous ice nucleation and phase transition of viscous α-pinene secondary organic aerosol

NASA Astrophysics Data System (ADS)

Ignatius, Karoliina; Kristensen, Thomas B.; Järvinen, Emma; Nichman, Leonid; Fuchs, Claudia; Gordon, Hamish; Herenz, Paul; Hoyle, Christopher R.; Duplissy, Jonathan; Baltensperger, Urs; Curtius, Joachim; Donahue, Neil M.; Gallagher, Martin W.; Kirkby, Jasper; Kulmala, Markku; Möhler, Ottmar; Saathoff, Harald; Schnaiter, Martin; Virtanen, Annele; Stratmann, Frank

2016-04-01

There are strong indications that particles containing secondary organic aerosol (SOA) exhibit amorphous solid or semi-solid phase states in the atmosphere. This may facilitate deposition ice nucleation and thus influence cirrus cloud properties. Global model simulations of monoterpene SOA particles suggest that viscous biogenic SOA are indeed present in regions where cirrus cloud formation takes place. Hence, they could make up an important contribution to the global ice nucleating particle (INP) budget. However, experimental ice nucleation studies of biogenic SOA are scarce. Here, we investigated the ice nucleation ability of viscous SOA particles at the CLOUD (Cosmics Leaving OUtdoor Droplets) experiment at CERN (Ignatius et al., 2015, Järvinen et al., 2015). In the CLOUD chamber, the SOA particles were produced from the ozone initiated oxidation of α-pinene at temperatures in the range from -38 to -10° C at 5-15 % relative humidity with respect to water (RHw) to ensure their formation in a highly viscous phase state, i.e. semi-solid or glassy. We found that particles formed and grown in the chamber developed an asymmetric shape through coagulation. As the RHw was increased to between 35 % at -10° C and 80 % at -38° C, a transition to spherical shape was observed with a new in-situ optical method. This transition confirms previous modelling of the viscosity transition conditions. The ice nucleation ability of SOA particles was investigated with a new continuous flow diffusion chamber SPIN (Spectrometer for Ice Nuclei) for different SOA particle sizes. For the first time, we observed heterogeneous ice nucleation of viscous α-pinene SOA in the deposition mode for ice saturation ratios between 1.3 and 1.4, significantly below the homogeneous freezing limit. The maximum frozen fractions found at temperatures between -36.5 and -38.3° C ranged from 6 to 20 % and did not depend on the particle surface area. References Ignatius, K. et al., Heterogeneous ice nucleation of secondary organic aerosol produced from ozonolysis of α-pinene, Atmos. Chem. Phys. Discuss., 15, 35719-35752, doi:10.5194/acpd-15-35719-2015, 2015. Järvinen, E. et al., Observation of viscosity transition in α-pinene secondary organic aerosol, Atmos. Chem. Phys. Discuss., 15, 28575-28617, doi:10.5194/acpd-15-28575-2015, 2015.

Chemical characterization of SOA formed from aqueous-phase reactions of phenols with the triplet excited state of carbonyl and hydroxyl radical

DOE PAGES

Yu, L.; Smith, J.; Laskin, A.; ...

2014-08-19

Phenolic compounds, which are emitted in significant amounts from biomass burning, can undergo fast reactions in atmospheric aqueous phases to form secondary organic aerosol (aqSOA). In this study, we investigate the reactions of phenol and two methoxy-phenols (syringol and guaiacol) with two major aqueous phase oxidants – the triplet excited states of an aromatic carbonyl ( 3C*) and hydroxyl radical (·OH). We thoroughly characterize the low-volatility species produced from these reactions and interpret their formation mechanisms using aerosol mass spectrometry (AMS), nanospray desorption electrospray ionization mass spectrometry (nano-DESI MS), and ion chromatography (IC). A large number of oxygenated molecules aremore » identified, including oligomers containing up to six monomer units, functionalized monomer and oligomers with carbonyl, carboxyl, and hydroxyl groups, and small organic acid anions (e.g., formate, acetate, oxalate, and malate). The average atomic oxygen-to-carbon (O / C) ratios of phenolic aqSOA are in the range of 0.85–1.23, similar to those of low-volatility oxygenated organic aerosol (LV-OOA) observed in ambient air. The aqSOA compositions are overall similar for the same precursor, but the reactions mediated by 3C* are faster than ·OH-mediated reactions and produce more oligomers and hydroxylated species at the point when 50% of the phenol had reacted. Profiles determined using a thermodenuder indicate that the volatility of phenolic aqSOA is influenced by both oligomer content and O / C ratio. In addition, the aqSOA shows enhanced light absorption in the UV-vis region, suggesting that aqueous-phase reactions of phenols are likely an important source of brown carbon in the atmosphere, especially in regions influenced by biomass burning.« less

Symmetric 40-Gb/s TWDM-PON with 51-dB loss budget by using a single SOA as preamplifier, booster and format converter in ONU.

PubMed

Li, Zhengxuan; Yi, Lilin; Hu, Weisheng

2014-10-06

In this paper, we propose to use a semiconductor optical amplifier (SOA) in the optical network unit (ONU) to improve the loss budget in time and wavelength division multiplexed-passive optical network (TWDM-PON) systems. The SOA boosts the upstream signal to increase the output power of the electro-absorption modulated laser (EML) and simultaneously pre-amplifies the downstream signal for sensitivity improvement. The penalty caused by cross gain modulation (XGM) effect is negligible due to the low extinction ratio (ER) of upstream signal and the large wavelength difference between upstream and downstream links. In order to achieve a higher output power, the SOA is driven into its saturation region, where the self-phase modulation (SPM) effect converts the intensity into phase information and realizes on-off-keying (OOK) to phase-shifted-keying (PSK) format conversion. In this way, the pattern effect is eliminated, which releases the requirement of gain-clamping on SOA. To further improve the loss budget of upstream link, an Erbium doped fiber amplifier (EDFA) is used in the optical line terminal (OLT) to pre-amplify the received signal. For the downstream direction, directly modulated laser (DML) is used as the laser source. Taking advantage of its carrier-less characteristic, directly modulated signal shows high tolerance to fiber nonlinearity, which could support a downstream launch power as high as + 16 dBm per channel. In addition, the signal is pre-amplified by the SOA in ONU before being detected, so the sensitivity limitation for downstream link is also removed. As a result, a truly passive symmetric 40-Gb/s TWDM-PON was demonstrated, achieving a link loss budget of 51 dB.

The chemical and microphysical properties of secondary organic aerosols from Holm Oak emissions

NASA Astrophysics Data System (ADS)

Lang-Yona, N.; Rudich, Y.; Mentel, Th. F.; Bohne, A.; Buchholz, A.; Kiendler-Scharr, A.; Kleist, E.; Spindler, C.; Tillmann, R.; Wildt, J.

2010-08-01

The Mediterranean region is expected to experience substantial climatic change in the next 50 years. But, possible effects of climate change on biogenic volatile organic compound (VOC) emissions as well as on the formation of secondary organic aerosols (SOA) produced from these VOC are yet unexplored. To address such issues, the effects of temperature on the VOC emissions of Mediterranean Holm Oak and small Mediterranean stand of Wild Pistacio, Aleppo Pine, and Palestine Oak have been studied in the Jülich plant aerosol atmosphere chamber. For Holm Oak the optical and microphysical properties of the resulting SOA were investigated. Monoterpenes dominated the VOC emissions from Holm Oak (97.5%) and Mediterranean stand (97%). Higher temperatures enhanced the overall VOC emission but with different ratios of the emitted species. The amount of SOA increased linearly with the emission strength with a fractional mass yield of 6.0±0.6%, independent of the detailed emission pattern. The investigated particles were highly scattering with no absorption abilities. Their average hygroscopic growth factor of 1.13±0.03 at 90% RH with a critical diameter of droplet activation was 100±4 nm at a supersaturation of 0.4%. All microphysical properties did not depend on the detailed emission pattern, in accordance with an invariant O/C ratio (0.57(+0.03/-0.1)) of the SOA observed by high resolution aerosol mass spectrometry. The increase of Holm oak emissions with temperature (≈20% per degree) was stronger than e.g. for Boreal tree species (≈10% per degree). The SOA yield for Mediterranean trees determined here is similar as for Boreal trees. Increasing mean temperature in Mediterranean areas could thus have a stronger impact on BVOC emissions and SOA formation than in areas with Boreal forests.

Real-Time Measurements of Gas/Particle Partitioning of Semivolatile Organic Compounds into Different Probe Particles in a Teflon Chamber

NASA Astrophysics Data System (ADS)

Liu, X.; Day, D. A.; Ziemann, P. J.; Krechmer, J. E.; Jimenez, J. L.

2017-12-01

The partitioning of semivolatile organic compounds (SVOCs) into and out of particles plays an essential role in secondary organic aerosol (SOA) formation and evolution. Most atmospheric models treat the gas/particle partitioning as an equilibrium between bulk gas and particle phases, despite potential kinetic limitations and differences in thermodynamics as a function of SOA and pre-existing OA composition. This study directly measures the partitioning of oxidized compounds in a Teflon chamber in the presence of single component seeds of different phases and polarities, including oleic acid, squalane, dioctyl sebacate, pentaethylene glycol, dry/wet ammonium sulfate, and dry/wet sucrose. The oxidized compounds are generated by a fast OH oxidation of a series of alkanols under high nitric oxide conditions. The observed SOA mass enhancements are highest with oleic acid, and lowest with wet ammonium sulfate and sucrose. A chemical ionization mass spectrometer (CIMS) was used to measure the decay of gas-phase organic nitrates, which reflects uptake by particles and chamber walls. We observed clear changes in equilibrium timescales with varying seed concentrations and in equilibrium gas-phase concentrations across different seeds. In general, the gas evolution can be reproduced by a kinetic box model that considers partitioning and evaporation with particles and chamber walls, except for the wet sucrose system. The accommodation coefficient and saturation mass concentration of each species in the presence of each seed are derived using the model. The changes in particle size distributions and composition monitored by a scanning mobility particle sizer (SMPS) and a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) are investigated to probe the SOA formation mechanism. Based on these results, the applicability of partitioning theory to these systems and the relevant quantitative parameters, including the dependencies on seed particle composition, will be discussed.

Secondary organic aerosol production from diesel vehicle exhaust: impact of aftertreatment, fuel chemistry and driving cycle

NASA Astrophysics Data System (ADS)

Gordon, T. D.; Presto, A. A.; Nguyen, N. T.; Robertson, W. H.; Na, K.; Sahay, K. N.; Zhang, M.; Maddox, C.; Rieger, P.; Chattopadhyay, S.; Maldonado, H.; Maricq, M. M.; Robinson, A. L.

2014-05-01

Environmental chamber ("smog chamber") experiments were conducted to investigate secondary organic aerosol (SOA) production from dilute emissions from two medium-duty diesel vehicles (MDDVs) and three heavy-duty diesel vehicles (HDDVs) under urban-like conditions. Some of the vehicles were equipped with emission control aftertreatment devices, including diesel particulate filters (DPFs), selective catalytic reduction (SCR) and diesel oxidation catalysts (DOCs). Experiments were also performed with different fuels (100% biodiesel and low-, medium- or high-aromatic ultralow sulfur diesel) and driving cycles (Unified Cycle,~Urban Dynamometer Driving Schedule, and creep + idle). During normal operation, vehicles with a catalyzed DPF emitted very little primary particulate matter (PM). Furthermore, photooxidation of dilute emissions from these vehicles produced essentially no SOA (below detection limit). However, significant primary PM emissions and SOA production were measured during active DPF regeneration experiments. Nevertheless, under reasonable assumptions about DPF regeneration frequency, the contribution of regeneration emissions to the total vehicle emissions is negligible, reducing PM trapping efficiency by less than 2%. Therefore, catalyzed DPFs appear to be very effective in reducing both primary PM emissions and SOA production from diesel vehicles. For both MDDVs and HDDVs without aftertreatment substantial SOA formed in the smog chamber - with the emissions from some vehicles generating twice as much SOA as primary organic aerosol after 3 h of oxidation at typical urban VOC / NOx ratios (3 : 1). Comprehensive organic gas speciation was performed on these emissions, but less than half of the measured SOA could be explained by traditional (speciated) SOA precursors. The remainder presumably originates from the large fraction (~30%) of the nonmethane organic gas emissions that could not be speciated using traditional one-dimensional gas chromatography. The unspeciated organics - likely comprising less volatile species such as intermediate volatility organic compounds - appear to be important SOA precursors; we estimate that the effective SOA yield (defined as the ratio of SOA mass to reacted precursor mass) was 9 ± 6% if both speciated SOA precursors and unspeciated organics are included in the analysis. SOA production from creep + idle operation was 3-4 times larger than SOA production from the same vehicle operated over the Urban Dynamometer Driving Schedule (UDDS). Fuel properties had little or no effect on primary PM emissions or SOA formation.

Sources and Characterization of Submicron Aerosols in a Rural Forest During the PROPHET-AMOS 2016 Campaign

NASA Astrophysics Data System (ADS)

Bui, A. T.; Wallace, H. W., IV; Alvarez, S. L.; Erickson, M.; Alwe, H. D.; May, N.; Cook, R.; Connor, M.; Slade, J. H., Jr.; Shi, Q.; Kavassalis, S.; Tyndall, G. S.; Shepson, P. B.; Pratt, K.; Ault, A. P.; Millet, D. B.; Murphy, J. G.; Usenko, S.; Sheesley, R. J.; Flynn, J. H., III; Griffin, R. J.; Wang, W.

2017-12-01

Forests are a rich source of biogenic volatile organic compounds (BVOCs). Oxidation of BVOCs can result in the formation of secondary organic aerosol (SOA) and in the presence of NOx (NO+NO2) produce organic nitrate-containing particles. However, the distribution of both BVOCs and oxidants can be dramatically altered by the physical barriers provided by a forest canopy. Global models currently neglect the effect of these canopies on SOA formation in forested regions. In this work, we characterize non-refractory submicron aerosol (NR-PM1) using a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) during the 2016 Program on Oxidants: Photochemistry, Emissions, and Transport-Atmospheric Measurements of Oxidants in Summer (PROPHET-AMOS) campaign. This site is located in a rural forest in northern Michigan and features a tower that allowed for both above and below canopy measurements. Our results indicate that organic aerosols (OA) account for a substantial portion of the NR-PM1 measured at this site. Organic nitrate aerosol can contribute up to 18% of the total OA and an average of 75% of the total measured nitrate aerosol. Episodes of above- and below-canopy NR-PM1 concentration differences indicate that above-canopy OA concentrations can be up to 40% greater than below-canopy, which represents an increase of up to 1.5 µg/m3. Organic fragment ions such as CxHy, CxHyOz, and CxHyO1 contribute to enhanced above-canopy OA concentrations. Positive matrix factorization analysis of the high-resolution OA mass spectra identified three SOA factors: low volatility oxygenated OA (LVOOA), isoprene-derived OOA (ISOOA), and oxygenated organic aerosol. Analysis of air mass backward trajectories and correlations with external data indicate that LVOOA correlates well with sulfate and aged, urban-influenced air masses, whereas ISOOA correlates well with isoprene SOA tracers and air masses originating from semi-remote areas. Our results indicate that the OA at this site is dominated by SOA formation and that vertical differences in OA can exist in the presence of a forest canopy. Results from this work have important implications in understanding the role that canopies play in SOA formation and provide useful data to help accurately validate biosphere-atmosphere exchange models.

Mechanism Reduction for the Formation of Secondary Organic Aerosol for Integration into a 3-Dimensional Regional Air Quality Model

NASA Astrophysics Data System (ADS)

Xia, A.; Michelangeli, D.; Makar, P.

2006-12-01

Secondary Organic Aerosol (SOA) plays an important role in atmospheric chemistry, regional and global climate, and human health. It is important to develop a reduced yet accurate chemical mechanism for the formation of both ozone and SOA in a regional air quality model to alleviate CPU time and memory burden. A subset of a near-explicit Master Chemical Mechanism (MCM v3.1) describing alpha-pinene oxidation (976 reactions and 331 compounds), coupled with a gas/particle absorptive partitioning model, is used as a benchmark for the study of SOA formation within a box model. Results from the detailed mechanism show that total SOA mass decreases as the NOx/HC ratio increases. Aerosol fractions for the PAN-like compounds and the nitrates increase with increasing NOx/HC ratio, and the aerosol fractions for the organic peroxides and organic acids decrease with increasing NOx/HC ratio. In addition, 28 out of 149 condensable products are identified as important compounds for the SOA formation and mechanism reduction purposes. The detailed alpha-pinene oxidation mechanism was reduced systematically through five mechanism reduction techniques, in sequence, to create reduced mechanism preserving the properties of the original mechanism, while using less species. Specifically, a directed relation graph method with error propagation (DRGEP) based on resolving species interaction has been shown, in the first stage, to remove efficiently a large number of redundant species and reactions under a wide range of conditions. Next, the application of principal component analysis (PCA) of the rate sensitivity matrix and the use of quasi-steady-state approximation (QSSA) have been used to eliminate some reactions and remove some QSS species, respectively. The fourth stage is to use an iterative screening method to remove redundant species and reactions simultaneously. Last, a new lumping approach, depended on the NOx/HC ratio, is developed and implemented to reduce the number of species in the final stage. This methodology results in a reduction ratio of 3 for the number of species and reactions compared with the full mechanism. The simplified mechanism is demonstrated to reproduce well the important gas and aerosol phase species, four functional groups (PANs, Nitrates, organic peroxides, and organic acids), and the total SOA mass accurately within 16% under a wide range of conditions.

Uptake of Semivolatile Secondary Organic Aerosol Formed from α-Pinene into Nonvolatile Polyethylene Glycol Probe Particles.

PubMed

Ye, Penglin; Ding, Xiang; Ye, Qing; Robinson, Ellis S; Donahue, Neil M

2016-03-10

Semivolatile organic compounds (SVOCs) play an essential role in secondary organic aerosol (SOA) formation, chemical aging, and mixing of organic aerosol (OA) from different sources. Polyethylene glycol (PEG400) particles are liquid, polar, and nearly nonvolatile; they provide a new vehicle to study the interaction between SVOCs with OA. With a unique fragment ion C4H9O2(+) (m/z 89), PEG400 can be easily separated from α-pinene SOA in aerosol mass spectra. By injecting separately prepared PEG probe particles into a chamber containing SOA coated on ammonium sulfate seeds, we show that a substantial pool of SVOCs exists in equilibrium with the original SOA particles. Quantitative findings are based on bulk mass spectra, size-dependent composition, and the evolution of individual particle mass spectra, which we use to separate the two particle populations. We observed a larger fraction of SVOC vapors with increased amounts of reacted α-pinene. For the same amount of reacted α-pinene, the SOA formed from α-pinene oxidized by OH radicals had a higher fraction of SOA vapors than SOA formed by α-pinene ozonolysis. Compared to the PEG400 probe particles, we observed a lower mass fraction of SVOCs in poly(ethylene glycol) dimethyl ether (MePEG500) probe particles under otherwise identical conditions; this may be due to the lower polarity of the MePEG500 or caused by esterification reactions between the PEG400 and organic acids in the SOA.

Epoxide as a precursor to secondary organic aerosol formation from isoprene photooxidation in the presence of nitrogen oxides

PubMed Central

Lin, Ying-Hsuan; Zhang, Haofei; Pye, Havala O. T.; Zhang, Zhenfa; Marth, Wendy J.; Park, Sarah; Arashiro, Maiko; Cui, Tianqu; Budisulistiorini, Sri Hapsari; Sexton, Kenneth G.; Vizuete, William; Xie, Ying; Luecken, Deborah J.; Piletic, Ivan R.; Edney, Edward O.; Bartolotti, Libero J.; Gold, Avram; Surratt, Jason D.

2013-01-01

Isoprene is a substantial contributor to the global secondary organic aerosol (SOA) burden, with implications for public health and the climate system. The mechanism by which isoprene-derived SOA is formed and the influence of environmental conditions, however, remain unclear. We present evidence from controlled smog chamber experiments and field measurements that in the presence of high levels of nitrogen oxides (NOx = NO + NO2) typical of urban atmospheres, 2-methyloxirane-2-carboxylic acid (methacrylic acid epoxide, MAE) is a precursor to known isoprene-derived SOA tracers, and ultimately to SOA. We propose that MAE arises from decomposition of the OH adduct of methacryloylperoxynitrate (MPAN). This hypothesis is supported by the similarity of SOA constituents derived from MAE to those from photooxidation of isoprene, methacrolein, and MPAN under high-NOx conditions. Strong support is further derived from computational chemistry calculations and Community Multiscale Air Quality model simulations, yielding predictions consistent with field observations. Field measurements taken in Chapel Hill, North Carolina, considered along with the modeling results indicate the atmospheric significance and relevance of MAE chemistry across the United States, especially in urban areas heavily impacted by isoprene emissions. Identification of MAE implies a major role of atmospheric epoxides in forming SOA from isoprene photooxidation. Updating current atmospheric modeling frameworks with MAE chemistry could improve the way that SOA has been attributed to isoprene based on ambient tracer measurements, and lead to SOA parameterizations that better capture the dependency of yield on NOx. PMID:23553832

Epoxide as a precursor to secondary organic aerosol formation from isoprene photooxidation in the presence of nitrogen oxides.

PubMed

Lin, Ying-Hsuan; Zhang, Haofei; Pye, Havala O T; Zhang, Zhenfa; Marth, Wendy J; Park, Sarah; Arashiro, Maiko; Cui, Tianqu; Budisulistiorini, Sri Hapsari; Sexton, Kenneth G; Vizuete, William; Xie, Ying; Luecken, Deborah J; Piletic, Ivan R; Edney, Edward O; Bartolotti, Libero J; Gold, Avram; Surratt, Jason D

2013-04-23

Isoprene is a substantial contributor to the global secondary organic aerosol (SOA) burden, with implications for public health and the climate system. The mechanism by which isoprene-derived SOA is formed and the influence of environmental conditions, however, remain unclear. We present evidence from controlled smog chamber experiments and field measurements that in the presence of high levels of nitrogen oxides (NO(x) = NO + NO2) typical of urban atmospheres, 2-methyloxirane-2-carboxylic acid (methacrylic acid epoxide, MAE) is a precursor to known isoprene-derived SOA tracers, and ultimately to SOA. We propose that MAE arises from decomposition of the OH adduct of methacryloylperoxynitrate (MPAN). This hypothesis is supported by the similarity of SOA constituents derived from MAE to those from photooxidation of isoprene, methacrolein, and MPAN under high-NOx conditions. Strong support is further derived from computational chemistry calculations and Community Multiscale Air Quality model simulations, yielding predictions consistent with field observations. Field measurements taken in Chapel Hill, North Carolina, considered along with the modeling results indicate the atmospheric significance and relevance of MAE chemistry across the United States, especially in urban areas heavily impacted by isoprene emissions. Identification of MAE implies a major role of atmospheric epoxides in forming SOA from isoprene photooxidation. Updating current atmospheric modeling frameworks with MAE chemistry could improve the way that SOA has been attributed to isoprene based on ambient tracer measurements, and lead to SOA parameterizations that better capture the dependency of yield on NO(x).

Fast in-situ measurements of glyoxal (CHOCHO) and nitrous acid (HONO) in northern Chinese plane during CAREBEIJING - NCP2014

NASA Astrophysics Data System (ADS)

Min, K. E.; Dube, W. P.; Washenfelder, R. A.; Langford, A. O.; Brown, S. S.; Broch, S.; Fuchs, H.; Gomm, S.; Hofzumahaus, A.; Holland, F.; Hu, M.; Huey, L. G.; Kubik, K.; Li, X.; Liu, X.; Lu, K.; Rohrer, F.; Shao, M.; Sjostedt, S. J.; Tan, Z.; Zhu, T.; Wahner, A.; Wang, B.; Wang, M.; Wang, Y.; Zeng, L.; Zhang, Y.

2014-12-01

The Northern China Plain has experienced visibility degradation and detrimental health impacts due to aerosol and photochemical pollution. To examine these air quality issues, CAREBEIJING-NCP2014 (Care Beijing - Northern China Plain 2014) was held in WangDu, Hebei province, China from 6 June to 15 July 2014. We deployed our newly developed instrument, ACES (Airborne Cavity Enhanced Spectrometer), for high time resolution in-situ measurement of glyoxal (CHOCHO), nitrous acid (HONO) and other trace gases (NO2, H2O) to investigate mechanisms of oxidation processes and secondary organic aerosol (SOA) formation. The in situ measurements of CHOCHO provide observational constraints on secondary organic aerosol formation and oxidation processes, since this molecule has been proposed to play a crucial role in forming aerosol due to its high water solubility, isomerization, and abundant production from the oxidation of many different volatile organic compounds (VOCs). A box model analysis incorporating secondary glyoxal sources from VOC oxidation and sinks to OH reaction, photolysis and heterogeneous uptake will be used to determine a budget and potential for SOA formation. This work was supported by the National Natural Science Foundation of China (21190052), the Strategic Priority Research Program of the Chinese Academy of Sciences (XDB05010500) and the U.S. National Science Foundation Atmospheric (AGS-1405805).

Effect of secondary organic aerosol from isoprene-derived hydroxyhydroperoxides on the expression of oxidative stress response genes in human bronchial epithelial cells.

PubMed

Arashiro, Maiko; Lin, Ying-Hsuan; Zhang, Zhenfa; Sexton, Kenneth G; Gold, Avram; Jaspers, Ilona; Fry, Rebecca C; Surratt, Jason D

2018-02-21

Isoprene-derived secondary organic aerosol (SOA), which comprise a large portion of atmospheric fine particulate matter (PM 2.5 ), can be formed through various gaseous precursors, including isoprene epoxydiols (IEPOX), methacrylic acid epoxide (MAE), and isoprene hydroxyhydroperoxides (ISOPOOH). The composition of the isoprene-derived SOA affects its reactive oxygen species (ROS) generation potential and its ability to alter oxidative stress-related gene expression. In this study we assess effects of isoprene SOA derived solely from ISOPOOH oxidation on human bronchial epithelial cells by measuring the gene expression changes in 84 oxidative stress-related genes. In addition, the thiol reactivity of ISOPOOH-derived SOA was measured through the dithiothreitol (DTT) assay. Our findings show that ISOPOOH-derived SOA alter more oxidative-stress related genes than IEPOX-derived SOA but not as many as MAE-derived SOA on a mass basis exposure. More importantly, we found that the different types of SOA derived from the various gaseous precursors (MAE, IEPOX, and ISOPOOH) have unique contributions to changes in oxidative stress-related genes that do not total all gene expression changes seen in exposures to atmospherically relevant compositions of total isoprene-derived SOA mixtures. This study suggests that amongst the different types of known isoprene-derived SOA, MAE-derived SOA are the most potent inducer of oxidative stress-related gene changes but highlights the importance of considering isoprene-derived SOA as a total mixture for pollution controls and exposure studies.

The lasting effect of limonene-induced particle formation on air quality in a genuine indoor environment.

PubMed

Rösch, Carolin; Wissenbach, Dirk K; von Bergen, Martin; Franck, Ulrich; Wendisch, Manfred; Schlink, Uwe

2015-09-01

Atmospheric ozone-terpene reactions, which form secondary organic aerosol (SOA) particles, can affect indoor air quality when outdoor air mixes with indoor air during ventilation. This study, conducted in Leipzig, Germany, focused on limonene-induced particle formation in a genuine indoor environment (24 m(3)). Particle number, limonene and ozone concentrations were monitored during the whole experimental period. After manual ventilation for 30 min, during which indoor ozone levels reached up to 22.7 ppb, limonene was introduced into the room at concentrations of approximately 180 to 250 μg m(-3). We observed strong particle formation and growth within a diameter range of 9 to 50 nm under real-room conditions. Larger particles with diameters above 100 nm were less affected by limonene introduction. The total particle number concentrations (TPNCs) after limonene introduction clearly exceed outdoor values by a factor of 4.5 to 41 reaching maximum concentrations of up to 267,000 particles cm(-3). The formation strength was influenced by background particles, which attenuated the formation of new SOA with increasing concentration, and by ozone levels, an increase of which by 10 ppb will result in a six times higher TPNC. This study emphasizes indoor environments to be preferred locations for particle formation and growth after ventilation events. As a consequence, SOA formation can produce significantly higher amounts of particles than transported by ventilation into the indoor air.

Aqueous SOA formation from radical oligomerization of methyl vinyl ketone (MVK) and methacrolein (MACR)

NASA Astrophysics Data System (ADS)

Renard, P.; Siekmann, F.; Ravier, S.; Temime-Roussel, B.; Clément, J.; Ervens, B.; Monod, A.

2013-12-01

It is now accepted that one of the important pathways of secondary organic aerosol (SOA) formation occurs through aqueous phase chemistry in the atmosphere. However, the chemical mechanisms leading to macromolecules are still not well understood. It was recently shown that oligomer production by OH radical oxidation in the aerosol aqueous phase from α-dicarbonyl precursors, such as methylglyoxal and glyoxal, is irreversible and fast. We have investigated the aqueous phase photooxidation of MACR and MVK, which are biogenic organic compounds derived from isoprene. Aqueous phase photooxidation of MVK and MACR was investigated in a photoreactor using photolysis of H2O2 as OH radical source. Electrospray high resolution mass spectrometry analysis of the solutions brought clear evidence for the formation of oligomer systems having a mass range of up to 1800 Da within less than 15 minutes of reaction. Highest oligomer formation rates were obtained under conditions of low dissolved oxygen, highest temperature (T = 298 K) and highest precursor initial concentrations ([MVK]0 = 20 mM). A radical mechanism of oligomerization is proposed to explain the formation of the high molecular weight products. Furthermore, we quantified the total amount of carbon present in oligomers. Kinetic parameters of the proposed oligomerization mechanism are constrained by means of a box model that is able to reproduce the temporal evolution of intermediates and products as observed in the laboratory experiments. Additional model simulations for atmospherically-relevant conditions will be presented that show the extent to which these radical processes contribute to SOA formation in the atmospheric multiphase system as compared to other aqueous phase as well as traditional SOA sources. MVK time profile (as measured by UV Spectroscopy) and mass spectra (obtained using UPLC-ESI-MS for the retention time range 0-5 min in the positive mode) at 5, 10 and 50 min of reaction (MVK 20 mM, 25° C, under supersaturated O2 initial conditions).

Development of an aerosol microphysical module: Aerosol Two-dimensional bin module for foRmation and Aging Simulation (ATRAS)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Matsui, H.; Koike, Makoto; Kondo, Yutaka

2014-09-30

Number concentrations, size distributions, and mixing states of aerosols are essential parameters for accurate estimation of aerosol direct and indirect effects. In this study, we developed an aerosol module, designated Aerosol Two-dimensional bin module for foRmation and Aging Simulation (ATRAS), that can represent these parameters explicitly by considering new particle formation (NPF), black carbon (BC) aging, and secondary organic aerosol (SOA) processes. A two-dimensional bin representation is used for particles with dry diameters from 40 nm to 10 µm to resolve both aerosol size (12 bins) and BC mixing state (10 bins) for a total of 120 bins. The particlesmore » with diameters from 1 to 40 nm are resolved using an additional 8 size bins to calculate NPF. The ATRAS module was implemented in the WRF-chem model and applied to examine the sensitivity of simulated mass, number, size distributions, and optical and radiative parameters of aerosols to NPF, BC aging and SOA processes over East Asia during the spring of 2009. BC absorption enhancement by coating materials was about 50% over East Asia during the spring, and the contribution of SOA processes to the absorption enhancement was estimated to be 10 – 20% over northern East Asia and 20 – 35% over southern East Asia. A clear north-south contrast was also found between the impacts of NPF and SOA processes on cloud condensation nuclei (CCN) concentrations: NPF increased CCN concentrations at higher supersaturations (smaller particles) over northern East Asia, whereas SOA increased CCN concentrations at lower supersaturations (larger particles) over southern East Asia. Application of ATRAS to East Asia also showed that the impact of each process on each optical and radiative parameter depended strongly on the process and the parameter in question. The module can be used in the future as a benchmark model to evaluate the accuracy of simpler aerosol models and examine interactions between NPF, BC aging, and SOA processes under different meteorological conditions and emissions.« less

Aqueous-phase mechanism for secondary organic aerosol ...

EPA Pesticide Factsheets

Isoprene emitted by vegetation is an important precursor of secondary organic aerosol (SOA), but the mechanism and yields are uncertain. Aerosol is prevailingly aqueous under the humid conditions typical of isoprene-emitting regions. Here we develop an aqueous-phase mechanism for isoprene SOA formation coupled to a detailed gas-phase isoprene oxidation scheme. The mechanism is based on aerosol reactive uptake coefficients (γ) for water-soluble isoprene oxidation products, including sensitivity to aerosol acidity and nucleophile concentrations. We apply this mechanism to simulation of aircraft (SEAC4RS) and ground-based (SOAS) observations over the southeast US in summer 2013 using the GEOS-Chem chemical transport model. Emissions of nitrogen oxides (NOx  ≡  NO + NO2) over the southeast US are such that the peroxy radicals produced from isoprene oxidation (ISOPO2) react significantly with both NO (high-NOx pathway) and HO2 (low-NOx pathway), leading to different suites of isoprene SOA precursors. We find a mean SOA mass yield of 3.3 % from isoprene oxidation, consistent with the observed relationship of total fine organic aerosol (OA) and formaldehyde (a product of isoprene oxidation). Isoprene SOA production is mainly contributed by two immediate gas-phase precursors, isoprene epoxydiols (IEPOX, 58 % of isoprene SOA) from the low-NOx pathway and glyoxal (28 %) from both low- and high-NOx pathways. This speciation is consistent with observati

Secondary organic aerosol production from diesel vehicle exhaust: impact of aftertreatment, fuel chemistry and driving cycle

NASA Astrophysics Data System (ADS)

Gordon, T. D.; Presto, A. A.; Nguyen, N. T.; Robertson, W. H.; Na, K.; Sahay, K. N.; Zhang, M.; Maddox, C.; Rieger, P.; Chattopadhyay, S.; Maldonado, H.; Maricq, M. M.; Robinson, A. L.

2013-09-01

Environmental chamber ("smog chamber") experiments were conducted to investigate secondary organic aerosol (SOA) production from dilute emissions from two medium-duty diesel vehicles (MDDVs) and three heavy-duty diesel vehicles (HDDVs) under urban-like conditions. Some of the vehicles were equipped with emission control aftertreatment devices including diesel particulate filters (DPF), selective catalytic reduction (SCR) and diesel oxidation catalysts (DOC). Experiments were also performed with different fuels (100% biodiesel and low-, medium- or high-aromatic ultralow sulfur diesel) and driving cycles (Unified Cycle, Urban Dynamometer Driving Schedule, and creep+idle). During normal operation, vehicles with a catalyzed DPF emitted very little primary particulate matter (PM). Furthermore, photo-oxidation of dilute emissions from these vehicles produced essentially no SOA (below detection limit). However, significant primary PM emissions and SOA production were measured during active DPF regeneration experiments. Nevertheless, under reasonable assumptions about DPF regeneration frequency, the contribution of regeneration emissions to the total vehicle emissions is negligible, reducing PM trapping efficiency by less than 2%. Therefore, catalyzed DPFs appear to be very effective in reducing both primary and secondary fine particulate matter from diesel vehicles. For both MDDVs and HDDVs without aftertreatment substantial SOA formed in the smog chamber - with the emissions from some vehicles generating twice as much SOA as primary organic aerosol after three hours of oxidation at typical urban VOC : NOx ratios (3:1). Comprehensive organic gas speciation was performed on these emissions, but less than half of the measured SOA could be explained by traditional (speciated) SOA precursors. The remainder presumably originates from the large fraction (~30%) of the non-methane organic gas emissions that could not be speciated using traditional one-dimensional gas-chromatography. The unspeciated organics - likely comprising less volatile species, such as intermediate volatility organic compounds - appear to be important SOA precursors; we estimate that the effective SOA yield (defined as the ratio of SOA mass to reacted precursor mass) was 9 ± 6% if both speciated SOA precursors and unspeciated organics are included in the analysis. SOA production from creep+idle operation was 3-4 times larger than SOA production from the same vehicle operated over the Urban Dynamometer Driving Schedule (UDDS). Fuel properties had little or no effect on primary PM emissions or SOA formation.

α-Pinene secondary organic aerosol at low temperature: chemical composition and implications for particle viscosity

NASA Astrophysics Data System (ADS)

Huang, Wei; Saathoff, Harald; Pajunoja, Aki; Shen, Xiaoli; Naumann, Karl-Heinz; Wagner, Robert; Virtanen, Annele; Leisner, Thomas; Mohr, Claudia

2018-02-01

Chemical composition, size distributions, and degree of oligomerization of secondary organic aerosol (SOA) from α-pinene (C10H16) ozonolysis were investigated for low-temperature conditions (223 K). Two types of experiments were performed using two simulation chambers at the Karlsruhe Institute of Technology: the Aerosol Preparation and Characterization (APC) chamber, and the Aerosol Interaction and Dynamics in the Atmosphere (AIDA) chamber. Experiment type 1 simulated SOA formation at upper tropospheric conditions: SOA was generated in the AIDA chamber directly at 223 K at 61 % relative humidity (RH; experiment termed cold humid, CH) and for comparison at 6 % RH (experiment termed cold dry, CD) conditions. Experiment type 2 simulated SOA uplifting: SOA was formed in the APC chamber at room temperature (296 K) and < 1 % RH (experiment termed warm dry, WD) or 21 % RH (experiment termed warm humid, WH) conditions, and then partially transferred to the AIDA chamber kept at 223 K, and 61 % RH (WDtoCH) or 30 % RH (WHtoCH), respectively. Precursor concentrations varied between 0.7 and 2.2 ppm α-pinene, and between 2.3 and 1.8 ppm ozone for type 1 and type 2 experiments, respectively. Among other instrumentation, a chemical ionization mass spectrometer (CIMS) coupled to a filter inlet for gases and aerosols (FIGAERO), deploying I- as reagent ion, was used for SOA chemical composition analysis. For type 1 experiments with lower α-pinene concentrations and cold SOA formation temperature (223 K), smaller particles of 100-300 nm vacuum aerodynamic diameter (dva) and higher mass fractions (> 40 %) of adducts (molecules with more than 10 carbon atoms) of α-pinene oxidation products were observed. For type 2 experiments with higher α-pinene concentrations and warm SOA formation temperature (296 K), larger particles ( ˜ 500 nm dva) with smaller mass fractions of adducts (< 35 %) were produced. We also observed differences (up to 20 °C) in maximum desorption temperature (Tmax) of individual compounds desorbing from the particles deposited on the FIGAERO Teflon filter for different experiments, indicating that Tmax is not purely a function of a compound's vapor pressure or volatility, but is also influenced by diffusion limitations within the particles (particle viscosity), interactions between particles deposited on the filter (particle matrix), and/or particle mass on the filter. Highest Tmax were observed for SOA under dry conditions and with higher adduct mass fraction; lowest Tmax were observed for SOA under humid conditions and with lower adduct mass fraction. The observations indicate that particle viscosity may be influenced by intra- and inter-molecular hydrogen bonding between oligomers, and particle water uptake, even under such low-temperature conditions. Our results suggest that particle physicochemical properties such as viscosity and oligomer content mutually influence each other, and that variation in Tmax of particle desorptions may have implications for particle viscosity and particle matrix effects. The differences in particle physicochemical properties observed between our different experiments demonstrate the importance of taking experimental conditions into consideration when interpreting data from laboratory studies or using them as input in climate models.

Aerosol formation by ozonolysis of α- and β-pinene with initial concentrations below 1 ppb

NASA Astrophysics Data System (ADS)

Saathoff, Harald; Naumann, Karl-Heinz; Möhler, Ottmar

2014-05-01

Secondary organic aerosols (SOA) from the oxidation of biogenic volatile organic compounds (BVOC) are a large fraction of the tropospheric aerosol especially over tropical continental regions. The dominant SOA forming compounds are monoterpenes of which pinene is the most abundant. The reactions of monoterpenes with OH radicals, NO3 radicals, and ozone yield secondary organic aerosol mass in highly variable yields. Despite the various studies on SOA formation the influence of temperature and precursor concentrations on SOA yields are still major uncertainties in tropospheric aerosol models. In previous studies we observed a negative temperature dependence of SOA yields for SOA from ozonolysis α-pinene and limonene (Saathoff et al., 2009). However, this study as well as most of the literature data for measured SOA yields is limited to terpene concentrations of several ppb and higher (e.g. Bernard et al., 2012), hence about an order of magnitude higher than terpene concentrations even near their sources. Monoterpene concentrations in and above tropical or boral forests reach values up to a few tenth of a ppb during daytime decreasing rapidly with altitude in the boundary layer (Kesselmeier et al. 2000; Boy et al., 2004). Therefore we investigated the yield of SOA material from the ozonolysis of α- and β-pinene under simulated tropospheric conditions in the large aerosol chamber AIDA on time scales of several hours and for terpene concentrations between 0.1 and 1 ppb. The temperatures investigated were 243, 274, and 296 K with relative humidities ranging from 25% to 41%. The organic aerosol was generated by controlled oxidation with an excess of ozone (220-930 ppb) and the aerosol yield is calculated from size distributions measured with differential mobility analysers (SMPS, TSI, 3071 & 3080N) in the size range between 2 and 820 nm. On the basis of the measured initial particle size distribution, particle number concentration (CPC, TSI, 3775, 3776, 3022), and trace gas evolution model calculations were done using the aerosol model COSIMA (Naumann, 2003; Saathoff et al., 2009) supplemented by an improved SOA module in combination with the master chemical mechanism (MCM 3.2). As previously reported for higher SOA concentrations the overall SOA yields from ozonolysis of α- and β-pinene increase significantly with decreasing temperature. However, compared to the yields extrapolated from experiments done with higher terpene concentrations the SOA yields at ambient like concentrations are surprisingly high. They reach values of up to 20% at 243 K for organic aerosol mass concentrations of about 0.5 µg m-3 even without additional seed aerosol. This paper discusses the temperature dependent SOA yields from the ozonolysis of α-pinene and β-pinene in comparison with data from literature. Bernard et al., (2012) J. Aerosol Sci. 43, 14-30. Boy et al., (2004) Atmos. Chem. Phys. 4, 657-678. Kesselmeier et al., (2000) Atmos. Environ. 34, 4063-4072 Naumann (2003) J. Aerosol Sci. 34 (10), 1371-1397. Saathoff et al., (2009) Atmos. Chem. Phys. 9 (5), 1551-1577.

A Comparison of Parameterizations of Secondary Organic Aerosol Production: Global Budget and Spatiotemporal Variability

NASA Astrophysics Data System (ADS)

Liu, J.; Chen, Z.; Horowitz, L. W.; Carlton, A. M. G.; Fan, S.; Cheng, Y.; Ervens, B.; Fu, T. M.; He, C.; Tao, S.

2014-12-01

Secondary organic aerosols (SOA) have a profound influence on air quality and climate, but large uncertainties exist in modeling SOA on the global scale. In this study, five SOA parameterization schemes, including a two-product model (TPM), volatility basis-set (VBS) and three cloud SOA schemes (Ervens et al. (2008, 2014), Fu et al. (2008) , and He et al. (2013)), are implemented into the global chemical transport model (MOZART-4). For each scheme, model simulations are conducted with identical boundary and initial conditions. The VBS scheme produces the highest global annual SOA production (close to 35 Tg·y-1), followed by three cloud schemes (26-30 Tg·y-1) and TPM (23 Tg·y-1). Though sharing a similar partitioning theory to the TPM scheme, the VBS approach simulates the chemical aging of multiple generations of VOCs oxidation products, resulting in a much larger SOA source, particularly from aromatic species, over Europe, the Middle East and Eastern America. The formation of SOA in VBS, which represents the net partitioning of semi-volatile organic compounds from vapor to condensed phase, is highly sensitivity to the aging and wet removal processes of vapor-phase organic compounds. The production of SOA from cloud processes (SOAcld) is constrained by the coincidence of liquid cloud water and water-soluble organic compounds. Therefore, all cloud schemes resolve a fairly similar spatial pattern over the tropical and the mid-latitude continents. The spatiotemporal diversity among SOA parameterizations is largely driven by differences in precursor inputs. Therefore, a deeper understanding of the evolution, wet removal, and phase partitioning of semi-volatile organic compounds, particularly above remote land and oceanic areas, is critical to better constrain the global-scale distribution and related climate forcing of secondary organic aerosols.

Volatility and lifetime against OH heterogeneous reaction of ambient isoprene-epoxydiols-derived secondary organic aerosol (IEPOX-SOA)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hu, Weiwei; Palm, Brett B.; Day, Douglas A.

Isoprene-epoxydiols-derived secondary organic aerosol (IEPOX-SOA) can contribute substantially to organic aerosol (OA) concentrations in forested areas under low NO conditions, hence significantly influencing the regional and global OA budgets, accounting, for example, for 16–36 % of the submicron OA in the southeastern United States (SE US) summer. Particle evaporation measurements from a thermodenuder show that the volatility of ambient IEPOX-SOA is lower than that of bulk OA and also much lower than that of known monomer IEPOX-SOA tracer species, indicating that IEPOX-SOA likely exists mostly as oligomers in the aerosol phase. The OH aging process of ambient IEPOX-SOA was investigatedmore » with an oxidation flow reactor (OFR). New IEPOX-SOA formation in the reactor was negligible, as the OFR does not accelerate processes such as aerosol uptake and reactions that do not scale with OH. Simulation results indicate that adding ~100 µg m -3 of pure H 2SO 4 to the ambient air allows IEPOX-SOA to be efficiently formed in the reactor. The heterogeneous reaction rate coefficient of ambient IEPOX-SOA with OH radical ( k OH) was estimated as 4.0 ± 2.0 ×10 -13 cm 3 molec -1 s -1, which is equivalent to more than a 2-week lifetime. A similar k OH was found for measurements of OH oxidation of ambient Amazon forest air in an OFR. At higher OH exposures in the reactor (> 1 × 10 12 molec cm -3 s), the mass loss of IEPOX-SOA due to heterogeneous reaction was mainly due to revolatilization of fragmented reaction products. We report, for the first time, OH reactive uptake coefficients ( γ OH = 0.59±0.33 in SE US and γ OH = 0.68±0.38 in Amazon) for SOA under ambient conditions. A relative humidity dependence of k OH and γ OH was observed, consistent with surface-area-limited OH uptake. No decrease of k OH was observed as OH concentrations increased. These observations of physicochemical properties of IEPOX-SOA can help to constrain OA impact on air quality and climate.« less

Secondary organic aerosols - formation and ageing studies in the SAPHIR chamber

NASA Astrophysics Data System (ADS)

Spindler, Christian; Müller, Lars; Trimborn, Achim; Mentel, Thomas; Hoffmann, Thorsten

2010-05-01

Secondary organic aerosol (SOA) formation from oxidation products of biogenic volatile organic compounds (BVOC) constitutes an important coupling between vegetation, atmospheric chemistry, and climate change. Such secondary organic aerosol components play an important role in particle formation in Boreal regions ((Laaksonen et al., 2008)), where biogenic secondary organic aerosols contribute to an overall negative radiative forcing, thus a negative feed back between vegetation and climate warming (Spracklen et al., 2008). Within the EUCAARI project we investigated SOA formation from mixtures of monoterpenes (and sesquiterpenes) as emitted typically from Boreal tree species in Southern Finland. The experiments were performed in the large photochemical reactor SAPHIR in Juelich at natural light and oxidant levels. Oxidation of the BVOC mixtures and SOA formation was induced by OH radicals and O3. The SOA was formed on the first day and then aged for another day. The resulting SOA was characterized by HR-ToF-AMS, APCI-MS, and filter samples with subsequent H-NMR, GC-MS and HPLC-MS analysis. The chemical evolution of the SOA is characterized by a fast increase of the O/C ratio during the formation process on the first day, stable O/C ratio during night, and a distinctive increase of O/C ratio at the second day. The increase of the O/C ratio on the second day is highly correlated to the OH dose and is accompanied by condensational growth of the particles. We will present simultaneous factor analysis of AMS times series (PMF, Ulbrich et al., 2009 ) and direct measurements of individual chemical species. We found that four factors were needed to represent the time evolution of the SOA composition (in the mass spectra) if oxidation by OH plays a mayor role. Corresponding to these factors we observed individual, representative molecules with very similar time behaviour. The correlation between tracers and AMS factors is astonishingly good as the molecular tracers represented only a very small mass fraction of the factors. There is indication that some factors grow at the cost of the other suggesting a set of successive generations of oxidation products. This conversion could proceed either by direct condensed phase processes or by an evaporation-oxidation-recondensation mechanism. On the other hand it seems that the factors evolve in parallel, representing products of multiple oxidation which appear on different time scales in the particulate phase. These findings will be discussed with respect to their importance for ageing processes of atmospheric organic aerosols. References Laaksonen, A., Kulmala, M., O'Dowd, C. D., Joutsensaari, J., Vaattovaara, P., Mikkonen, S., Lehtinen, K. E. J., Sogacheva, L., Dal Maso, M., Aalto, P., Petaja, T., Sogachev, A., Yoon, Y. J., Lihavainen, H., Nilsson, D., Facchini, M. C., Cavalli, F., Fuzzi, S., Hoffmann, T., Arnold, F., Hanke, M., Sellegri, K., Umann, B., Junkermann, W., Coe, H., Allan, J. D., Alfarra, M. R., Worsnop, D. R., Riekkola, M. L., Hyotylainen, T., and Viisanen, Y.: The role of VOC oxidation products in continental new particle formation, Atmospheric Chemistry and Physics, 8, 2657-2665, 2008 Spracklen, D. V., Bonn, B., and Carslaw, K. S.: Boreal forests, aerosols and the impacts on clouds and climate, Philosophical Transactions of the Royal Society a-Mathematical Physical and Engineering Sciences, 366, 4613-4626, 10.1098/rsta.2008.0201, 2008 Ulbrich, I. M., Canagaratna, M. R., Zhang, Q., Worsnop, D. R., and Jimenez, J. L.: Interpretation of organic components from Positive Matrix Factorization of aerosol mass spectrometric data, Atmospheric Chemistry and Physics, 9, 2891-2918, 2009

Contributions and source identification of biogenic and anthropogenic hydrocarbons to secondary organic aerosols at Mt. Tai in 2014.

PubMed

Zhu, Yanhong; Yang, Lingxiao; Kawamura, Kimitaka; Chen, Jianmin; Ono, Kaori; Wang, Xinfeng; Xue, Likun; Wang, Wenxing

2017-01-01

Ambient fine particulate matter (PM 2.5 ) and volatile organic compounds (VOCs) collected at Mt. Tai in summer 2014 were analysed and the data were used to identify the contribution of biogenic and anthropogenic hydrocarbons to secondary organic aerosols (SOA) and their sources and potential source areas in high mountain regions. Compared with those in 2006, the 2014 anthropogenic SOA tracers in PM 2.5 aerosols and VOC species related to vehicular emissions exhibited higher concentrations, whereas the levels of biogenic SOA tracers were lower, possibly due to decreased biomass burning. Using the SOA tracer and parameterisation method, we estimated the contributions from biogenic and anthropogenic VOCs, respectively. The results showed that the average concentration of biogenic SOA was 1.08 ± 0.51 μg m -3 , among which isoprene SOA tracers were dominant. The anthropogenic VOC-derived SOA were 7.03 ± 1.21 μg m -3 and 1.92 ± 1.34 μg m -3 under low- and high-NO x conditions, respectively, and aromatics made the greatest contribution. However, the sum of biogenic and anthropogenic SOA only contributed 18.1-49.1% of the total SOA. Source apportionment by positive matrix factorisation (PMF) revealed that secondary oxidation and biomass burning were the major sources of biogenic SOA tracers. Anthropogenic aromatics mainly came from solvent use, fuel and plastics combustion and vehicular emissions. However, for > C6 alkanes and cycloalkanes, vehicular emissions and fuel and plastics combustion were the most important contributors. The potential source contribution function (PSCF) identified the Bohai Sea Region (BSR) as the major source area for organic aerosol compounds and VOC species at Mt. Tai. Copyright © 2016 Elsevier Ltd. All rights reserved.

Secondary organic aerosol formation and composition from the photo-oxidation of methyl chavicol (estragole)

NASA Astrophysics Data System (ADS)

Pereira, K. L.; Hamilton, J. F.; Rickard, A. R.; Bloss, W. J.; Alam, M. S.; Camredon, M.; Muñoz, A.; Vásquez, M.; Borrás, E.; Ródenas, M.

2013-12-01

The increasing demand for palm oil for uses in biofuel and food products is leading to rapid expansion of oil palm agriculture. Methyl chavicol (also known as estragole and 1-allyl-4-methoxybenzene) is an oxygenated biogenic volatile organic compound that was recently identified as the main floral emission from an oil palm plantation in Malaysian Borneo. The emissions of methyl chavicol observed may impact regional atmospheric chemistry, but little is known of its ability to form secondary organic aerosol (SOA). The photo-oxidation of methyl chavicol was investigated at the European Photoreactor chamber as a part of the atmospheric chemistry of methyl chavicol (ATMECH) project. Aerosol samples were collected using a particle into liquid sampler (PILS) and analysed offline using an extensive range of instruments including; high performance liquid chromatography mass spectrometry (HPLC-ITMS), high performance liquid chromatography quadrupole time-of-flight mass spectrometry (HPLC-QTOFMS) and Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS). The SOA yield was determined as 18-29% depending on initial precursor (VOC : NOx) mixing ratios. In total, 59 SOA compounds were observed and the structures of 10 compounds have been identified using high resolution tandem mass spectrometry. The addition of hydroxyl and/or nitro functional groups to the aromatic ring appears to be an important mechanistic pathway for aerosol formation. This results in the formation of compounds with both low volatility and high O : C ratios, where functionalisation rather than fragmentation is mainly observed as a~result of the stability of the ring. The SOA species observed can be characterized as semi-volatile to low volatile oxygenated organic aerosol (SVOOA and LVOOA) components and therefore may be important in aerosol formation and growth.

Physical parameters effect on ozone-initiated formation of indoor secondary organic aerosols with emissions from cleaning products.

PubMed

Huang, Yu; Ho, Kin Fai; Ho, Steven Sai Hang; Lee, Shun Cheng; Yau, P S; Cheng, Yan

2011-09-15

The effect of air exchange rate (ACH), temperature (T), and relative humidity (RH) on the formation of indoor secondary organic aerosols (SOAs) through ozonolysis of biogenic organic compounds (BVOCs) emitted from floor cleaner was investigated in this study. The total particle count (with D(p) of 6-225 nm) was up to 1.2 × 10(3)#cm(-3) with ACH of 1.08 h(-1), and it became much more significant with ACH of 0.36 h(-1) (1.1 × 10(4)#cm(-3)). This suggests that a higher ventilation rate can effectively dilute indoor BVOCs, resulting in a less ultrafine particle formation. The total particle count increased when temperature changed from 15 to 23 °C but it decreased when the temperature further increased to 30 °C. It could be explained that high temperature restrained the condensation of formed semi-volatile compounds resulting in low yields of SOAs. When the RH was at 50% and 80%, SOA formation (1.1-1.2 × 10(4)#cm(-3)) was the more efficient compared with that at RH of 30% (5.9 × 10(3)#cm(-3)), suggesting higher RH facilitating the initial nucleation processes. Oxidation generated secondary carbonyl compounds were also quantified. Acetone was the most abundant carbonyl compound. The formation mechanisms of formaldehyde and acetone were proposed. Copyright © 2011 Elsevier B.V. All rights reserved.

Relationship between chemical composition and oxidative potential of secondary organic aerosol from polycyclic aromatic hydrocarbons

NASA Astrophysics Data System (ADS)

Wang, Shunyao; Ye, Jianhuai; Soong, Ronald; Wu, Bing; Yu, Legeng; Simpson, André J.; Chan, Arthur W. H.

2018-03-01

Owing to the complex nature and dynamic behaviors of secondary organic aerosol (SOA), its ability to cause oxidative stress (known as oxidative potential, or OP) and adverse health outcomes remains poorly understood. In this work, we probed the linkages between the chemical composition of SOA and its OP, and investigated impacts from various SOA evolution pathways, including atmospheric oligomerization, heterogeneous oxidation, and mixing with metal. SOA formed from photooxidation of the two most common polycyclic aromatic hydrocarbons (naphthalene and phenanthrene) were studied as model systems. OP was evaluated using the dithiothreitol (DTT) assay. The oligomer-rich fraction separated by liquid chromatography dominates DTT activity in both SOA systems (52 ± 10 % for naphthalene SOA (NSOA), and 56 ± 5 % for phenanthrene SOA (PSOA)). Heterogeneous ozonolysis of NSOA was found to enhance its OP, which is consistent with the trend observed in selected individual oxidation products. DTT activities from redox-active organic compounds and metals were found to be not additive. When mixing with highly redox-active metal (Cu), OP of the mixture decreased significantly for 1,2-naphthoquinone (42 ± 7 %), 2,3-dihydroxynaphthalene (35 ± 1 %), NSOA (50 ± 6 %), and PSOA (43 ± 4 %). Evidence from proton nuclear magnetic resonance (1H NMR) spectroscopy illustrates that such OP reduction upon mixing can be ascribed to metal-organic binding interactions. Our results highlight the role of aerosol chemical composition under atmospheric aging processes in determining the OP of SOA, which is needed for more accurate and explicit prediction of the toxicological impacts from particulate matter.

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

NASA Astrophysics Data System (ADS)

Chirico, R.; Decarlo, P. F.; Heringa, M. F.; Tritscher, T.; Richter, R.; Prevot, A. S. H.; Dommen, J.; Weingartner, E.; Wehrle, G.; Gysel, M.; Laborde, M.; Baltensperger, U.

2010-06-01

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.

Studies on the Effect of Sub-zero Temperatures on the Formation of Extremely Low Volatility Dimer Esters in Secondary Organic Aerosol from Alpha-Pinene

NASA Astrophysics Data System (ADS)

Kristensen, Kasper; Normann Jensen, Louise; Bilde, Merete

2016-04-01

The oxidation of volatile organic compounds (VOC) is considered a major source of secondary organic aerosols (SOA) in the atmosphere. Recently, extremely low volatility organic compounds, or ELVOC, formed from the oxidation of VOCs have been shown to play a crucial role in new particle formation (Ehn et al., 2014). In addition, higher molecular weight dimer esters originating from the oxidation of the biogenic VOC alpha-pinene have been observed in both laboratory-generated and ambient SOA (Kristensen et al., 2013). The low volatility of the dimer esters along with an observed rapid formation makes these high molecular weight compounds likely candidates involved in new particle formation from the oxidation of alpha-pinene. Furthermore, laboratory experiments show that the dimer esters only form in the presence of ozone, thus may be used as tracers for the ozone-initiated oxidation of alpha-pinene, and are therefore indicative of enhanced anthropogenic activities. In this work, we present the results of a series of oxidation experiments performed in the newly constructed cold-room smog chamber at Aarhus University. This unique and state-of-the-art Teflon chamber allows for atmospheric simulations of the oxidation VOCs and subsequent SOA formation at temperatures down to -16 °C. In this study, ozonolysis and photochemical oxidations of alpha-pinene are performed at temperatures ranging from +20 to -16 °C. Chemical characterization of the formed SOA is performed using liquid chromatography coupled to quadrupole time-of-flight mass spectrometry. The results show significant differences in the chemical composition related to the experiment temperature. In particularly, the concentration of the high molecular weight dimer esters showed to be highly affected by temperature. Interestingly, preliminary results show higher formation of dimer esters related to increased SOA formation rate, thus indicating that these particle-phase ELVOCs may be linked with new particle formation. Ehn, M., Thornton, J. A., Kleist, E., Sipila, M., Junninen, H., Pullinen, I., Springer, M., Rubach, F., Tillmann, R., Lee, B., Lopez-Hilfiker, F., Andres, S., Acir, I. H., Rissanen, M., Jokinen, T., Schobesberger, S., Kangasluoma, J., Kontkanen, J., Nieminen, T., Kurten, T., Nielsen, L. B., Jorgensen, S., Kjaergaard, H. G., Canagaratna, M., Dal Maso, M., Berndt, T., Petaja, T., Wahner, A., Kerminen, V. M., Kulmala, M., Worsnop, D. R., Wildt, J., and Mentel, T. F.: A large source of low-volatility secondary organic aerosol, Nature, 506, 476-+, 10.1038/nature13032, 2014. Kristensen, K., Enggrob, K. L., King, S. M., Worton, D. R., Platt, S. M., Mortensen, R., Rosenoern, T., Surratt, J. D., Bilde, M., Goldstein, A. H., and Glasius, M.: Formation and occurrence of dimer esters of pinene oxidation products in atmospheric aerosols, Atmospheric Chemistry and Physics, 13, 3763-3776, 2013.

Characterization of a real-time tracer for Isoprene Epoxydiols-derived Secondary Organic Aerosol (IEPOX-SOA) from aerosol mass spectrometer measurements

NASA Astrophysics Data System (ADS)

Hu, W. W.; Campuzano-Jost, P.; Palm, B. B.; Day, D. A.; Ortega, A. M.; Hayes, P. L.; Krechmer, J. E.; Chen, Q.; Kuwata, M.; Liu, Y. J.; de Sá, S. S.; Martin, S. T.; Hu, M.; Budisulistiorini, S. H.; Riva, M.; Surratt, J. D.; St. Clair, J. M.; Isaacman-Van Wertz, G.; Yee, L. D.; Goldstein, A. H.; Carbone, S.; Artaxo, P.; de Gouw, J. A.; Koss, A.; Wisthaler, A.; Mikoviny, T.; Karl, T.; Kaser, L.; Jud, W.; Hansel, A.; Docherty, K. S.; Robinson, N. H.; Coe, H.; Allan, J. D.; Canagaratna, M. R.; Paulot, F.; Jimenez, J. L.

2015-04-01

Substantial amounts of secondary organic aerosol (SOA) can be formed from isoprene epoxydiols (IEPOX), which are oxidation products of isoprene mainly under low-NO conditions. Total IEPOX-SOA, which may include SOA formed from other parallel isoprene low-NO oxidation pathways, was quantified by applying Positive Matrix Factorization (PMF) to aerosol mass spectrometer (AMS) measurements. The IEPOX-SOA fractions of OA in multiple field studies across several continents are summarized here and show consistent patterns with the concentration of gas-phase IEPOX simulated by the GEOS-Chem chemical transport model. During the SOAS study, 78% of IEPOX-SOA is accounted for the measured molecular tracers, making it the highest level of molecular identification of an ambient SOA component to our knowledge. Enhanced signal at C5H6O+ (m/z 82) is found in PMF-resolved IEPOX-SOA spectra. To investigate the suitability of this ion as a tracer for IEPOX-SOA, we examine fC5H6O ( fC5H6O = C5H6O+/OA) across multiple field, chamber and source datasets. A background of ~ 1.7 ± 0.1‰ is observed in studies strongly influenced by urban, biomass-burning and other anthropogenic primary organic aerosol (POA). Higher background values of 3.1 ± 0.8‰ are found in studies strongly influenced by monoterpene emissions. The average laboratory monoterpene SOA value (5.5 ± 2.0‰) is 4 times lower than the average for IEPOX-SOA (22 ± 7‰). Locations strongly influenced by isoprene emissions under low-NO levels had higher fC5H6O (~ 6.5 ± 2.2‰ on average) than other sites, consistent with the expected IEPOX-SOA formation in those studies. fC5H6O in IEPOX-SOA is always elevated (12-40‰) but varies substantially between locations, which is shown to reflect large variations in its detailed molecular composition. The low fC5H6O (< 3‰) observed in non IEPOX-derived isoprene-SOA indicates that this tracer ion is specifically enhanced from IEPOX-SOA, and is not a tracer for all SOA from isoprene. We introduce a graphical diagnostic to study the presence and aging of IEPOX-SOA as a "triangle plot" of fCO2 vs. fC5H6O. Finally, we develop a simplified method to estimate ambient IEPOX-SOA mass concentrations, which is shown to perform well compared to the full PMF method. The uncertainty of the tracer method is up to a factor of ~ 2 if the fC5H6O of the local IEPOX-SOA is not available. When only unit mass resolution data is available, as with the aerosol chemical speciation monitor (ACSM), all methods may perform less well because of increased interferences from other ions at m/z 82. This study clarifies the strengths and limitations of the different AMS methods for detection of IEPOX-SOA and will enable improved characterization of this OA component.

SOA derived from isoprene epoxydiols: Insights into formation, aging and distribution over the continental US from the DC3 and SEAC4RS campaigns

NASA Astrophysics Data System (ADS)

Campuzano Jost, P.; Hu, W.; Palm, B. B.; Day, D. A.; Jimenez, J. L.; Rivera, J. C.; Keutsch, F. N.; Zhao, R.; Lee, A.; Abbatt, J.; Marais, E. A.; Liao, J.; Froyd, K. D.; Pollack, I. B.; Peischl, J.; Ryerson, T. B.; St Clair, J. M.; Crounse, J. D.; Wennberg, P. O.; Mikoviny, T.; Armin, W.; Scarino, A. J.; Hair, J. W.; Ferrare, R. A.

2017-12-01

Secondary Organic Aerosol (SOA) formed by uptake of isoprene epoxide (IEPOX), a key isoprene oxidation product under low-NO conditions (<100 pptv), has been recently shown to be a major contributor to the total aerosol burden in many regions of the world with high isoprene emissions, such as the SE US or Amazonia. In the present study, we have used Positive Matrix Factorization (PMF) to extract and identify IEPOX-SOA factors from data recorded by the CU High-Resolution Aerosol Mass Spectrometer (AMS) during the DC3 and SEAC4RS aircraft missions on the NASA DC-8. These campaigns sampled the continental US over the Spring of 2012 and the Summer of 2013, respectively. The contribution of IEPOX-SOA to total OA mass in the SE US was substantial for both DC3 (28% on average) and SEAC4RS flights (26%). IEPOX-SOA was observed in isoprene-rich areas in the W US, albeit with smaller contributions (up to 10% of OA). Highest concentrations of IEPOX-SOA were mostly found downwind and/or aloft of source regions, where IEPOX was already depleted but both inorganic sulfate and particle water/relative humidity were higher. IEPOX sulfate, a specific product of IEPOX uptake, correlates reasonably well with total IEPOX-SOA close to sources at low RH, with an observed contribution between 1-10% to total IEPOX-SOA in the SEUS. While the IEPOX-SOA mass spectrum near the ground was very similar to other ground studies in the SEUS, at higher altitudes differences were observed, likely reflecting aging chemistry aloft. In particular we identify, near the top of the boundary layer/cloud deck, a new OA factor likely resulting from aqueous oxidation of IEPOX-SOA. This factor closely matches the spectrum obtained in recent laboratory experiments simulating aqueous IEPOX-SOA aging, and contributed about 25% to total IEPOX-SOA during SEAC4RS; modeling of this new factor in GEOS-Chem will be presented. Measured IEPOX-SOA concentrations and their overall contribution to the total OA burden were substantially higher for SEAC4RS than those measured at the SOAS ground site the same summer (both total and site overflights). Average daily ground temperatures were substantially higher during the SEAC4RS period, with the overall dependence of concentrations of IEPOX-SOA closely following the isoprene source temperature dependence used in the MEGAN inventory.

The Influence of Monoterpene and Isoprene Nitrates on the Chemistry and Phase State of Secondary Organic Aerosol in a Low-NOx Mixed Deciduous/Coniferous Forest

NASA Astrophysics Data System (ADS)

Slade, J. H., Jr.; Shepson, P. B.; Desrochers, S. J.; Harvey, R. M.; Wallace, W.; Bui, A.; Griffin, R. J.; Kavassalis, S.; Shi, Q.; Murphy, J. G.; Cook, R.; Connor, M.; Ault, A. P.; Pratt, K.; Alwe, H. D.; Millet, D. B.; Bertman, S. B.; Stevens, P. S.; Wennberg, P. O.; Boor, B.; Petrucci, G.

2016-12-01

Particle phase state plays a key role in secondary organic aerosol (SOA) growth, reactive uptake of gas-phase radicals, and condensed phase reactions, influencing atmospheric composition and clouds. While biogenic SOA derived from isoprene and monoterpene oxidation can exhibit glassy or highly viscous semisolid phase states depending on relative humidity, the lifetimes of important SOA precursors including organic nitrates (ON) can depend on the liquid water content (LWC) and particle acidity. Reactions such as acid-catalyzed hydrolysis of particulate ON (pON) are especially sensitive to changes in aerosol LWC. However, the role of particle phase state on the chemistry of pON, and the chemical transformations of pON on the phase of SOA are poorly understood. During the summer of 2016, as part of the PROPHET - Atmospheric Measurements of Oxidants in Summer (AMOS) field study in a northern Michigan mixed deciduous/coniferous forest, we investigated the production of isoprene (IN) and monoterpene nitrates (MTN) at the ground and canopy levels and their role in particle formation, growth, and phase using a combination of high-resolution chemical ionization and aerosol mass spectrometry techniques, size distribution measurements, and particle bounce factors (BF) using two electrical low pressure impactors operating in parallel. Preliminary derived BF suggest the particles may be in a liquid-like state similar to those measured in other high-humidity and isoprene-rich regions such as the Amazon and Southeastern US. However, maxima in BF are observed during periods of high pON, NO, and IN during the day and high NO2 and MTN at night. Some periods were marked with low pON followed by an increase in particulate organic sulfate (pOS), and decrease in BF. Based on these observations, we hypothesize that acid-catalyzed hydrolysis of pON from IN- and MTN-derived SOA may be driving the transition of pON to pOS, leading to a change in the phase state of SOA. Preliminary results also indicate that the smallest particles can be acidic. We will further explore the role of LWC on the phase state of the particles applying ISORROPIA analysis. Although the PROPHET forest is generally NOx-limited, the work presented here highlights the potential importance of NOx and pON chemistry in dictating the phase state of SOA.

Organic Aerosol Formation Photoenhanced by the Formation of Secondary Photo-sensitizers in ageing Aerosols

NASA Astrophysics Data System (ADS)

Aregahegn, Kifle; Nozière, Barbara; George, Christian

2013-04-01

Humankind is facing a changing environment possibly due to anthropogenic stress on the atmosphere. In this context, aerosols play a key role by affecting the radiative climate forcing, hydrological cycle, and by their adverse effect on health. The role of organic compounds in these processes is however still poorly understood because of their massive chemical complexity and numerous transformations. This is particularly true for Secondary Organic Aerosol (SOA), which are produced in the atmosphere by organic gases. Traditionally, the driving forces for SOA growth is believed to be the partitioning onto aerosol seeds of condensable gases, either emitted primarily or resulting from the gas phase oxidation of organic gases. However, even the most up-to-date models based on such mechanisms can not account for the SOA mass observed in the atmosphere, suggesting the existence of other, yet unknown formation processes. The present study shows experimental evidence that particulate phase chemistry produces photo-sensitizers that lead to photo-induced formation and growth of secondary organic aerosol in the near UV and the presence of volatile organic compounds (VOC) such as terpenes. By means of an aerosol flow tube reactor equipped with Scanning Mobility Particle Sizer (SMPS) having Kr-85 source aerosol neutralizer, Differential Mobility Analyser (DMA) and Condensation Particle Sizer (CPC), we identified that traces of the aerosol phase product of glyoxal chemistry as is explained in Gallway et al., and Yu et al., namely imidazole-2-carboxaldehyde (IC) is a strong photo-sensitizer when irradiated by near-UV in the presence of volatile organic compounds such as terpenes. Furthermore, the influence of pH, type and concentration of VOCs, composition of seed particles, relative humidity and irradiation intensity on particle growth were studied. This novel photo-sensitizer contributed to more than 30% of SOA growth in 19min irradiation time in the presence of terpenes in the system and has linear relationship with the irradiation intensity. These results demonstrate that, upon ageing, organic aerosols can produce photo-sensitizers which auto-photo-catalyses their SOA growth.

Field Observation of Heterogeneous Formation of Dicarboxylic acids, Keto-carboxylic acids, α-Dicarbonyls and Nitrate in Xi'an, China during Asian dust storm periods

NASA Astrophysics Data System (ADS)

Wang, G.; Wang, J.; Ren, Y.; Li, J.

2015-12-01

To understand the formation mechanism of secondary organic aerosols (SOA) on dust surfaces, this study investigated the concentrations and compositions of dicarboxylic acids (C2-C11), keto-carboxylic acids (C3-C7), α-dicarbonyls and inorganic ions in size-segregated aerosols (9-stages) collected in Xi'an, China during the nondust storm and dust storm periods of 2009 and 2011. During the events the ambient particulate dicarboxylic acids were 932-2240 ng m-3, which are comparable and even higher than those in nondust periods. Molecular compositions of the above SOA are similar to those in nondust periods with oxalic acid being the leading species. In the presence of the dust storms, all the above mentioned SOA species in Xi'an were predominantly enriched on the coarse particles (>2.1μm), and oxalic acid well correlated with NO3- (R2=0.72, p<0.001) rather than SO42-.This phenomenon differs greatly from the SOA in any other nondust period that is characterized by an enrichment of oxalic acid in fine particles and a strong correlation of oxalic acid with SO42-. Our results further demonstrate that NO3- in the dust periods in Xi'an was mostly derived from secondary oxidation, whereas SO42- during the events was largely derived from surface soil of Gobi deserts. We propose a formation pathway to explain these observations, in which nitric acid and/or nitrogen oxides react with dust to produce Ca(NO3)2 and form a liquid phase on the surface of dust aerosols via water vapor-absorption of Ca(NO3)2, followed by a partitioning of the gas-phase water-soluble organic precursors (e.g.,glyoxal and methylglyoxal) into the aqueous-phase and a subsequent oxidation into oxalic acid. To the best of our knowledge, we found for the first time the enrichment of glyoxal and methylglyoxal on dust surface. Our data suggest an important role of nitrate in the heterogeneous formation process of SOA on the surface of Asian dust.

Field observation on secondary organic aerosols during Asian dust storm periods: Formation mechanism of oxalic acid and related compounds on dust surface

NASA Astrophysics Data System (ADS)

Wang, Gehui; Cheng, Chunlei; Meng, Jingjing; Huang, Yao; Li, Jianjun; Ren, Yanqin

2015-07-01

Chemical evolution of East Asian dust during transpacific transport has been given much attention for inorganic species such as sulfate, nitrate and ammonium. However, the role of organic species during the transport has almost entirely been ignored. To understand the formation mechanism of secondary organic aerosols (SOA) on dust surfaces, this study investigated the concentrations and compositions of dicarboxylic acids, keto-carboxylic acids, α-dicarbonyls and inorganic ions in size-segregated aerosols (9-stages) collected in Xi'an, central China during the two dust storm episodes in the springs of 2009 and 2011 and compared with those in nondust storm periods. During the events the ambient particulate dicarboxylic acids were 932-2240 ng m-3, which are comparable and even higher than those in nondust periods. Molecular compositions of the above SOA are similar to those in nondust periods with oxalic acid being the leading species. In the presence of the dust storms, all the above mentioned SOA species in Xi'an were predominantly enriched on the coarse particles (>2.1 μm), and oxalic acid well correlated with NO3- (R2 = 0.72, p < 0.001) rather than SO42-. This phenomenon differs greatly from the SOA in any other nondust period that is usually characterized by an enrichment of oxalic acid in fine mode and a strong correlation of oxalic acid with SO42-. We propose a formation pathway to explain these observations, in which nitric acid and/or nitrogen oxides react with dust to produce Ca(NO3)2 and form a liquid phase on the surface of dust aerosols via water vapor-absorption of Ca(NO3)2, followed by a partitioning of the gas-phase water-soluble organic precursors (e.g.,glyoxal and methylglyoxal) into the aqueous-phase and a subsequent oxidation into oxalic acid. To the best of our knowledge, we found for the first time the enrichment of glyoxal and methylglyoxal on dust surface. Our data suggest an important role of nitrate in the heterogeneous formation process of SOA on the surface of dust.

Integrable high order UWB pulse photonic generator based on cross phase modulation in a SOA-MZI.

PubMed

Moreno, Vanessa; Rius, Manuel; Mora, José; Muriel, Miguel A; Capmany, José

2013-09-23

We propose and experimentally demonstrate a potentially integrable optical scheme to generate high order UWB pulses. The technique is based on exploiting the cross phase modulation generated in an InGaAsP Mach-Zehnder interferometer containing integrated semiconductor optical amplifiers, and is also adaptable to different pulse modulation formats through an optical processing unit which allows to control of the amplitude, polarity and time delay of the generated taps.

How stimulation speed affects Event-Related Potentials and BCI performance.

PubMed

Höhne, Johannes; Tangermann, Michael

2012-01-01

In most paradigms for Brain-Computer Interfaces (BCIs) that are based on Event-Related Potentials (ERPs), stimuli are presented with a pre-defined and constant speed. In order to boost BCI performance by optimizing the parameters of stimulation, this offline study investigates the impact of the stimulus onset asynchrony (SOA) on ERPs and the resulting classification accuracy. The SOA is defined as the time between the onsets of two consecutive stimuli, which represents a measure for stimulation speed. A simple auditory oddball paradigm was tested in 14 SOA conditions with a SOA between 50 ms and 1000 ms. Based on an offline ERP analysis, the BCI performance (quantified by the Information Transfer Rate, ITR in bits/min) was simulated. A great variability in the simulated BCI performance was observed within subjects (N=11). This indicates a potential increase in BCI performance (≥ 1.6 bits/min) for ERP-based paradigms, if the stimulation speed is specified for each user individually.

Primary to secondary organic aerosol: evolution of organic emissions from mobile combustion sources

NASA Astrophysics Data System (ADS)

Presto, A. A.; Gordon, T. D.; Robinson, A. L.

2014-05-01

A series of smog chamber experiments were conducted to investigate the transformation of primary organic aerosol (POA) and formation of secondary organic aerosol (SOA) during the photooxidation of dilute exhaust from a fleet of gasoline and diesel motor vehicles and two gas-turbine engines. In experiments where POA was present in the chamber at the onset of photooxidation, positive matrix factorization (PMF) was used to determine separate POA and SOA factors from aerosol mass spectrometer data. A 2-factor solution, with one POA factor and one SOA factor, was sufficient to describe the organic aerosol for gasoline vehicles, diesel vehicles, and one of the gas-turbine engines. Experiments with the second gas-turbine engine required a 3-factor PMF solution with a POA factor and two SOA factors. Results from the PMF analysis were compared to the residual method for determining SOA and POA mass concentrations. The residual method apportioned a larger fraction of the organic aerosol mass as POA because it assumes that all mass at m / z 57 is associated with POA. The POA mass spectrum for the gasoline and diesel vehicles exhibited high abundances of the CnH2n+1 series of ions (m / z 43, 57, etc.) and was similar to the mass spectra of the hydrocarbon-like organic aerosol factor determined from ambient data sets with one exception, a diesel vehicle equipped with a diesel oxidation catalyst. POA mass spectra for the gas-turbine engines are enriched in the CnH2n-1 series of ions (m / z 41, 55, etc.), consistent with the composition of the lubricating oil used in these engines. The SOA formed from the three sources exhibits high abundances of m / z 44 and 43, indicative of mild oxidation. The SOA mass spectra are consistent with less-oxidized ambient SV-OOA (semivolatile oxygenated organic aerosols) and fall within the triangular region of f44 versus f43 defined by ambient measurements. However there is poor absolute agreement between the experimentally derived SOA mass spectra and ambient OOA factors, though this poor agreement should be expected based on the variability of ambient OOA factors. Van Krevelen analysis of the POA and SOA factors for gasoline and diesel experiments reveal slopes of -0.50 and -0.40, respectively. This suggests that the oxidation chemistry in these experiments is a combination of carboxylic acid and alcohol/peroxide formation, consistent with ambient oxidation chemistry.

Reactive Uptake of Ammonia to Secondary Organic Aerosols: Kinetics of Organonitrogen Formation

NASA Astrophysics Data System (ADS)

Liu, Yongchun; Liggio, John; Staebler, Ralf; Li, Shao-Meng

2015-04-01

Organonitrogen compounds originating from the heterogeneous uptake of NH3 or amines by secondary organic aerosol (SOA) has received significant attention recently. This is primarily due to its potential contribution to brown carbon (BrC), which can absorb solar radiation and affect climate. In addition, particle phase Organonitrogen species may represent a means of altering regional nitrogen cycles and/or nitrogen deposition patterns though the sequestering of ambient ammonia which is ultimately deposited downwind. Several reduced nitrogen forming heterogeneous reactions have previously been proposed, including Schiff base and/or Mannich reactions between NH3, ammonium salts or amines and organic carbonyl functional groups in particles. In order to assess and model the possible impact of Schiff base, Mannich or other N-forming reactions (via NH3) on the radiative forcing ability of ambient SOA and/or its impact on N-deposition, the kinetics of such heterogeneous reactions are required, and yet remain largely unknown. In the current study, the uptake kinetics of NH3 to form organonitrogen compounds in SOA derived from the ozonolysis of α-pinene and the OH oxidation of m-xylene is reported for the first time from experiments performed in a 9 m3 smog chamber equipped with a High Resolution Time-of-Flight Aerosol Mass Spectrometer. The results demonstrate that particle bound organonitrogen compounds are mainly formed by NH3 uptake onto newly formed SOA (~1 hr), but relatively little onto more aged SOA. The uptake coefficients of NH3 to form organonitrogen compounds (between 0-150 min) are on the order of 10-4-10-3 and are prominently dependent upon particle acidity. Following 6 hours of reaction, the total organonitrogen mass contributed up to 10.0±1.5 wt% and 31.5±4.4 wt% to the total SOA mass from the ozonolysis of α-pinene and OH oxidation of m-xylene. The influence of VOC precursors, seed particle acidity and gaseous NH3 concentration on the obtained uptake coefficients is described. The implications of the kinetics on atmospheric BrC and N-deposition are also discussed.

Particle-bound reactive oxygen species (PB-ROS) emissions and formation pathways in residential wood smoke under different combustion and aging conditions

NASA Astrophysics Data System (ADS)

Zhou, Jun; Zotter, Peter; Bruns, Emily A.; Stefenelli, Giulia; Bhattu, Deepika; Brown, Samuel; Bertrand, Amelie; Marchand, Nicolas; Lamkaddam, Houssni; Slowik, Jay G.; Prévôt, André S. H.; Baltensperger, Urs; Nussbaumer, Thomas; El-Haddad, Imad; Dommen, Josef

2018-05-01

Wood combustion emissions can induce oxidative stress in the human respiratory tract by reactive oxygen species (ROS) in the aerosol particles, which are emitted either directly or formed through oxidation in the atmosphere. To improve our understanding of the particle-bound ROS (PB-ROS) generation potential of wood combustion emissions, a suite of smog chamber (SC) and potential aerosol mass (PAM) chamber experiments were conducted under well-determined conditions for different combustion devices and technologies, different fuel types, operation methods, combustion regimes, combustion phases, and aging conditions. The PB-ROS content and the chemical properties of the aerosols were quantified by a novel ROS analyzer using the DCFH (2',7'-dichlorofluorescin) assay and a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS). For all eight combustion devices tested, primary PB-ROS concentrations substantially increased upon aging. The level of primary and aged PB-ROS emission factors (EFROS) were dominated by the combustion device (within different combustion technologies) and to a greater extent by the combustion regimes: the variability within one device was much higher than the variability of EFROS from different devices. Aged EFROS under bad combustion conditions were ˜ 2-80 times higher than under optimum combustion conditions. EFROS from automatically operated combustion devices were on average 1 order of magnitude lower than those from manually operated devices, which indicates that automatic combustion devices operated at optimum conditions to achieve near-complete combustion should be employed to minimize PB-ROS emissions. The use of an electrostatic precipitator decreased the primary and aged ROS emissions by a factor of ˜ 1.5 which is however still within the burn-to-burn variability. The parameters controlling the PB-ROS formation in secondary organic aerosol were investigated by employing a regression model, including the fractions of the mass-to-charge ratios m/z 44 and 43 in secondary organic aerosol (SOA; f44 - SOA and f43 - SOA), the OH exposure, and the total organic aerosol mass. The regression model results of the SC and PAM chamber aging experiments indicate that the PB-ROS content in SOA seems to increase with the SOA oxidation state, which initially increases with OH exposure and decreases with the additional partitioning of semi-volatile components with lower PB-ROS content at higher OA concentrations, while further aging seems to result in a decay of PB-ROS. The results and the special data analysis methods deployed in this study could provide a model for PB-ROS analysis of further wood or other combustion studies investigating different combustion conditions and aging methods.

Observation of SOA tracers at a mountainous site in Hong Kong: Chemical characteristics, origins and implication on particle growth.

PubMed

Lyu, X P; Guo, H; Cheng, H R; Wang, X M; Ding, X; Lu, H X; Yao, D W; Xu, C

2017-12-15

Secondary organic aerosol (SOA) is an important constituent of airborne fine particles. PM 2.5 (particles with aerodynamic diameters≤2.5μm) samples were collected at a mountainous site in Hong Kong in autumn of 2010, and analyzed for SOA tracers. Results indicated that the concentrations of isoprene SOA tracers (54.7±22.7ng/m 3 ) and aromatics SOA tracers (2.1±1.6ng/m 3 ) were on relatively high levels in Hong Kong. Secondary organic carbon (SOC) derived from isoprene, monoterpenes, sesquiterpenes and aromatics was estimated with the SOA tracer based approach, which constituted 0.35±0.15μg/m 3 (40.6±5.7%), 0.20±0.03μg/m 3 (30.4±5.5%), 0.05±0.02μg/m 3 (5.6±1.7%) and 0.26±0.20μg/m 3 (21.3±8.2%) of the total estimated SOC. Biogenic SOC (0.60±0.18μg/m 3 ) dominated over anthropogenic SOC (0.26±0.20μg/m 3 ) at this site. In addition to the total estimated SOC (17.8±4.6% of organic carbon (OC) in PM 2.5 ), primary organic carbon (POC) emitted from biomass burning also accounted for a considerable proportion of OC (11.6±3.2%). Insight into the OC origins found that regional transport significantly (p<0.05) elevated SOC from 0.37±0.17 to 1.04±0.39μg/m 3 . Besides, SOC load could also increase significantly if there was influence from local ship emission. Biomass burning related POC in regional air masses (0.81±0.24μg/m 3 ) was also higher (p<0.05) than that in samples affected by local air (0.29±0.35μg/m 3 ). Evidences indicated that SOA formation was closely related to new particle formation and the growth of nucleation mode particles, while biomass burning was responsible for some particle burst events in Hong Kong. This is the first SOA study in afforested areas of Hong Kong. Copyright © 2017 Elsevier B.V. All rights reserved.

Effects of Relative Humidity on Ozone and Secondary Organic Aerosol Formation from the Photooxidation of Benzene and Ethylbenzene

NASA Astrophysics Data System (ADS)

Jia, L.; Xu, Y.

2012-12-01

The formation of ozone and secondary organic aerosol from benzene-NOx and ethylbenzene-NOx irradiations was investigated under different levels of relative humidity (RH) in a smog chamber. The results show that the increase in RH can greatly reduce the maximum O3 by the transformation of -NO2 and -ONO2-containing products into the particle phase. In benzene irradiations, the SOA number concentration increases over 26 times as RH rises from <5% to 80%, and the intensity of the bands of -OH, -C=O and C-OH from SOA samples also greatly increases with RH. In ethylbenzene irradiations, ethylglyoxal favors the formation of monohydrate, which limits the RH effects. During evaporating processes, the lost substances have similar structures for both benzene and ethylbenzene. This demonstrates that ethyl-containing substances are very stable and difficult to evaporate. For benzene some of glyoxal hydrates are left to form C-O-C and C=O-containing species like hemiacetal and acetal after evaporation, whereas for ethylbenzene, glyoxal favors cross reactions with ethylglyoxal during the evaporating process. It is concluded that the increase in RH can irreversibly enhance the yields of SOA from both benzene and ethylbenzene.

Evidence for C5 organosulfur secondary organic aerosol components from in-cloud processing of isoprene: Role of reactive SO4 and SO3 radicals

NASA Astrophysics Data System (ADS)

Szmigielski, Rafal

2016-04-01

Isoprene, an aliphatic unsaturated hydrocarbon (C5H8), is a key volatile released to the atmosphere by broad-leaf forest vegetation. Data obtained from field and laboratory experiments clearly prove that isoprene is a precursor of secondary organic aerosol (SOA). In this work evidence is provided that in-cloud transformations of isoprene coupled with S(IV)-autoxidation is a potentially important route for aqueous SOA through the formation of polar organosulfates and organosulfites with MWs of 182, 180 and 166, 164, respectively. Recently, MW 182 organosulfates have been observed in substantial abundance in ambient fine aerosol. Results from comprehensive LC/(-)ESI-QTRAP-MS/MS analysis revealed oxygenated polar species with a C5 skeleton bearing - OSO3H (MW 182, 180) and -OSO2H (MW 166, 164) moieties. The structures of these products were elucidated by detailed interpretation of negative-ion electrospray-ionization mass spectra, and additionally, in case of the MW 182 organosulfates, by comparison of chromatographic and mass spectrometric profiles with synthesized standards. The formation of C5 organosulfur products is explained through sulfate/sulfite radical-induced oxidation in the aqueous particle phase.

Photooxidation of Alpha-Pinene at High Relative Humidity in the Presence of Increasing Concentrations of NOx

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yu, Yong; Ezell, Michael J.; Zelenyuk, Alla

2008-06-01

The photooxidation of ~1 ppm alpha-pinene in the presence of increasing concentrations of NO2 was studied in a Teflon chamber at relative humidities from 70 - 88% and temperatures from 296 - 304 K. The loss of alpha-pinene and formation of gas phase products were followed using proton transfer reaction mass spectrometry (PTR-MS). Gas phase reaction products measured by PTR-MS and their yields include formaldehyde (5 + 1%), formic acid (2.5 + 1.4%), methanol (0.6 + 0.3%), acetaldehyde (3.9 + 1.7%), acetic acid (10 + 2%), acetone (11.5 + 3.1%), pinonaldehyde (22 + 6%), and pinene oxide (0.9 + 0.1%).more » There was evidence of organic nitrates in the gas phase and small peaks were tentatively assigned to norpinonaldehyde, 4-oxopinonaldehyde, propanedial, 2,3-dioxobutanal and 3,5,6-trioxoheptanal or 3-hydroxymethyl-2,2-dimethylcyclobutylethanone. The formation and growth of new particles were followed using a scanning mobility particle sizer (SMPS), and their chemical composition was probed using single particle mass spectrometry (SPLAT II). SPLAT II analysis also provided measurements of the vacuum aerodynamic diameters of the newly formed secondary organic aerosol (SOA) particles and, in combination with the electrical mobility diameter, a particle density of 1.21 + 0.02 g cm-3 was calculated, 20% larger than often assumed in calculating SOA yields. SPLAT II showed that the suspended SOA consisted of a complex mixture of organic nitrates and organics, possibly including pinonic acid, pinic acid and trans-sobrerol. Three-wavelength light scattering measurements made using an integrating nephelometer were consistent with particles having a refractive index characteristic of organic compounds, but the data could not be well matched at all three wavelengths with a single refractive index. The effect of addition of cyclohexane or NO on particle formation showed that ozonolysis was the major mechanism of SOA formation in this system. However, unlike simple ozonolysis, organic nitrates are formed in both the gas and particle phases. Identifying and measuring specific organic nitrates in both the gas and particle phases in air may help to elucidate why SOA formation has been reported in field studies to be associated with polluted urban areas, yet the carbon in these particles is largely contemporary, i.e., non-fossil fuel carbon.« less

10.7 Gb/s uncompensated transmission over a 470 km hybrid fiber link with in-line SOAs using MLSE and duobinary signals.

PubMed

Downie, John D; Hurley, Jason; Mauro, Yihong

2008-09-29

We experimentally demonstrate uncompensated 8-channel wavelength division multiplexing (WDM) and single channel transmission at 10.7 Gb/s over a 470 km hybrid fiber link with in-line semiconductor optical amplifiers (SOAs). Two different forms of the duobinary modulation format are investigated and compared. Maximum Likelihood Sequence Estimation (MLSE) receiver technology is found to significantly mitigate nonlinear effects from the SOAs and to enable the long transmission, especially for optical duobinary signals derived from differential phase shift keying (DPSK) signals directly detected after narrowband optical filter demodulation. The MLSE also helps to compensate for a non-optimal Fabry-Perot optical filter demodulator.

Campholenic aldehyde ozonolysis: a possible mechanism for the formation of specific biogenic secondary organic aerosol constituents

NASA Astrophysics Data System (ADS)

Kahnt, A.; Iinuma, Y.; Mutzel, A.; Böge, O.; Claeys, M.; Herrmann, H.

2013-08-01

In the present study, campholenic aldehyde ozonolysis was performed to investigate pathways leading to specific biogenic secondary organic aerosol (SOA) marker compounds. Campholenic aldehyde, a known α-pinene oxidation product, is suggested to be a key intermediate in the formation of terpenylic acid upon α-pinene ozonolysis. It was reacted with ozone in the presence and absence of an OH radical scavenger leading to SOA formation with a yield of 0.75 and 0.8, respectively. The resulting oxidation products in the gas and particle phases were investigated employing a denuder/filter sampling combination. Gas-phase oxidation products bearing a carbonyl group, which were collected by the denuder, were derivatised with 2,4-dinitrophenylhydrazine (DNPH) followed by Liquid Chromatography/negative ion Electrospray Ionisation Time-of-Flight Mass Spectrometry analysis and were compared to the gas-phase compounds detected by online Proton-Transfer-Reaction Mass Spectrometry. Particle-phase products were also analysed, directly or after DNPH derivatisation, to derive information about specific compounds leading to SOA formation. Among the detected compounds, the aldehydic precursor of terpenylic acid was identified and its presence was confirmed in ambient aerosol samples from the DNPH derivatisation, accurate mass data, and MS2 and MS3 fragmentation studies. Furthermore, the present investigation sheds light on a reaction pathway leading to the formation of terpenylic acid, involving α-pinene, α-pinene oxide, campholenic aldehyde, and terpenylic aldehyde. Additionally, the formation of diaterpenylic acid acetate could be connected to campholenic aldehyde oxidation. The present study also provides insights into the source of other highly functionalised oxidation products (e.g. m/z 201, C9H14O5 and m/z 215, C10H16O5), which have been observed in ambient aerosol samples and smog chamber-generated monoterpene SOA. The m/z 201 and 215 compounds were tentatively identified as a C9- and C10-carbonyl-dicarboxylic acid, respectively, based on reaction mechanisms of campholenic aldehyde and ozone, detailed interpretation of mass spectral data, in conjunction with the formation of corresponding DNPH-derivatives.

The effects of isoprene and NOx on secondary organic aerosols formed through reversible and irreversible uptake to aerosol water

NASA Astrophysics Data System (ADS)

El-Sayed, Marwa M. H.; Ortiz-Montalvo, Diana L.; Hennigan, Christopher J.

2018-01-01

Isoprene oxidation produces water-soluble organic gases capable of partitioning to aerosol liquid water. The formation of secondary organic aerosols through such aqueous pathways (aqSOA) can take place either reversibly or irreversibly; however, the split between these fractions in the atmosphere is highly uncertain. The aim of this study was to characterize the reversibility of aqSOA formed from isoprene at a location in the eastern United States under substantial influence from both anthropogenic and biogenic emissions. The reversible and irreversible uptake of water-soluble organic gases to aerosol water was characterized in Baltimore, Maryland, USA, using measurements of particulate water-soluble organic carbon (WSOCp) in alternating dry and ambient configurations. WSOCp evaporation with drying was observed systematically throughout the late spring and summer, indicating reversible aqSOA formation during these times. We show through time lag analyses that WSOCp concentrations, including the WSOCp that evaporates with drying, peak 6 to 11 h after isoprene concentrations, with maxima at a time lag of 9 h. The absolute reversible aqSOA concentrations, as well as the relative amount of reversible aqSOA, increased with decreasing NOx / isoprene ratios, suggesting that isoprene epoxydiol (IEPOX) or other low-NOx oxidation products may be responsible for these effects. The observed relationships with NOx and isoprene suggest that this process occurs widely in the atmosphere, and is likely more important in other locations characterized by higher isoprene and/or lower NOx levels. This work underscores the importance of accounting for both reversible and irreversible uptake of isoprene oxidation products to aqueous particles.

Consideration of HOMs in α- and β-pinene SOA model

NASA Astrophysics Data System (ADS)

Gatzsche, Kathrin; Iinuma, Yoshiteru; Mutzel, Anke; Berndt, Torsten; Wolke, Ralf

2016-04-01

Secondary organic aerosol (SOA) is the major burden of the atmospheric organic particulate matter with 140 - 910 TgC yr-1 (Hallquist et al., 2009). SOA particles are formed via the oxidation of volatile organic carbons (VOCs), where the volatility of the VOCs is lowered due to the increase in their functionalization as well as their binding ability. Therefore, gaseous compounds can either nucleate to form new particles or condense on existing particles. The framework of SOA formation under natural conditions is very complex, because there are a multitude of gas-phase precursors, atmospheric degradation processes and products after oxidation. A lacking understanding about chemical and physical processes associated with SOA formation makes modeling of SOA processes difficult, leading to discrepancy between measured and modeled global SOA burdens. The present study utilizes a parcel model SPACCIM (SPectral Aerosol Cloud Chemistry Interaction Model, Wolke et al., 2005) that couples a multiphase chemical model with a microphysical model. For SOA modeling a further development of SPACCIM was necessary. Therefore, two components are added (i) a gas-phase chemistry mechanism for the VOC oxidation and (ii) a partitioning approach for the gas-to-particle phase transfer. An aggregated gas-phase chemistry mechanism for α- and β-pinene was adapted from Chen and Griffin (2005). For the phase transfer an absorptive partitioning approach (Pankow, 1994) and a kinetic approach (Zaveri et al., 2014) are implemented. Whereby the kinetic approach serves some advantages. The organic aerosol can be resolved in different size sections, whereby the particle radius is involved in the partitioning equations. The phase state of the organic material and the reactivity of the organic compounds in the particle-phase directly influence the modeled SOA yields. Recently, highly oxidized multifunctional organic compounds (HOMs) were found in the gas phase from lab and field studies. They are also known as extremely low-volatile organic compounds (ELVOCs) (Ehn et al. 2014). The importance of HOMs for the early aerosol growth makes them indispensable in SOA modeling. Thus, we included HOMs in our model framework. The measurements from the institute's own smog chamber LEAK are used as a base for model evaluation and process analysis, especially since HOMs were lately identified from LEAK data (Mutzel et al., 2015). The presentation will provide a sensitivity study for the kinetic approach as well as a comparison of measured and modeled SOA yields. References: Ehn, M., Thornton, J. A., Kleist, E. et al. (2014) Nature, 506, 476 - 479 Hallquist, M., Wenger, J. C., Baltensperger, U., et al. (2009) Atmos. Chem. Phys., 9, 5155 - 5236 Mutzel, A., Poulain, L., Berndt, T. et al. (2015) Environ. Sci. Technol., 49, 7754 - 7761 Pankow, J. F. (1994) Atmos. Environ., 28, 2, 189 - 193 Wolke, R., Sehili, A. M., Simmel, M., Knoth, O., Tilgner, A. and Herrmann, H. (2005) Atmos. Environ., 39, 4375 - 4388 Zaveri, R. A., Easter, R. C., Shilling J. E. and Seinfeld, J. H. (2014) Atmos. Chem. Phys., 14, 5153 - 5181

Characterization of a real-time tracer for isoprene epoxydiols-derived secondary organic aerosol (IEPOX-SOA) from aerosol mass spectrometer measurements

NASA Astrophysics Data System (ADS)

Hu, W. W.; Campuzano-Jost, P.; Palm, B. B.; Day, D. A.; Ortega, A. M.; Hayes, P. L.; Krechmer, J. E.; Chen, Q.; Kuwata, M.; Liu, Y. J.; de Sá, S. S.; McKinney, K.; Martin, S. T.; Hu, M.; Budisulistiorini, S. H.; Riva, M.; Surratt, J. D.; St. Clair, J. M.; Isaacman-Van Wertz, G.; Yee, L. D.; Goldstein, A. H.; Carbone, S.; Brito, J.; Artaxo, P.; de Gouw, J. A.; Koss, A.; Wisthaler, A.; Mikoviny, T.; Karl, T.; Kaser, L.; Jud, W.; Hansel, A.; Docherty, K. S.; Alexander, M. L.; Robinson, N. H.; Coe, H.; Allan, J. D.; Canagaratna, M. R.; Paulot, F.; Jimenez, J. L.

2015-10-01

Substantial amounts of secondary organic aerosol (SOA) can be formed from isoprene epoxydiols (IEPOX), which are oxidation products of isoprene mainly under low-NO conditions. Total IEPOX-SOA, which may include SOA formed from other parallel isoprene oxidation pathways, was quantified by applying positive matrix factorization (PMF) to aerosol mass spectrometer (AMS) measurements. The IEPOX-SOA fractions of organic aerosol (OA) in multiple field studies across several continents are summarized here and show consistent patterns with the concentration of gas-phase IEPOX simulated by the GEOS-Chem chemical transport model. During the Southern Oxidant and Aerosol Study (SOAS), 78 % of PMF-resolved IEPOX-SOA is accounted by the measured IEPOX-SOA molecular tracers (2-methyltetrols, C5-Triols, and IEPOX-derived organosulfate and its dimers), making it the highest level of molecular identification of an ambient SOA component to our knowledge. An enhanced signal at C5H6O+ (m/z 82) is found in PMF-resolved IEPOX-SOA spectra. To investigate the suitability of this ion as a tracer for IEPOX-SOA, we examine fC5H6O (fC5H6O= C5H6O+/OA) across multiple field, chamber, and source data sets. A background of ~ 1.7 ± 0.1 ‰ (‰ = parts per thousand) is observed in studies strongly influenced by urban, biomass-burning, and other anthropogenic primary organic aerosol (POA). Higher background values of 3.1 ± 0.6 ‰ are found in studies strongly influenced by monoterpene emissions. The average laboratory monoterpene SOA value (5.5 ± 2.0 ‰) is 4 times lower than the average for IEPOX-SOA (22 ± 7 ‰), which leaves some room to separate both contributions to OA. Locations strongly influenced by isoprene emissions under low-NO levels had higher fC5H6O (~ 6.5 ± 2.2 ‰ on average) than other sites, consistent with the expected IEPOX-SOA formation in those studies. fC5H6O in IEPOX-SOA is always elevated (12-40 ‰) but varies substantially between locations, which is shown to reflect large variations in its detailed molecular composition. The low fC5H6O (< 3 ‰) reported in non-IEPOX-derived isoprene-SOA from chamber studies indicates that this tracer ion is specifically enhanced from IEPOX-SOA, and is not a tracer for all SOA from isoprene. We introduce a graphical diagnostic to study the presence and aging of IEPOX-SOA as a triangle plot of fCO2 vs. fC5H6O. Finally, we develop a simplified method to estimate ambient IEPOX-SOA mass concentrations, which is shown to perform well compared to the full PMF method. The uncertainty of the tracer method is up to a factor of ~ 2, if the fC5H6O of the local IEPOX-SOA is not available. When only unit mass-resolution data are available, as with the aerosol chemical speciation monitor (ACSM), all methods may perform less well because of increased interferences from other ions at m/z 82. This study clarifies the strengths and limitations of the different AMS methods for detection of IEPOX-SOA and will enable improved characterization of this OA component.

Characterization of a real-time tracer for isoprene epoxydiols-derived secondary organic aerosol (IEPOX-SOA) from aerosol mass spectrometer measurements

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hu, W. W.; Campuzano-Jost, P.; Palm, B. B.

Substantial amounts of secondary organic aerosol (SOA) can be formed from isoprene epoxydiols (IEPOX), which are oxidation products of isoprene mainly under low-NO conditions. Total IEPOX-SOA, which may include SOA formed from other parallel isoprene oxidation pathways, was quantified by applying positive matrix factorization (PMF) to aerosol mass spectrometer (AMS) measurements. The IEPOX-SOA fractions of organic aerosol (OA) in multiple field studies across several continents are summarized here and show consistent patterns with the concentration of gas-phase IEPOX simulated by the GEOS-Chem chemical transport model. During the Southern Oxidant and Aerosol Study (SOAS), 78 % of PMF-resolved IEPOX-SOA is accountedmore » by the measured IEPOX-SOA molecular tracers (2-methyltetrols, C5-Triols, and IEPOX-derived organosulfate and its dimers), making it the highest level of molecular identification of an ambient SOA component to our knowledge. An enhanced signal at C 5H 6O + ( m/z 82) is found in PMF-resolved IEPOX-SOA spectra. To investigate the suitability of this ion as a tracer for IEPOX-SOA, we examine f C5H6O ( f C5H6O= C 5H 6O +/OA) across multiple field, chamber, and source data sets. A background of ~ 1.7 ± 0.1 ‰ (‰ = parts per thousand) is observed in studies strongly influenced by urban, biomass-burning, and other anthropogenic primary organic aerosol (POA). Higher background values of 3.1 ± 0.6 ‰ are found in studies strongly influenced by monoterpene emissions. The average laboratory monoterpene SOA value (5.5 ± 2.0 ‰) is 4 times lower than the average for IEPOX-SOA (22 ± 7 ‰), which leaves some room to separate both contributions to OA. Locations strongly influenced by isoprene emissions under low-NO levels had higher f C5H6O (~ 6.5 ± 2.2 ‰ on average) than other sites, consistent with the expected IEPOX-SOA formation in those studies. f C5H6O in IEPOX-SOA is always elevated (12–40 ‰) but varies substantially between locations, which is shown to reflect large variations in its detailed molecular composition. The low f C5H6O (< 3 ‰) reported in non-IEPOX-derived isoprene-SOA from chamber studies indicates that this tracer ion is specifically enhanced from IEPOX-SOA, and is not a tracer for all SOA from isoprene. We introduce a graphical diagnostic to study the presence and aging of IEPOX-SOA as a triangle plot of f CO2 vs. f C5H6O. Finally, we develop a simplified method to estimate ambient IEPOX-SOA mass concentrations, which is shown to perform well compared to the full PMF method. The uncertainty of the tracer method is up to a factor of ~ 2, if the f C5H6O of the local IEPOX-SOA is not available. When only unit mass-resolution data are available, as with the aerosol chemical speciation monitor (ACSM), all methods may perform less well because of increased interferences from other ions at m/z 82. This study clarifies the strengths and limitations of the different AMS methods for detection of IEPOX-SOA and will enable improved characterization of this OA component.« less

Characterization of a real-time tracer for isoprene epoxydiols-derived secondary organic aerosol (IEPOX-SOA) from aerosol mass spectrometer measurements

DOE PAGES

Hu, W. W.; Campuzano-Jost, P.; Palm, B. B.; ...

2015-10-23

Substantial amounts of secondary organic aerosol (SOA) can be formed from isoprene epoxydiols (IEPOX), which are oxidation products of isoprene mainly under low-NO conditions. Total IEPOX-SOA, which may include SOA formed from other parallel isoprene oxidation pathways, was quantified by applying positive matrix factorization (PMF) to aerosol mass spectrometer (AMS) measurements. The IEPOX-SOA fractions of organic aerosol (OA) in multiple field studies across several continents are summarized here and show consistent patterns with the concentration of gas-phase IEPOX simulated by the GEOS-Chem chemical transport model. During the Southern Oxidant and Aerosol Study (SOAS), 78 % of PMF-resolved IEPOX-SOA is accountedmore » by the measured IEPOX-SOA molecular tracers (2-methyltetrols, C5-Triols, and IEPOX-derived organosulfate and its dimers), making it the highest level of molecular identification of an ambient SOA component to our knowledge. An enhanced signal at C 5H 6O + ( m/z 82) is found in PMF-resolved IEPOX-SOA spectra. To investigate the suitability of this ion as a tracer for IEPOX-SOA, we examine f C5H6O ( f C5H6O= C 5H 6O +/OA) across multiple field, chamber, and source data sets. A background of ~ 1.7 ± 0.1 ‰ (‰ = parts per thousand) is observed in studies strongly influenced by urban, biomass-burning, and other anthropogenic primary organic aerosol (POA). Higher background values of 3.1 ± 0.6 ‰ are found in studies strongly influenced by monoterpene emissions. The average laboratory monoterpene SOA value (5.5 ± 2.0 ‰) is 4 times lower than the average for IEPOX-SOA (22 ± 7 ‰), which leaves some room to separate both contributions to OA. Locations strongly influenced by isoprene emissions under low-NO levels had higher f C5H6O (~ 6.5 ± 2.2 ‰ on average) than other sites, consistent with the expected IEPOX-SOA formation in those studies. f C5H6O in IEPOX-SOA is always elevated (12–40 ‰) but varies substantially between locations, which is shown to reflect large variations in its detailed molecular composition. The low f C5H6O (< 3 ‰) reported in non-IEPOX-derived isoprene-SOA from chamber studies indicates that this tracer ion is specifically enhanced from IEPOX-SOA, and is not a tracer for all SOA from isoprene. We introduce a graphical diagnostic to study the presence and aging of IEPOX-SOA as a triangle plot of f CO2 vs. f C5H6O. Finally, we develop a simplified method to estimate ambient IEPOX-SOA mass concentrations, which is shown to perform well compared to the full PMF method. The uncertainty of the tracer method is up to a factor of ~ 2, if the f C5H6O of the local IEPOX-SOA is not available. When only unit mass-resolution data are available, as with the aerosol chemical speciation monitor (ACSM), all methods may perform less well because of increased interferences from other ions at m/z 82. This study clarifies the strengths and limitations of the different AMS methods for detection of IEPOX-SOA and will enable improved characterization of this OA component.« less

US NDC Modernization: Service Oriented Architecture Study Status

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hamlet, Benjamin R.; Encarnacao, Andre Villanova; Harris, James M.

2014-12-01

This report is a progress update on the USNDC Modernization Service Oriented Architecture (SOA) study describing results from Inception Iteration 1, which occurred between October 2012 and March 2013. The goals during this phase are 1) discovering components of the system that have potential service implementations, 2) identifying applicable SOA patterns for data access, service interfaces, and service orchestration/choreography, and 3) understanding performance tradeoffs for various SOA patterns

Formation kinetics and abundance of organic nitrates in α-pinene ozonolysis

NASA Astrophysics Data System (ADS)

Berkemeier, Thomas; Ammann, Markus; Pöschl, Ulrich; Shiraiwa, Manabu

2016-04-01

Formation of organic nitrates affects the total atmospheric budget of oxidized nitrogen (NOy) and alters the total aerosol mass yield from secondary sources. We investigated the formation of organic nitrate species during ozonolysis of α-pinene and subsequent formation of secondary organic aerosols (SOA) using the short-lived radioactive tracer 13N inside an aerosol flow reactor (Ammann et al., 2001). The results represent direct measurements of the organic nitrate content of α-pinene secondary aerosol and give insight into the kinetics of organic nitrate formation. Organic nitrates constituted up to 40 % of aerosol mass with a pronounced influence during the initial period of particle growth. Kinetic modelling, as well as additional experiments using OH scavengers and UV irradiation, suggests that organic peroxy radicals (RO2) from the reaction of α-pinene with secondarily produced OH are important intermediates in the organic nitrate formation process. Direct oxidation of α-pinene by NO3 was found to be a less efficient pathway for formation of particle phase nitrate. The organic nitrate content decreased very slightly with an increase of relative humidity on the experimental time scale. The experiments show a tight correlation between organic nitrate content and SOA number concentrations, implying that organic nitrates play an important role in nucleation and growth of nanoparticles. Since present in large amounts in organic aerosol, organic nitrates deposited in the lung might have implications for human health as they release nitric acid upon hydrolysis, especially in regions influenced by urban pollution and large sources of monoterpene SOA precursors. References Ammann et al. (2001) Radiochimica Acta 89, 831.

Identification of light absorbing oligomers from glyoxal and methylglyoxal aqueous processing: a comparative study at the molecular level

NASA Astrophysics Data System (ADS)

Finessi, Emanuela; Hamilton, Jacqueline; Rickard, Andrew; Baeza-Romero, Maria; Healy, Robert; Peppe, Salvatore; Adams, Tom; Daniels, Mark; Ball, Stephen; Goodall, Iain; Monks, Paul; Borras, Esther; Munoz, Amalia

2014-05-01

Numerous studies point to the reactive uptake of gaseous low molecular weight carbonyls onto atmospheric waters (clouds/fog droplets and wet aerosols) as an important SOA formation route not yet included in current models. However, the evaluation of these processes is challenging because water provides a medium for a complex array of reactions to take place such as self-oligomerization, aldol condensation and Maillard-type browning reactions in the presence of ammonium salts. In addition to adding to SOA mass, aqueous chemistry products have been shown to include light absorbing, surface-active and high molecular weight oligomeric species, and can therefore affect climatically relevant aerosol properties such as light absorption and hygroscopicity. Glyoxal (GLY) and methylglyoxal (MGLY) are the gaseous carbonyls that have perhaps received the most attention to date owing to their ubiquity, abundance and reactivity in water, with the majority of studies focussing on bulk physical properties. However, very little is known at the molecular level, in particular for MGLY, and the relative potential of these species as aqueous SOA precursors in ambient air is still unclear. We have conducted experiments with both laboratory solutions and chamber-generated particles to simulate the aqueous processing of GLY and MGLY with ammonium sulphate (AS) under typical atmospheric conditions and investigated their respective aging products. Both high performance liquid chromatography coupled with UV-Vis detection and ion trap mass spectrometry (HPLC-DAD-MSn) and high resolution mass spectrometry (FTICRMS) have been used for molecular identification purposes. Comprehensive gas chromatography with nitrogen chemiluminescence detection (GCxGC-NCD) has been applied for the first time to these systems, revealing a surprisingly high number of nitrogen-containing organics (ONs), with a large extent of polarities. GCxGC-NCD proved to be a valuable tool to determine overall amount and rates of formation of the light absorbing species. Data obtained from laboratory solutions were merged with those from SOA generated in chamber experiments conducted at the European PhotoReactor (EUPHORE) from the uptake of gas-phase GLY and MGLY onto AS seeds. While in general the results confirm previous studies in ranking MGLY as more effective than GLY in brown carbon formation, the link between overall optical properties and the identified molecular species is reported here for the first time for both systems.

Secondary organic aerosol formation from isoprene photo-oxidation during cloud condensation-evaporation cycles (CUMULUS project)

NASA Astrophysics Data System (ADS)

Brégonzio-Rozier, Lola; Siekmann, Frank; Giorio, Chiara; Temime-Roussel, Brice; Pangui, Edouard; Morales, Sébastien; Gratien, Aline; Ravier, Sylvain; Monod, Anne; Doussin, Jean-Francois

2014-05-01

It is acknowledged that atmospheric photo-oxidation of Volatile Organic Compounds (VOC) leads to the formation of less volatile oxidized species. These compounds can undergo gas-to-particle conversion, leading to the formation of Secondary Organic Aerosols (SOA) in the atmosphere. Nevertheless, some of these oxidized species are water soluble and could also partition into cloud droplets. Higher molecular weight and less volatile compounds could be produced in the aqueous phase and remain in the particle phase after water evaporation (Ervens et al., 2011). The aim of the present work is to study SOA formation in the presence of cloud droplets during isoprene photo-oxidation. To this end, an original multiphase approach in a simulation chamber was set up in order to investigate the chemistry occurring in the gaseous, particulate and aqueous phases, and the exchange between these phases. Experiments were performed, within the CUMULUS project (CloUd MULtiphase chemistry of organic compoUndS in the troposphere), in the CESAM chamber (Wang et al., 2011). This chamber was designed to investigate multiphase processes under realistic actinic flux, and accurate control of both temperature and relative humidity. A specific protocol was set up to produce cloud events in the simulation chamber exhibiting a significant lifetime in the presence of light (10-12 minutes). By using this protocol, many clouds could be generated in a single experiment. In each experiment, around 800 ppb of isoprene was injected in the chamber together with HONO under dry conditions before irradiation. A Fourier Transform Infrared Spectrometer (FTIR), a Proton Transfer Reaction Mass Spectrometer (PTR-TOF-MS) and NOx and O3 analyzers were used to analyze gas-phase composition. Dried SOA size distributions and total concentrations were measured by a Scanning Mobility Particle Sizer (SMPS). An Aerodyne High Resolution Time-Of-Flight Aerosol Mass Spectrometer (HR-TOF-AMS) was also used to investigate aerosol composition. Cloud droplets size distributions were measured by a white light Optical Particle Counter (OPC). In all experiments, the dissolution of gaseous oxidation products into aqueous phase and SOA production have been observed during isoprene photo-oxidation in the presence of a cloud event. The overall results in additional SOA mass production and the dynamic of gaseous oxidation products and SOA mass concentrations will be presented. Ervens, B. et al. (2011). Atmospheric Chemistry and Physics 11(21): 11069-11102. Wang, J. et al. (2011). Atmospheric Measurement Techniques 4(11): 2465-2494.

Biogenic VOC Oxidation is Modulated by Anthropogenic Pollution in the South East US

NASA Astrophysics Data System (ADS)

Misztal, P. K.; Romer, P.; Duffey, K.; Cohen, R. C.; Kaser, L.; Seco, R.; Park, J.; Kim, S.; Guenther, A. B.; Goldstein, A. H.

2013-12-01

Biogenic volatile organic compounds (VOC) are known to play important roles for atmospheric chemistry, formation of secondary organic aerosol (SOA), and thus climate. However, the impacts of anthropogenic emissions on the BVOC oxidation mechanisms and SOA formation processes are not yet well understood. The SOAS summer 2013 campaign goals include looking holistically at physicochemical processes of BVOC emission, oxidation, and subsequent SOA formation and the role of anthropogenic emissions in those processes. Gas-phase composition changes of the broad range of VOCs were measured by PTR-ToF-MS at the Centreville SEARCH site located in a mixed deciduous forest near Brent, Alabama. The instrument sampled from the top of the tower at a high acquisition rate (10 Hz) using an inlet collocated with other measurements (wind, radicals, nitrogen oxides, etc.). Isoprene concentrations were extremely high, peaking at up to approximately 10 ppb during the hottest and sunniest days. Isoprene oxidation chemistry was clearly affected by anthropogenic influences. The rate of isoprene oxidation and the abundance of the first (MVK, MAC, etc.) and second (hydroxyacetone, etc.) order products were significantly different under cleaner conditions than under more polluted conditions. Isoprene oxidation likely is more dominated by the hydroperoxyl pathway under clean conditions while the NO pathway is more important under pollution conditions. Observations of the full range of detected isoprene oxidation products will be discussed and examined under relatively clean and polluted conditions. Both daytime and nighttime oxidation pathways will be examined, and comparison with airborne measurements will be shown to relate our ground based observations to more regional photochemical VOC processing.

Modeling the Explicit Chemistry of Anthropogenic and Biogenic Organic Aerosols

DOE Office of Scientific and Technical Information (OSTI.GOV)

Madronich, Sasha

2015-12-09

The atmospheric burden of Secondary Organic Aerosols (SOA) remains one of the most important yet uncertain aspects of the radiative forcing of climate. This grant focused on improving our quantitative understanding of SOA formation and evolution, by developing, applying, and improving a highly detailed model of atmospheric organic chemistry, the Generation of Explicit Chemistry and Kinetics of Organics in the Atmosphere (GECKO-A) model. Eleven (11) publications have resulted from this grant.

Secondary organic aerosol: a comparison between foggy and nonfoggy days.

PubMed

Kaul, D S; Gupta, Tarun; Tripathi, S N; Tare, V; Collett, J L

2011-09-01

Carbonaceous species, meteorological parameters, trace gases, and fogwater chemistry were measured during winter in the Indian city of Kanpur to study secondary organic aerosol (SOA) during foggy and clear (nonfoggy) days. Enhanced SOA production was observed during fog episodes. It is hypothesized that aqueous phase chemistry in fog drops is responsible for increasing SOA production. SOA concentrations on foggy days exceeded those on clear days at all times of day; peak foggy day SOA concentrations were observed in the evening vs peak clear day SOA concentrations which occurred in the afternoon. Changes in biomass burning emissions on foggy days were examined because of their potential to confound estimates of SOA production based on analysis of organic to elemental carbon (OC/EC) ratios. No evidence of biomass burning influence on SOA during foggy days was found. Enhanced oxidation of SO(2) to sulfate during foggy days was observed, possibly causing the regional aerosol to become more acidic. No evidence was found in this study, either, for effects of temperature or relative humidity on SOA production. In addition to SOA production, fogs can also play an important role in cleaning the atmosphere of carbonaceous aerosols. Preferential scavenging of water-soluble organic carbon (WSOC) by fog droplets was observed. OC was found to be enriched in smaller droplets, limiting the rate of OC deposition by droplet sedimentation. Lower EC concentrations were observed on foggy days, despite greater stagnation and lower mixing heights, suggesting fog scavenging and removal of EC was active as well.

Molecular characterization and volatility evolution of α-pinene ozonolysis SOA during isothermal evaporations

NASA Astrophysics Data System (ADS)

D'Ambro, E.; Schobesberger, S.; Lopez-Hilfiker, F.; Shilling, J. E.; Lee, B. H.; Thornton, J. A.

2017-12-01

α-Pinene (C10H16), the most abundantly emitted monoterpene, is a large contributor to global biogenic secondary organic aerosol (SOA) budgets due to its high SOA yields upon oxidation. We probe the volatility and evaporation behavior upon dilution of α-pinene SOA to further our understanding of the nascent volatility distribution, viscosity, and how these evolve in time absent photochemical oxidation. We present molecular composition measurements of the gas and particle phases of α-pinene ozonolysis SOA formed at 0% and 50% relative humidity (RH), followed by room-temperature evaporation in ultra-high purity N2 humidified to 20-90% RH. Experiments were performed in the Pacific Northwest National Laboratory 10.6 m3 and the University of Washington 0.7 m3 environmental chambers utilizing a Filter Inlet for Gases and AEROsols (FIGAERO) coupled to a high-resolution time of flight chemical ionization mass spectrometer utilizing iodide adduct ionization. We present novel insights into the total mass that evaporates as a function of time from 10 min to 24 hours without heating, the molecular speciation of the evaporate, as well as the effective volatility and composition of the SOA mass remaining. Consistent with previous studies, we find two stages of evaporation: a rapid loss of a large portion of the total signal over the course of ≤3 hours, followed by a stage of much slower evaporation over the proceeding 21 hours. Varying the RH of formation effects evaporation rate on timescales ≤3 hours, however the mass fraction remaining after 24 hours converges to 30-50% under all formation and evaporation RHs. We simulate the evaporation behavior and remaining fractions desorbed via temperature programmed thermal desorption to derive effective saturation vapor concentrations, mass accommodation coefficients, and rates of chemical evolution producing both higher and lower volatility components during the evaporation time period.

Aqueous phase oligomerization of methyl vinyl ketone through photooxidation - Part 1: Aging processes of oligomers

NASA Astrophysics Data System (ADS)

Renard, P.; Siekmann, F.; Salque, G.; Smaani, A.; Demelas, C.; Coulomb, B.; Vassalo, L.; Ravier, S.; Temime-Roussel, B.; Voisin, D.; Monod, A.

2014-06-01

Secondary organic aerosol (SOA) represents a substantial part of organic aerosol, which affects climate and human health. It is now accepted that one of the important pathways of SOA formation occurs via aqueous phase chemistry in the atmosphere. Recently, we have shown in a previous study (Renard et al., 2013) the mechanism of oligomerization of MVK (methyl vinyl ketone), and suggested that unsaturated water soluble organic compounds (UWSOC) might efficiently form SOA in wet aerosol particles, even for weakly soluble ones like MVK. The atmospheric relevance of these processes is explored by means of process model studies (in a companion paper). In the present study we investigate the aging of these aqueous phase MVK-oligomers (Part 1). We compared aqueous phase composition and SOA composition after nebulization, mainly by means of UPLC-ESI-MS and AMS, respectively. Both instruments match and show similar trend of oligomer formation and aging. The SMPS analysis performed on the nebulized solutions allow to quantify these SOA and to measure their mass yields. We have highlighted in the current study that MVK •OH-oxidation undergoes kinetic competition between functionalization and oligomerization. The SOA composition and its evolution highly depend on the precursor initial concentration. We determined the threshold of MVK concentration, i.e. 2 mM, from which oligomerization prevails over functionalization. Hence, at these concentrations, •OH-oxidation of MVK forms oligomers that are SV-OOA, with low O / C and high f43. Oligomers are then fragmented, via unidentified intermediates that have the properties of LV-OOA which then end into succinic, malonic and oxalic diacids. For lower initial MVK concentrations, the oligomerization is not the major process, and functionalization dominates, resulting in small carbonyls, dicarbonyls and mainly monoacids. The aging of these oligomers could be an explanation for the presence of a part of the diacids observed in aerosol.

Role of secondary aerosols in haze formation in summer in the Megacity Beijing.

PubMed

Han, Tingting; Liu, Xingang; Zhang, Yuanhang; Qu, Yu; Zeng, Limin; Hu, Min; Zhu, Tong

2015-05-01

A field experiment from 18 August to 8 September 2006 in Beijing, China, was carried out. A hazy day was defined as visibility

High-time resolved measurements of biogenic and anthropogenic secondary organic aerosol precursors and products in urban air

NASA Astrophysics Data System (ADS)

Flores, Rosa M.; Doskey, Paul V.

2016-04-01

Volatile organic compounds (VOCs), which are present in the atmosphere entirely in the gas phase are directly emitted by biogenic (~1089 Tg yr-1) and anthropogenic sources (~185 Tg yr-1). However, the sources and molecular speciation of intermediate VOCs (IVOCs), which are for the most part also present almost entirely in the gas phase, are not well characterized. The VOCs and IVOCs participate in reactions that form ozone and semivolatile OC (SVOC) that partition into the aerosol phase. Formation and evolution of secondary organic aerosol (SOA) are part of a complex dynamic process that depends on the molecular speciation and concentration of VOCs, IVOCs, primary organic aerosol (POA), and the level of oxidants (NO3, OH, O3). The current lack of understanding of OA properties and their impact on radiative forcing, ecosystems, and human health is partly due to limitations of models to predict SOA production on local, regional, and global scales. More accurate forecasting of SOA production requires high-temporal resolution measurement and molecular characterization of SOA precursors and products. For the subject study, the IVOCs and aerosol-phase organic matter were collected using the high-volume sampling technique and were analyzed by multidimensional gas chromatography with time-of-flight mass spectrometry (GCxGC-ToFMS). The IVOCs included terpenes, terpenoids, n-alkanes, branched alkanes, isoprenoids, alkylbenzenes, cycloalkylbenzenes, PAH, alkyl PAH, and an unresolved complex mixture (UCM). Diurnal variations of OA species containing multiple oxygenated functionalities and selected SOA tracers of isorprene, α-pinene, toluene, cyclohexene, and n-dodecane oxidation were also quantified. The data for SOA precursor and oxidation products presented here will be useful for evaluating the ability of molecular-specific SOA models to forecast SOA production in and downwind of urban areas.

Volatility and lifetime against OH heterogeneous reaction of ambient isoprene-epoxydiols-derived secondary organic aerosol (IEPOX-SOA)

DOE PAGES

Hu, Weiwei; Palm, Brett B.; Day, Douglas A.; ...

2016-09-19

Isoprene-epoxydiols-derived secondary organic aerosol (IEPOX-SOA) can contribute substantially to organic aerosol (OA) concentrations in forested areas under low NO conditions, hence significantly influencing the regional and global OA budgets, accounting, for example, for 16–36 % of the submicron OA in the southeastern United States (SE US) summer. Particle evaporation measurements from a thermodenuder show that the volatility of ambient IEPOX-SOA is lower than that of bulk OA and also much lower than that of known monomer IEPOX-SOA tracer species, indicating that IEPOX-SOA likely exists mostly as oligomers in the aerosol phase. The OH aging process of ambient IEPOX-SOA was investigated withmore » an oxidation flow reactor (OFR). New IEPOX-SOA formation in the reactor was negligible, as the OFR does not accelerate processes such as aerosol uptake and reactions that do not scale with OH. Simulation results indicate that adding  ∼  100 µg m −3 of pure H 2SO 4 to the ambient air allows IEPOX-SOA to be efficiently formed in the reactor. The heterogeneous reaction rate coefficient of ambient IEPOX-SOA with OH radical ( k OH) was estimated as 4.0 ± 2.0  ×  10 −13 cm 3 molec −1 s −1, which is equivalent to more than a 2-week lifetime. A similar k OH was found for measurements of OH oxidation of ambient Amazon forest air in an OFR. At higher OH exposures in the reactor (>  1  ×  10 12 molec cm −3 s), the mass loss of IEPOX-SOA due to heterogeneous reaction was mainly due to revolatilization of fragmented reaction products. We report, for the first time, OH reactive uptake coefficients ( γ OH =  0.59 ± 0.33 in SE US and γ OH =  0.68 ± 0.38 in Amazon) for SOA under ambient conditions. A relative humidity dependence of k OH and γ OH was observed, consistent with surface-area-limited OH uptake. No decrease of k OH was observed as OH concentrations increased. These observations of physicochemical properties of IEPOX-SOA can help to constrain OA impact on air quality and climate.« less

Volatility and lifetime against OH heterogeneous reaction of ambient isoprene-epoxydiols-derived secondary organic aerosol (IEPOX-SOA)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hu, Weiwei; Palm, Brett B.; Day, Douglas A.

Isoprene-epoxydiols-derived secondary organic aerosol (IEPOX-SOA) can contribute substantially to organic aerosol (OA) concentrations in forested areas under low NO conditions, hence significantly influencing the regional and global OA budgets, accounting, for example, for 16–36 % of the submicron OA in the southeastern United States (SE US) summer. Particle evaporation measurements from a thermodenuder show that the volatility of ambient IEPOX-SOA is lower than that of bulk OA and also much lower than that of known monomer IEPOX-SOA tracer species, indicating that IEPOX-SOA likely exists mostly as oligomers in the aerosol phase. The OH aging process of ambient IEPOX-SOA was investigated withmore » an oxidation flow reactor (OFR). New IEPOX-SOA formation in the reactor was negligible, as the OFR does not accelerate processes such as aerosol uptake and reactions that do not scale with OH. Simulation results indicate that adding  ∼  100 µg m −3 of pure H 2SO 4 to the ambient air allows IEPOX-SOA to be efficiently formed in the reactor. The heterogeneous reaction rate coefficient of ambient IEPOX-SOA with OH radical ( k OH) was estimated as 4.0 ± 2.0  ×  10 −13 cm 3 molec −1 s −1, which is equivalent to more than a 2-week lifetime. A similar k OH was found for measurements of OH oxidation of ambient Amazon forest air in an OFR. At higher OH exposures in the reactor (>  1  ×  10 12 molec cm −3 s), the mass loss of IEPOX-SOA due to heterogeneous reaction was mainly due to revolatilization of fragmented reaction products. We report, for the first time, OH reactive uptake coefficients ( γ OH =  0.59 ± 0.33 in SE US and γ OH =  0.68 ± 0.38 in Amazon) for SOA under ambient conditions. A relative humidity dependence of k OH and γ OH was observed, consistent with surface-area-limited OH uptake. No decrease of k OH was observed as OH concentrations increased. These observations of physicochemical properties of IEPOX-SOA can help to constrain OA impact on air quality and climate.« less

Production of extremely low volatile organic compounds from biogenic emissions: Measured yields and atmospheric implications

PubMed Central

Jokinen, Tuija; Berndt, Torsten; Makkonen, Risto; Kerminen, Veli-Matti; Junninen, Heikki; Stratmann, Frank; Herrmann, Hartmut; Guenther, Alex B.; Worsnop, Douglas R.; Kulmala, Markku; Ehn, Mikael; Sipilä, Mikko

2015-01-01

Oxidation products of monoterpenes and isoprene have a major influence on the global secondary organic aerosol (SOA) burden and the production of atmospheric nanoparticles and cloud condensation nuclei (CCN). Here, we investigate the formation of extremely low volatility organic compounds (ELVOC) from O3 and OH radical oxidation of several monoterpenes and isoprene in a series of laboratory experiments. We show that ELVOC from all precursors are formed within the first minute after the initial attack of an oxidant. We demonstrate that under atmospherically relevant concentrations, species with an endocyclic double bond efficiently produce ELVOC from ozonolysis, whereas the yields from OH radical-initiated reactions are smaller. If the double bond is exocyclic or the compound itself is acyclic, ozonolysis produces less ELVOC and the role of the OH radical-initiated ELVOC formation is increased. Isoprene oxidation produces marginal quantities of ELVOC regardless of the oxidant. Implementing our laboratory findings into a global modeling framework shows that biogenic SOA formation in general, and ELVOC in particular, play crucial roles in atmospheric CCN production. Monoterpene oxidation products enhance atmospheric new particle formation and growth in most continental regions, thereby increasing CCN concentrations, especially at high values of cloud supersaturation. Isoprene-derived SOA tends to suppress atmospheric new particle formation, yet it assists the growth of sub-CCN-size primary particles to CCN. Taking into account compound specific monoterpene emissions has a moderate effect on the modeled global CCN budget. PMID:26015574

Secondary organic aerosol formation from low-NO(x) photooxidation of dodecane: evolution of multigeneration gas-phase chemistry and aerosol composition.

PubMed

Yee, Lindsay D; Craven, Jill S; Loza, Christine L; Schilling, Katherine A; Ng, Nga Lee; Canagaratna, Manjula R; Ziemann, Paul J; Flagan, Richard C; Seinfeld, John H

2012-06-21

The extended photooxidation of and secondary organic aerosol (SOA) formation from dodecane (C(12)H(26)) under low-NO(x) conditions, such that RO(2) + HO(2) chemistry dominates the fate of the peroxy radicals, is studied in the Caltech Environmental Chamber based on simultaneous gas and particle-phase measurements. A mechanism simulation indicates that greater than 67% of the initial carbon ends up as fourth and higher generation products after 10 h of reaction, and simulated trends for seven species are supported by gas-phase measurements. A characteristic set of hydroperoxide gas-phase products are formed under these low-NO(x) conditions. Production of semivolatile hydroperoxide species within three generations of chemistry is consistent with observed initial aerosol growth. Continued gas-phase oxidation of these semivolatile species produces multifunctional low volatility compounds. This study elucidates the complex evolution of the gas-phase photooxidation chemistry and subsequent SOA formation through a novel approach comparing molecular level information from a chemical ionization mass spectrometer (CIMS) and high m/z ion fragments from an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS). Combination of these techniques reveals that particle-phase chemistry leading to peroxyhemiacetal formation is the likely mechanism by which these species are incorporated in the particle phase. The current findings are relevant toward understanding atmospheric SOA formation and aging from the "unresolved complex mixture," comprising, in part, long-chain alkanes.

Production of extremely low volatile organic compounds from biogenic emissions: Measured yields and atmospheric implications.

PubMed

Jokinen, Tuija; Berndt, Torsten; Makkonen, Risto; Kerminen, Veli-Matti; Junninen, Heikki; Paasonen, Pauli; Stratmann, Frank; Herrmann, Hartmut; Guenther, Alex B; Worsnop, Douglas R; Kulmala, Markku; Ehn, Mikael; Sipilä, Mikko

2015-06-09

Oxidation products of monoterpenes and isoprene have a major influence on the global secondary organic aerosol (SOA) burden and the production of atmospheric nanoparticles and cloud condensation nuclei (CCN). Here, we investigate the formation of extremely low volatility organic compounds (ELVOC) from O3 and OH radical oxidation of several monoterpenes and isoprene in a series of laboratory experiments. We show that ELVOC from all precursors are formed within the first minute after the initial attack of an oxidant. We demonstrate that under atmospherically relevant concentrations, species with an endocyclic double bond efficiently produce ELVOC from ozonolysis, whereas the yields from OH radical-initiated reactions are smaller. If the double bond is exocyclic or the compound itself is acyclic, ozonolysis produces less ELVOC and the role of the OH radical-initiated ELVOC formation is increased. Isoprene oxidation produces marginal quantities of ELVOC regardless of the oxidant. Implementing our laboratory findings into a global modeling framework shows that biogenic SOA formation in general, and ELVOC in particular, play crucial roles in atmospheric CCN production. Monoterpene oxidation products enhance atmospheric new particle formation and growth in most continental regions, thereby increasing CCN concentrations, especially at high values of cloud supersaturation. Isoprene-derived SOA tends to suppress atmospheric new particle formation, yet it assists the growth of sub-CCN-size primary particles to CCN. Taking into account compound specific monoterpene emissions has a moderate effect on the modeled global CCN budget.

Improving the representation of secondary organic aerosol (SOA) in the MOZART-4 global chemical transport model

NASA Astrophysics Data System (ADS)

Mahmud, A.; Barsanti, K. C.

2012-12-01

The secondary organic aerosol (SOA) module in the Model for Ozone and Related chemical Tracers, version 4 (MOZART-4) has been updated by replacing existing two-product (2p) parameters with those obtained from two-product volatility basis set (2p-VBS) fits, and by treating SOA formation from the following volatile organic compounds (VOCs): isoprene, propene and lumped alkenes. Strong seasonal and spatial variations in global SOA distributions were demonstrated, with significant differences in the predicted concentrations between the base-case and updated model versions. The base-case MOZART-4 predicted annual average SOA of 0.36 ± 0.50 μg m-3 in South America, 0.31 ± 0.38 μg m-3 in Indonesia, 0.09 ± 0.05 μg m-3 in the USA, and 0.12 ± 0.07 μg m-3 in Europe. Concentrations from the updated versions of the model showed a~marked increase in annual average SOA. Using the updated set of parameters alone (MZ4-v1) increased annual average SOA by ~8%, ~16%, ~56%, and ~108% from the base-case in South America, Indonesia, USA, and Europe, respectively. Treatment of additional parent VOCs (MZ4-v2) resulted in an even more dramatic increase of ~178-406% in annual average SOA for these regions over the base-case. The increases in predicted SOA concentrations further resulted in increases in corresponding SOA contributions to annual average total aerosol optical depth (AOD) by <1% for MZ4-v1 and ~1-6% for MZ4-v2. Estimated global SOA production was ~6.6 Tg yr-1 and ~19.1 Tg yr-1 with corresponding burdens of ~0.24 Tg and ~0.59 Tg using MZ4-v1 and MZ4-v2, respectively. The SOA budgets predicted in the current study fall well within reported ranges for similar modeling studies, 6.7 to 96 Tg yr-1, but are lower than recently reported observationally-constrained values, 50 to 380 Tg yr-1. With MZ4-v2, simulated SOA concentrations at the surface were also in reasonable agreement with comparable modeling studies and observations. Concentrations of estimated organic aerosol (OA) at the surface, however, showed under-prediction in Europe and over-prediction in the Amazonian regions and Malaysian Borneo during certain months of the year. Overall, the updated version of MOZART-4, MZ4-v2, showed consistently better skill in predicting SOA and OA levels and spatial distributions as compared with unmodified MOZART-4. The MZ4-v2 updates may be particularly important when MOZART-4 output is used to generate boundary conditions for regional air quality simulations that require more accurate representation of SOA concentrations and distributions.

Campholenic aldehyde ozonolysis: a mechanism leading to specific biogenic secondary organic aerosol constituents

NASA Astrophysics Data System (ADS)

Kahnt, A.; Iinuma, Y.; Mutzel, A.; Böge, O.; Claeys, M.; Herrmann, H.

2014-01-01

In the present study, campholenic aldehyde ozonolysis was performed to investigate pathways leading to specific biogenic secondary organic aerosol (SOA) marker compounds. Campholenic aldehyde, a known α-pinene oxidation product, is suggested to be a key intermediate in the formation of terpenylic acid upon α-pinene ozonolysis. It was reacted with ozone in the presence and absence of an OH radical scavenger, leading to SOA formation with a yield of 0.75 and 0.8, respectively. The resulting oxidation products in the gas and particle phases were investigated employing a denuder/filter sampling combination. Gas-phase oxidation products bearing a carbonyl group, which were collected by the denuder, were derivatised by 2,4-dinitrophenylhydrazine (DNPH) followed by liquid chromatography/negative ion electrospray ionisation time-of-flight mass spectrometry analysis and were compared to the gas-phase compounds detected by online proton-transfer-reaction mass spectrometry. Particle-phase products were also analysed, directly or after DNPH derivatisation, to derive information about specific compounds leading to SOA formation. Among the detected compounds, the aldehydic precursor of terpenylic acid was identified and its presence was confirmed in ambient aerosol samples from the DNPH derivatisation, accurate mass data, and additional mass spectrometry (MS2 and MS3 fragmentation studies). Furthermore, the present investigation sheds light on a reaction pathway leading to the formation of terpenylic acid, involving α-pinene, α-pinene oxide, campholenic aldehyde, and terpenylic aldehyde. Additionally, the formation of diaterpenylic acid acetate could be connected to campholenic aldehyde oxidation. The present study also provides insights into the source of other highly functionalised oxidation products (e.g. m / z 201, C9H14O5 and m / z 215, C10H16O5), which have been observed in ambient aerosol samples and smog chamber-generated monoterpene SOA. The m / z 201 and 215 compounds were tentatively identified as a C9- and C10-carbonyl-dicarboxylic acid, respectively, based on reaction mechanisms of campholenic aldehyde and ozone, as well as detailed interpretation of mass spectral data, in conjunction with the formation of corresponding DNPH derivatives.

Multiday production of condensing organic aerosol mass in urban and forest outflow

DOE PAGES

Lee-Taylor, J.; Hodzic, A.; Madronich, S.; ...

2014-07-03

Secondary organic aerosol (SOA) production in air masses containing either anthropogenic or biogenic (terpene-dominated) emissions is investigated using the explicit gas-phase chemical mechanism generator GECKO-A. Simulations show several-fold increases in SOA mass continuing for several days in the urban outflow, even as the initial air parcel is diluted into the regional atmosphere. The SOA mass increase in the forest outflow is more modest (∼50%) and of shorter duration (1–2 days). The production in the urban outflow stems from continuing oxidation of gas-phase precursors which persist in equilibrium with the particle phase, and can be attributed to multigenerational reaction products ofmore » both aromatics and alkanes. In particular we find large contributions from substituted maleic anhydrides and multi-substituted peroxide-bicyclic alkenes. The results show that the predicted production is a robust feature of our model even under changing atmospheric conditions, and contradict the notion that SOA undergoes little mass production beyond a short initial formation period. The results imply that anthropogenic aerosol precursors could influence the chemical and radiative characteristics of the atmosphere over an extremely wide region, and that SOA measurements near precursor sources may routinely underestimate this influence.« less

Aerosol mass spectrometric features of biogenic SOA: observations from a plant chamber and in rural atmospheric environments.

PubMed

Kiendler-Scharr, Astrid; Zhang, Qi; Hohaus, Thorsten; Kleist, Einhard; Mensah, Amewu; Mentel, Thomas F; Spindler, Christian; Uerlings, Ricarda; Tillmann, Ralf; Wildt, Jürgen

2009-11-01

Secondary organic aerosol (SOA) is known to form from a variety of anthropogenic and biogenic precursors. Current estimates of global SOA production vary over 2 orders of magnitude. Since no direct measurement technique for SOA exists, quantifying SOA remains a challenge for atmospheric studies. The identification of biogenic SOA (BSOA) based on mass spectral signatures offers the possibility to derive source information of organic aerosol (OA) with high time resolution. Here we present data from simulation experiments. The BSOA from tree emissions was characterized with an Aerodyne quadrupole aerosol mass spectrometer (Q-AMS). Collection efficiencies were close to 1, and effective densities of the BSOA were found to be 1.3 +/- 0.1 g/cm(3). The mass spectra of SOA from different trees were found to be highly similar. The average BSOA mass spectrum from tree emissions is compared to a BSOA component spectrum extracted from field data. It is shown that overall the spectra agree well and that the mass spectral features of BSOA are distinctively different from those of OA components related to fresh fossil fuel and biomass combustions. The simulation chamber mass spectrum may potentially be useful for the identification and interpretation of biogenic SOA components in ambient data sets.

Ultra-broad band, low power, highly efficient coherent wavelength conversion in quantum dot SOA.

PubMed

Contestabile, G; Yoshida, Y; Maruta, A; Kitayama, K

2012-12-03

We report broadband, all-optical wavelength conversion over 100 nm span, in full S- and C-band, with positive conversion efficiency with low optical input power exploiting dual pump Four-Wave-Mixing in a Quantum Dot Semiconductor Optical Amplifier (QD-SOA). We also demonstrate by Error Vector Magnitude analysis the full transparency of the conversion scheme for coherent modulation formats (QPSK, 8-PSK, 16-QAM, OFDM-16QAM) in the whole C-band.

Isomerization of Second-Generation Isoprene Peroxy Radicals: Epoxide Formation and Implications for Secondary Organic Aerosol Yields

DOE Office of Scientific and Technical Information (OSTI.GOV)

D’Ambro, Emma L.; Møller, Kristian H.; Lopez-Hilfiker, Felipe D.

2017-04-11

We report chamber measurements of secondary organic aerosol (SOA) formation from isoprene photochemical oxidation, where radical concentrations were systematically varied and the molecular composition of semi to low volatility gases and SOA were measured online. Using a detailed chemical mechanism, we find that to explain the behavior of low volatility products and SOA mass yields relative to input H2O2 concentrations, the second generation dihydroxy hydroperoxy peroxy radical (C5H11O6•) must undergo an intra-molecular H-shift with a net forward rate constant of order 0.1 s-1 or higher, consistent with quantum chemical calculations which suggest a net forward rate constant of 0.3-0.9 s-1.more » Furthermore, these calculations suggest the dominant product of this isomerization is a dihydroxy hydroperoxy epoxide (C5H10O5) which is expected to have a saturation vapor pressure ~2 orders of magnitude higher than the dihydroxy dihydroperoxide, ISOP(OOH)2 (C5H12O6), a major product of the peroxy radical reacting with HO2. These results provide strong constraints on the likely volatility distribution of isoprene oxidation products under atmospheric conditions and thus on the importance of non-reactive gas-particle partitioning of isoprene oxidation products as an SOA source.« less

Smog chamber experiments to investigate Henry's law constants of glyoxal using different seed aerosols as well as imidazole formation in the presence of ammonia

NASA Astrophysics Data System (ADS)

Jakob, Ronit

2015-04-01

Aerosols play an important role in the chemistry and physics of the atmosphere. Hence, they have a direct as well as an indirect impact on the earth's climate. Depending on their formation, one distinguishes between primary and secondary aerosols[1]. Important groups within the secondary aerosols are the secondary organic aerosols (SOAs). In order to improve predictions about these impacts on the earth's climate the existing models need to be optimized, because they still underestimate SOA formation[2]. Glyoxal, the smallest α-dicarbonyl, not only acts as a tracer for SOA formation but also as a direct contributor to SOA. Because glyoxal has such a high vapour pressure, it was common knowledge that it does not take part in gas-particle partitioning and therefore has no impact on direct SOA formation. However, the Henry's law constant for glyoxal is surprisingly high. This has been explained by the hydration of the aldehyde groups, which means that a species with a lower vapour pressure is produced. Therefore the distribution of glyoxal between gas- and particle phase is atmospherically relevant and the direct contribution of glyoxal to SOA can no longer be neglected[3]. Besides this particulate glyoxal is able to undergo heterogeneous chemistry with gaseous ammonia to form imidazoles. This plays an important role for regions with aerosols exhibiting alkaline pH values for example from lifestock or soil dust because imidazoles as nitrogen containing compounds change the optical properties of aerosols[4]. A high salt concentration present in chamber seed aerosols leads to an enhanced glyoxal uptake into the particle. This effect is called "salting-in". The salting effect depends on the composition of the seed aerosol as well as the soluble compound. For very polar compounds, like glyoxal, a "salting-in" is observed[3]. Glyoxal particle formation during a smog chamber campaign at Paul-Scherrer-Institut (PSI) in Switzerland was examined using different seed aerosols such as ammonium sulfate, sodium chloride and sodium nitrate. The aim of this campaign was to investigate Henry's law constants for different seed aerosols. Additionally imidazole formation was studied. During the campaign filter samples were taken to investigate the amount of glyoxal and imidazole in the particle phase. After filter extraction and derivatisation of glyoxal, the compounds were measured using UHPLC-ESI-HR-MS. Additionally, gas-phase glyoxal has been analysed during the campaign. The results will be used to calculate the Henry's law constants. In this work, results of the glyoxal study as well as imidazole formation are presented. [1] J. Schnelle-Kreis, M. Sklorz, H. Herrmann, R. Zimmermann, Chem. Unserer Zeit, 2007, 41, 220-230 [2] M. M. Galloway, P. S. Chhabra, A. W. H. Chan, J. D. Surratt, R. C. Flagan, J. H. Seinfeld, F. N. Keutsch, Atmos. Chem. Phys, 9, 3331-3345, 2009 [3] C. J. Kampf, E. M. Waxman, J. G. Slowik, J. Dommen, L. Pfaffenberger, A. P. Praplan, A. S. H. Prévôt, U. Baltensperger, T. Hoffmann, R. Volkamer, Environ. Sci. Technol., 2013, 47, 4236-4244 [4] C. J. Kampf, R. Jakob, T. Hoffmann, Atmos. Chem. Phys., 12, 6323-6333, 2012

Heterogeneous ice nucleation of α-pinene SOA particles before and after ice cloud processing

NASA Astrophysics Data System (ADS)

Wagner, Robert; Höhler, Kristina; Huang, Wei; Kiselev, Alexei; Möhler, Ottmar; Mohr, Claudia; Pajunoja, Aki; Saathoff, Harald; Schiebel, Thea; Shen, Xiaoli; Virtanen, Annele

2017-05-01

The ice nucleation ability of α-pinene secondary organic aerosol (SOA) particles was investigated at temperatures between 253 and 205 K in the Aerosol Interaction and Dynamics in the Atmosphere cloud simulation chamber. Pristine SOA particles were nucleated and grown from pure gas precursors and then subjected to repeated expansion cooling cycles to compare their intrinsic ice nucleation ability during the first nucleation event with that observed after ice cloud processing. The unprocessed α-pinene SOA particles were found to be inefficient ice-nucleating particles at cirrus temperatures, with nucleation onsets (for an activated fraction of 0.1%) as high as for the homogeneous freezing of aqueous solution droplets. Ice cloud processing at temperatures below 235 K only marginally improved the particles' ice nucleation ability and did not significantly alter their morphology. In contrast, the particles' morphology and ice nucleation ability was substantially modified upon ice cloud processing in a simulated convective cloud system, where the α-pinene SOA particles were first activated to supercooled cloud droplets and then froze homogeneously at about 235 K. As evidenced by electron microscopy, the α-pinene SOA particles adopted a highly porous morphology during such a freeze-drying cycle. When probing the freeze-dried particles in succeeding expansion cooling runs in the mixed-phase cloud regime up to 253 K, the increase in relative humidity led to a collapse of the porous structure. Heterogeneous ice formation was observed after the droplet activation of the collapsed, freeze-dried SOA particles, presumably caused by ice remnants in the highly viscous material or the larger surface area of the particles.

Simultaneous wavelength and format conversion in SDN/NFV for flexible optical network based on FWM in SOA

NASA Astrophysics Data System (ADS)

Zhan, Yueying; Wang, Danshi; Zhang, Min

2018-04-01

We propose an all-optical wavelength and format conversion model (CM) for a dynamic data center interconnect node and coherent passive optical network (PON) optical network unit (ONU) in software-defined networking and network function virtualization system based on four-wave mixing in a semiconductor optical amplifier. Five wavelength converted DQPSK signals and two format converted DPSK signals are generated; the performances of the generated signals for two strategies of setting CM in the data center interconnect node and coherent PON ONU, which are over 10 km fiber transmission, have been verified. All of the converted signals are with a power penalty less than 2.2 dB at FEC threshold of 3.8 × 10 - 3, and the optimum bias current of SOA is 300 mA.

Interpretation of Secondary Organic Aerosol Formation from Diesel Exhaust Photooxidation in an Environmental Chamber

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nakao, Shunsuke; Shrivastava, ManishKumar B.; Nguyen, Anh

2011-04-14

Secondary organic aerosol (SOA) formation from diesel exhaust in a smog chamber was investigated. Particle volume measurement based on mobility diameter is shown to underestimate SOA formation from diesel exhaust due to the external void space of agglomerate particles, in which case mass-based measurement technique is necessary. Rapid determination of particle effective density as a function of particle mass was performed by an Aerosol Particle Mass analyzer – Scanning Mobility Particle Sizer (APM-SMPS) to obtain particle mass concentration and fractal dimension. Continuous aging of aerosol was observed in terms of atomic ratio (O/C), from 0.05 to 0.25 in 12 hours,more » underscoring the importance of multi-generational oxidation of low-volatile organic vapors emitted from diesel engine as the significant source of oxygenated SOA. Experimental conditions possibly have strong impacts on physical evolution of diesel particulates in a smog chamber. Higher particle effective densities were observed when raw exhaust was injected into a full bag as opposed to filling a bag with diluted exhaust using an ejector diluter. When longer transfer line was used for injecting diesel exhaust into the smog chamber, rapid particle coagulation was observed, leading to increasing particle volume concentration in dark while its mass concentration is decreasing.« less

Oligomer formation in the troposphere: from experimental knowledge to 3-D modeling

NASA Astrophysics Data System (ADS)

Lemaire, V.; Coll, I.; Couvidat, F.; Mouchel-Vallon, C.; Seigneur, C.; Siour, G.

2015-10-01

The organic fraction of atmospheric aerosols has proven to be a critical element of air quality and climate issues. However, its composition and the aging processes it undergoes remain insufficiently understood. This work builds on laboratory knowledge to simulate the formation of oligomers from biogenic secondary organic aerosol (BSOA) in the troposphere at the continental scale. We compare the results of two different modeling approaches, a 1st-order kinetic process and a pH-dependent parameterization, both implemented in the CHIMERE air quality model (AQM), to simulate the spatial and temporal distribution of oligomerized SOA over western Europe. Our results show that there is a strong dependence of the results on the selected modeling approach: while the irreversible kinetic process leads to the oligomerization of about 50 % of the total BSOA mass, the pH-dependent approach shows a broader range of impacts, with a strong dependency on environmental parameters (pH and nature of aerosol) and the possibility for the process to be reversible. In parallel, we investigated the sensitivity of each modeling approach to the representation of SOA precursor solubility (Henry's law constant values). Finally, the pros and cons of each approach for the representation of SOA aging are discussed and recommendations are provided to improve current representations of oligomer formation in AQMs.

Secondary Organic Aerosol Formation from Glyoxal: photochemical versus dark uptake and reversible versus irreversible SOA formation

NASA Astrophysics Data System (ADS)

Waxman, E.; Slowik, J. G.; Kampf, C. J.; Timkovsky, J.; Noziere, B.; Praplan, A. P.; Pfaffenberger, L.; Holzinger, R.; Hoffmann, T.; Dommen, J.; Prevot, A. S.; Baltensperger, U.; Volkamer, R.

2011-12-01

Glyoxal forms secondary organic aerosol (SOA) by partitioning to the aerosol aqueous phase according to Henry's law. The subsequent processing by heterogeneous and multiphase reactions shifts the partitioning towards aerosols. Currently it is not well understood whether these reactions result in reversible or irreversible SOA formation, and what parameters influence the rate limiting step of multiphase processing. We conducted a series of simulation chamber experiments at PSI in April and May 2011 to investigate processing under dark conditions, UV and/or visible light irradiated conditions, and in the presence and absence of OH radicals. Experiments used ammonium sulfate or ammonium sulfate/fulvic acid mixtures as seed aerosols, and were conducted between 50% and 85% relative humidity at approximately constant RH over the course of any given experiment. Glyoxal was produced photochemically from acetylene, using HONO photolysis as the OH radical source. Gas-phase glyoxal was measured by the CU LED-Cavity Enhanced-DOAS. The Thermal-Desorption Proton-Transfer-Reaction Mass Spectrometer (TD-PTR-MS) and Ion Chromatography Mass Spectrometer (IC-MS) monitored both gas and aerosol-phase organic reaction products. Particle composition was monitored by High-Resolution Time-of-Flight Aerosol Mass Spectrometry (HR-ToF-AMS), and HPLC-ESI MS/MS and LC-MS analysis of filter samples.

Secondary Organic Aerosol Formation from Glyoxal: photochemical versus dark uptake and reversible versus irreversible SOA formation

NASA Astrophysics Data System (ADS)

Waxman, E.; Slowik, J.; Kampf, C.; Timkovsky, J.; Noziere, B.; Praplan, A.; Pffafenberger, L.; Holzinger, R.; Hoffmann, T.; Dommen, J.; Prevot, A.; Baltensperger, U.; Volkamer, R.

2012-04-01

Glyoxal forms secondary organic aerosol (SOA) by partitioning to the aerosol aqueous phase according to Henry's law. The subsequent processing by heterogeneous and multiphase reactions shifts the partitioning towards aerosols. Currently it is not well understood whether these reactions result in reversible or irreversible SOA formation, and what parameters influence the rate limiting step of multiphase processing. We conducted a series of simulation chamber experiments at PSI in April and May 2011 to investigate processing under dark conditions, UV and/or visible light irradiated conditions, and in the presence and absence of OH radicals. Experiments used ammonium sulfate or ammonium sulfate/fulvic acid mixtures as seed aerosols, and were conducted between 50% and 85% relative humidity at approximately constant RH over the course of any given experiment. Glyoxal was produced photochemically from acetylene, using HONO photolysis as the OH radical source. Gas-phase glyoxal was measured by the CU LED-Cavity Enhanced-DOAS. The Thermal-Desorption Proton-Transfer-Reaction Mass Spectrometer (TD-PTR-MS) and Ion Chromatography Mass Spectrometer (IC-MS) monitored both gas and aerosol-phase organic reaction products. Particle composition was monitored by High-Resolution Time-of-Flight Aerosol Mass Spectrometry (HR-ToF-AMS), and HPLC-ESI MS/MS and LC-MS analysis of filter samples.

A Role for 2-Methyl Pyrrole in the Browning of 4-Oxopentanal and Limonene Secondary Organic Aerosol

DOE Office of Scientific and Technical Information (OSTI.GOV)

Aiona, Paige K.; Lee, Hyun Ji; Lin, Peng

“Brown Carbon” (BrC) is a type of organic particulate matter that absorbs visible and near ultraviolet radiation. Reactions of carbonyls in secondary organic aerosol (SOA) produced from limonene with ammonia (NH3) or ammonium sulfate (AS) are known to produce BrC with a distinctive absorption band at 500 nm. Although the general mechanism for this process has been proposed in previous studies, the specific molecular structures of the light-absorbing species remain unclear. This study examined the browning processes occurring in aqueous solutions of AS and 4-oxopentanal (4-OPA), which has a 1,4-dicarbonyl structural motif present in many limonene SOA compounds. The reactionmore » of 4-OPA with AS in a bulk aqueous solution produces a 2-methyl pyrrole (2-MP) intermediate, which is not a strong light absorber by itself, but can react further with carbonyl compounds leading to the eventual formation of BrC chromophores. The direct involvement of 2-MP in the browning process was demonstrated by reacting 2-MP with 4-OPA and with limonene SOA, both of which produced BrC chromophores with distinctive absorption bands at visible wavelengths. The formation of BrC in reaction of 4-OPA with AS and ammonium nitrate (AN) was found to be accelerated by evaporation of the solution suggesting an important role of the dehydration processes in BrC formation from 1,4- dicarbonyls. 4-OPA was also found to produce BrC in aqueous reactions with a broad spectrum of amino acids and amines. The results suggest that 4-OPA may be the smallest atmospherically relevant compound capable of browning by the same mechanism as limonene SOA.« less

Composition and formation of organic aerosol particles in the Amazon

NASA Astrophysics Data System (ADS)

Pöhlker, C.; Wiedemann, K.; Sinha, B.; Shiraiwa, M.; Gunthe, S. S.; Artaxo, P.; Gilles, M. K.; Kilcoyne, A. L. D.; Moffet, R. C.; Smith, M.; Weigand, M.; Martin, S. T.; Pöschl, U.; Andreae, M. O.

2012-04-01

We applied scanning transmission X-ray microscopy with near edge X-ray absorption fine structure (STXM-NEXAFS) analysis to investigate the morphology and chemical composition of aerosol samples from a pristine tropical environment, the Amazon Basin. The samples were collected in the Amazonian rainforest during the rainy season and can be regarded as a natural background aerosol. The samples were found to be dominated by secondary organic aerosol (SOA) particles in the fine and primary biological aerosol particles (PBAP) in the coarse mode. Lab-generated SOA-samples from isoprene and terpene oxidation as well as pure organic compounds from spray-drying of aqueous solution were measured as reference samples. The aim of this study was to investigate the microphysical and chemical properties of a tropical background aerosol in the submicron size range and its internal mixing state. The lab-generated SOA and pure organic compounds occurred as spherical and mostly homogenous droplet-like particles, whereas the Amazonian SOA particles comprised a mixture of homogeneous droplets and droplets having internal structures due to atmospheric aging. In spite of the similar morphological appearance, the Amazon samples showed considerable differences in elemental and functional group composition. According to their NEXAFS spectra, three chemically distinct types of organic material were found and could be assigned to the following three categories: (1) particles with a pronounced carboxylic acid (COOH) peak similar to those of laboratory-generated SOA particles from terpene oxidation; (2) particles with a strong hydroxy (COH) signal similar to pure carbohydrate particles; and (3) particles with spectra resembling a mixture of the first two classes. In addition to the dominant organic component, the NEXAFS spectra revealed clearly resolved potassium (K) signals for all analyzed particles. During the rainy season and in the absence of anthropogenic influence, active biota is regarded to be the major potassium source. In addition a strong size dependence of the K mass fraction in the SOA particles has been found, with highest K content in small particles. We suggest that K-rich biogenic salts act as a template for condensational growth by low-volatility organic compounds from atmospheric isoprene and terpene oxidation. The presence of K-rich salts in SOA particles has been confirmed by scanning electron microscopy (SEM) and secondary ion mass spectrometry (nanoSIMS) techniques. Seeding of SOA particles by biogenic salts may explain the absence of new particle formation events in pristine boundary layer air over the Amazonian rainforest.

Secondary organic aerosol formation and composition from the photo-oxidation of methyl chavicol (estragole)

NASA Astrophysics Data System (ADS)

Pereira, K. L.; Hamilton, J. F.; Rickard, A. R.; Bloss, W. J.; Alam, M. S.; Camredon, M.; Muñoz, A.; Vázquez, M.; Borrás, E.; Ródenas, M.

2014-06-01

The increasing demand for palm oil for uses in biofuel and food products is leading to rapid expansion of oil palm agriculture. Methyl chavicol (also known as estragole and 1-allyl-4-methoxybenzene) is an oxygenated biogenic volatile organic compound (VOC) that was recently identified as the main floral emission from an oil palm plantation in Malaysian Borneo. The emissions of methyl chavicol observed may impact regional atmospheric chemistry, but little is known of its ability to form secondary organic aerosol (SOA). The photo-oxidation of methyl chavicol was investigated at the European Photoreactor chamber as a part of the atmospheric chemistry of methyl chavicol (ATMECH) project. Aerosol samples were collected using a particle into liquid sampler (PILS) and analysed offline using an extensive range of instruments including; high-performance liquid chromatography mass spectrometry (HPLC-ITMS), high-performance liquid chromatography quadrupole time-of-flight mass spectrometry (HPLC-QTOFMS) and Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS). The SOA yield was determined as 18 and 29% for an initial VOC mixing ratio of 212 and 460 ppbv (parts per billion by volume) respectively; using a VOC:NOx ratio of ~5:1. In total, 59 SOA compounds were observed and the structures of 10 compounds have been identified using high-resolution tandem mass spectrometry. The addition of hydroxyl and/or nitro-functional groups to the aromatic ring appears to be an important mechanistic pathway for aerosol formation. This results in the formation of compounds with both low volatility and high O:C ratios, where functionalisation rather than fragmentation is mainly observed as a result of the stability of the ring. The SOA species observed can be characterised as semi-volatile to low-volatility oxygenated organic aerosol (SVOOA and LVOOA) components and therefore may be important in aerosol formation and growth.

Aerosol-halogen interaction: Change of physico-chemical properties of SOA by naturally released halogen species

NASA Astrophysics Data System (ADS)

Ofner, J.; Balzer, N.; Buxmann, J.; Grothe, H.; Krüger, H.; Platt, U.; Schmitt-Kopplin, P.; Zetzsch, C.

2011-12-01

Reactive halogen species are released by various sources like photo-activated sea-salt aerosol or salt pans and salt lakes. These heterogeneous release mechanisms have been overlooked so far, although their potential of interaction with organic aerosols like Secondary Organic Aerosol (SOA), Biomass Burning Organic Aerosol (BBOA) or Atmospheric Humic LIke Substances (HULIS) is completely unknown. Such reactions can constitute sources of gaseous organo-halogen compounds or halogenated organic particles in the atmospheric boundary layer. To study the interaction of organic aerosols with reactive halogen species (RHS), SOA was produced from α-pinene, catechol and guaiacol using an aerosol smog-chamber. The model SOAs were characterized in detail using a variety of physico-chemical methods (Ofner et al., 2011). Those aerosols were exposed to molecular halogens in the presence of UV/VIS irradiation and to halogens, released from simulated natural halogen sources like salt pans, in order to study the complex aerosol-halogen interaction. The heterogeneous reaction of RHS with those model aerosols leads to different gaseous species like CO2, CO and small reactive/toxic molecules like phosgene (COCl2). Hydrogen containing groups on the aerosol particles are destroyed to form HCl or HBr, and a significant formation of C-Br bonds could be verified in the particle phase. Carbonyl containing functional groups of the aerosol are strongly affected by the halogenation process. While changes of functional groups and gaseous species were visible using FTIR spectroscopy, optical properties were studied using Diffuse Reflectance UV/VIS spectroscopy. Overall, the optical properties of the processed organic aerosols are significantly changed. While chlorine causes a "bleaching" of the aerosol particles, bromine shifts the maximum of UV/VIS absorption to the red end of the UV/VIS spectrum. Further physico-chemical changes were recognized according to the aerosol size-distributions or the averaged carbon oxidation state (OSc). The heterogeneous reaction of SOA with molecular halogens released from the simulated salt-pan at different simulated environmental conditions leads to changes of several physico-chemical features of the aerosol. However, the halogen release mechanisms are also affected by the presence of organic aerosols. One order of magnitude less BrO was detected by an active Differential Optical Absorption Spectroscopy (DOAS) instrument in the presence of SOA compared to experiments without SOA. This work was supported by the German Research Foundation within the HALOPROC project. Ofner, J., Krüger, H.-U., Grothe, H., Schmitt-Kopplin, P., Whitmore, K., and Zetzsch, C. (2011), Atmos. Chem. Phys., 11, 1-15.

Simultaneous odour-face presentation strengthens hedonic evaluations and event-related potential responses influenced by unpleasant odour.

PubMed

Cook, Stephanie; Kokmotou, Katerina; Soto, Vicente; Wright, Hazel; Fallon, Nicholas; Thomas, Anna; Giesbrecht, Timo; Field, Matt; Stancak, Andrej

2018-04-13

Odours alter evaluations of concurrently presented visual stimuli, such as faces. Stimulus onset asynchrony (SOA) is known to affect evaluative priming in various sensory modalities. However, effects of SOA on odour priming of visual stimuli are not known. The present study aimed to analyse whether subjective and cortical activation changes during odour priming would vary as a function of SOA between odours and faces. Twenty-eight participants rated faces under pleasant, unpleasant, and no-odour conditions using visual analogue scales. In half of trials, faces appeared one-second after odour offset (SOA 1). In the other half of trials, faces appeared during the odour pulse (SOA 2). EEG was recorded continuously using a 128-channel system, and event-related potentials (ERPs) to face stimuli were evaluated using statistical parametric mapping (SPM). Faces presented during unpleasant-odour stimulation were rated significantly less pleasant than the same faces presented one-second after offset of the unpleasant odour. Scalp-time clusters in the late-positive-potential (LPP) time-range showed an interaction between odour and SOA effects, whereby activation was stronger for faces presented simultaneously with the unpleasant odour, compared to the same faces presented after odour offset. Our results highlight stronger unpleasant odour priming with simultaneous, compared to delayed, odour-face presentation. Such effects were represented in both behavioural and neural data. A greater cortical and subjective response during simultaneous presentation of faces and unpleasant odour may have an adaptive role, allowing for a prompt and focused behavioural reaction to a concurrent stimulus if an aversive odour would signal danger, or unwanted social interaction. Copyright © 2018 Elsevier B.V. All rights reserved.

Excitation-emission spectra and fluorescence quantum yields for fresh and aged biogenic secondary organic aerosols

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lee, Hyun Ji; Laskin, Alexander; Laskin, Julia

2013-05-10

Certain biogenic secondary organic aerosols (SOA) become absorbent and fluorescent when exposed to reduced nitrogen compounds such as ammonia, amines and their salts. Fluorescent SOA may potentially be mistaken for biological particles by detection methods relying on fluorescence. This work quantifies the spectral distribution and effective quantum yields of fluorescence of SOA generated from two monoterpenes, limonene and a-pinene, and two different oxidants, ozone (O3) and hydroxyl radical (OH). The SOA was generated in a smog chamber, collected on substrates, and aged by exposure to ~100 ppb ammonia vapor in air saturated with water vapor. Absorption and excitation-emission matrix (EEM)more » spectra of aqueous extracts of aged and control SOA samples were measured, and the effective absorption coefficients and fluorescence quantum yields (~0.005 for 349 nm excitation) were determined from the data. The strongest fluorescence for the limonene-derived SOA was observed for excitation = 420+- 50 nm and emission = 475 +- 38 nm. The window of the strongest fluorescence shifted to excitation = 320 +- 25 nm and emission = 425 +- 38 nm for the a-pinene-derived SOA. Both regions overlap with the excitation-emission matrix (EEM) spectra of some of the fluorophores found in primary biological aerosols. Our study suggests that, despite the low quantum yield, the aged SOA particles should have sufficient fluorescence intensities to interfere with the fluorescence detection of common bioaerosols.« less

Excitation-emission spectra and fluorescence quantum yields for fresh and aged biogenic secondary organic aerosols.

PubMed

Lee, Hyun Ji Julie; Laskin, Alexander; Laskin, Julia; Nizkorodov, Sergey A

2013-06-04

Certain biogenic secondary organic aerosols (SOA) become absorbent and fluorescent when exposed to reduced nitrogen compounds such as ammonia, amines, and their salts. Fluorescent SOA may potentially be mistaken for biological particles by detection methods relying on fluorescence. This work quantifies the spectral distribution and effective quantum yields of fluorescence of water-soluble SOA generated from two monoterpenes, limonene and α-pinene, and two different oxidants, ozone (O3) and hydroxyl radical (OH). The SOA was generated in a smog chamber, collected on substrates, and aged by exposure to ∼100 ppb ammonia in air saturated with water vapor. Absorption and excitation-emission matrix (EEM) spectra of aqueous extracts of aged and control SOA samples were measured, and the effective absorption coefficients and fluorescence quantum yields (∼0.005 for 349 nm excitation) were determined from the data. The strongest fluorescence for the limonene-derived SOA was observed for λexcitation = 420 ± 50 nm and λemission = 475 ± 38 nm. The window of the strongest fluorescence shifted to λexcitation = 320 ± 25 nm and λemission = 425 ± 38 nm for the α-pinene-derived SOA. Both regions overlap with the EEM spectra of some of the fluorophores found in primary biological aerosols. Despite the low quantum yield, the aged SOA particles may have sufficient fluorescence intensities to interfere with the fluorescence detection of common bioaerosols.

Transformation of logwood combustion emissions in a smog chamber: formation of secondary organic aerosol and changes in the primary organic aerosol upon daytime and nighttime aging

NASA Astrophysics Data System (ADS)

Tiitta, Petri; Leskinen, Ari; Hao, Liqing; Yli-Pirilä, Pasi; Kortelainen, Miika; Grigonyte, Julija; Tissari, Jarkko; Lamberg, Heikki; Hartikainen, Anni; Kuuspalo, Kari; Kortelainen, Aki-Matti; Virtanen, Annele; Lehtinen, Kari E. J.; Komppula, Mika; Pieber, Simone; Prévôt, André S. H.; Onasch, Timothy B.; Worsnop, Douglas R.; Czech, Hendryk; Zimmermann, Ralf; Jokiniemi, Jorma; Sippula, Olli

2016-10-01

Organic aerosols (OA) derived from small-scale wood combustion emissions are not well represented by current emissions inventories and models, although they contribute substantially to the atmospheric particulate matter (PM) levels. In this work, a 29 m3 smog chamber in the ILMARI facility of the University of Eastern Finland was utilized to investigate the formation of secondary organic aerosol (SOA) from a small-scale modern masonry heater commonly used in northern Europe. Emissions were oxidatively aged in the smog chamber for a variety of dark (i.e., O3 and NO3) and UV (i.e., OH) conditions, with OH concentration levels of (0.5-5) × 106 molecules cm-3, achieving equivalent atmospheric aging of up to 18 h. An aerosol mass spectrometer characterized the direct OA emissions and the SOA formed from the combustion of three wood species (birch, beech and spruce) using two ignition processes (fast ignition with a VOC-to-NOx ratio of 3 and slow ignition with a ratio of 5).Dark and UV aging increased the SOA mass fraction with average SOA productions 2.0 times the initial OA mass loadings. SOA enhancement was found to be higher for the slow ignition compared with fast ignition conditions. Positive matrix factorization (PMF) was used to separate SOA, primary organic aerosol (POA) and their subgroups from the total OA mass spectra. PMF analysis identified two POA and three SOA factors that correlated with the three major oxidizers: ozone, the nitrate radical and the OH radical. Organonitrates (ONs) were observed to be emitted directly from the wood combustion and additionally formed during oxidation via NO3 radicals (dark aging), suggesting small-scale wood combustion may be a significant ON source. POA was oxidized after the ozone addition, forming aged POA, and after 7 h of aging more than 75 % of the original POA was transformed. This process may involve evaporation and homogeneous gas-phase oxidation as well as heterogeneous oxidation of particulate organic matter. The results generally prove that logwood burning emissions are the subject of intensive chemical processing in the atmosphere, and the timescale for these transformations is relatively short, i.e., hours.

A model study of laboratory photooxidation experiments of mono- and sesquiterpenes

NASA Astrophysics Data System (ADS)

Capouet, M.; Vereecken, L.; Peeters, J.; Müller, J.

2006-12-01

The importance of monoterpenes in the atmosphere stems from their large emissions from plants, their high reactivity, and their role as precursors for Secondary Organic Aerosol (SOA) production. In order to quantify the impact of α-pinene oxidation (as representative of the monoterpenes) using a CTM, a detailed understanding of its oxidation mechanism is necessary. Past studies have investigated successfully the gas- phase OH-oxidation mechanism of α-pinene [Peeters et al., 2001; Vereecken and Peeters 2004; Capouet et al., 2004]. However, the SOA formation measured in laboratory experiments remains difficult to model, partly due to a poor understanding of the ozonolysis mechanism believed to be the dominant path to formation of condensable compounds. Very recently, Peeters and co-workers have developed a detailed mechanism for the α-pinene ozonolysis based on objective theoretical grounds. Both OH- and O3- oxidation mechanisms have been implemented in a box model and coupled to a module describing the gas/particle partitioning of the semi-volatile products on the basis of a vapour pressure prediction method [Capouet and Müller, 2006]. The photooxidation of primary products has been parameterized in order to evaluate the role of condensable compounds formed by secondary reactions. Simulations of a wide set of α-pinene photooxidation experiments reported in the literature have been performed. Results indicate that the calculated SOA contain a significant fraction of second generation products. Note in particular that our box model simulations as well as theoretical arguments contradict the gas-phase formation routes for pinic acid proposed in the literature and suggest a secondary origin for this compound. Contribution of the sesquiterpenes to biogenic non methane hydrocarbon emissions has been estimated from 9% to 28% in some regions in the U.S. Their high reactivity towards ozone and their complex chemistry make these compounds hardly accessible to theoretical and experimental study. Lately an increasing number of laboratory experiments have been performed and have reported that sesquiterpenes such as β- caryophyllene and α-humulene have much higher aerosol formation potentials than α-pinene on a mass basis. Using parameterizations similar to those developed previously for α-pinene, a simplified box model describing the oxidation of the sesquiterpenes and the related aerosol formation has been developed. Preliminary simulations of photooxidation experiments have been performed and are compared with the monoterpenes model results.

Molecular characterization of polar organosulfates in secondary organic aerosol from the green leaf volatile 3-Z-hexenal

NASA Astrophysics Data System (ADS)

Safi Shalamzari, Mohammad; Kahnt, Ariane; Wang, Wu; Vermeylen, Reinhilde; Kleindienst, Tadeusz; Lewandovski, Michael; Maenhaut, Willy; Claeys, Magda

2014-05-01

Much information is available about secondary organic aerosol (SOA) formation from terpenes, including mono- and sesquiterpenes, and isoprene. However, information about SOA formation from green leaf volatiles (GLVs), an important class of biogenic volatile organic compounds, which are emitted when plants are wounded or attacked by insects, is very scarce. In the present study, we provide evidence that 3-Z-hexenal is a potential precursor for SOA through formation of organosulfates. Organosulfate formation from 3-Z-hexenal was studied by conducting smog chamber photooxidation experiments in the presence of NO and acidic ammonium seed aerosol, where OH radicals were generated from the NOx mediated photochemical chain reactions. The focus of the study was on the structural characterization of products, i.e., organosulfates (OSs) with a molecular weight (MW) of 226, which are also present in ambient fine aerosol from a forested site (K puszta, Hungary) at a substantial relative abundance that is comparable to that of the MW 216 isoprene-related OSs. Polar OSs are of climatic relevance because of their capacity to increase the hydrophilic properties of aerosols and as such their cloud-condensation nuclei effects. Two different liquid chromatography (LC) techniques were employed to separate the polar OSs: the first technique uses a reversed-phase trifunctionally bonded C18 stationary phase, whereas the second one is based on ion-pairing C18 LC using dibutylammonium acetate as ion-pairing reagent. With regard to mass spectrometry (MS) techniques, use was made of high-resolution MS to determine the accurate mass (measured mass, 225.00809; elemental composition, C6H9O7S) as well as linear ion trap MS to obtain detailed structural information. The MW 226 OSs were structurally characterized as sulfated derivatives of 3,4-dihydroxyhex-2-enoic acid with the sulfate group positioned at C-3 or C-4. The formation of these OSs is explained through photooxidation in the gas phase resulting in a hydroperoxide, followed by acid-catalyzed rearrangement into an epoxyhydroxide and subsequent sulfation of the epoxy group in the particle phase. This work was supported by the Belgian Federal Science Policy Office through the network project "Biogenic Influence on Oxidants and Secondary Organic Aerosol: theoretical, laboratory and modeling investigations (BIOSOA)" and the Research Foundation - Flanders (FWO).

Improving the Performance of an Auditory Brain-Computer Interface Using Virtual Sound Sources by Shortening Stimulus Onset Asynchrony

PubMed Central

Sugi, Miho; Hagimoto, Yutaka; Nambu, Isao; Gonzalez, Alejandro; Takei, Yoshinori; Yano, Shohei; Hokari, Haruhide; Wada, Yasuhiro

2018-01-01

Recently, a brain-computer interface (BCI) using virtual sound sources has been proposed for estimating user intention via electroencephalogram (EEG) in an oddball task. However, its performance is still insufficient for practical use. In this study, we examine the impact that shortening the stimulus onset asynchrony (SOA) has on this auditory BCI. While very short SOA might improve its performance, sound perception and task performance become difficult, and event-related potentials (ERPs) may not be induced if the SOA is too short. Therefore, we carried out behavioral and EEG experiments to determine the optimal SOA. In the experiments, participants were instructed to direct attention to one of six virtual sounds (target direction). We used eight different SOA conditions: 200, 300, 400, 500, 600, 700, 800, and 1,100 ms. In the behavioral experiment, we recorded participant behavioral responses to target direction and evaluated recognition performance of the stimuli. In all SOA conditions, recognition accuracy was over 85%, indicating that participants could recognize the target stimuli correctly. Next, using a silent counting task in the EEG experiment, we found significant differences between target and non-target sound directions in all but the 200-ms SOA condition. When we calculated an identification accuracy using Fisher discriminant analysis (FDA), the SOA could be shortened by 400 ms without decreasing the identification accuracies. Thus, improvements in performance (evaluated by BCI utility) could be achieved. On average, higher BCI utilities were obtained in the 400 and 500-ms SOA conditions. Thus, auditory BCI performance can be optimized for both behavioral and neurophysiological responses by shortening the SOA. PMID:29535602

Integrating phase and composition of secondary organic aerosol from the ozonolysis of α-pinene

PubMed Central

Kidd, Carla; Perraud, Véronique; Wingen, Lisa M.; Finlayson-Pitts, Barbara J.

2014-01-01

Airborne particles are important for public health, visibility, and climate. Predicting their concentrations, effects, and responses to control strategies requires accurate models of their formation and growth in air. This is challenging, as a large fraction is formed by complex reactions of volatile organic compounds, generating secondary organic aerosol (SOA), which grows to sizes important for visibility, climate, and deposition in the lung. Growth of SOA is particularly sensitive to the phase/viscosity of the particles and remains poorly understood. We report studies using a custom-designed impactor with a germanium crystal as the impaction surface to study SOA formed from the ozonolysis of α-pinene at relative humidities (RHs) up to 87% at 297 ± 2 K (which corresponds to a maximum RH of 70–86% inside the impactor). The impaction patterns provide insight into changes in phase/viscosity as a function of RH. Attenuated total reflectance-Fourier transform infrared spectroscopy and aerosol mass spectrometry provide simultaneous information on composition changes with RH. The results show that as the RH at which the SOA is formed increases, there is a decrease in viscosity, accompanied by an increasing contribution from carboxylic acids and a decreasing contribution from higher molecular mass products. In contrast, SOA that is formed dry and subsequently humidified remains solid to high RH. The results of these studies have significant implications for modeling the growth, aging, and ultimately, lifetime of SOA in the atmosphere. PMID:24821796

Probing the Evaporation Dynamics of Mixed SOA/Squalane Particles Using Size-Resolved Composition and Single-Particle Measurements.

PubMed

Robinson, Ellis Shipley; Saleh, Rawad; Donahue, Neil M

2015-08-18

An analysis of the formation and evaporation of mixed-particles containing squalane (a surrogate for hydrophobic primary organic aerosol, POA) and secondary organic aerosol (SOA) is presented. In these experiments, one material (D62-squalane or SOA from α-pinene + O3) was prepared first to serve as surface area for condensation of the other, forming the mixed-particles. The mixed-particles were then subjected to a heating-ramp from 22 to 44 °C. We were able to determine that (1) almost all of the SOA mass is comprised of material less volatile than D62-squalane; (2) AMS collection efficiency in these mixed-particle systems can be parametrized as a function of the relative mass fraction of the components; and (3) the vast majority of D62-squalane is able to evaporate from the mixed particles, and does so on the same time scale regardless of the order of preparation. We also performed two-population mixing experiments to directly test whether D62-squalane and SOA from α-pinene + O3 form a single solution or two separate phases. We find that these two OA types are immiscible, which informs our inference of the morphology of the mixed-particles. If the morphology is core-shell and dictated by the order of preparation, these data indicate that squalane is able to diffuse relatively quickly through the SOA shell, implying that there are no major diffusion limitations.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Seinfeld, John H.

This project addressed the following research need in the Atmospheric System Research (ASR) Science and Program Plan: "Measurements downwind of urban sources of aerosol particles and precursor gases have shown that the mass concentration of secondary organic aerosol (SOA) can be several-fold greater than can be explained on the basis of current model calculations using observed precursor concentrations. ASR will continue conducting laboratory experiments on both gas-phase and aqueous-phase SOA formation to characterize the particle formation and the organic gases that react to form new organic aerosol material on aerosol seeds. ASR will use these experiments to guide the developmentmore » of comprehensive chemical mechanisms... to guide the development of parameterizations that are simple enough to be applied to aerosol life cycle models."« less

Cloud Processing of Secondary Organic Aerosol from Isoprene and Methacrolein Photooxidation.

PubMed

Giorio, Chiara; Monod, Anne; Brégonzio-Rozier, Lola; DeWitt, Helen Langley; Cazaunau, Mathieu; Temime-Roussel, Brice; Gratien, Aline; Michoud, Vincent; Pangui, Edouard; Ravier, Sylvain; Zielinski, Arthur T; Tapparo, Andrea; Vermeylen, Reinhilde; Claeys, Magda; Voisin, Didier; Kalberer, Markus; Doussin, Jean-François

2017-10-12

Aerosol-cloud interaction contributes to the largest uncertainties in the estimation and interpretation of the Earth's changing energy budget. The present study explores experimentally the impacts of water condensation-evaporation events, mimicking processes occurring in atmospheric clouds, on the molecular composition of secondary organic aerosol (SOA) from the photooxidation of methacrolein. A range of on- and off-line mass spectrometry techniques were used to obtain a detailed chemical characterization of SOA formed in control experiments in dry conditions, in triphasic experiments simulating gas-particle-cloud droplet interactions (starting from dry conditions and from 60% relative humidity (RH)), and in bulk aqueous-phase experiments. We observed that cloud events trigger fast SOA formation accompanied by evaporative losses. These evaporative losses decreased SOA concentration in the simulation chamber by 25-32% upon RH increase, while aqueous SOA was found to be metastable and slowly evaporated after cloud dissipation. In the simulation chamber, SOA composition measured with a high-resolution time-of-flight aerosol mass spectrometer, did not change during cloud events compared with high RH conditions (RH > 80%). In all experiments, off-line mass spectrometry techniques emphasize the critical role of 2-methylglyceric acid as a major product of isoprene chemistry, as an important contributor to the total SOA mass (15-20%) and as a key building block of oligomers found in the particulate phase. Interestingly, the comparison between the series of oligomers obtained from experiments performed under different conditions show a markedly different reactivity. In particular, long reaction times at high RH seem to create the conditions for aqueous-phase processing to occur in a more efficient manner than during two relatively short cloud events.

Explicit modeling of organic chemistry and secondary organic aerosol partitioning for Mexico City and its outflow plume

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lee-Taylor, J.; Madronich, Sasha; Aumont, B.

2011-12-21

The evolution of organic aerosols (OA) in Mexico City and its outflow is investigated with the nearly explicit gas phase photochemistry model GECKO-A (Generator of Explicit Chemistry and Kinetics of Organics in the Atmosphere), wherein precursor hydrocarbons are oxidized to numerous intermediate species for which vapor pressures are computed and used to determine gas/particle partitioning in a chemical box model. Precursor emissions included observed C3-10 alkanes, alkenes, and light aromatics, as well as larger n-alkanes (up to C25) not directly observed but estimated by scaling to particulate emissions according to their volatility. Conditions were selected for comparison with observations mademore » in March 2006 (MILAGRO). The model successfully reproduces the magnitude and diurnal shape for both primary (POA) and secondary (SOA) organic aerosols, with POA peaking in the early morning at 15-20 ug m-3, and SOA peaking at 10-15 μg m-3 during mid-day. The majority (> 75%) of the model SOA stems from the large n-alkanes, with the remainder mostly from the light aromatics. Simulated OA elemental composition reproduces observed H/C and O/C ratios reasonably well, although modeled ratios develop more slowly than observations suggest. SOA chemical composition is initially dominated by *- hydroxy ketones and nitrates from the large alkanes, with contributions from peroxy acyl nitrates and, at later times when NOx is lower, organic hydroperoxides. The simulated plume-integrated OA mass continues to increase for several days downwind despite dilution-induced particle evaporation, since oxidation chemistry leading to SOA formation remains strong. In this model, the plume SOA burden several days downwind exceeds that leaving the city by a factor of >3. These results suggest significant regional radiative impacts of SOA.« less

Multiday production of condensing organic aerosol mass in urban and forest outflow

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lee-Taylor, J.; Hodzic, A.; Madronich, S.

2015-01-16

Secondary organic aerosol (SOA) production in air masses containing either anthropogenic or biogenic (terpene-dominated) emissions is investigated using the explicit gas-phase chemical mechanism generator GECKO-A. Simulations show several-fold increases in SOA mass continuing for multiple days in the urban outflow, even as the initial air parcel is diluted into the regional atmosphere. The SOA mass increase in the forest outflow is more modest (~50%) and of shorter duration (1–2 days). The multiday production in the urban outflow stems from continuing oxidation of gas-phase precursors which persist in equilibrium with the particle phase, and can be attributed to multigenerational reaction productsmore » of both aromatics and alkanes, especially those with relatively low carbon numbers (C4–15). In particular we find large contributions from substituted maleic anhydrides and multi-substituted peroxide-bicyclic alkenes. The results show that the predicted production is a robust feature of our model even under changing atmospheric conditions and different vapor pressure schemes, and contradict the notion that SOA undergoes little mass production beyond a short initial formation period. The results imply that anthropogenic aerosol precursors could influence the chemical and radiative characteristics of the atmosphere over an extremely wide region, and that SOA measurements near precursor sources may routinely underestimate this influence.« less

Multiday production of condensing organic aerosol mass in urban and forest outflow

DOE PAGES

Lee-Taylor, J.; Hodzic, A.; Madronich, S.; ...

2015-01-16

Secondary organic aerosol (SOA) production in air masses containing either anthropogenic or biogenic (terpene-dominated) emissions is investigated using the explicit gas-phase chemical mechanism generator GECKO-A. Simulations show several-fold increases in SOA mass continuing for multiple days in the urban outflow, even as the initial air parcel is diluted into the regional atmosphere. The SOA mass increase in the forest outflow is more modest (~50%) and of shorter duration (1–2 days). The multiday production in the urban outflow stems from continuing oxidation of gas-phase precursors which persist in equilibrium with the particle phase, and can be attributed to multigenerational reaction productsmore » of both aromatics and alkanes, especially those with relatively low carbon numbers (C4–15). In particular we find large contributions from substituted maleic anhydrides and multi-substituted peroxide-bicyclic alkenes. The results show that the predicted production is a robust feature of our model even under changing atmospheric conditions and different vapor pressure schemes, and contradict the notion that SOA undergoes little mass production beyond a short initial formation period. Here, the results imply that anthropogenic aerosol precursors could influence the chemical and radiative characteristics of the atmosphere over an extremely wide region, and that SOA measurements near precursor sources may routinely underestimate this influence.« less

Microphysical Properties of Single Secondary Organic Aerosol (SOA) Particles

NASA Astrophysics Data System (ADS)

Rovelli, Grazia; Song, Young-Chul; Pereira, Kelly; Hamilton, Jacqueline; Topping, David; Reid, Jonathan

2017-04-01

Secondary Organic Aerosols (SOA) deriving from the oxidation of volatile organic compounds (VOCs) can account for a substantial fraction of the overall atmospheric aerosol mass.[1] Therefore, the investigation of SOA microphysical properties is crucial to better comprehend their role in the atmospheric processes they are involved in. This works describes a single particle approach to accurately characterise the hygroscopic response, the optical properties and the gas-particle partitioning kinetics of water and semivolatile components for laboratory generated SOA. SOA was generated from the oxidation of different VOCs precursors (e.g. α-pinene, toluene) in a photo-chemical flow reactor, which consists of a temperature and relative humidity controlled 300 L polyvinyl fluoride bag. Known VOC, NOx and ozone concentrations are introduced in the chamber and UV irradiation is performed by means of a Hg pen-ray. SOA samples were collected with an electrical low pressure impactor, wrapped in aluminium foil and kept refrigerated at -20°C. SOA samples were extracted in a 1:1 water/methanol mixture. Single charged SOA particles were generated from the obtained solution using a microdispenser and confined within an electrodynamic balance (EDB), where they sit in a T (250-320 K) and RH (0-95%) controlled nitrogen flow. Suspended droplets are irradiated with a 532 nm laser and the evolving angularly resolved scattered light is used to keep track of changes in droplet size. One of the key features of this experimental approach is that very little SOA solution is required because of the small volumes needed to load the dispensers (<20 μL). A number of diverse experiments were performed in order to characterise different microphysical properties of SOA. The equilibrium hygroscopic response of SOA was determined with comparative evaporation kinetics experiments (CK-EDB) of suspended probe and sample droplets.[2] The variation of the refractive index of SOA droplets following to water or SVOCs evaporative loss was measured as a function of water activity by fitting the collected light scattering patterns with a generated Mie-Theory library of phase functions.[3] Long trapping experiments (up to >20000 s) allow the observation of slow SVOCs evaporation kinetics at different T and RH conditions. Water condensation/evaporation kinetics experiments onto/from trapped SOA droplets following fast RH step changes (<0.5 s) were also performed in order to evaluate possible kinetics limitations to water diffusion in the condensed phase resulting from the formation of a viscous matrix. [1] Fuzzi et al., Atmos. Chem. Phys. 15, 8217-8299 (2015). [2] Rovelli et al., J. Phys. Chem. A 120, 4376-4388 (2016). [3] Cotterell et al., Phys. Chem. Chem. Phys. 17, 15843-15856 (2015).

Differences in BVOC oxidation and SOA formation above and below the forest canopy

NASA Astrophysics Data System (ADS)

Schulze, Benjamin C.; Wallace, Henry W.; Flynn, James H.; Lefer, Barry L.; Erickson, Matt H.; Jobson, B. Tom; Dusanter, Sebastien; Griffith, Stephen M.; Hansen, Robert F.; Stevens, Philip S.; VanReken, Timothy; Griffin, Robert J.

2017-02-01

Gas-phase biogenic volatile organic compounds (BVOCs) are oxidized in the troposphere to produce secondary pollutants such as ozone (O3), organic nitrates (RONO2), and secondary organic aerosol (SOA). Two coupled zero-dimensional models have been used to investigate differences in oxidation and SOA production from isoprene and α-pinene, especially with respect to the nitrate radical (NO3), above and below a forest canopy in rural Michigan. In both modeled environments (above and below the canopy), NO3 mixing ratios are relatively small (< 0.5 pptv); however, daytime (08:00-20:00 LT) mixing ratios below the canopy are 2 to 3 times larger than those above. As a result of this difference, NO3 contributes 12 % of total daytime α-pinene oxidation below the canopy while only contributing 4 % above. Increasing background pollutant levels to simulate a more polluted suburban or peri-urban forest environment increases the average contribution of NO3 to daytime below-canopy α-pinene oxidation to 32 %. Gas-phase RONO2 produced through NO3 oxidation undergoes net transport upward from the below-canopy environment during the day, and this transport contributes up to 30 % of total NO3-derived RONO2 production above the canopy in the morning (˜ 07:00). Modeled SOA mass loadings above and below the canopy ultimately differ by less than 0.5 µg m-3, and extremely low-volatility organic compounds dominate SOA composition. Lower temperatures below the canopy cause increased partitioning of semi-volatile gas-phase products to the particle phase and up to 35 % larger SOA mass loadings of these products relative to above the canopy in the model. Including transport between above- and below-canopy environments increases above-canopy NO3-derived α-pinene RONO2 SOA mass by as much as 45 %, suggesting that below-canopy chemical processes substantially influence above-canopy SOA mass loadings, especially with regard to monoterpene-derived RONO2.

Modelling secondary organic aerosol in the United Kingdom

NASA Astrophysics Data System (ADS)

Redington, A. L.; Derwent, R. G.

2013-01-01

The Lagrangian atmospheric dispersion model, NAME, has been used to model the formation and transport of anthropogenic and biogenic secondary organic aerosol (SOA) over North-West Europe in 2008. The model has been tested against daily organic carbon measurements at Harwell, a rural site in southern UK, where it was able to represent adequately the observed values in summer, with some under-prediction in winter. The model has been used to look at the contribution of SOA to total measured PM10 at four selected UK sites. The site with the greatest contribution (32%) of SOA to PM10 was Auchencorth, a rural site in Scotland and least (9%) at London Bloomsbury. The biogenic SOA (BSOA) dominated over the anthropogenic SOA (ASOA) in the UK and showed a strong seasonal cycle peaking in the summer. There was also a slight summer increase in ASOA. The model has been employed to provide source attribution between UK sources and sources in the rest of Europe. The contribution from Europe was generally small but varied considerably due to meteorology. The UK component showed a seasonal cycle, peaking in the summer months. On an annual basis, considering the four measurement sites, the percentage of SOA arriving from outside the UK was least at Auchencorth (9.8%) and most at London (28.4%). Total modelled SOA had a maximum contribution of 2-3 μg m-3 as a monthly average. (It should be noted that in addition there will be a small contribution from background SOA to these figures.) Emission sensitivity studies revealed that the response of ASOA was highly non-linear, showing both positive and negative responses to a 30% reduction in all man-made NOx sources and the response was greater than 1:1 to a 30% reduction in all man-made VOC sources. BSOA showed only a small negative response to a 30% NOx reduction and no change to a 30% VOC reduction.

Observed secondary organic aerosol (SOA) and organic nitrate yields from NO3 oxidation of isoprene

NASA Astrophysics Data System (ADS)

Rollins, A. W.; Fry, J. L.; Kiendler-Scharr, A.; Wooldridge, P. J.; Brown, S. S.; Fuchs, H.; Dube, W.; Mensah, A.; Tillmann, R.; Dorn, H.; Brauers, T.; Cohen, R. C.

2008-12-01

Formation of organic nitrates and secondary organic aerosol (SOA) from the NO3 oxidation of isoprene has been studied at atmospheric concentrations of VOC (10 ppb) and oxidant (<100 ppt NO3) in the presence of ammonium sulfate seed aerosol in the atmosphere simulation chamber SAPHIR at Forschungszentrum Jülich. Cavity Ringdown (CaRDS) and thermal dissociation - CaRDS measurements of NO3 and N2O5 as well as Thermal Dissociation - Laser Induced Fluorescence (TD-LIF) detection of alkyl nitrates (RONO2) and Aerodyne Aerosol Mass Spectrometer (AMS) measurements of aerosol composition were all used in comparison to a Master Chemical Mechanism (MCM) based chemical kinetics box model to quantify the product yields from two stages in isoprene oxidation. We find significant yields of organic nitrate formation from both the initial isoprene + NO3 reaction (71%) as well as from the reaction of NO3 with the initial oxidation products (30% - 60%). Under these low concentration conditions (~1 μg / m3), measured SOA production was greater than instrument noise only for the second oxidation step. Based on the modeled chemistry, we estimate an SOA mass yield of 10% (relative to isoprene mass reacted) for the reaction of the initial oxidation products with NO3. This yield is found to be consistent with the estimated saturation concentration (C*) of the presumed gas products of the doubly oxidized isoprene, where both oxidations lead to the addition of nitrate, carbonyl, and hydroxyl groups.

Nonequilibrium atmospheric secondary organic aerosol formation and growth

PubMed Central

Perraud, Véronique; Bruns, Emily A.; Ezell, Michael J.; Johnson, Stanley N.; Yu, Yong; Alexander, M. Lizabeth; Zelenyuk, Alla; Imre, Dan; Chang, Wayne L.; Dabdub, Donald; Pankow, James F.; Finlayson-Pitts, Barbara J.

2012-01-01

Airborne particles play critical roles in air quality, health effects, visibility, and climate. Secondary organic aerosols (SOA) formed from oxidation of organic gases such as α-pinene account for a significant portion of total airborne particle mass. Current atmospheric models typically incorporate the assumption that SOA mass is a liquid into which semivolatile organic compounds undergo instantaneous equilibrium partitioning to grow the particles into the size range important for light scattering and cloud condensation nuclei activity. We report studies of particles from the oxidation of α-pinene by ozone and NO3 radicals at room temperature. SOA is primarily formed from low-volatility ozonolysis products, with a small contribution from higher volatility organic nitrates from the NO3 reaction. Contrary to expectations, the particulate nitrate concentration is not consistent with equilibrium partitioning between the gas phase and a liquid particle. Rather the fraction of organic nitrates in the particles is only explained by irreversible, kinetically determined uptake of the nitrates on existing particles, with an uptake coefficient that is 1.6% of that for the ozonolysis products. If the nonequilibrium particle formation and growth observed in this atmospherically important system is a general phenomenon in the atmosphere, aerosol models may need to be reformulated. The reformulation of aerosol models could impact the predicted evolution of SOA in the atmosphere both outdoors and indoors, its role in heterogeneous chemistry, its projected impacts on air quality, visibility, and climate, and hence the development of reliable control strategies. PMID:22308444

Public Health Impacts of Secondary Particulate Formation from Aromatic Hydrocarbons in Gasoline

EPA Science Inventory

Background: Aromatic hydrocarbons emitted from gasoline‐powered vehicles contribute to the formation of secondary organic aerosol (SOA), which increases the atmospheric mass concentration of fine particles (PM_2.5). Here we estimate the public health burden associated w...

Reassessing the atmospheric oxidation mechanism of toluene

NASA Astrophysics Data System (ADS)

Ji, Yuemeng; Zhao, Jun; Terazono, Hajime; Misawa, Kentaro; Levitt, Nicholas P.; Li, Yixin; Lin, Yun; Peng, Jianfei; Wang, Yuan; Duan, Lian; Pan, Bowen; Zhang, Fang; Feng, Xidan; An, Taicheng; Marrero-Ortiz, Wilmarie; Secrest, Jeremiah; Zhang, Annie L.; Shibuya, Kazuhiko; Molina, Mario J.; Zhang, Renyi

2017-08-01

Photochemical oxidation of aromatic hydrocarbons leads to tropospheric ozone and secondary organic aerosol (SOA) formation, with profound implications for air quality, human health, and climate. Toluene is the most abundant aromatic compound under urban environments, but its detailed chemical oxidation mechanism remains uncertain. From combined laboratory experiments and quantum chemical calculations, we show a toluene oxidation mechanism that is different from the one adopted in current atmospheric models. Our experimental work indicates a larger-than-expected branching ratio for cresols, but a negligible formation of ring-opening products (e.g., methylglyoxal). Quantum chemical calculations also demonstrate that cresols are much more stable than their corresponding peroxy radicals, and, for the most favorable OH (ortho) addition, the pathway of H extraction by O2 to form the cresol proceeds with a smaller barrier than O2 addition to form the peroxy radical. Our results reveal that phenolic (rather than peroxy radical) formation represents the dominant pathway for toluene oxidation, highlighting the necessity to reassess its role in ozone and SOA formation in the atmosphere.

Limitations in Using Chemical Oxidative Potential to Understand Oxidative Stress from Particulate Matter

NASA Astrophysics Data System (ADS)

Chan, A. W. H.; Wang, S.; Wang, X.; Kohl, L.; Chow, C. W.

2017-12-01

Particulate matter (PM) in the atmosphere is known to cause adverse cardiorespiratory health effects. It has been suggested that the ability of PM to generate oxidative stress leads to a proinflammatory response. In this work, we study the biological relevance of using a chemical oxidative potential (OP) assay to evaluate proinflammatory response in airway epithelial cells. Here we study the OPs of laboratory secondary organic aerosol (SOA) and metal mixtures, ambient PM from India, ash from the 2016 Alberta wildfires, and diesel exhaust particles. We use SOA derived from naphthalene and from monoterpenes as model systems for SOA. We measure OP using the dithiothreitol (DTT) assay, and cytosolic reactive oxygen species (ROS) production in BEAS-2B cell culture was measured using CellROX assay. We found that both SOA and copper show high OPs individually, but the OP of the combined SOA/copper mixture, which is more atmospherically relevant, was lower than either of the individual OPs. The reduced activity is attributed to chelation between metals and organic compounds using proton nuclear magnetic resonance. There is reasonable association between DTT activity and cellular ROS production within each particle type, but weak association across different particle types, suggesting that particle composition plays an important role in distinguishing between antioxidant consumption and ROS production. Our results highlight that while oxidative potential is a useful metric of PM's ability to generate oxidative stress, the chemical composition and cellular environment should be considered in understanding health impacts of PM.

Atmospheric Degradation Initiated by OH Radicals of the Potential Foam Expansion Agent, CF3(CF2)2CH═CH2 (HFC-1447fz): Kinetics and Formation of Gaseous Products and Secondary Organic Aerosols.

PubMed

Jiménez, Elena; González, Sergio; Cazaunau, Mathieu; Chen, Hui; Ballesteros, Bernabé; Daële, Véronique; Albaladejo, José; Mellouki, Abdelwahid

2016-02-02

The assessment of the atmospheric impact of the potential foam expansion agent, CF3(CF2)2CH═CH2 (HFC-1447fz), requires the knowledge of its degradation routes, oxidation products, and radiative properties. In this paper, the gas-phase reactivity of HFC-1447fz with OH radicals is presented as a function of temperature, obtaining kOH (T = 263-358 K) = (7.4 ± 0.4) × 10(-13)exp{(161 ± 16)/T} (cm(3)·molecule(-1)·s(-1)) (uncertainties: ±2σ). The formation of gaseous oxidation products and secondary organic aerosols (SOAs) from the OH + HFC-1447fz reaction was investigated in the presence of NOx at 298 K. CF3(CF2)2CHO was observed at low- and high-NOx conditions. Evidence of SOA formation (ultrafine particles in the range 10-100 nm) is reported with yields ranging from 0.12 to 1.79%. In addition, the absolute UV (190-368 nm) and IR (500-4000 cm(-1)) absorption cross-sections of HFC-1447fz were determined at room temperature. No appreciable absorption in the solar actinic region (λ > 290 nm) was observed, leaving the removal by OH radicals as the main atmospheric loss process for HFC-1447fz. The major contribution of the atmospheric loss of HFC-1447fz is due to OH reaction (84%), followed by ozone (10%) and chlorine atoms (6%). Correction of the instantaneous radiative efficiency (0.36 W m(-2)·ppbv(-1)) with the relatively short lifetime of HFC-1447fz (ca. 8 days) implies that its global warming potential at a time horizon of 100 year is negligible (0.19) compared to that of HCFC-141b (782) and to that of modern foam-expansion blowing agents (148, 882, and 804 for HFC-152a, HFC-245fa and HFC-365mfc, respectively).

Ozonolysis of α-phellandrene - Part 2: Compositional analysis of secondary organic aerosol highlights the role of stabilised Criegee intermediates

NASA Astrophysics Data System (ADS)

Mackenzie-Rae, Felix A.; Wallis, Helen J.; Rickard, Andrew R.; Pereira, Kelly L.; Saunders, Sandra M.; Wang, Xinming; Hamilton, Jacqueline F.

2018-04-01

The molecular composition of the water-soluble fraction of secondary organic aerosol (SOA) generated from the ozonolysis of α-phellandrene is investigated for the first time using high-pressure liquid chromatography coupled to high-resolution quadrupole-Orbitrap tandem mass spectrometry. In total, 21 prominent products or isomeric product groups were identified using both positive and negative ionisation modes, with potential formation mechanisms discussed. The aerosol was found to be composed primarily of polyfunctional first- and second-generation species containing one or more carbonyl, acid, alcohol and hydroperoxide functionalities, with the products significantly more complex than those proposed from basic gas-phase chemistry in the companion paper (Mackenzie-Rae et al., 2017). Mass spectra show a large number of dimeric products are also formed. Both direct scavenging evidence using formic acid and indirect evidence from double bond equivalency factors suggest the dominant oligomerisation mechanism is the bimolecular reaction of stabilised Criegee intermediates (SCIs) with non-radical ozonolysis products. Saturation vapour concentration estimates suggest monomeric species cannot explain the rapid nucleation burst of fresh aerosol observed in chamber experiments; hence, dimeric species are believed to be responsible for new particle formation, with detected first- and second-generation products driving further particle growth in the system. Ultimately, identification of the major constituents and formation pathways of α-phellandrene SOA leads to a greater understanding of the atmospheric processes and implications of monoterpene emissions and SCIs, especially around eucalypt forests where α-phellandrene is primarily emitted.

Insights Into Atmospheric Aqueous Organic Chemistry Through Controlled Experiments with Cloud Water Surrogates

NASA Astrophysics Data System (ADS)

Turpin, B. J.; Ramos, A.; Kirkland, J. R.; Lim, Y. B.; Seitzinger, S.

2011-12-01

There is considerable laboratory and field-based evidence that chemical processing in clouds and wet aerosols alters organic composition and contributes to the formation of secondary organic aerosol (SOA). Single-compound laboratory experiments have played an important role in developing aqueous-phase chemical mechanisms that aid prediction of SOA formation through multiphase chemistry. In this work we conduct similar experiments with cloud/fog water surrogates, to 1) evaluate to what extent the previously studied chemistry is observed in these more realistic atmospheric waters, and 2) to identify additional atmospherically-relevant precursors and products that require further study. We used filtered Camden and Pinelands, NJ rainwater as a surrogate for cloud water. OH radical (~10-12 M) was formed by photolysis of hydrogen peroxide and samples were analyzed in real-time by electrospray ionization mass spectroscopy (ESI-MS). Discrete samples were also analyzed by ion chromatography (IC) and ESI-MS after IC separation. All experiments were performed in duplicate. Standards of glyoxal, methylglyoxal and glycolaldehyde and their major aqueous oxidation products were also analyzed, and control experiments performed. Decreases in the ion abundance of many positive mode compounds and increases in the ion abundance of many negative mode compounds (e.g., organic acids) suggest that precursors are predominantly aldehydes, organic peroxides and/or alcohols. Real-time ESI mass spectra were consistent with the expected loss of methylglyoxal and subsequent formation of pyruvate, glyoxylate, and oxalate. New insights regarding other potential precursors and products will be provided.

Gas- and particle-phase primary emissions from in-use, on-road gasoline and diesel vehicles

NASA Astrophysics Data System (ADS)

May, Andrew A.; Nguyen, Ngoc T.; Presto, Albert A.; Gordon, Timothy D.; Lipsky, Eric M.; Karve, Mrunmayi; Gutierrez, Alváro; Robertson, William H.; Zhang, Mang; Brandow, Christopher; Chang, Oliver; Chen, Shiyan; Cicero-Fernandez, Pablo; Dinkins, Lyman; Fuentes, Mark; Huang, Shiou-Mei; Ling, Richard; Long, Jeff; Maddox, Christine; Massetti, John; McCauley, Eileen; Miguel, Antonio; Na, Kwangsam; Ong, Richard; Pang, Yanbo; Rieger, Paul; Sax, Todd; Truong, Tin; Vo, Thu; Chattopadhyay, Sulekha; Maldonado, Hector; Maricq, M. Matti; Robinson, Allen L.

2014-05-01

Tailpipe emissions from sixty-four unique light-duty gasoline vehicles (LDGVs) spanning model years 1987-2012, two medium-duty diesel vehicles and three heavy-duty diesel vehicles with varying levels of aftertreatment were characterized at the California Air Resources Board Haagen-Smit and Heavy-Duty Engine Testing Laboratories. Each vehicle was tested on a chassis dynamometer using a constant volume sampler, commercial fuels and standard duty cycles. Measurements included regulated pollutants such as carbon monoxide (CO), total hydrocarbons (THC), nitrogen oxides (NOx), and particulate matter (PM). Off-line analyses were performed to speciate gas- and particle-phase emissions. The data were used to investigate trends in emissions with vehicle age and to quantify the effects of different aftertreatment technologies on diesel vehicle emissions (e.g., with and without a diesel particulate filter). On average, newer LDGVs that met the most recent emissions standards had substantially lower emissions of regulated gaseous pollutants (CO, THC and NOx) than older vehicles. For example, THC emissions from the median LDGV that met the LEV2 standard was roughly a factor of 10 lower than the median pre-LEV vehicle; there were also substantial reductions in NOx (factor of ∼100) and CO (factor of ∼10) emissions from pre-LEV to LEV2 vehicles. However, reductions in LDGV PM mass emissions were much more modest. For example, PM emission from the median LEV2 vehicle was only a factor of three lower than the median pre-LEV vehicle, mainly due to the reductions in organic carbon emissions. In addition, LEV1 and LEV2 LDGVs had similar PM emissions. Catalyzed diesel particulate filters reduced CO, THC and PM emissions from HDDVs by one to two orders of magnitude. Comprehensive organic speciation was performed to quantify priority air toxic emissions and to estimate the secondary organic aerosol (SOA) formation potential. The data suggest that the SOA production from cold-start LDGVs exhaust will likely exceed primary PM emissions from LDGVs and could potentially exceed SOA formation from on-road diesel vehicles.

Multi-format all-optical processing based on a large-scale, hybridly integrated photonic circuit.

PubMed

Bougioukos, M; Kouloumentas, Ch; Spyropoulou, M; Giannoulis, G; Kalavrouziotis, D; Maziotis, A; Bakopoulos, P; Harmon, R; Rogers, D; Harrison, J; Poustie, A; Maxwell, G; Avramopoulos, H

2011-06-06

We investigate through numerical studies and experiments the performance of a large scale, silica-on-silicon photonic integrated circuit for multi-format regeneration and wavelength-conversion. The circuit encompasses a monolithically integrated array of four SOAs inside two parallel Mach-Zehnder structures, four delay interferometers and a large number of silica waveguides and couplers. Exploiting phase-incoherent techniques, the circuit is capable of processing OOK signals at variable bit rates, DPSK signals at 22 or 44 Gb/s and DQPSK signals at 44 Gbaud. Simulation studies reveal the wavelength-conversion potential of the circuit with enhanced regenerative capabilities for OOK and DPSK modulation formats and acceptable quality degradation for DQPSK format. Regeneration of 22 Gb/s OOK signals with amplified spontaneous emission (ASE) noise and DPSK data signals degraded with amplitude, phase and ASE noise is experimentally validated demonstrating a power penalty improvement up to 1.5 dB.

Salting Constants of Small Organic Molecules in Aerosol-Relevant Salts and Application to Aerosol Formation in the Southeastern United States

NASA Astrophysics Data System (ADS)

Waxman, E.; Carlton, A. M. G.; Ziemann, P. J.; Volkamer, R. M.

2014-12-01

Secondary organic aerosol (SOA) formation from small water-soluble molecules such as glyoxal and methyl glyoxal is a topic of emerging interest. Results from recent field campaigns, e.g. Waxman et al. (2013, GRL) and Knote et al. (2014, ACP), show that these molecules can form significant SOA mass as a result of 'salting-in'. Salting-in happens when a molecule's solubility increases with salt concentration and salting-out is the reverse. Salting effects modify the solubility exponentially with increasing salt concentration, and thus the effective Henry's law constant can strongly modify partitioning, and multiphase chemical reaction rates in aerosol water. Moreover, the solubility in aerosol water cannot easily inferred based on the solubility in cloud water, as the salting effects could change the solubility by a factor of 104 or more. In this work, we have devised and applied a novel experimental setup to measure salting constants using an ion trap mass spectrometer. We focus on small, water soluble molecules like methyl glyoxal and similar compounds and measure salting constants for aerosol-relevant salts including ammonium sulfate, ammonium nitrate, and sodium chloride. The Setschenow salting-constant values are then used to parameterize the effects of salting in CMAQ. We present a series of sensitivity studies of the effects that inorganic aerosols have on the SOA formation from small soluble molecules in the southeastern United States.

Science opportunity analyzer - a multi-mission tool for planning

NASA Technical Reports Server (NTRS)

Streiffert, B. A.; Polanskey, C. A.; O'Reilly, T.; Colwell, J.

2002-01-01

For many years the diverse scientific community that supports JPL's wide variety ofinterplanetary space missions has needed a tool in order to plan and develop their experiments. The tool needs to be easily adapted to various mission types and portable to the user community. The Science Opportunity Analyzer, SOA, now in its third year of development, is intended to meet this need. SOA is a java-based application that is designed to enable scientists to identify and analyze opportunities for science observations from spacecraft. It differs from other planning tools in that it does not require an in-depth knowledge of the spacecraft command system or operation modes to begin high level planning. Users can, however, develop increasingly detailed levels of design. SOA consists of six major functions: Opportunity Search, Visualization, Observation Design, Constraint Checking, Data Output and Communications. Opportunity Search is a GUI driven interface to existing search engines that can be used to identify times when a spacecraft is in a specific geometrical relationship with other bodies in the solar system. This function can be used for advanced mission planning as well as for making last minute adjustments to mission sequences in response to trajectory modifications. Visualization is a key aspect of SOA. The user can view observation opportunities in either a 3D representation or as a 2D map projection. The user is given extensive flexibility to customize what is displayed in the view. Observation Design allows the user to orient the spacecraft and visualize the projection of the instrument field of view for that orientation using the same views as Opportunity Search. Constraint Checking is provided to validate various geometrical and physical aspects of an observation design. The user has the ability to easily create custom rules or to use official project-generated flight rules. This capability may also allow scientists to easily impact the cost to science if flight rule changes occur. Data Output generates information based on the spacecraft's trajectory, opportunity search results or based on a created observation. The data can be viewed either in tabular format or as a graph. Finally, SOA is unique in that it is designed to be able to communicate with a variety of existing planning and sequencing tools. From the very beginning SOA was designed with the user in mind. Extensive surveys of the potential user community were conducted in order to develop the software requirements. Throughout the development period, close ties have been maintained with the science community to insure that the tool maintains its user focus. Although development is still in its early stages, SOA is already developing a user community on the Cassini project, which is depending on this tool for their science planning. There are other tools at JPL that do various pieces of what SOA can do; however, there is no other tool which combines all these functions and presents them to the user in such a convenient, cohesive, and easy to use fashion.

Photooxidation of farnesene mixtures in the presence of NOx: Analysis of reaction products and their implication to ambient PM2.5

EPA Pesticide Factsheets

Chemical analysis of SOA produced from the irradiation of a mixture of 03b1/03b2-farnesene/NOx was conducted in a 14.5 cubic meter smog chamber. SOA collected on glass-fiber filters was solvent extracted, derivatized using BSTFA, and analyzed by GC-MS. Gas-phase products were analyzed using a combination of GC-FID and GC-MS. This analysis showed the occurrence of more than 30 SOA oxygenated species and more than 20 in the gas phase. The major SOA components measured include conjugated 03b1 farnesene trienols, C3??C7 linear dicarboxylic acids, carbonyl compounds, and hydroxy/carbonyl/carboxylic compounds. In the gas phase, the main species identified were formaldehyde, glyoxal, methylglyoxal, acetone, 2,3-dimethyl-oxirane, 2(3H)-furanone, 2-butenedioic acid, 4 oxopentanal, 4-methylenehex-5-enal, and 6-methylhept-5-en-2-one. Proposed reaction schemes are provided for selected compounds. H-atom abstraction and OH addition in 03b1/03b2-farnesene oxidation seem to play an important role via the formation of unsaturated radicals containing different numbers of delocalized electrons. Allylic hydrogen abstraction and hydroperoxyalkyl radical channels might play a key role in the oxidation of 03b1/03b2-farnesene. The contribution of farnesene SOA products to ambient PM2.5 was investigated by analyzing PM2.5 samples collected during SOAS 2013 field study at a site in Research Triangle Park (RTP), NC. The importance of these findings was supported by the occurrence of seve

Characterization of Secondary Organic Aerosol Precursors Using Two-Dimensional Gas-Chromatography

NASA Astrophysics Data System (ADS)

Roskamp, M.; Lou, W.; Pankow, J. F.; Harley, P. C.; Turnipseed, A.; Barsanti, K. C.

2012-12-01

The oxidation of volatile organic compounds (VOCs) plays a role in both regional and global air quality. However, field and laboratory research indicate that the body of knowledge around the identities, quantities and oxidation processes of these compounds in the ambient atmosphere is still incomplete (e.g., Goldstein & Galbally, 2007; Robinson et al., 2009). VOCs emitted to the atmosphere largely are of biogenic origin (Guenther et al., 2006), and many studies of ambient secondary organic aerosol (SOA) suggest that SOA is largely of biogenic origin (albeit closely connected to anthropogenic activities, e.g., de Gouw and Jimenez, 2009). Accurate modeling of SOA levels and properties will require a more complete understanding of biogenic VOCs (BOCs) and their atmospheric oxidation products. For example, satellite measurements indicate that biogenic VOC emissions are two to three times greater than levels currently included in models (Heald et al., 2010). Two-dimensional gas chromatography (GC×GC) is a powerful analytical technique that shows much promise in advancing the state-of-knowledge regarding BVOCs and their role in SOA formation. In this work, samples were collected during BEACHON-RoMBAS (Bio-hydro-atmosphere Interactions of Energy, Aerosols, Carbon, H2O, Organics & Nitrogen - Rocky Mountain Biogenic Aerosol Study) in July and August of 2011. The field site was a Ponderosa Pine forest near Woodland, CO, inside the Manitou Experimental Forest, which is operated by the US Forest Service. The area is characteristic of the central Rocky Mountains and trace gas monitoring indicates that little anthropogenic pollution is transported from the nearby urban areas (Kim et al. 2010 and references therein). Ambient and enclosure samples were collected on ATD (adsorption/thermal desorption) cartridges and analyzed for BVOCs using two-dimensional gas chromatography (GC×GC) with time of flight mass spectrometry (TOFMS) and flame ionized detection (FID). Measurements of BVOC species, including mono- and sesquiterpenes and oxygenated mono- and sesquiterpenes, will be presented. The results will be discussed in the context of atmospheric composition and SOA formation.

Experimental determination of the partitioning coefficient and volatility of important BVOC oxidation products using the Aerosol Collection Module (ACM) coupled to a PTR-ToF-MS

NASA Astrophysics Data System (ADS)

Gkatzelis, G.; Hohaus, T.; Tillmann, R.; Schmitt, S. H.; Yu, Z.; Schlag, P.; Wegener, R.; Kaminski, M.; Kiendler-Scharr, A.

2015-12-01

Atmospheric aerosol can alter the Earth's radiative budget and global climate but can also affect human health. A dominant contributor to the submicrometer particulate matter (PM) is organic aerosol (OA). OA can be either directly emitted through e.g. combustion processes (primary OA) or formed through the oxidation of organic gases (secondary organic aerosol, SOA). A detailed understanding of SOA formation is of importance as it constitutes a major contribution to the total OA. The partitioning between the gas and particle phase as well as the volatility of individual components of SOA is yet poorly understood adding uncertainties and thus complicating climate modelling. In this work, a new experimental methodology was used for compound-specific analysis of organic aerosol. The Aerosol Collection Module (ACM) is a newly developed instrument that deploys an aerodynamic lens to separate the gas and particle phase of an aerosol. The particle phase is directed to a cooled sampling surface. After collection particles are thermally desorbed and transferred to a detector for further analysis. In the present work, the ACM was coupled to a Proton Transfer Reaction-Time of Flight-Mass Spectrometer (PTR-ToF-MS) to detect and quantify organic compounds partitioning between the gas and particle phase. This experimental approach was used in a set of experiments at the atmosphere simulation chamber SAPHIR to investigate SOA formation. Ozone oxidation with subsequent photochemical aging of β-pinene, limonene and real plant emissions from Pinus sylvestris (Scots pine) were studied. Simultaneous measurement of the gas and particle phase using the ACM-PTR-ToF-MS allows to report partitioning coefficients of important BVOC oxidation products. Additionally, volatility trends and changes of the SOA with photochemical aging are investigated and compared for all systems studied.

75 FR 52267 - Waiver of Statement of Account Filing Deadline for the 2010/1 Period

Federal Register 2010, 2011, 2012, 2013, 2014

2010-08-25

... available in a print format, a PDF format, and a software ``fill-in'' format created by Gralin Associates... retransmission of multicast streams. The paper and PDF versions of the form have been available to cable... recognize that the paper and PDF versions of the SOA have been available since July, many large and small...

DOE Office of Scientific and Technical Information (OSTI.GOV)

Goldstein, A. H.; Yee, L. D.; Issacman-VanWertz, G.

In areas where biogenic emissions are oxidized in the presence of anthropogenic pollutants such as SO2, NOx, and black carbon, it has become increasingly apparent that secondary organic aerosol (SOA) formation from biogenic volatile organic compounds (VOCs) is substantially enhanced. Research is urgently needed to elucidate fundamental processes of natural and anthropogenically influenced VOC oxidation and the contribution of these processes to SOA formation. GoAmazon 2014/15 afforded study of the chemical transformations in the region downwind of Manaus, Brazil, where local biogenic VOC emissions are high, and their chemical oxidation can be studied both inside and outside of the urbanmore » plume to differentiate the role of anthropogenic influence on secondary aerosol formation during oxidation of these natural VOC emissions. To understand the connection between primary biogenic VOC emissions and their secondary products that form aerosols, we made time-resolved molecular level measurements by deploying a Semi-Volatile Thermal Desorption Aerosol Gas Chromatograph (SV-TAG) and a sequential filter sampler during two intensive operational periods (IOPs) of the GoAmazon 2014/15 field campaign. The SV-TAG measured semi-volatile organic compounds in both the gas and particle phases and the sequential filter sampler collected aerosols on quartz fiber filters in four-hour increments used for offline analysis. SV-TAG employed novel online derivatization that provided chemical speciation of highly oxygenated or functionalized compounds that comprise a substantial fraction of secondary organic aerosols, yet are poorly characterized. It also provided partitioning of these compounds between the vapor and particle phases at sufficient time resolution to define the importance of competing atmospheric processes. These measurements were supported by offline analysis of the filters using two-dimensional gas chromatography (GC x GC) with high-resolution time-of-flight mass spectrometry (HR-TOF-MS) using both electron impact (EI) and soft vacuum ultraviolet (VUV) ionization with derivatization. Speciated chemical data from SV-TAG and filter measurements were used to elucidate the relative importance of potential oxidation pathways by providing detailed information on the product distribution from atmospheric reactions and the quantification of known tracers for various oxidation pathways. Together, these techniques provided unequivocal molecular identification of a wide range of atmospheric organic compounds spanning the volatile, semi-volatile, and non-volatile phases. This level of chemical characterization provided insight into the chemical and physical processes that control the atmospheric oxidation of biogenic VOC and subsequent formation of SOA.« less

Primary emissions and chemical oxidation of volatile organic compounds emitted from laboratory biomass burning sources during the 2016 FIREX FireLab campaign: measurements from a H3O+ chemical ionization mass spectrometer

NASA Astrophysics Data System (ADS)

Coggon, M. M.; Warneke, C.; Koss, A.; Sekimoto, K.; Yuan, B.; Lim, C. Y.; Hagan, D. H.; Kroll, J. H.; Cappa, C. D.; Gilman, J.; Lerner, B. M.; Jimenez, J. L.; Yokelson, R. J.; Roberts, J. M.; De Gouw, J. A.

2017-12-01

Non-methane organic gases (NMOG) emitted by biomass burning constitute a large source of reactive carbon in the atmosphere. Once emitted, these compounds may undergo series of reactions with the OH radical and nitrogen oxides to form secondary organic aerosol (SOA), ozone, or other health-impacting products. The complex emission profile and strong variability of biomass burning NMOG play an important, yet understudied, role in the variability of air quality outcomes such as SOA and ozone. In this study, we summarize measurements of biomass burning volatile organic compounds (VOCs) conducted using a H3O+ chemical ionization mass spectrometer (H3O+-CIMS) during the 2016 FIREX laboratory campaign in Missoula, MT. Specifically, we will present data demonstrating the chemical evolution of biomass burning VOCs artificially aged in a field-deployable photooxidation chamber and an oxidation flow reactor. More than 50 OH-oxidation experiments were conducted with biomass types representing a range of North American fuels. Across many fuel types, VOCs with high SOA and ozone formation potential, such as aromatics and furans, were observed to quickly react with the OH radical while oxidized species were generated. We compare the calculated OH reactivity of the primary emissions to the calculated OH reactivity used in many photochemical models and highlight areas requiring additional research in order to improve model/measurement comparisons.

Aqueous photooxidation of ambient Po Valley Italy air samples: Insights into secondary organic aerosol formation

NASA Astrophysics Data System (ADS)

Kirkland, J. R.; Lim, Y. B.; Sullivan, A. P.; Decesari, S.; Facchini, C.; Collett, J. L.; Keutsch, F. N.; Turpin, B. J.

2012-12-01

In this work, we conducted aqueous photooxidation experiments with ambient samples in order to develop insights concerning the formation of secondary organic aerosol through gas followed by aqueous chemistry (SOAaq). Water-soluble organics (e.g., glyoxal, methylglyoxal, glycolaldehyde, acetic acid, acetone) are formed through gas phase oxidation of alkene and aromatic emissions of anthropogenic and biogenic origin. Their further oxidation in clouds, fogs and wet aerosols can form lower volatility products (e.g., oligomers, organic acids) that remain in the particle phase after water evaporation, thus producing SOA. The aqueous OH radical oxidation of several individual potentially important precursors has been studied in the laboratory. In this work, we used a mist-chamber apparatus to collect atmospheric mixtures of water-soluble gases from the ambient air at San Pietro Capofiume, Italy during the PEGASOS field campaign. We measured the concentration dynamics after addition of OH radicals, in order to develop new insights regarding formation of SOA through aqueous chemistry. Specifically, batch aqueous reactions were conducted with 33 ml mist-chamber samples (TOC ~ 50-100μM) and OH radicals (~10-12M) in a new low-volume aqueous reaction vessel. OH radicals were formed in-situ, continuously by H2O2 photolysis. Products were analyzed by ion chromatography (IC), electrospray ionization mass spectrometry (ESI-MS +/-), and ESI-MS with IC pre-separation (IC/ESI-MS-). Reproducible formation of pyruvate and oxalate were observed both by IC and ESI-MS. These compounds are known to form from aldehyde oxidation in the aqueous phase. New insights regarding the aqueous chemistry of these "more atmospherically-realistic" experiments will be discussed.

Service oriented architecture for clinical decision support: a systematic review and future directions.

PubMed

Loya, Salvador Rodriguez; Kawamoto, Kensaku; Chatwin, Chris; Huser, Vojtech

2014-12-01

The use of a service-oriented architecture (SOA) has been identified as a promising approach for improving health care by facilitating reliable clinical decision support (CDS). A review of the literature through October 2013 identified 44 articles on this topic. The review suggests that SOA related technologies such as Business Process Model and Notation (BPMN) and Service Component Architecture (SCA) have not been generally adopted to impact health IT systems' performance for better care solutions. Additionally, technologies such as Enterprise Service Bus (ESB) and architectural approaches like Service Choreography have not been generally exploited among researchers and developers. Based on the experience of other industries and our observation of the evolution of SOA, we found that the greater use of these approaches have the potential to significantly impact SOA implementations for CDS.

Service Oriented Architecture for Clinical Decision Support: A Systematic Review and Future Directions

PubMed Central

Loya, Salvador Rodriguez; Kawamoto, Kensaku; Chatwin, Chris; Huser, Vojtech

2017-01-01

The use of a service-oriented architecture (SOA) has been identified as a promising approach for improving health care by facilitating reliable clinical decision support (CDS). A review of the literature through October 2013 identified 44 articles on this topic. The review suggests that SOA related technologies such as Business Process Model and Notation (BPMN) and Service Component Architecture (SCA) have not been generally adopted to impact health IT systems’ performance for better care solutions. Additionally, technologies such as Enterprise Service Bus (ESB) and architectural approaches like Service Choreography have not been generally exploited among researchers and developers. Based on the experience of other industries and our observation of the evolution of SOA, we found that the greater use of these approaches have the potential to significantly impact SOA implementations for CDS PMID:25325996

Ozonolysis of a series of biogenic organic volatile compounds and secondary organic aerosol formation

NASA Astrophysics Data System (ADS)

Bernard, François; Quilgars, Alain; Cazaunau, Mathieu; Grosselin, Benoît.; Daele, Véronique; Mellouki, Abdelwahid; Winterhalter, Richard; Moortgat, Geert K.

2010-05-01

Secondary organic aerosols are formed via nucleation of atmospheric organic vapours on pre-existing particles observed in various rural environments where the organic fraction represents the major part of the observed nano-particle (Kavouras and Stephanou, 2002; Kulmala et al., 2004a). However, nucleation of organic vapors appears to be unlikely thermodynamically in relevant atmospheric conditions (Kulmala et al., 2004b). In this work, a systematic study has been conducted to investigate the aerosol formation through the ozonolysis of a series of monotepenes using a newly developed aerosol flow reactor and the ICARE indoor simulation chamber. The nucleation thresholds have been determined for SOA formed through the reaction of ozone with a-Pinene, sabinene, myrcene and limonene in absence of any observable existing particles. The measurements were performed using the flow reactor combined to a particle counter (CPC 3022). Number concentrations of SOA have been measured for different concentration of consumed monoterpenes. The data obtained allow us to estimate the nucleation threshold for a range of 0.2 - 45 ppb of consumed monoterpenes. The nucleation threshold values obtained here (≤ 1 ppb of the consumed monoterpenes) have been found to be lower than the previously reported ones (Berndt et al., 2003; Bonn and Moortgat, 2003; Koch et al., 2000; Lee and Kamens, 2005). The ICARE simulation chamber has been used to study the mechanism of the reaction of ozone with various acyclic terpenes (myrcene, ocimene, linalool and a-farnesene) and to derive the SOA mass formation yield. The time-concentration profiles of reactants and products in gas-phase were obtained using in-situ Fourier Transform Infrared Spectroscopy. In addition, the number and mass concentrations of SOA have been monitored with a Scanning Mobility Particle Sizer. The chemical composition of the SOA formed has been tentatively characterised using Liquid Chromatography - Mass Spectrometry. The results obtained will be compared with those from the literature when available and discussed in terms of their atmospheric impact. Berndt, T., O. Böge and F. Stratmann (2003). Gas-phase ozonolysis of a-pinene: gaseous products and particle formation. Atmospheric Environment, 37: 3933-3945. Bonn, B. and G.K. Moortgat (2003). Sesquiterpene ozonolysis: Origin of atmospheric new particle formation from biogenic hydrocarbons. Journal of Geophysical Research, 30(11). Kavouras, I. and E.G. Stephanou (2002). Direct evidence of atmospheric secondary organic aerosol formation in forest atmosphere through heteromolecular nucleation. Environmental Science and Technology, 36: 5083-5091. Koch, S., R. Winterhalter, E. Uherek, A. Kolloff, P. Neeb and G.K. Moortagt (2000). Formation of new particles in the gas-phase ozonolysis of monoterpenes. Atmospheric Environment, 34: 4031-4042. Kulmala, M., V.-M. Kerminen, T. Anttila, A. Laaksonen and C.D. O'Dowd (2004b). Organic aerosol formation via sulphate cluster activation. Journal of Geophysical Research, 109(D04205): 1-7. Kulmala, M., H. Vehkamäki, T. Petäjä, M. Dal Maso, A. Lauri, V.-M. Kerminen, W. Birmili and P.H. McMurry (2004a). Formation and growth rates of ultra-fine atmospheric particles: a review of observations. Journal of Aerosol Science, 35: 143-176. Lee, S. and R.M. Kamens (2005). Particle nucleation from the reaction of a-pinene and O3. Atmospheric Environment, 39: 6822-6832.

Open burning of rice, corn and wheat straws: primary emissions, photochemical aging, and secondary organic aerosol formation

NASA Astrophysics Data System (ADS)

Fang, Zheng; Deng, Wei; Zhang, Yanli; Ding, Xiang; Tang, Mingjin; Liu, Tengyu; Hu, Qihou; Zhu, Ming; Wang, Zhaoyi; Yang, Weiqiang; Huang, Zhonghui; Song, Wei; Bi, Xinhui; Chen, Jianmin; Sun, Yele; George, Christian; Wang, Xinming

2017-12-01

Agricultural residues are among the most abundant biomass burned globally, especially in China. However, there is little information on primary emissions and photochemical evolution of agricultural residue burning. In this study, indoor chamber experiments were conducted to investigate primary emissions from open burning of rice, corn and wheat straws and their photochemical aging as well. Emission factors of NOx, NH3, SO2, 67 non-methane hydrocarbons (NMHCs), particulate matter (PM), organic aerosol (OA) and black carbon (BC) under ambient dilution conditions were determined. Olefins accounted for > 50 % of the total speciated NMHCs emission (2.47 to 5.04 g kg-1), indicating high ozone formation potential of straw burning emissions. Emission factors of PM (3.73 to 6.36 g kg-1) and primary organic carbon (POC, 2.05 to 4.11 gC kg-1), measured at dilution ratios of 1300 to 4000, were lower than those reported in previous studies at low dilution ratios, probably due to the evaporation of semi-volatile organic compounds under high dilution conditions. After photochemical aging with an OH exposure range of (1.97-4.97) × 1010 molecule cm-3 s in the chamber, large amounts of secondary organic aerosol (SOA) were produced with OA mass enhancement ratios (the mass ratio of total OA to primary OA) of 2.4-7.6. The 20 known precursors could only explain 5.0-27.3 % of the observed SOA mass, suggesting that the major precursors of SOA formed from open straw burning remain unidentified. Aerosol mass spectrometry (AMS) signaled that the aged OA contained less hydrocarbons but more oxygen- and nitrogen-containing compounds than primary OA, and carbon oxidation state (OSc) calculated with AMS resolved O / C and H / C ratios increased linearly (p < 0.001) with OH exposure with quite similar slopes.

The influence of ocean halogen and sulfur emissions in the air quality of a coastal megacity: The case of Los Angeles.

PubMed

Muñiz-Unamunzaga, Maria; Borge, Rafael; Sarwar, Golam; Gantt, Brett; de la Paz, David; Cuevas, Carlos A; Saiz-Lopez, Alfonso

2018-01-01

The oceans are the main source of natural halogen and sulfur compounds, which have a significant influence on the oxidizing capacity of the marine atmosphere; however, their impact on the air quality of coastal cities is currently unknown. We explore the effect of marine halogens (Cl, Br and I) and dimethyl sulfide (DMS) on the air quality of a large coastal city through a set of high-resolution (4-km) air quality simulations for the urban area of Los Angeles, US, using the Community Multiscale Air Quality (CMAQ model). The results indicate that marine halogen emissions decrease ozone and nitrogen dioxide levels up to 5ppbv and 2.5ppbv, respectively, in the city of Los Angeles. Previous studies suggested that the inclusion of chlorine in air quality models leads to the generation of ozone in urban areas through photolysis of nitryl chloride (ClNO 2 ). However, we find that when considering the chemistry of Cl, Br and I together the net effect is a reduction of surface ozone concentrations. Furthermore, combined ocean emissions of halogens and DMS cause substantial changes in the levels of key urban atmospheric oxidants such as OH, HO 2 and NO 3 , and in the composition and mass of fine particles. Although the levels of ozone, NO 3 and HO x are reduced, we find a 10% increase in secondary organic aerosol (SOA) mean concentration, attributed to the increase in aerosol acidity and sulfate aerosol formation when combining DMS and bromine. Therefore, this new pathway for enhanced SOA formation may potentially help with current model under predictions of urban SOA. Although further observations and research are needed to establish these preliminary conclusions, this first city-scale investigation suggests that the inclusion of oceanic halogens and DMS in air quality models may improve regional air quality predictions over coastal cities around the world. Copyright © 2017 Elsevier B.V. All rights reserved.

Transmission performance of a wavelength and NRZ-to-RZ format conversion with pulsewidth tunability by combination of SOA- and fiber-based switches.

PubMed

Tan, Hung Nguyen; Matsuura, Motoharu; Kishi, Naoto

2008-11-10

An all-optical signal processing scheme coupling wavelength conversion and NRZ-to-RZ data format conversion with pulsewidth tunability into one by combination of SOA- and fiber-based switches, is experimentally demonstrated, and its transmission performance is investigated. An 1558 nm NRZ data signal is converted to RZ data format at 1546 nm with widely tunable pulsewidth from 20 % to 80 % duty cycle at the bit-rate of 10 Gb/s. The investigation on transmission performance of the converted RZ signals at each different pulsewidth is carried out over various standard single-mode fiber (SSMF) links up to 65 km long without dispersion compensation. The results clarify a significant improvement on transmission performance of converted signal in comparison with the conventional NRZ signal through tunable pulsewidth management and show the existence of an optimal pulsewidth for the RZ data format at each transmission distance with particular cumulative dispersion. The optimal pulsewidths of the converted RZ signal and its corresponding power penalties against the NRZ signal are also investigated in different SSMF links.

Measuring Uptake Coefficients and Henry's Law Constants of Gas-Phase Species with Models for Secondary Organic Aerosol

NASA Astrophysics Data System (ADS)

Fairhurst, M. C.; Waring-Kidd, C.; Ezell, M. J.; Finlayson-Pitts, B. J.

2014-12-01

Volatile organic compounds (VOC) are oxidized in the atmosphere and their products contribute to secondary organic aerosol (SOA) formation. These particles have been shown to have effects on visibility, climate, and human health. Current models typically under-predict SOA concentrations from field measurements. Underestimation of these concentrations could be a result of how models treat particle growth. It is often assumed that particles grow via instantaneous thermal equilibrium partitioning between liquid particles and gas-phase species. Recent work has shown that growth may be better represented by irreversible, kinetically limited uptake of gas-phase species onto more viscous, tar-like SOA. However, uptake coefficients for these processes are not known. The goal of this project is to measure uptake coefficients and solubilities for different gases onto models serving as proxies for SOA and determine how they vary based on the chemical composition of the gas and the condensed phase. Experiments were conducted using two approaches: attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy and a flow system coupled to a mass spectrometer. The ATR crystal was coated with the SOA proxy and the gas-phase species introduced via a custom flow system. Uptake of the gas-phase species was characterized by measuring the intensity of characteristic IR bands as a function of time, from which a Henry's law constant and initial estimate of uptake coefficients could be obtained. Uptake coefficients were also measured in a flow system where the walls of the flow tube were coated with the SOA proxy and gas-phase species introduced via a moveable inlet. Uptake coefficients were derived from the decay in gas-phase species measured by mass spectrometry. The results of this work will establish a structure-interaction relationship for uptake of gases into SOA that can be implemented into regional and global models.

Primary gas- and particle-phase emissions and secondary organic aerosol production from gasoline and diesel off-road engines.

PubMed

Gordon, Timothy D; Tkacik, Daniel S; Presto, Albert A; Zhang, Mang; Jathar, Shantanu H; Nguyen, Ngoc T; Massetti, John; Truong, Tin; Cicero-Fernandez, Pablo; Maddox, Christine; Rieger, Paul; Chattopadhyay, Sulekha; Maldonado, Hector; Maricq, M Matti; Robinson, Allen L

2013-12-17

Dilution and smog chamber experiments were performed to characterize the primary emissions and secondary organic aerosol (SOA) formation from gasoline and diesel small off-road engines (SOREs). These engines are high emitters of primary gas- and particle-phase pollutants relative to their fuel consumption. Two- and 4-stroke gasoline SOREs emit much more (up to 3 orders of magnitude more) nonmethane organic gases (NMOGs), primary PM and organic carbon than newer on-road gasoline vehicles (per kg of fuel burned). The primary emissions from a diesel transportation refrigeration unit were similar to those of older, uncontrolled diesel engines used in on-road vehicles (e.g., premodel year 2007 heavy-duty diesel trucks). Two-strokes emitted the largest fractional (and absolute) amount of SOA precursors compared to diesel and 4-stroke gasoline SOREs; however, 35-80% of the NMOG emissions from the engines could not be speciated using traditional gas chromatography or high-performance liquid chromatography. After 3 h of photo-oxidation in a smog chamber, dilute emissions from both 2- and 4-stroke gasoline SOREs produced large amounts of semivolatile SOA. The effective SOA yield (defined as the ratio of SOA mass to estimated mass of reacted precursors) was 2-4% for 2- and 4-stroke SOREs, which is comparable to yields from dilute exhaust from older passenger cars and unburned gasoline. This suggests that much of the SOA production was due to unburned fuel and/or lubrication oil. The total PM contribution of different mobile source categories to the ambient PM burden was calculated by combining primary emission, SOA production and fuel consumption data. Relative to their fuel consumption, SOREs are disproportionately high total PM sources; however, the vastly greater fuel consumption of on-road vehicles renders them (on-road vehicles) the dominant mobile source of ambient PM in the Los Angeles area.

Size resolved fog water chemistry and its atmospheric implications

NASA Astrophysics Data System (ADS)

Chakraborty, Abhishek; Gupta, Tarun; Tripathi, Sachchida; Ervens, Barbara; Bhattu, Deepika

2015-04-01

Fog is a natural meteorological phenomenon that occurs throughout the world. It usually contains substantial quantity of liquid water and results in severe visibility reduction leading to disruption of normal life. Fog is generally seen as a natural cleansing agent but it also has the potential to form Secondary Organic Aerosol (SOA) via aqueous processing of ambient aerosols. Size- resolved fog water chemistry for inorganics were reported in previous studies but processing of organics inside the fog water and quantification of aqSOA remained a challenge. To assess the organics processing via fog aqueous processing, size resolved fog water samples were collected in two consecutive winter seasons (2012-13, 2013-14) at Kanpur, a heavily polluted urban area of India. Caltech 3 stage fog collector was used to collect the fog droplets in 3 size fraction; coarse (droplet diameter > 22 µm), medium (22> droplet diameter >16 µm) and fine (16> droplet diameter >4 µm). Collected samples were atomized into various instruments such as Aerosol Mass Spectrometer (AMS), Cloud Condensation Nucleus Counter (CCNc), Total Organic Carbon (TOC) and a thermo denuder (TD) for the physico-chemical characterization of soluble constituents. Fine droplets are found to be more enriched with different aerosol species and interestingly contain more aged and less volatile organics compared to other coarser sizes. Organics inside fine droplets have an average O/C = 0.87 compared to O/C of 0.67 and 0.74 of coarse and medium droplets. Metal chemistry and higher residence time of fine droplets are seemed to be the two most likely reasons for this outcome from as the results of a comprehensive modeling carried out on the observed data indicate. CCN activities of the aerosols from fine droplets are also much higher than that of coarse or medium droplets. Fine droplets also contain light absorbing material as was obvious from their 'yellowish' solution. Source apportionment of fog water organics via PMF (Positive matrix factorization) revealed presence of some very highly oxidized OA inside fog water samples. From PMF results a method for aqSOA estimation is developed and aqSOA was found to be substantially contributing to total SOA. These findings indicate that light fog with large number of fine droplets can process the ambient aerosols more efficiently than very dense fog with larger droplets where scavenging becomes more important. These findings also highlight the need of incorporating fog size resolved chemistry along with metal chemistry into global models for accurately predicting aqSOA formation and contribution to total organic aerosol loading.

Science Opportunity Analyzer (SOA): Science Planning Made Simple

NASA Technical Reports Server (NTRS)

Streiffert, Barbara A.; Polanskey, Carol A.

2004-01-01

.For the first time at JPL, the Cassini mission to Saturn is using distributed science operations for developing their experiments. Remote scientists needed the ability to: a) Identify observation opportunities; b) Create accurate, detailed designs for their observations; c) Verify that their designs meet their objectives; d) Check their observations against project flight rules and constraints; e) Communicate their observations to other scientists. Many existing tools provide one or more of these functions, but Science Opportunity Analyzer (SOA) has been built to unify these tasks into a single application. Accurate: Utilizes JPL Navigation and Ancillary Information Facility (NAIF) SPICE* software tool kit - Provides high fidelity modeling. - Facilitates rapid adaptation to other flight projects. Portable: Available in Unix, Windows and Linux. Adaptable: Designed to be a multi-mission tool so it can be readily adapted to other flight projects. Implemented in Java, Java 3D and other innovative technologies. Conclusion: SOA is easy to use. It only requires 6 simple steps. SOA's ability to show the same accurate information in multiple ways (multiple visualization formats, data plots, listings and file output) is essential to meet the needs of a diverse, distributed science operations environment.

Modelling non-equilibrium secondary organic aerosol formation and evaporation with the aerosol dynamics, gas- and particle-phase chemistry kinetic multilayer model ADCHAM

DOE Office of Scientific and Technical Information (OSTI.GOV)

Roldin, P.; Eriksson, A. C.; Nordin, E. Z.

2014-08-11

We have developed the novel Aerosol Dynamics, gas- and particle- phase chemistry model for laboratory CHAMber studies (ADCHAM). The model combines the detailed gas phase Master Chemical Mechanism version 3.2, an aerosol dynamics and particle phase chemistry module (which considers acid catalysed oligomerization, heterogeneous oxidation reactions in the particle phase and non-ideal interactions between organic compounds, water and inorganic ions) and a kinetic multilayer module for diffusion limited transport of compounds between the gas phase, particle surface and particle bulk phase. In this article we describe and use ADCHAM to study: 1) the mass transfer limited uptake of ammonia (NH3)more » and formation of organic salts between ammonium (NH4+) and carboxylic acids (RCOOH), 2) the slow and almost particle size independent evaporation of α-pinene secondary organic aerosol (SOA) particles, and 3) the influence of chamber wall effects on the observed SOA formation in smog chambers.« less

Wintertime Secondary Organic Aerosol (SOA) Formation from Oxidation of Volatile Organic Compounds (VOCs) Associated with Oil and Gas Extraction

NASA Astrophysics Data System (ADS)

Murphy, S. M.; Soltis, J.; Field, R. A.; Bates, T. S.; Quinn, P.; De Gouw, J. A.; Veres, P. R.; Warneke, C.; Graus, M.; Gilman, J.; Lerner, B. M.; Koss, A.

2013-12-01

The Uintah Basin is located in a lightly populated area of Northeastern Utah near Dinosaur National Monument. Oil and gas extraction activities in the basin have dramatically increased in recent years due to the application of hydraulic fracturing. The Uintah Basin has experienced numerous high-ozone events during the past several winters with concentrations often exceeding 100 ppb. PM 2.5 monitoring by the city of Vernal, located at the edge of the basin, have shown wintertime concentrations in excess of the EPA 8-hour national standard, though the source and composition of particulates during these events is unclear. The Energy and Environment - Uintah Basin Winter Ozone Study (E&E UBWOS) was conducted during the winters of 2012 and 2013. During the study, intensive measurements of aerosol composition and speciated VOCs were made at a monitoring site near oil and gas extraction activities. Organic aerosol was found to be a major component of PM 2.5 and organic aerosol formation was highly correlated with the production of secondary VOC's. This correlation suggests that the organic aerosol is secondary in nature even though O:C ratios suggest a less oxidized aerosol than often observed in summertime SOA. The ozone levels and organic aerosol mass during 2012 were much lower than those observed in 2013. Calculations of the aerosol yield during both years will be presented along with an analysis of how well observed yields match predictions based on smog-chamber data. The potential for additional aerosol formation in the system will also be discussed.

A quantification method for heat-decomposable methylglyoxal oligomers and its application on 1,3,5-trimethylbenzene SOA

NASA Astrophysics Data System (ADS)

Rodigast, Maria; Mutzel, Anke; Herrmann, Hartmut

2017-03-01

Methylglyoxal forms oligomeric compounds in the atmospheric aqueous particle phase, which could establish a significant contribution to the formation of aqueous secondary organic aerosol (aqSOA). Thus far, no suitable method for the quantification of methylglyoxal oligomers is available despite the great effort spent for structure elucidation. In the present study a simplified method was developed to quantify heat-decomposable methylglyoxal oligomers as a sum parameter. The method is based on the thermal decomposition of oligomers into methylglyoxal monomers. Formed methylglyoxal monomers were detected using PFBHA (o-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine hydrochloride) derivatisation and gas chromatography-mass spectrometry (GC/MS) analysis. The method development was focused on the heating time (varied between 15 and 48 h), pH during the heating process (pH = 1-7), and heating temperature (50, 100 °C). The optimised values of these method parameters are presented. The developed method was applied to quantify heat-decomposable methylglyoxal oligomers formed during the OH-radical oxidation of 1,3,5-trimethylbenzene (TMB) in the Leipzig aerosol chamber (LEipziger AerosolKammer, LEAK). Oligomer formation was investigated as a function of seed particle acidity and relative humidity. A fraction of heat-decomposable methylglyoxal oligomers of up to 8 % in the produced organic particle mass was found, highlighting the importance of those oligomers formed solely by methylglyoxal for SOA formation. Overall, the present study provides a new and suitable method for quantification of heat-decomposable methylglyoxal oligomers in the aqueous particle phase.

Novel pathway of SO2 oxidation in the atmosphere: reactions with monoterpene ozonolysis intermediates and secondary organic aerosol

NASA Astrophysics Data System (ADS)

Ye, Jianhuai; Abbatt, Jonathan P. D.; Chan, Arthur W. H.

2018-04-01

Ozonolysis of monoterpenes is an important source of atmospheric biogenic secondary organic aerosol (BSOA). While enhanced BSOA formation has been associated with sulfate-rich conditions, the underlying mechanisms remain poorly understood. In this work, the interactions between SO2 and reactive intermediates from monoterpene ozonolysis were investigated under different humidity conditions (10 % vs. 50 %). Chamber experiments were conducted with ozonolysis of α-pinene or limonene in the presence of SO2. Limonene SOA formation was enhanced in the presence of SO2, while no significant changes in SOA yields were observed during α-pinene ozonolysis. Under dry conditions, SO2 primarily reacted with stabilized Criegee intermediates (sCIs) produced from ozonolysis, but at 50 % RH heterogeneous uptake of SO2 onto organic aerosol was found to be the dominant sink of SO2, likely owing to reactions between SO2 and organic peroxides. This SO2 loss mechanism to organic peroxides in SOA has not previously been identified in experimental chamber studies. Organosulfates were detected and identified using an electrospray ionization-ion mobility spectrometry-high-resolution time-of-flight mass spectrometer (ESI-IMS-TOF) when SO2 was present in the experiments. Our results demonstrate the synergistic effects between BSOA formation and SO2 oxidation through sCI chemistry and SO2 uptake onto organic aerosol and illustrate the importance of considering the chemistry of organic and sulfur-containing compounds holistically to properly account for their reactive sinks.

Effective absorption cross sections and photolysis rates of anthropogenic and biogenic secondary organic aerosols

NASA Astrophysics Data System (ADS)

Romonosky, Dian E.; Ali, Nujhat N.; Saiduddin, Mariyah N.; Wu, Michael; Lee, Hyun Ji (Julie); Aiona, Paige K.; Nizkorodov, Sergey A.

2016-04-01

Mass absorption coefficient (MAC) values were measured for secondary organic aerosol (SOA) samples produced by flow tube ozonolysis and smog chamber photooxidation of a wide range of volatile organic compounds (VOC), specifically: α-pinene, β-pinene, β-myrcene, d-limonene, farnesene, guaiacol, imidazole, isoprene, linalool, ocimene, p-xylene, 1-methylpyrrole, and 2-methylpyrrole. Both low-NOx and high-NOx conditions were employed during the chamber photooxidation experiments. MAC values were converted into effective molecular absorption cross sections assuming an average molecular weight of 300 g/mol for SOA compounds. The upper limits for the effective photolysis rates of SOA compounds were calculated by assuming unity photolysis quantum yields and convoluting the absorption cross sections with a time-dependent solar spectral flux. A more realistic estimate for the photolysis rates relying on the quantum yield of acetone was also obtained. The results show that condensed-phase photolysis of SOA compounds can potentially occur with effective lifetimes ranging from minutes to days, suggesting that photolysis is an efficient and largely overlooked mechanism of SOA aging.

All-optical UWB generation and modulation using SOA-XPM effect and DWDM-based multi-channel frequency discrimination.

PubMed

Wang, Fei; Dong, Jianji; Xu, Enming; Zhang, Xinliang

2010-11-22

An all-optical UWB pulses generation and modulation scheme using cross phase modulation (XPM) effect of semiconductor optical amplifier (SOA) and DWDM-based multi-channel frequency discrimination is proposed and demonstrated, which has potential application in multiuser UWB-Over-Fiber communication systems. When a Gaussian pulse light and a wavelength-tunable CW probe light are together injected into the SOA, the probe light out from the SOA will have a temporal chirp due to SOA-XPM effect. When the chirped probe light is tuned to the slopes of single DWDM channel transmittance curve, the optical phase modulation to intensity modulation conversion is achieved at DWDM that serves as a multi-channel frequency discriminator, the inverted polarity Gaussian monocycle and doublet pulse is detected by a photodetector, respectively. If the probe lights are simultaneously aimed to different slopes of several DWDM channels, multi-channel or binary-phase-coded UWB signal generation can be acquired. Using proposed scheme, pulse amplitude modulation (PAM), pulse polarity modulation (PPM) and pulse shape modulation (PSM) to UWB pulses also can be conveniently realized.

Dynamic consideration of smog chamber experiments

NASA Astrophysics Data System (ADS)

Chuang, Wayne K.; Donahue, Neil M.

2017-08-01

Recent studies of the α-pinene + ozone reaction that address particle nucleation show relatively high molar yields of highly oxidized multifunctional organic molecules with very low saturation concentrations that can form and grow new particles on their own. However, numerous smog-chamber experiments addressing secondary organic aerosol (SOA) mass yields, interpreted via equilibrium partitioning theory, suggest that the vast majority of SOA from α-pinene is semivolatile. We explore this paradox by employing a dynamic volatility basis set (VBS) model that reproduces the new-particle growth rates observed in the CLOUD experiment at CERN and then modeling SOA mass yield experiments conducted at Carnegie Mellon University (CMU). We find that the base-case simulations do overpredict observed SOA mass but by much less than an equilibrium analysis would suggest; this is because delayed condensation of vapors suppresses the apparent mass yields early in the chamber experiments. We further find that a second VBS model featuring substantial oligomerization of semivolatile monomers can match the CLOUD growth rates with substantially lower SOA mass yields; this is because the lighter monomers have a higher velocity and thus a higher condensation rate for a given mass concentration. The oligomerization simulations are a closer match to the CMU experiments than the base-case simulations, though they overpredict the observations somewhat. However, we also find that if the chemical conditions in CLOUD and the CMU chamber were identical, substantial nucleation would have occurred in the CMU experiments when in fact none occurred. This suggests that the chemical mechanisms differed in the two experiments, perhaps because the high oxidation rates in the SOA formation experiments led to rapid termination of peroxy radical chemistry.

Global combustion sources of organic aerosols: model comparison with 84 AMS factor-analysis data sets

NASA Astrophysics Data System (ADS)

Tsimpidi, Alexandra P.; Karydis, Vlassis A.; Pandis, Spyros N.; Lelieveld, Jos

2016-07-01

Emissions of organic compounds from biomass, biofuel, and fossil fuel combustion strongly influence the global atmospheric aerosol load. Some of the organics are directly released as primary organic aerosol (POA). Most are emitted in the gas phase and undergo chemical transformations (i.e., oxidation by hydroxyl radical) and form secondary organic aerosol (SOA). In this work we use the global chemistry climate model ECHAM/MESSy Atmospheric Chemistry (EMAC) with a computationally efficient module for the description of organic aerosol (OA) composition and evolution in the atmosphere (ORACLE). The tropospheric burden of open biomass and anthropogenic (fossil and biofuel) combustion particles is estimated to be 0.59 and 0.63 Tg, respectively, accounting for about 30 and 32 % of the total tropospheric OA load. About 30 % of the open biomass burning and 10 % of the anthropogenic combustion aerosols originate from direct particle emissions, whereas the rest is formed in the atmosphere. A comprehensive data set of aerosol mass spectrometer (AMS) measurements along with factor-analysis results from 84 field campaigns across the Northern Hemisphere are used to evaluate the model results. Both the AMS observations and the model results suggest that over urban areas both POA (25-40 %) and SOA (60-75 %) contribute substantially to the overall OA mass, whereas further downwind and in rural areas the POA concentrations decrease substantially and SOA dominates (80-85 %). EMAC does a reasonable job in reproducing POA and SOA levels during most of the year. However, it tends to underpredict POA and SOA concentrations during winter indicating that the model misses wintertime sources of OA (e.g., residential biofuel use) and SOA formation pathways (e.g., multiphase oxidation).

Chemical climatology of the southeastern United States, 1999-2013

NASA Astrophysics Data System (ADS)

Hidy, G. M.; Blanchard, C. L.; Baumann, K.; Edgerton, E.; Tanenbaum, S.; Shaw, S.; Knipping, E.; Tombach, I.; Jansen, J.; Walters, J.

2014-06-01

A series of experiments (the Southern Oxidant and Aerosol Study-SOAS) took place in central Alabama in June-July 2013 as part of the broader Southern Atmosphere Study (SAS). These projects were aimed at studying oxidant photochemistry and formation and impacts of aerosols at a detailed process level in a location where high biogenic organic vapor emissions interact with anthropogenic emissions, and the atmospheric chemistry occurs in a subtropical climate in North America. The majority of the ground-based experiments were located at the Southeastern Aerosol Research and Characterization (SEARCH) Centreville (CTR) site near Brent, Alabama, where extensive, unique aerometric measurements of meteorology, trace gases and particles have been made from the early 1990s through 2013. The SEARCH network data permits a characterization of temporal and spatial context of the SOAS findings. The long-term measurements show that the SOAS experiments took place during the second wettest and coolest year in the 2000-2013 period, with lower than average solar radiation. The pollution levels at CTR and other SEARCH sites were the lowest since full measurements began in 1999. This dataset provides a perspective for the SOAS program in terms of long-term average chemistry (chemical climatology) and short-term comparisons of summer average spatial variability across the Southeast at high temporal (hourly) resolution. Changes in anthropogenic gas and particle emissions between 1999 and 2013, account for the decline in pollutant concentrations at the monitoring sites in the region. The long-term and short-term data provide an opportunity to contrast SOAS results with temporally and spatially variable conditions in support for the development of tests for the robustness of SOAS findings.

Effect of ammonia on ozone-initiated formation of indoor secondary products with emissions from cleaning products

NASA Astrophysics Data System (ADS)

Huang, Yu; Lee, Shun Cheng; Ho, Kin Fai; Ho, Steven Sai Hang; Cao, Nanying; Cheng, Yan; Gao, Yuan

2012-11-01

Biogenic volatile organic compounds (BVOCs) emitted from cleaning products and air fresheners indoors are prone to oxidation resulting in the formation of secondary pollutants that can pose health risks on residents. Ammonia (NH3) is ubiquitous in ambient and indoor environments. In this study, we investigated the effect of ammonia (NH3) on secondary pollutants formation from the ozonolysis of BVOCs emitted from cleaning products including floor cleaner (FC), kitchen cleaner (KC) and dishwashing detergent (DD) in a large environmental chamber. Our results demonstrated that the presence of NH3 (maximum concentration is 240 ppb) could significantly enhance secondary organic aerosols (SOAs) formation from the ozonolysis of all the three categories of cleaning products. For example, for the FC sample, the maximum total particle concentration was up to 2.0 × 104 # cm-3 in the presence of NH3, while it was 1.3 × 104 # cm-3 which was 35% lower without NH3. However, it was found that the extent of NH3 effect on SOAs formation from the ozonolysis of BVOCs emissions was component-dependent. The presence of NH3 in the reaction systems could increase the consumptions of d-limonene that is the dominant BVOC species as identified in cleaning products. The percent yields (%) of secondary carbonyl compounds generated from the ozonolysis of BVOCs emitted from three categories of cleaning products were identified in the presence and absence of NH3, respectively. The increase in SOAs particle number concentration can be attributed to the formation of condensable salts from reactions between NH3 and organic compounds generated from the BVOCs ozonolysis processes. By investigating the NH3 effect on the ozonolysis of BVOCs mixtures in contrast to the chemistry of individual compounds, a better assessment can be made of the overall impact cleaning products have on real indoor environments.

Gas-phase products and secondary organic aerosol formation from the ozonolysis and photooxidation of myrcene

NASA Astrophysics Data System (ADS)

Böge, Olaf; Mutzel, Anke; Iinuma, Yoshiteru; Yli-Pirilä, Pasi; Kahnt, Ariane; Joutsensaari, Jorma; Herrmann, Hartmut

2013-11-01

In this study, the ozone and OH-radical reactions of myrcene were investigated in an aerosol chamber (at 292-295 K and 50% relative humidity) to examine the gas-phase oxidation products and secondary organic aerosol (SOA) formation. The ozone reaction studies were performed in the presence and absence of CO, which serves as an OH radical scavenger. In the photooxidation experiments OH radicals were generated by photolysis of methyl nitrite. The ozonolysis of myrcene in the presence of CO resulted in a substantial yield of 4-vinyl-4-pentenal (55.3%), measured as m/z 111 plus m/z 93 using proton transfer reaction-mass spectrometry (PTR-MS) and confirmed unambiguously as C7H10O by denuder measurements and HPLC/ESI-TOFMS analysis of its 2,4-dinitrophenylhydrazine (DNPH) derivative. Additionally, the formation of two different organic dicarbonyls with m/z 113 and a molecular formula of C6H8O2 were observed (2.1%). The yields of these dicarbonyls were higher in the ozonolysis experiments without an OH scavenger (5.4%) and even higher (13.8%) in the myrcene OH radical reaction. The formation of hydroxyacetone as a direct product of the myrcene reaction with ozone with a molar yield of 17.6% was also observed. The particle size distribution and volume concentrations were monitored and facilitated the calculation of SOA yields, which ranged from 0 to 0.01 (ozonolysis in the presence of CO) to 0.39 (myrcene OH radical reaction). Terpenylic acid was found in the SOA samples collected from the ozonolysis of myrcene in the absence of an OH scavenger and the OH radical-initiated reaction of myrcene but not in samples collected from the ozonolysis in the presence of CO as an OH radical scavenger, suggesting that terpenylic acid formation involves the reaction of myrcene with an OH radical. A reaction mechanism describing the formation of terpenylic acid is proposed.

Modeling biogenic secondary organic aerosol (BSOA) formation from monoterpene reactions with NO3: A case study of the SOAS campaign using CMAQ

NASA Astrophysics Data System (ADS)

Qin, Momei; Hu, Yongtao; Wang, Xuesong; Vasilakos, Petros; Boyd, Christopher M.; Xu, Lu; Song, Yu; Ng, Nga Lee; Nenes, Athanasios; Russell, Armistead G.

2018-07-01

Monoterpenes react with nitrate radicals (NO3), contributing substantially to nighttime organic aerosol (OA) production. In this study, the role of reactions of monoterpenes + NO3 in forming biogenic secondary organic aerosol (BSOA) was examined using the Community Multiscale Air Quality (CMAQ) model, with extended emission profiles of biogenic volatile organic compounds (BVOCs), species-specific representations of BSOA production from individual monoterpenes and updated aerosol yields for monoterpene + NO3. The model results were compared to detailed measurements from the Southern Oxidants and Aerosol Study (SOAS) at Centreville, Alabama. With the more detailed model, monoterpene-derived BSOA increased by ∼1 μg m-3 at night, accounting for one-third of observed less-oxidized oxygenated OA (LO-OOA), more closely agreeing with observations (lower error, stronger correlation). Implementation of a multigenerational oxidation approach resulted in the model capturing elevated OA episodes. With the aging model, aged semi-volatile organic compounds (ASVOCs) contributed over 60% of the monoterpene-derived BSOA, followed by SOA formation via nitrate radical chemistry, making up to 34% of that formed at night. Among individual monoterpenes, β-pinene and limonene contributed most to the monoterpene-derived BSOA from nighttime reactions.