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

2018 ◽  
Vol 18 (24) ◽  
pp. 18079-18100 ◽  
Author(s):  
Mounir Chrit ◽  
Karine Sartelet ◽  
Jean Sciare ◽  
Marwa Majdi ◽  
José Nicolas ◽  
...  
Keyword(s):  
Volatile Organic Compounds ◽  
Organic Compounds ◽  
Oxidation State ◽  
Organic Aerosol ◽  
Single Step ◽  
Basis Set ◽  
Organic Nitrate ◽  
Residential Heating ◽  
Volatile Organic ◽  
Northwestern Mediterranean

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

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

2018 ◽  
Author(s):  
Mounir Chrit ◽  
Karine Sartelet ◽  
Jean Sciare ◽  
Marwa Majdi ◽  
José Nicolas ◽  
...  
Keyword(s):  
Air Quality ◽  
Volatile Organic Compounds ◽  
Organic Compounds ◽  
Oxidation State ◽  
Organic Aerosol ◽  
Single Step ◽  
Basis Set ◽  
Residential Heating ◽  
Volatile Organic ◽  
Northwestern Mediterranean

Abstract. Organic aerosols are measured at a remote site (Ersa) on Corsica Cape in the northwestern Mediterranean basin during the Chemistry-Aerosol Mediterranean Experiment (CharMEx) winter campaign of 2014, when high organic concentrations from anthropogenic origin are observed. This work aims at representing the observed organic aerosol concentrations and properties (oxidation state) using the air-quality model Polyphemus with a surrogate approach for secondary organic aerosol (SOA) formation. Because intermediate/semi-volatile organic compounds (I/S-VOC) are the main precursors of SOA at Ersa during the winter 2014, different parameterizations to represent the emission and ageing of I/S-VOC were implemented in the chemistry-transport model of the air-quality platform Polyphemus (different volatility distribution emissions, single-step oxidation vs multi-step oxidation within a Volatility Basis Set framework, inclusion of non-traditional volatile organic compounds NTVOC). Simulations using the different parameterizations are compared to each other and to the measurements (concentration and oxidation state). The high observed organic concentrations are well reproduced whatever the parameterizations. They are slightly under-estimated with most parameterizations, but they are slightly over-estimated when the ageing of NTVOC is taken into account. The volatility distribution at emissions influences more strongly the concentrations than the choice of the parameterization that may be used for ageing (single-step oxidation vs multi-step oxidation), stressing the importance of an accurate characterization of emissions. Assuming the volatility distribution of sectors other than residential heating to be the same as residential heating may lead to a strong under-estimation of organic concentrations. The observed organic oxidation and oxygenation states are strongly under-estimated in all simulations, even when a recently developed parameterization for modeling the ageing of I/S-VOC from residential heating is used. This suggests that uncertainties in the ageing of I/S-VOC emissions remain to be elucidated, with a potential role of organic nitrate from anthropogenic precursors and highly oxygenated organic molecules.

scholarly journals Nitrate radicals and biogenic volatile organic compounds: oxidation, mechanisms and organic aerosol

2016 ◽  
Author(s):  
N. L. Ng ◽  
S. S. Brown ◽  
A. T. Archibald ◽  
E. Atlas ◽  
R. C. Cohen ◽  
...  
Keyword(s):  
Air Quality ◽  
Volatile Organic Compounds ◽  
Organic Compounds ◽  
Atmospheric Chemistry ◽  
Climate Models ◽  
Large Body ◽  
Organic Aerosol ◽  
Organic Nitrate ◽  
Biogenic Volatile Organic Compounds ◽  
Volatile Organic

Abstract. Oxidation of biogenic volatile organic compounds (BVOC) by the nitrate radical (NO3) represents one of the important interactions between anthropogenic emissions related to combustion and natural emissions from the biosphere. This interaction has been recognized for more than three decades, during which time a large body of research has emerged from laboratory, field and modeling studies. NO3-BVOC reactions influence air quality, climate and visibility through regional and global budgets for reactive nitrogen (particularly organic nitrates), ozone and organic aerosol. Despite its long history of research and the significance of this topic in atmospheric chemistry, a number of important uncertainties remain. These include an incomplete understanding of the rates, mechanisms and organic aerosol yields for NO3-BVOC reactions, lack of constraints on the role of heterogeneous oxidative processes associated with the NO3 radical, the difficulty of characterizing the spatial distributions of BVOC and NO3 within the poorly mixed nocturnal atmosphere and the challenge of constructing appropriate boundary layer schemes and non-photochemical mechanisms for use in state-of-the-art chemical transport and chemistry-climate models. This review is the result of a workshop of the same title held at the Georgia Institute of Technology in June 2015. The first section summarizes the current literature on NO3-BVOC chemistry, with a particular focus on recent advances in instrumentation and models, and in organic nitrate and secondary organic aerosol (SOA) formation chemistry. Building on this current understanding, the second half of the review outlines impacts of NO3-BVOC chemistry on air quality and climate, and suggests critical research needs to better constrain this interaction to improve the predictive capabilities of atmospheric models.

scholarly journals The role of semi-volatile organic compounds in the mesoscale evolution of biomass burning aerosol: a modelling case study of the 2010 mega-fire event in Russia

2015 ◽  
Vol 15 (6) ◽  
pp. 9107-9172 ◽  
Author(s):  
I. B. Konovalov ◽  
M. Beekmann ◽  
E. V. Berezin ◽  
H. Petetin ◽  
T. Mielonen ◽  
...  
Keyword(s):  
Air Pollution ◽  
Volatile Organic Compounds ◽  
Organic Compounds ◽  
Biomass Burning ◽  
Organic Aerosol ◽  
Conventional Approach ◽  
Pollution Monitoring ◽  
Basis Set ◽  
Aerosol Emission ◽  
Volatile Organic

Abstract. Chemistry transport models (CTMs) are an indispensable tool for studying and predicting atmospheric and climate effects associated with carbonaceous aerosol from open biomass burning (BB); this type of aerosol is known to contribute significantly to both global radiative forcing and to episodes of air pollution in regions affected by wildfires. Improving model performance requires systematic comparison of simulation results with measurements of BB aerosol and elucidating possible reasons for discrepancies between them, which, "by default", are frequently attributed in the literature to uncertainties in emission data. Based on published laboratory data regarding atmospheric evolution of BB aerosol and by using the volatility basis set (VBS) approach to organic aerosol modeling along with a "conventional" approach, we examined the importance of taking gas-particle partitioning and oxidation of semi-volatile organic compounds (SVOCs) into account in simulations of the mesoscale evolution of smoke plumes from intense wildfires that occurred in western Russia in 2010. BB emissions of primary aerosol components were constrained with the PM10 and CO data from the air pollution monitoring network in the Moscow region. The results of the simulations performed with the CHIMERE CTM were evaluated by considering, in particular, the ratio of smoke-related enhancements in PM10 and CO concentrations (ΔPM10 and ΔCO) measured in Finland (in the city of Kuopio), nearly 1000 km downstream of the fire emission sources. It is found that while the conventional approach (disregarding oxidation of SVOCs and assuming organic aerosol material to be non-volatile) strongly underestimates values of ΔPM10/ΔCO observed in Kuopio (by almost a factor of two), the VBS approach is capable to bring the simulations to a reasonable agreement with the ground measurements both in Moscow and in Kuopio. Using the VBS instead of the conventional approach is also found to result in a major improvement of the agreement of simulations and satellite measurements of aerosol optical depth, as well as in considerable changes in predicted aerosol composition and top-down BB aerosol emission estimates derived from AOD measurements.

scholarly journals The role of semi-volatile organic compounds in the mesoscale evolution of biomass burning aerosol: a modeling case study of the 2010 mega-fire event in Russia

2015 ◽  
Vol 15 (23) ◽  
pp. 13269-13297 ◽  
Author(s):  
I. B. Konovalov ◽  
M. Beekmann ◽  
E. V. Berezin ◽  
H. Petetin ◽  
T. Mielonen ◽  
...  
Keyword(s):  
Air Pollution ◽  
Volatile Organic Compounds ◽  
Organic Compounds ◽  
Biomass Burning ◽  
Organic Aerosol ◽  
Pollution Monitoring ◽  
Basis Set ◽  
Aerosol Emission ◽  
Volatile Organic ◽  
Aerosol Modeling

Abstract. Chemistry transport models (CTMs) are an indispensable tool for studying and predicting atmospheric and climate effects associated with carbonaceous aerosol from open biomass burning (BB); this type of aerosol is known to contribute significantly to both global radiative forcing and to episodes of air pollution in regions affected by wildfires. Improving model performance requires systematic comparison of simulation results with measurements of BB aerosol and elucidation of possible reasons for discrepancies between them, which, by default, are frequently attributed in the literature to uncertainties in emission data. Based on published laboratory data on the atmospheric evolution of BB aerosol and using the volatility basis set (VBS) framework for organic aerosol modeling, we examined the importance of taking gas-particle partitioning and oxidation of semi-volatile organic compounds (SVOCs) into account in simulations of the mesoscale evolution of smoke plumes from intense wildfires that occurred in western Russia in 2010. Biomass burning emissions of primary aerosol components were constrained with PM10 and CO data from the air pollution monitoring network in the Moscow region. The results of the simulations performed with the CHIMERE CTM were evaluated by considering, in particular, the ratio of smoke-related enhancements in PM10 and CO concentrations (ΔPM10 and ΔCO) measured in Finland (in the city of Kuopio), nearly 1000 km downstream of the fire emission sources. It is found that while the simulations based on a "conventional" approach to BB aerosol modeling (disregarding oxidation of SVOCs and assuming organic aerosol material to be non-volatile) strongly underestimated values of ΔPM10/ΔCO observed in Kuopio (by a factor of 2), employing the "advanced" representation of atmospheric processing of organic aerosol material resulted in bringing the simulations to a much closer agreement with the ground measurements. Furthermore, taking gas-particle partitioning and oxidation of SVOCs into account is found to result in a major improvement of the agreement of simulations and satellite measurements of aerosol optical depth, as well as in considerable changes in predicted aerosol composition and top-down BB aerosol emission estimates derived from AOD measurements.

scholarly journals Modeling the formation and composition of secondary organic aerosol from diesel exhaust using parameterized and semi-explicit chemistry and thermodynamic models

2018 ◽  
Vol 18 (19) ◽  
pp. 13813-13838 ◽  
Author(s):  
Sailaja Eluri ◽  
Christopher D. Cappa ◽  
Beth Friedman ◽  
Delphine K. Farmer ◽  
Shantanu H. Jathar
Keyword(s):  
Volatile Organic Compounds ◽  
Gas Phase ◽  
Organic Compounds ◽  
Secondary Organic Aerosol ◽  
Organic Aerosol ◽  
Basis Set ◽  
Oxidation Catalyst ◽  
Ionization Mass ◽  
Model Predictions ◽  
Volatile Organic

Abstract. Laboratory-based studies have shown that combustion sources emit volatile organic compounds that can be photooxidized in the atmosphere to form secondary organic aerosol (SOA). In some cases, this SOA can exceed direct emissions of primary organic aerosol (POA). Jathar et al. (2017a) recently reported on experiments that used an oxidation flow reactor (OFR) to measure the photochemical production of SOA from a diesel engine operated at two different engine loads (idle, load), two fuel types (diesel, biodiesel), and two aftertreatment configurations (with and without an oxidation catalyst and particle filter). In this work, we used two different SOA models, the Volatility Basis Set (VBS) model and the Statistical Oxidation Model (SOM), to simulate the formation and composition of SOA for those experiments. Leveraging recent laboratory-based parameterizations, both frameworks accounted for a semi-volatile and reactive POA; SOA production from semi-volatile, intermediate-volatility, and volatile organic compounds (SVOC, IVOC and VOC); NOx-dependent parameterizations; multigenerational gas-phase chemistry; and kinetic gas–particle partitioning. Both frameworks demonstrated that for model predictions of SOA mass to agree with measurements across all engine load–fuel–aftertreatment combinations, it was necessary to model the kinetically limited gas–particle partitioning in OFRs and account for SOA formation from IVOCs, which were on average found to account for 70 % of the model-predicted SOA. Accounting for IVOCs, however, resulted in an average underprediction of 28 % for OA atomic O : C ratios. Model predictions of the gas-phase organic compounds (resolved in carbon and oxygen space) from the SOM compared favorably to gas-phase measurements from a chemical ionization mass spectrometer (CIMS), substantiating the semi-explicit chemistry captured by the SOM. Model–measurement comparisons were improved on using SOA parameterizations corrected for vapor wall loss. As OFRs are increasingly used to study SOA formation and evolution in laboratory and field environments, models such as those developed in this work can be used to interpret the OFR data.

scholarly journals Nitrate radicals and biogenic volatile organic compounds: oxidation, mechanisms, and organic aerosol

2017 ◽  
Vol 17 (3) ◽  
pp. 2103-2162 ◽  
Author(s):  
Nga Lee Ng ◽  
Steven S. Brown ◽  
Alexander T. Archibald ◽  
Elliot Atlas ◽  
Ronald C. Cohen ◽  
...  
Keyword(s):  
Air Quality ◽  
Volatile Organic Compounds ◽  
Organic Compounds ◽  
Atmospheric Chemistry ◽  
Climate Models ◽  
Large Body ◽  
Organic Aerosol ◽  
Organic Nitrate ◽  
Biogenic Volatile Organic Compounds ◽  
Volatile Organic

Abstract. Oxidation of biogenic volatile organic compounds (BVOC) by the nitrate radical (NO3) represents one of the important interactions between anthropogenic emissions related to combustion and natural emissions from the biosphere. This interaction has been recognized for more than 3 decades, during which time a large body of research has emerged from laboratory, field, and modeling studies. NO3-BVOC reactions influence air quality, climate and visibility through regional and global budgets for reactive nitrogen (particularly organic nitrates), ozone, and organic aerosol. Despite its long history of research and the significance of this topic in atmospheric chemistry, a number of important uncertainties remain. These include an incomplete understanding of the rates, mechanisms, and organic aerosol yields for NO3-BVOC reactions, lack of constraints on the role of heterogeneous oxidative processes associated with the NO3 radical, the difficulty of characterizing the spatial distributions of BVOC and NO3 within the poorly mixed nocturnal atmosphere, and the challenge of constructing appropriate boundary layer schemes and non-photochemical mechanisms for use in state-of-the-art chemical transport and chemistry–climate models. This review is the result of a workshop of the same title held at the Georgia Institute of Technology in June 2015. The first half of the review summarizes the current literature on NO3-BVOC chemistry, with a particular focus on recent advances in instrumentation and models, and in organic nitrate and secondary organic aerosol (SOA) formation chemistry. Building on this current understanding, the second half of the review outlines impacts of NO3-BVOC chemistry on air quality and climate, and suggests critical research needs to better constrain this interaction to improve the predictive capabilities of atmospheric models.

scholarly journals Constraining a hybrid volatility basis set model for aging of wood burning emissions using smog chamber experiments

2016 ◽  
Author(s):  
Giancarlo Ciarelli ◽  
Imad El Haddad ◽  
Emily Bruns ◽  
Sebnem Aksoyoglu ◽  
Ottmar Möhler ◽  
...  
Keyword(s):  
Volatile Organic Compounds ◽  
Organic Compounds ◽  
Organic Aerosol ◽  
Reaction Rates ◽  
Box Model ◽  
Basis Set ◽  
Smog Chamber ◽  
Aerosol Mass ◽  
Volatile Organic ◽  
Different Temperatures

Abstract. Semi-volatile and intermediate volatility organic compounds (SVOCs, IVOCs) are not included in the current non-methane volatile organic compounds (NMVOCs) emission inventories but may be important for the formation of secondary organic aerosol (SOA). In this study, novel wood combustion aging experiments performed at different temperatures (263 K and 288 K) in a ~7 m3 smog chamber were modelled using a hybrid volatility basis set (VBS) box model, representing the emission partitioning and their oxidation against OH. We combine aerosol-chemistry box model simulations with unprecedented measurements of nontraditional volatile organic compounds (NTVOCs) from a high-resolution proton transfer reaction mass spectrometer (PTR-MS) and with organic aerosol measurements from an aerosol mass spectrometer (AMS). In so-doing, we are able to observationally-constrain the amounts of different NTVOCs aerosol precursors (in the model) relative to low-volatility and semi-volatile primary organic material (OMsv) which is partitioned based on current published volatility distribution data. By comparing the NTVOCs/OMsv ratios at different temperatures, we determine the enthalpies of vaporization of primary biomass burning organic aerosols. Further, the developed model allows for evaluating the evolution of oxidation products of the semi-volatile and volatile precursors with aging. More than 30,000 box model simulations were performed to retrieve the combination of parameters that fit best the observed organic aerosol mass and O:C ratios. The parameters investigated include the NTVOC reaction rates and yields as well as enthalpies of vaporization and the O:C of secondary organic aerosol surrogates. Our results suggest an average ratio of NTVOCs to the sum of non-volatile and semi-volatile organic compounds of ~4.75. The mass yields of these compounds determined for a wide range of atmospherically relevant temperatures and organic aerosol (OA) concentrations were predicted to vary between 8 and 30 % after 5 hours of continuous aging. Based on the reaction scheme used, reaction rates of the NTVOC mixture range from 3.0 × 10–11 cm3 molec−1 s−1 to 4.0 × 10–11 cm3 molec−1 s−1. The average enthalpy of vaporization of SOA surrogates was determined to be between 55,000 J mol−1 and 35,000 J mol−1 which implies a yield increase of 0.03–0.06 % K−1 with decreasing temperature. The improved VBS scheme is suitable for implementation into chemical transport models to predict the burden and oxidation state of primary and secondary biomass burning aerosols.

scholarly journals Contributions of individual reactive biogenic volatile organic compounds to organic nitrates above a mixed forest

2012 ◽  
Vol 12 (21) ◽  
pp. 10125-10143 ◽  
Author(s):  
K. A. Pratt ◽  
L. H. Mielke ◽  
P. B. Shepson ◽  
A. M. Bryan ◽  
A. L. Steiner ◽  
...  
Keyword(s):  
Volatile Organic Compounds ◽  
Organic Compounds ◽  
Mixed Forest ◽  
Organic Aerosol ◽  
Oxidation Products ◽  
Organic Nitrate ◽  
Organic Nitrates ◽  
Biogenic Volatile Organic Compounds ◽  
Nitrate Production ◽  
Volatile Organic

Abstract. Biogenic volatile organic compounds (BVOCs) can react in the atmosphere to form organic nitrates, which serve as NOx (NO + NO2) reservoirs, impacting ozone and secondary organic aerosol production, the oxidative capacity of the atmosphere, and nitrogen availability to ecosystems. To examine the contributions of biogenic emissions and the formation and fate of organic nitrates in a forest environment, we simulated the oxidation of 57 individual BVOCs emitted from a rural mixed forest in northern Michigan. Key BVOC-oxidant reactions were identified for future laboratory and field investigations into reaction rate constants, yields, and speciation of oxidation products. Of the total simulated organic nitrates, monoterpenes contributed ~70% in the early morning at ~12 m above the forest canopy when isoprene emissions were low. In the afternoon, when vertical mixing and isoprene nitrate production were highest, the simulated contribution of isoprene-derived organic nitrates was greater than 90% at all altitudes, with the concentration of secondary isoprene nitrates increasing with altitude. Notably, reaction of isoprene with NO3 leading to isoprene nitrate formation was found to be significant (~8% of primary organic nitrate production) during the daytime, and monoterpene reactions with NO3 were simulated to comprise up to ~83% of primary organic nitrate production at night. Lastly, forest succession, wherein aspen trees are being replaced by pine and maple trees, was predicted to lead to increased afternoon concentrations of monoterpene-derived organic nitrates. This further underscores the need to understand the formation and fate of these species, which have different chemical pathways and oxidation products compared to isoprene-derived organic nitrates and can lead to secondary organic aerosol formation.

scholarly journals Modeling the Formation and Composition of Secondary Organic Aerosol from Diesel Exhaust Using Parameterized and Semi-Explicit Chemistry and Thermodynamic Models

2017 ◽  
Author(s):  
Sailaja Eluri ◽  
Christopher D. Cappa ◽  
Beth Friedman ◽  
Delphine K. Farmer ◽  
Shantanu H. Jathar
Keyword(s):  
Volatile Organic Compounds ◽  
Gas Phase ◽  
Organic Compounds ◽  
Secondary Organic Aerosol ◽  
Organic Aerosol ◽  
Basis Set ◽  
Oxidation Catalyst ◽  
Ionization Mass ◽  
Model Predictions ◽  
Volatile Organic

Abstract. Laboratory-based studies have shown that combustion sources emit volatile organic compounds that can be photo-oxidized in the atmosphere to form secondary organic aerosol (SOA). In some cases, this SOA can exceed direct emissions of primary organic aerosol (POA). Jathar et al. (2017) recently reported on experiments that used an oxidation flow reactor (OFR) to measure the photochemical production of SOA from a diesel engine operated at two different engine loads (idle, load), two fuel types (diesel, biodiesel) and two aftertreatment configurations (with and without an oxidation catalyst and particle filter). In this work, we used two different SOA models, the volatility basis set (VBS) model and the statistical oxidation model (SOM), to simulate the formation and composition of SOA for those experiments. Leveraging recent laboratory-based parameterizations, both frameworks accounted for a semi-volatile and reactive POA; SOA production from semi-volatile, intermediate-volatility and volatile organic compounds (SVOC, IVOC and VOC); multigenerational gas-phase chemistry; and kinetic gas/particle partitioning. Both frameworks demonstrated that for model predictions of SOA mass to agree with measurements across all engine load-fuel-aftertreatment combinations, it was necessary to model the kinetically-limited gas-particle partitioning in OFRs as well as account for SOA formation from IVOCs, which were found to account for more than 90 % of the model-predicted SOA. Accounting for IVOCs however resulted in an underprediction of a factor of two for OA atomic O : C ratios. Model predictions of the gas-phase organic compounds (resolved in carbon and oxygen space) from the SOM compared favorably to gas-phase measurements from a Chemical Ionization Mass Spectrometer (CIMS), substantiating the semi-explicit chemistry captured by the SOM. Model-measurement comparisons were improved on using vapor wall-loss corrected SOA parameterizations. As OFRs are increasingly used to study SOA formation and evolution in laboratory and field environments, models such as those developed in this work can be used to interpret the OFR data.

scholarly journals Aging of atmospheric aerosols and the role of iron in catalyzing brown carbon formation

2021 ◽  
Author(s):  
Hind A. A. Al-Abadleh
Keyword(s):  
Volatile Organic Compounds ◽  
Organic Compounds ◽  
Atmospheric Aerosols ◽  
Secondary Organic Aerosol ◽  
Organic Aerosol ◽  
Atmospheric Oxidation ◽  
Carbon Formation ◽  
Brown Carbon ◽  
Volatile Organic

Extensive research has been done on the processes that lead to the formation of secondary organic aerosol (SOA) including atmospheric oxidation of volatile organic compounds (VOCs) from biogenic and anthropogenic...

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