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 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 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 Sensitivity of biogenic volatile organic compounds to land surface parameterizations and vegetation distributions in California

2016 ◽  
Vol 9 (5) ◽  
pp. 1959-1976 ◽  
Author(s):  
Chun Zhao ◽  
Maoyi Huang ◽  
Jerome D. Fast ◽  
Larry K. Berg ◽  
Yun Qian ◽  
...  
Keyword(s):  
Air Quality ◽  
Volatile Organic Compounds ◽  
Organic Compounds ◽  
Land Surface ◽  
Aerosol Formation ◽  
Biogenic Volatile Organic Compounds ◽  
Vegetation Map ◽  
Near Surface ◽  
Volatile Organic ◽  
The Impact

Abstract. Current climate models still have large uncertainties in estimating biogenic trace gases, which can significantly affect atmospheric chemistry and secondary aerosol formation that ultimately influences air quality and aerosol radiative forcing. These uncertainties result from many factors, including uncertainties in land surface processes and specification of vegetation types, both of which can affect the simulated near-surface fluxes of biogenic volatile organic compounds (BVOCs). In this study, the latest version of Model of Emissions of Gases and Aerosols from Nature (MEGAN v2.1) is coupled within the land surface scheme CLM4 (Community Land Model version 4.0) in the Weather Research and Forecasting model with chemistry (WRF-Chem). In this implementation, MEGAN v2.1 shares a consistent vegetation map with CLM4 for estimating BVOC emissions. This is unlike MEGAN v2.0 in the public version of WRF-Chem that uses a stand-alone vegetation map that differs from what is used by land surface schemes. This improved modeling framework is used to investigate the impact of two land surface schemes, CLM4 and Noah, on BVOCs and examine the sensitivity of BVOCs to vegetation distributions in California. The measurements collected during the Carbonaceous Aerosol and Radiative Effects Study (CARES) and the California Nexus of Air Quality and Climate Experiment (CalNex) conducted in June of 2010 provided an opportunity to evaluate the simulated BVOCs. Sensitivity experiments show that land surface schemes do influence the simulated BVOCs, but the impact is much smaller than that of vegetation distributions. This study indicates that more effort is needed to obtain the most appropriate and accurate land cover data sets for climate and air quality models in terms of simulating BVOCs, oxidant chemistry and, consequently, secondary organic aerosol formation.

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 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 Emissions of Volatile Organic Compounds (VOCs) from an Open-Circuit Dry Cleaning Machine Using a Petroleum-Based Organic Solvent: Implications for Impacts on Air Quality

Atmosphere ◽  
2021 ◽  
Vol 12 (5) ◽  
pp. 637
Author(s):  
Hyeonji Lee ◽  
Kyunghoon Kim ◽  
Yelim Choi ◽  
Daekeun Kim
Keyword(s):  
Air Quality ◽  
Volatile Organic Compounds ◽  
Organic Compounds ◽  
Organic Solvents ◽  
Secondary Organic Aerosol ◽  
Organic Aerosol ◽  
Tropospheric Chemistry ◽  
Dry Cleaning ◽  
Volatile Organic ◽  
Vocs Emission

Volatile organic compounds (VOCs) are known to play an important role in tropospheric chemistry, contributing to ozone and secondary organic aerosol (SOA) generation. Laundry facilities, using petroleum-based organic solvents, are one of the sources of VOCs emissions. However, little is known about the significance of VOCs, emitted from laundry facilities, in the ozone and SOA generation. In this study, we characterized VOCs emission from a dry-cleaning process using petroleum-based organic solvents. We also assessed the impact of the VOCs on air quality by using photochemical ozone creation potential and secondary organic aerosol potential. Among 94 targeted compounds including toxic organic air pollutants and ozone precursors, 36 compounds were identified in the exhaust gas from a drying machine. The mass emitted from one cycle of drying operation (40 min) was the highest in decane (2.04 g/dry cleaning). Decane, nonane, and n-undecane were the three main contributors to ozone generation (more than 70% of the total generation). N-undecane, decane, and n-dodecane were the three main contributors to the SOA generation (more than 80% of the total generation). These results help to understand VOCs emission from laundry facilities and impacts on air quality.

scholarly journals Seasonal and diurnal variations of biogenic volatile organic compounds in highland and lowland ecosystems in southern Kenya

2021 ◽  
Author(s):  
Yang Liu ◽  
Simon Schallhart ◽  
Ditte Taipale ◽  
Toni Tykkä ◽  
Matti Räsänen ◽  
...  
Keyword(s):  
Volatile Organic Compounds ◽  
Organic Compounds ◽  
Atmospheric Chemistry ◽  
Daily Maximum ◽  
Mixing Ratio ◽  
Biogenic Volatile Organic Compounds ◽  
Mixing Ratios ◽  
Seasonal And Diurnal Variations ◽  
Volatile Organic ◽  
Dry Seasons

Abstract. The East African lowland and highland areas consist of water-limited and humid ecosystems. The magnitude and seasonality of biogenic volatile organic compounds (BVOCs) emissions from these functionally contrasting ecosystems are limited due to a scarcity of direct observations. We measured mixing ratios of BVOCs from two contrasting ecosystems, humid highlands with agroforestry and dry lowlands with bushland, grassland, and agriculture mosaics, during both the rainy and dry seasons of 2019 in southern Kenya. We present the diurnal and seasonal characteristics of BVOC mixing ratios and their reactivity, and estimated emission factors (EFs) for certain BVOCs from the African lowland ecosystem based on field measurements. The most abundant BVOCs were isoprene and monoterpenoids (MTs), with isoprene contributing > 70 % of the total BVOC mixing ratio during daytime, while MTs accounted for > 50 % of the total BVOC mixing ratio during nighttime at both sites. The contributions of BVOCs to the local atmospheric chemistry were estimated by calculating the reactivity towards the hydroxyl radical (OH), ozone (O3), and the nitrate radical (NO3). Isoprene and MTs contributed the most to the reactivity of OH and NO3, while sesquiterpenes dominated the contribution of organic compounds to the reactivity of O3. The mixing ratio of isoprene measured in this study was lower to that measured in the relevant ecosystems in west and south Africa, while that of monoterpenoids was similar. Isoprene mixing ratios peaked daily between 16:00 and 20:00 with a maximum mixing ratio of 809 parts per trillion by volume (pptv) and 156 pptv in the highlands, and 115 pptv and 25 pptv in the lowlands, during the rainy and dry seasons, respectively. MT mixing ratios reached their daily maximum between midnight and early morning (usually 04:00 to 08:00) with mixing ratios of 254 pptv and 56 pptv in the highlands, and 89 pptv and 7 pptv in the lowlands, in the rainy and dry seasons, respectively. The dominant species within the MT group were limonene, α-pinene, and β-pinene. EFs for isoprene, MTs, and 2-methyl-3-buten-2-ol (MBO) were estimated using an inverse modeling approach. The estimated EFs for isoprene and β-pinene agreed very well with what is currently assumed in the world’s most extensively used biogenic emissions model, the Model of Emissions of Gases and Aerosols from Nature (MEGAN), for warm C4 grass, but the estimated EFs for MBO, α-pinene, and especially limonene, were significantly higher than that assumed in MEGAN for the relevant plant functional type. Additionally, our results indicate that the EF for limonene might be seasonally dependent in savanna ecosystems.

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