scholarly journals Modeling Biomass Burning Organic Aerosol Atmospheric Evolution and Chemical Aging

Atmosphere ◽  
2021 ◽  
Vol 12 (12) ◽  
pp. 1638
Author(s):  
David Patoulias ◽  
Evangelos Kallitsis ◽  
Laura Posner ◽  
Spyros N. Pandis
Keyword(s):  
Dilution Rate ◽  
Organic Compounds ◽  
Biomass Burning ◽  
Transport Model ◽  
Organic Aerosol ◽  
Base Case ◽  
Chemical Transport Model ◽  
Fire Plume ◽  
Case Scenario ◽  
Base Case Scenario

The changes in the concentration and composition of biomass-burning organic aerosol (OA) downwind of a major wildfire are simulated using the one-dimensional Lagrangian chemical transport model PMCAMx-Trj. A base case scenario is developed based on realistic fire-plume conditions and a series of sensitivity tests are performed to quantify the effects of different conditions and processes. Temperature, oxidant concentration and dilution rate all affect the evolution of biomass burning OA after its emission. The most important process though is the multi-stage oxidation of both the originally emitted organic vapors (volatile and intermediate volatility organic compounds) and those resulting from the evaporation of the OA as it is getting diluted. The emission rates of the intermediate volatility organic compounds (IVOCs) and their chemical fate have a large impact on the formed secondary OA within the plume. The assumption that these IVOCs undergo only functionalization leads to an overestimation of the produced SOA suggesting that fragmentation is also occurring. Assuming a fragmentation probability of 0.2 resulted in predictions that are more consistent with available observations. Dilution leads to OA evaporation and therefore reduction of the OA levels downwind of the fire. However, the evaporated material can return to the particulate phase later on after it gets oxidized and recondenses. The sensitivity of the OA levels and total mass balance on the dilution rate depends on the modeling assumptions. The high variability of OA mass enhancement observed in past field studies downwind of fires may be partially due to the variability of the dilution rates of the plumes.

scholarly journals Functionalization and fragmentation during ambient organic aerosol aging: application of the 2-D volatility basis set to field studies

2012 ◽  
Vol 12 (4) ◽  
pp. 9857-9901 ◽  
Author(s):  
B. N. Murphy ◽  
N. M. Donahue ◽  
C. Fountoukis ◽  
M. Dall'Osto ◽  
C. O'Dowd ◽  
...  
Keyword(s):  
Organic Compounds ◽  
Aqueous Phase ◽  
Transport Model ◽  
Field Studies ◽  
Organic Aerosol ◽  
Basis Set ◽  
Base Case ◽  
Chemical Transport Model ◽  
Heterogeneous Oxidation ◽  
Phase Chemistry

Abstract. Multigenerational oxidation chemistry of atmospheric organic compounds and its effects on aerosol loadings and chemical composition is investigated by implementing the Two-Dimensional Volatility Basis Set (2-D-VBS) in a Lagrangian host chemical transport model. Three model formulations were chosen to explore the complex interactions between functionalization and fragmentation processes during gas-phase oxidation of organic compounds by the hydroxyl radical. The base case model employs a conservative transformation by assuming a reduction of one order of magnitude in effective saturation concentration and an increase of oxygen content by one or two oxygen atoms per oxidation generation. A second scheme simulates functionalization in more detail using group contribution theory to estimate the effects of oxygen addition to the carbon backbone on the compound volatility. Finally, a fragmentation scheme is added to the detailed functionalization scheme to create a functionalization-fragmentation parameterization. Two condensed-phase chemistry pathways are also implemented as additional sensitivity tests to simulate (1) heterogeneous oxidation via OH uptake to the particle-phase and (2) aqueous-phase chemistry of glyoxal and methylglyoxal. The model is applied to summer and winter periods at three sites where observations of organic aerosol (OA) mass and O:C were obtained during the European Integrated Project on Aerosol Cloud Climate and Air Quality Interactions (EUCAARI) campaigns. The base case model reproduces observed mass concentrations and O:C well, with fractional errors (FE) lower than 55% and 25%, respectively. The detailed functionalization scheme tends to overpredict OA concentrations, especially in the summertime, and also underpredicts O:C by approximately a factor of 2. The detailed functionalization model with fragmentation agrees well with the observations for OA concentration, but still underpredicts O:C. Both heterogeneous oxidation and aqueous-phase processing have small effects on OA levels but heterogeneous oxidation, as implemented here, does enhance O:C by about 0.1. The different schemes result in very different fractional attribution for OA between anthropogenic and biogenic sources.

scholarly journals Functionalization and fragmentation during ambient organic aerosol aging: application of the 2-D volatility basis set to field studies

2012 ◽  
Vol 12 (22) ◽  
pp. 10797-10816 ◽  
Author(s):  
B. N. Murphy ◽  
N. M. Donahue ◽  
C. Fountoukis ◽  
M. Dall'Osto ◽  
C. O'Dowd ◽  
...  
Keyword(s):  
Organic Compounds ◽  
Aqueous Phase ◽  
Transport Model ◽  
Field Studies ◽  
Organic Aerosol ◽  
Basis Set ◽  
Base Case ◽  
Chemical Transport Model ◽  
Heterogeneous Oxidation ◽  
Phase Chemistry

Abstract. Multigenerational oxidation chemistry of atmospheric organic compounds and its effects on aerosol loadings and chemical composition is investigated by implementing the Two-Dimensional Volatility Basis Set (2-D-VBS) in a Lagrangian host chemical transport model. Three model formulations were chosen to explore the complex interactions between functionalization and fragmentation processes during gas-phase oxidation of organic compounds by the hydroxyl radical. The base case model employs a conservative transformation by assuming a reduction of one order of magnitude in effective saturation concentration and an increase of oxygen content by one or two oxygen atoms per oxidation generation. A second scheme simulates functionalization in more detail using group contribution theory to estimate the effects of oxygen addition to the carbon backbone on the compound volatility. Finally, a fragmentation scheme is added to the detailed functionalization scheme to create a functionalization-fragmentation parameterization. Two condensed-phase chemistry pathways are also implemented as additional sensitivity tests to simulate (1) heterogeneous oxidation via OH uptake to the particle-phase and (2) aqueous-phase chemistry of glyoxal and methylglyoxal. The model is applied to summer and winter periods at three sites where observations of organic aerosol (OA) mass and O:C were obtained during the European Integrated Project on Aerosol Cloud Climate and Air Quality Interactions (EUCAARI) campaigns. The base case model reproduces observed mass concentrations and O:C well, with fractional errors (FE) lower than 55% and 25%, respectively. The detailed functionalization scheme tends to overpredict OA concentrations, especially in the summertime, and also underpredicts O:C by approximately a factor of 2. The detailed functionalization model with fragmentation agrees well with the observations for OA concentration, but still underpredicts O:C. Both heterogeneous oxidation and aqueous-phase processing have small effects on OA levels but heterogeneous oxidation, as implemented here, does enhance O:C by about 0.1. The different schemes result in very different fractional attribution for OA between anthropogenic and biogenic sources.

scholarly journals Simulation of the evolution of biomass burning organic aerosol with different volatility basis set schemes in PMCAMx-SRv1.0

2020 ◽  
Author(s):  
Georgia N. Theodoritsi ◽  
Giancarlo Ciarelli ◽  
Spyros N. Pandis
Keyword(s):  
Biomass Burning ◽  
Transport Model ◽  
Three Dimensional ◽  
Organic Aerosol ◽  
Basis Set ◽  
Base Case ◽  
Chemical Transport Model ◽  
Alternative Scheme ◽  
Average Maximum ◽  
The Impact

Abstract. A source-resolved three-dimensional chemical transport model, PMCAMx-SR, was applied in the continental U.S. to investigate the contribution of the various components (primary and secondary) of biomass burning organic aerosol (bbOA) to organic aerosol levels. Two different schemes based on the volatility basis set were used for the simulation of the bbOA during different seasons. The first is the default scheme of PMCAMx-SR and the second is a recently developed scheme based on laboratory experiments of the bbOA evolution. The simulations with the alternative bbOA scheme predict much higher total bbOA concentrations when compared with the base case ones. This is mainly due to the high emissions of intermediate volatility organic compounds (IVOCs) assumed in the alternative scheme. The oxidation of these compounds is predicted to be a significant source of secondary organic aerosol. The impact of the other parameters that differ in the two schemes is low to negligible. The monthly average maximum predicted concentrations of the alternative bbOA scheme were approximately an order of magnitude higher than those of the default scheme during all seasons. The performance of the two schemes was evaluated against observed total organic aerosol concentrations from several measurement sites across the US. The results were mixed. The default scheme performed better during July and September while the alternative scheme performed a little better during April. These results illustrate the uncertainty of the corresponding predictions, the need to quantify the emissions and reactions of IVOCs from specific biomass sources, and to better constrain the total (primary and secondary) bbOA levels.

scholarly journals Influence of aquifer and streambed heterogeneity on the distribution of groundwater discharge

2009 ◽  
Vol 13 (1) ◽  
pp. 69-77 ◽  
Author(s):  
E. Kalbus ◽  
C. Schmidt ◽  
J. W. Molson ◽  
F. Reinstorf ◽  
M. Schirmer
Keyword(s):  
Groundwater Flow ◽  
Transport Model ◽  
Regional Scale ◽  
Base Case ◽  
Case Scenario ◽  
Base Case Scenario ◽  
Heterogeneous Distribution ◽  
Heterogeneous Aquifer ◽  
The Impact ◽  
Low K

Abstract. The spatial distribution of groundwater fluxes through a streambed can be highly variable, most often resulting from a heterogeneous distribution of aquifer and streambed permeabilities along the flow pathways. Using a groundwater flow and heat transport model, we defined four scenarios of aquifer and streambed permeability distributions to simulate and assess the impact of subsurface heterogeneity on the distribution of groundwater fluxes through the streambed: (a) a homogeneous low-K streambed within a heterogeneous aquifer; (b) a heterogeneous streambed within a homogeneous aquifer; (c) a well connected heterogeneous low-K streambed within a heterogeneous aquifer; and (d) a poorly connected heterogeneous low-K streambed within a heterogeneous aquifer. The simulation results were compared with a base case scenario, in which the streambed had the same properties as the aquifer, and with observed data. The results indicated that the aquifer has a stronger influence on the distribution of groundwater fluxes through the streambed than the streambed itself. However, a homogeneous low-K streambed, a case often implemented in regional-scale groundwater flow models, resulted in a strong homogenization of fluxes, which may have important implications for the estimation of peak mass flows. The flux distributions simulated with heterogeneous low-K streambeds were similar to the flux distributions of the base case scenario, despite the lower permeability. The representation of heterogeneous distributions of aquifer and streambed properties in the model has been proven to be beneficial for the accuracy of flow simulations.

scholarly journals On the implications of aerosol liquid water and phase separation for organic aerosol mass

2017 ◽  
Vol 17 (1) ◽  
pp. 343-369 ◽  
Author(s):  
Havala O. T. Pye ◽  
Benjamin N. Murphy ◽  
Lu Xu ◽  
Nga L. Ng ◽  
Annmarie G. Carlton ◽  
...  
Keyword(s):  
Organic Carbon ◽  
Organic Compounds ◽  
Water Uptake ◽  
Liquid Water ◽  
Transport Model ◽  
Organic Aerosol ◽  
Water Soluble ◽  
Organic Nitrates ◽  
Monitoring Networks ◽  
Chemical Transport Model

Abstract. Organic compounds and liquid water are major aerosol constituents in the southeast United States (SE US). Water associated with inorganic constituents (inorganic water) can contribute to the partitioning medium for organic aerosol when relative humidities or organic matter to organic carbon (OM ∕ OC) ratios are high such that separation relative humidities (SRH) are below the ambient relative humidity (RH). As OM ∕ OC ratios in the SE US are often between 1.8 and 2.2, organic aerosol experiences both mixing with inorganic water and separation from it. Regional chemical transport model simulations including inorganic water (but excluding water uptake by organic compounds) in the partitioning medium for secondary organic aerosol (SOA) when RH  >  SRH led to increased SOA concentrations, particularly at night. Water uptake to the organic phase resulted in even greater SOA concentrations as a result of a positive feedback in which water uptake increased SOA, which further increased aerosol water and organic aerosol. Aerosol properties, such as the OM ∕ OC and hygroscopicity parameter (κorg), were captured well by the model compared with measurements during the Southern Oxidant and Aerosol Study (SOAS) 2013. Organic nitrates from monoterpene oxidation were predicted to be the least water-soluble semivolatile species in the model, but most biogenically derived semivolatile species in the Community Multiscale Air Quality (CMAQ) model were highly water soluble and expected to contribute to water-soluble organic carbon (WSOC). Organic aerosol and SOA precursors were abundant at night, but additional improvements in daytime organic aerosol are needed to close the model–measurement gap. When taking into account deviations from ideality, including both inorganic (when RH  >  SRH) and organic water in the organic partitioning medium reduced the mean bias in SOA for routine monitoring networks and improved model performance compared to observations from SOAS. Property updates from this work will be released in CMAQ v5.2.

scholarly journals Precursors and formation of secondary organic aerosols from wildfires in the Euro-Mediterranean region

2019 ◽  
Vol 19 (8) ◽  
pp. 5543-5569 ◽  
Author(s):  
Marwa Majdi ◽  
Karine Sartelet ◽  
Grazia Maria Lanzafame ◽  
Florian Couvidat ◽  
Youngseob Kim ◽  
...  
Keyword(s):  
Organic Compounds ◽  
Mediterranean Region ◽  
Transport Model ◽  
Organic Aerosol ◽  
Moderate Increase ◽  
Fire Plume ◽  
Voc Emissions ◽  
The Balkans ◽  
Relative Contribution ◽  
Sensitivity Studies

Abstract. This work aims at quantifying the relative contribution of secondary organic aerosol (SOA) precursors emitted by wildfires to organic aerosol (OA) formation during summer of 2007 over the Euro-Mediterranean region, where intense wildfires occurred. A new SOA formation mechanism, H2Oaro, including recently identified aromatic volatile organic compounds (VOCs) emitted from wildfires, is developed based on smog chamber experiment measurements under low- and high-NOx regimes. The aromatic VOCs included in the mechanism are toluene, xylene, benzene, phenol, cresol, catechol, furan, naphthalene, methylnaphthalene, syringol, guaiacol, and structurally assigned and unassigned compounds with at least six carbon atoms per molecule (USC>6). This mechanism H2Oaro is an extension of the H2O (hydrophilic–hydrophobic organic) aerosol mechanism: the oxidation of the precursor forms surrogate species with specific thermodynamic properties (volatility, oxidation degree and affinity to water). The SOA concentrations over the Euro-Mediterranean region in summer of 2007 are simulated using the chemistry transport model (CTM) Polair3D of the air-quality platform Polyphemus, where the mechanism H2Oaro was implemented. To estimate the relative contribution of the aromatic VOCs, intermediate volatility, semi-volatile and low-volatility organic compounds (I/S/L-VOCs), to wildfires OA concentrations, different estimations of the gaseous I/S/L-VOC emissions (from primary organic aerosol – POA – using a factor of 1.5 or from non-methanic organic gas – NMOG – using a factor of 0.36) and their ageing (one-step oxidation vs. multi-generational oxidation) are also tested in the CTM. Most of the particle OA concentrations are formed from I/S/L-VOCs. On average during the summer of 2007 and over the Euro-Mediterranean domain, they are about 10 times higher than the OA concentrations formed from VOCs. However, locally, the OA concentrations formed from VOCs can represent up to 30 % of the OA concentrations from biomass burning. Amongst the VOCs, the main contributors to SOA formation are phenol, benzene and catechol (CAT; 47 %); USC>6 compounds (23 %); and toluene and xylene (12 %). Sensitivity studies of the influence of the VOCs and the I/S/L-VOC emissions and chemical ageing mechanisms on PM2.5 concentrations show that surface PM2.5 concentrations are more sensitive to the parameterization used for gaseous I/S/L-VOC emissions than for ageing. Estimating the gaseous I/S/L-VOC emissions from POA or from NMOG has a high impact on local surface PM2.5 concentrations (reaching −30 % in the Balkans, −8 % to −16 % in the fire plume and +8 % to +16 % in Greece). Considering the VOC as SOA precursors results in a moderate increase in PM2.5 concentrations mainly in the Balkans (up to 24 %) and in the fire plume (+10 %).

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

2012 ◽  
Vol 5 (4) ◽  
pp. 4187-4232 ◽  
Author(s):  
A. Mahmud ◽  
K. C. Barsanti
Keyword(s):  
South America ◽  
Secondary Organic Aerosol ◽  
Transport Model ◽  
Organic Aerosol ◽  
Basis Set ◽  
Base Case ◽  
Chemical Transport Model ◽  
Annual Average ◽  
Modeling Studies ◽  
The Usa

Abstract. 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.

scholarly journals Simulation of the chemical evolution of biomass burning organic aerosol

2019 ◽  
Vol 19 (8) ◽  
pp. 5403-5415 ◽  
Author(s):  
Georgia N. Theodoritsi ◽  
Spyros N. Pandis
Keyword(s):  
Biomass Burning ◽  
Transport Model ◽  
Organic Aerosol ◽  
Early Summer ◽  
Oxidation Products ◽  
Winter Period ◽  
Chemical Transport Model ◽  
Wood Combustion ◽  
Aerosol Mass ◽  
Photochemical Aging

Abstract. The chemical transport model PMCAMx was extended to investigate the effects of partitioning and photochemical aging of biomass burning emissions on organic aerosol (OA) concentrations. A source-resolved version of the model, PMCAMx-SR, was developed in which biomass burning emissions and their oxidation products are represented separately from the other OA components. The volatility distribution and chemical aging of biomass burning OA (BBOA) were simulated based on recent laboratory measurements. PMCAMx-SR was applied to Europe during an early summer period (1–29 May 2008) and a winter period (25 February–22 March 2009). During the early summer, the contribution of biomass burning (both primary and secondary species) to total OA levels over continental Europe was estimated to be approximately 16 %. During winter the contribution was nearly 47 %, due to both extensive residential wood combustion but also wildfires in Portugal and Spain. The intermediate volatility compounds (IVOCs) with effective saturation concentration values of 105 and 106 µg m−3 are predicted to contribute around one third of the BBOA during the summer and 15 % during the winter by forming secondary OA (SOA). The uncertain emissions of these compounds and their SOA formation potential require additional attention. Evaluation of PMCAMx-SR predictions against aerosol mass spectrometer measurements in several sites around Europe suggests reasonably good performance for OA (fractional bias less than 35 % and fractional error less than 50 %). The performance was weaker during the winter suggesting uncertainties in residential heating emissions and the simulation of the resulting BBOA in this season.

scholarly journals Sources and production of organic aerosol in Mexico City: insights from the combination of a chemical transport model (PMCAMx-2008) and measurements during MILAGRO

2011 ◽  
Vol 11 (11) ◽  
pp. 5153-5168 ◽  
Author(s):  
A. P. Tsimpidi ◽  
V. A. Karydis ◽  
M. Zavala ◽  
W. Lei ◽  
N. Bei ◽  
...  
Keyword(s):  
Mexico City ◽  
Biomass Burning ◽  
Urban Areas ◽  
Transport Model ◽  
Three Dimensional ◽  
Chemical Transport ◽  
Organic Aerosol ◽  
Basis Set ◽  
Chemical Transport Model ◽  
Aerosol Mass

Abstract. Urban areas are large sources of organic aerosols and their precursors. Nevertheless, the contributions of primary (POA) and secondary organic aerosol (SOA) to the observed particulate matter levels have been difficult to quantify. In this study the three-dimensional chemical transport model PMCAMx-2008 is used to investigate the temporal and geographic variability of organic aerosol in the Mexico City Metropolitan Area (MCMA) during the MILAGRO campaign that took place in the spring of 2006. The organic module of PMCAMx-2008 includes the recently developed volatility basis-set framework in which both primary and secondary organic components are assumed to be semi-volatile and photochemically reactive and are distributed in logarithmically spaced volatility bins. The MCMA emission inventory is modified and the POA emissions are distributed by volatility based on dilution experiments. The model predictions are compared with observations from four different types of sites, an urban (T0), a suburban (T1), a rural (T2), and an elevated site in Pico de Tres Padres (PTP). The performance of the model in reproducing organic mass concentrations in these sites is encouraging. The average predicted PM1 organic aerosol (OA) concentration in T0, T1, and T2 is 18 μg m−3, 11.7 μg m−3, and 10.5 μg m−3 respectively, while the corresponding measured values are 17.2 μg m−3, 11 μg m−3, and 9 μg m−3. The average predicted locally-emitted primary OA concentrations, 4.4 μg m−3 at T0, 1.2 μg m−3 at T1 and 1.7 μg m−3 at PTP, are in reasonably good agreement with the corresponding PMF analysis estimates based on the Aerosol Mass Spectrometer (AMS) observations of 4.5, 1.3, and 2.9 μg m−3 respectively. The model reproduces reasonably well the average oxygenated OA (OOA) levels in T0 (7.5 μg m−3 predicted versus 7.5 μg m−3 measured), in T1 (6.3 μg m−3 predicted versus 4.6 μg m−3 measured) and in PTP (6.6 μg m−3 predicted versus 5.9 μg m−3 measured). The rest of the OA mass (6.1 μg m−3 and 4.2 μg m−3 in T0 and T1 respectively) is assumed to originate from biomass burning activities and is introduced to the model as part of the boundary conditions. Inside Mexico City (at T0), the locally-produced OA is predicted to be on average 60 % locally-emitted primary (POA), 6 % semi-volatile (S-SOA) and intermediate volatile (I-SOA) organic aerosol, and 34 % traditional SOA from the oxidation of VOCs (V-SOA). The average contributions of the OA components to the locally-produced OA for the entire modelling domain are predicted to be 32 % POA, 10 % S-SOA and I-SOA, and 58 % V-SOA. The long range transport from biomass burning activities and other sources in Mexico is predicted to contribute on average almost as much as the local sources during the MILAGRO period.

Sign in / Sign up

Export Citation Format

Share Document