scholarly journals Investigation of particle and vapor wall-loss effects on controlled wood-smoke smog-chamber experiments

2015 ◽  
Vol 15 (11) ◽  
pp. 15243-15288
Author(s):  
Q. Bian ◽  
A. A. May ◽  
S. M. Kreidenweis ◽  
J. R. Pierce
Keyword(s):  
Mass Loss ◽  
Gas Phase ◽  
Basis Set ◽  
Wood Smoke ◽  
Smog Chamber ◽  
Organic Mass ◽  
Final Particle ◽  
Wall Losses ◽  
Wall Loss ◽  
Smog Chambers

Abstract. Smog chambers are extensively used to study processes that drive gas and particle evolution in the atmosphere. A limitation of these experiments is that particles and gas-phase species may be lost to chamber walls on shorter timescales than the timescales of the atmospheric processes being studied in the chamber experiments. These particle and vapor wall losses have been investigated in recent studies of secondary organic aerosol (SOA) formation, but they have not been systematically investigated in experiments of primary emissions from combustion. The semi-volatile nature of combustion emissions (e.g. from wood smoke) may complicate the behavior of particle and vapor wall deposition in the chamber over the course of the experiments due to the competition between gas/particle and gas/wall partitioning. Losses of vapors to the walls may impact particle evaporation in these experiments, and potential precursors for SOA formation from combustion may be lost to the walls, causing underestimates of aerosol yields. Here, we conduct simulations to determine how particle and gas-phase wall losses contributed to the observed evolution of the aerosol during experiments in the third Fire Lab At Missoula Experiment (FLAME III). We use the TwO-Moment Aerosol Sectional (TOMAS) microphysics algorithm coupled with the organic volatility basis set (VBS) and wall-loss formulations to examine the predicted extent of particle and vapor wall losses. We limit the scope of our study to the dark periods in the chamber before photo-oxidation to simplify the aerosol system for this initial study. Our model simulations suggest that over one third of the initial particle-phase organic mass (36%) was lost during the experiments, and roughly half of this particle organic mass loss was from direct particle wall loss (56% of the loss) with the remainder from evaporation of the particles driven by vapor losses to the walls (44% of the loss). We perform a series of sensitivity tests to understand uncertainties in our simulations. Uncertainty in the initial wood-smoke volatility distribution contributes 23% uncertainty to the final particle organic mass remaining in the chamber (relative to base-assumptions simulation). We show that the total mass loss may depend on the effective saturation concentration of vapor with respect to the walls as these values currently vary widely in the literature. The details of smoke dilution during the filling of smog chambers may influence the mass loss to the walls, and a dilution of ~ 25:1 during the experiments increased particle organic mass loss by 64% compared to a simulation where we assume the particles and vapors are initially in equilibrium in the chamber. Finally, we discuss how our findings may influence interpretations of emission factors and SOA production in wood-smoke smog-chamber experiments.

scholarly journals Investigation of particle and vapor wall-loss effects on controlled wood-smoke smog-chamber experiments

2015 ◽  
Vol 15 (19) ◽  
pp. 11027-11045 ◽  
Author(s):  
Q. Bian ◽  
A. A. May ◽  
S. M. Kreidenweis ◽  
J. R. Pierce
Keyword(s):  
Mass Loss ◽  
Gas Phase ◽  
Basis Set ◽  
Wood Smoke ◽  
Smog Chamber ◽  
Organic Mass ◽  
Final Particle ◽  
Wall Losses ◽  
Wall Loss ◽  
Smog Chambers

Abstract. Smog chambers are extensively used to study processes that drive gas and particle evolution in the atmosphere. A limitation of these experiments is that particles and gas-phase species may be lost to chamber walls on shorter timescales than the timescales of the atmospheric processes being studied in the chamber experiments. These particle and vapor wall losses have been investigated in recent studies of secondary organic aerosol (SOA) formation, but they have not been systematically investigated in experiments of primary emissions from combustion. The semi-volatile nature of combustion emissions (e.g. from wood smoke) may complicate the behavior of particle and vapor wall deposition in the chamber over the course of the experiments due to the competition between gas/particle and gas/wall partitioning. Losses of vapors to the walls may impact particle evaporation in these experiments, and potential precursors for SOA formation from combustion may be lost to the walls, causing underestimations of aerosol yields. Here, we conduct simulations to determine how particle and gas-phase wall losses contributed to the observed evolution of the aerosol during experiments in the third Fire Lab At Missoula Experiment (FLAME III). We use the TwO-Moment Aerosol Sectional (TOMAS) microphysics algorithm coupled with the organic volatility basis set (VBS) and wall-loss formulations to examine the predicted extent of particle and vapor wall losses. We limit the scope of our study to the dark periods in the chamber before photo-oxidation to simplify the aerosol system for this initial study. Our model simulations suggest that over one-third of the initial particle-phase organic mass (41 %) was lost during the experiments, and over half of this particle-organic mass loss was from direct particle wall loss (65 % of the loss) with the remainder from evaporation of the particles driven by vapor losses to the walls (35 % of the loss). We perform a series of sensitivity tests to understand uncertainties in our simulations. Uncertainty in the initial wood-smoke volatility distribution contributes 18 % uncertainty to the final particle-organic mass remaining in the chamber (relative to base-assumption simulation). We show that the total mass loss may depend on the effective saturation concentration of vapor with respect to the walls as these values currently vary widely in the literature. The details of smoke dilution during the filling of smog chambers may influence the mass loss to the walls, and a dilution of ~ 25:1 during the experiments increased particle-organic mass loss by 33 % compared to a simulation where we assume the particles and vapors are initially in equilibrium in the chamber. Finally, we discuss how our findings may influence interpretations of emission factors and SOA production in wood-smoke smog-chamber experiments.

scholarly journals Secondary organic aerosol formation in biomass-burning plumes: theoretical analysis of lab studies and ambient plumes

2017 ◽  
Vol 17 (8) ◽  
pp. 5459-5475 ◽  
Author(s):  
Qijing Bian ◽  
Shantanu H. Jathar ◽  
John K. Kodros ◽  
Kelley C. Barsanti ◽  
Lindsay E. Hatch ◽  
...  
Keyword(s):  
Biomass Burning ◽  
Secondary Organic Aerosol ◽  
Organic Aerosol ◽  
Smog Chamber ◽  
Particle Phase ◽  
Wall Losses ◽  
Wall Loss ◽  
The Mean ◽  
Mass Enhancement ◽  
Fire Conditions

Abstract. Secondary organic aerosol (SOA) has been shown to form in biomass-burning emissions in laboratory and field studies. However, there is significant variability among studies in mass enhancement, which could be due to differences in fuels, fire conditions, dilution, and/or limitations of laboratory experiments and observations. This study focuses on understanding processes affecting biomass-burning SOA formation in laboratory smog-chamber experiments and in ambient plumes. Vapor wall losses have been demonstrated to be an important factor that can suppress SOA formation in laboratory studies of traditional SOA precursors; however, impacts of vapor wall losses on biomass-burning SOA have not yet been investigated. We use an aerosol-microphysical model that includes representations of volatility and oxidation chemistry to estimate the influence of vapor wall loss on SOA formation observed in the FLAME III smog-chamber studies. Our simulations with base-case assumptions for chemistry and wall loss predict a mean OA mass enhancement (the ratio of final to initial OA mass, corrected for particle-phase wall losses) of 1.8 across all experiments when vapor wall losses are modeled, roughly matching the mean observed enhancement during FLAME III. The mean OA enhancement increases to over 3 when vapor wall losses are turned off, implying that vapor wall losses reduce the apparent SOA formation. We find that this decrease in the apparent SOA formation due to vapor wall losses is robust across the ranges of uncertainties in the key model assumptions for wall-loss and mass-transfer coefficients and chemical mechanisms.We then apply similar assumptions regarding SOA formation chemistry and physics to smoke emitted into the atmosphere. In ambient plumes, the plume dilution rate impacts the organic partitioning between the gas and particle phases, which may impact the potential for SOA to form as well as the rate of SOA formation. We add Gaussian dispersion to our aerosol-microphysical model to estimate how SOA formation may vary under different ambient-plume conditions (e.g., fire size, emission mass flux, atmospheric stability). Smoke from small fires, such as typical prescribed burns, dilutes rapidly, which drives evaporation of organic vapor from the particle phase, leading to more effective SOA formation. Emissions from large fires, such as intense wildfires, dilute slowly, suppressing OA evaporation and subsequent SOA formation in the near field. We also demonstrate that different approaches to the calculation of OA enhancement in ambient plumes can lead to different conclusions regarding SOA formation. OA mass enhancement ratios of around 1 calculated using an inert tracer, such as black carbon or CO, have traditionally been interpreted as exhibiting little or no SOA formation; however, we show that SOA formation may have greatly contributed to the mass in these plumes.In comparison of laboratory and plume results, the possible inconsistency of OA enhancement between them could be in part attributed to the effect of chamber walls and plume dilution. Our results highlight that laboratory and field experiments that focus on the fuel and fire conditions also need to consider the effects of plume dilution or vapor losses to walls.

scholarly journals Design and characterization of a smog chamber for studying gas-phase chemical mechanisms and aerosol formation

2014 ◽  
Vol 7 (1) ◽  
pp. 301-313 ◽  
Author(s):  
X. Wang ◽  
T. Liu ◽  
F. Bernard ◽  
X. Ding ◽  
S. Wen ◽  
...  
Keyword(s):  
Gas Phase ◽  
Chemical Mechanism ◽  
Quality Data ◽  
Smog Chamber ◽  
Aerosol Formation ◽  
Product Model ◽  
Yield Data ◽  
Dry Conditions ◽  
Wall Loss

Abstract. We describe here characterization of a new state-of-the-art smog chamber facility for studying atmospheric gas-phase and aerosol chemistry. The chamber consists of a 30 m3 fluorinated ethylene propylene (FEP) Teflon film reactor housed in a temperature-controlled enclosure equipped with black lamps as the light source. Temperature can be set in the range from −10 to 40 °C at accuracy of ±1 °C as measured by eight temperature sensors inside the enclosure and one just inside the reactor. Matrix air can be purified with non-methane hydrocarbons (NMHCs) < 0.5 ppb, NOx/O3/carbonyls < 1 ppb and particles < 1 cm−3. The photolysis rate of NO2 is adjustable between 0 and 0.49 min−1. At 298 K under dry conditions, the average wall loss rates of NO, NO2 and O3 were measured to be 1.41 × 10−4 min−1, 1.39 × 10−4 min−1 and 1.31 × 10−4 min−1, respectively, and the particle number wall loss rate was measured to be 0.17 h−1. Auxiliary mechanisms of this chamber are determined and included in the Master Chemical Mechanism to evaluate and model propene–NOx–air irradiation experiments. The results indicate that this new smog chamber can provide high-quality data for mechanism evaluation. Results of α-pinene dark ozonolysis experiments revealed secondary organic aerosol (SOA) yields comparable to those from other chamber studies, and the two-product model gives a good fit for the yield data obtained in this work. Characterization experiments demonstrate that our Guangzhou Institute of Geochemistry, Chinese Academy Sciences (GIG-CAS), smog chamber facility can be used to provide valuable data for gas-phase chemistry and secondary aerosol formation.

scholarly journals Investigation of levoglucosan decay in wood smoke smog-chamber experiments: The importance of aerosol loading, temperature, and vapor wall losses in interpreting results

2019 ◽  
Vol 199 ◽  
pp. 224-232 ◽  
Author(s):  
Vikram Pratap ◽  
Qijing Bian ◽  
S. Aditya Kiran ◽  
Philip K. Hopke ◽  
Jeffrey R. Pierce ◽  
...  
Keyword(s):  
Wood Smoke ◽  
Smog Chamber ◽  
Aerosol Loading ◽  
Wall Losses

scholarly journals Inter-comparison of laboratory smog chamber and flow reactor systems on organic aerosol yield and composition

2015 ◽  
Vol 8 (6) ◽  
pp. 2315-2332 ◽  
Author(s):  
E. A. Bruns ◽  
I. El Haddad ◽  
A. Keller ◽  
F. Klein ◽  
N. K. Kumar ◽  
...  
Keyword(s):  
Chemical Composition ◽  
Gas Phase ◽  
Organic Aerosol ◽  
Emission Factors ◽  
Smog Chamber ◽  
Wood Combustion ◽  
Flow Reactors ◽  
Atmospheric Aging ◽  
Aerosol Mass ◽  
Smog Chambers

Abstract. A variety of tools are used to simulate atmospheric aging, including smog chambers and flow reactors. Traditional, large-scale smog chambers age emissions over the course of hours to days, whereas flow reactors rapidly age emissions using high oxidant concentrations to reach higher degrees of oxygenation than typically attained in smog chamber experiments. The atmospheric relevance of the products generated under such rapid oxidation warrants further study. However, no previously published studies have compared the yields and chemical composition of products generated in flow reactors and smog chambers from the same starting mixture. The yields and composition of the organic aerosol formed from the photo-oxidation of α-pinene and of wood-combustion emissions in a smog chamber (SC) and two flow reactors: a potential aerosol mass reactor (PAM) and a micro-smog chamber (MSC), were determined using aerosol mass spectrometry. Reactants were sampled from the SC and aged in the MSC and the PAM using a range of hydroxyl radical (OH) concentrations and then photo-chemically aged in the SC. The chemical composition, as well as the maximum yields and emission factors, of the products in both the α-pinene and wood-combustion systems determined with the PAM and the SC agreed reasonably well. High OH exposures have been shown previously to lower yields by breaking carbon–carbon bonds and forming higher volatility species, which reside largely in the gas phase; however, fragmentation in the PAM was not observed. The yields determined using the PAM for the α-pinene system were slightly lower than in the SC, possibly from increased wall losses of gas phase species due to the higher surface area to volume ratios in the PAM, even when offset with better isolation of the sampled flow from the walls. The α-pinene SOA results for the MSC were not directly comparable, as particles were smaller than the optimal AMS transmission range. The higher supersaturation in the flow reactors resulted in more nucleation than in the SC. For the wood-combustion system, emission factors measured from the MSC were typically lower than those measured from the SC. Lower emission factors in the MSC may have been due to considerable nucleation mode particles formed in the MSC which were not detected by the AMS or due to condensational loss of gases to the walls inside or after the MSC. More comprehensive coverage of the potential particle size range is needed in future SOA measurements to improve our understanding of the differences in yields when comparing the MSC to the SC. The PAM and the SC agreed within measurement uncertainties in terms of yields and composition for the systems and conditions studied here and this agreement supports the continued use of the PAM to study atmospheric aging.

scholarly journals Secondary organic aerosol formation in biomass-burning plumes: Theoretical analysis of lab studies and ambient plumes

2016 ◽  
Author(s):  
Qijing Bian ◽  
Shantanu H. Jathar ◽  
John K. Kodros ◽  
Kelley C. Barsanti ◽  
Lindsay E. Hatch ◽  
...  
Keyword(s):  
Biomass Burning ◽  
Secondary Organic Aerosol ◽  
Organic Aerosol ◽  
Smog Chamber ◽  
Particle Phase ◽  
Wall Losses ◽  
Wall Loss ◽  
The Mean ◽  
Mass Enhancement ◽  
Fire Conditions

Abstract. Secondary organic aerosol (SOA) has been shown to form in biomass-burning emissions in laboratory and field studies. However, there is significant variability among studies in mass enhancement, which could be due to differences in fuels, fire conditions, dilution, and/or limitations of laboratory experiments and observations. This study focuses on understanding processes affecting biomass-burning SOA formation in laboratory smog-chamber experiments and in ambient plumes. Vapor wall losses have been demonstrated to be an important factor that can suppress SOA formation in laboratory studies of traditional SOA precursors; however, impacts of vapor wall losses on biomass-burning SOA have not yet been investigated. We use an aerosol microphysics model that includes representations of volatility and oxidation chemistry to estimate the influence of vapor wall loss on SOA formation observed in the FLAME-III smog-chamber studies. Our simulations with base-case assumptions for chemistry and wall loss predict a mean OA mass enhancement (the ratio of final to initial OA mass, corrected for particle-phase wall losses) of 1.8 across all experiments when vapor wall losses are modeled, roughly matching the mean observed enhancement during FLAME-III. The mean OA enhancement increases to over 3 when vapor wall losses are turned off, implying that vapor wall losses reduce the apparent SOA formation. We find that this decrease in the apparent SOA formation due to vapor wall losses is robust across the ranges of uncertainties in the key model assumptions for wall-loss and mass-transfer coefficients and chemical mechanisms. We then apply similar assumptions regarding SOA formation chemistry and physics to smoke emitted into the atmosphere. In ambient plumes, the plume dilution rate impacts the organic partitioning between the gas and particle phases, which may impact the potential for SOA to form as well as the rate of SOA formation. We add Gaussian dispersion to our aerosol microphysical model to estimate how SOA formation may vary under different ambient-plume conditions (e.g. fire size, emission mass flux, atmospheric stability). Smoke from small fires, such as typical prescribed burns, dilutes rapidly, which drives evaporation of organic vapor from the particle phase, leading to more effective SOA formation. Emissions from large fires, such as intense wildfires, dilute slowly, suppressing OA evaporation and subsequent SOA formation in the near field. We also demonstrate that different approaches to the calculation of OA enhancement in ambient plumes can lead to different conclusions regarding SOA formation. OA mass enhancement ratios of around 1 calculated using an inert tracer, such as BC or CO, have traditionally been interpreted as exhibiting little or no SOA formation; however, we show that SOA formation may have greatly contributed to the mass in these plumes. In comparison of laboratory and plume results, the possible inconsistency of OA enhancement between them could be in part attributed to the effect of chamber walls and plume dilution. Our results highlight that laboratory and field experiments that focus on the fuel and fire conditions also need to consider the effects of plume dilution or vapor losses to walls.

Development of a new smog chamber for studying the impact of different UV lamps on SAPRC chemical mechanism predictions and aerosol formation

2018 ◽  
Vol 15 (3) ◽  
pp. 171 ◽  
Author(s):  
Stephen White ◽  
Dennys Angove ◽  
Kangwei Li ◽  
Ian Campbell ◽  
Adrian Element ◽  
...  
Keyword(s):  
Light Source ◽  
Atmospheric Chemistry ◽  
Chemical Mechanism ◽  
Light Sources ◽  
Smog Chamber ◽  
Aerosol Formation ◽  
Wall Loss ◽  
Smog Chambers ◽  
Uv Lamps ◽  
The Impact

Environmental contextChemical mechanisms are an important component of predictive air quality models that are developed using smog chambers. In smog chamber experiments, UV lamps are often used to simulate sunlight, and the choice of lamp can influence the obtained data, leading to differences in model predictions. We investigate the effect of various UV lamps on the prediction accuracy of a key mechanism in atmospheric chemistry. AbstractA new smog chamber was constructed at CSIRO following the decommissioning of the previous facility. The new chamber has updated instrumentation, is 35 % larger, and has been designed for chemical mechanism and aerosol formation studies. To validate its performance, characterisation experiments were conducted to determine wall loss and radical formation under irradiation by UV lamps. Two different types of blacklights commonly used in indoor chambers are used as light sources, and the results using these different lamps are investigated. Gas-phase results were compared against predictions from the latest version of the SAPRC chemical mechanism. The SAPRC mechanism gave accurate results for hydrocarbon reaction and oxidation formation for propene and o-xylene experiments, regardless of the light source used, with variations in ozone concentrations between experiment and modelled results typically less than 10 % over 6-h irradiation. The SAPRC predictions for p-xylene photooxidation showed overprediction in the rate of oxidation, although no major variations were determined in mechanism results for different blacklight sources. Additionally, no significant differences in the yields of aerosol arising from new particle formation were discernible regardless of the light source used under these conditions.

scholarly journals Absorption mechanism, structural and electronic properties of MC19 (M = B and Si) fullerenes with 1-acetylpiperazine

2017 ◽  
Vol 36 (1-2) ◽  
pp. 797-804
Author(s):  
Özgür Alver ◽  
Cemal Parlak ◽  
Mohamed I Elzagheid ◽  
Ponnadurai Ramasami
Keyword(s):  
Electronic Properties ◽  
Gas Phase ◽  
Basis Set ◽  
Stable Complex ◽  
Absorption Mechanism ◽  
Boron Doped ◽  
Structural And Electronic Properties ◽  
Influence Of Water ◽  
Vibrational Bands ◽  
Silicon Doped

The interaction mechanisms of undoped, silicon- and boron-doped C20 fullerenes and 1-acetylpiperazine (1-ap) were investigated. Stability, electronic properties, influence of water on the solubility and stability, molecular parameters, descriptive vibrational bands and nuclear magnetic resonance shielding values are reported. The quantum mechanical calculations were carried out using the M06-2X functional and the 6-31G(d) basis set. It is observed that all the complexes are more stabilized in water compared to the gas phase. The most stable complex was found as silicon-doped fullerene interacting with the carbonyl edge of 1-ap releasing energy of 64.13 kcal/mol in water.

scholarly journals Unknown Knowns: Case Studies in Uncertainties in the Computation of Thermochemical Parameters

2020 ◽  
Author(s):  
John Simmie
Keyword(s):  
Heat Capacity ◽  
Gas Phase ◽  
Basis Set ◽  
Statistical Thermodynamic ◽  
Vibrational Modes ◽  
Heavy Atoms ◽  
New Methods ◽  
Formation Enthalpies ◽  
Thermochemical Parameters

<div>Both the computation of, and the uncertainties associated, with gas-phase molar formation enthalpies are now quite well established for systems comprised of tens of ‘heavy’ atoms chosen from the commonest elements. The same cannot be said for derived thermochemical quantities such as entropy, heat capacity and an enthalpy function. Whilst the application of well known statistical thermodynamic relations is mostly understood, the determination of the uncertainty with which such values can be obtained has been little studied — apart, that is, for a general protocol devised by Goldsmith et al. [J. Phys. Chem. A, 2012, 116, 9033–9057]. Specific examples from that work are explored here and it is shown that their estimates are overly pessimistic. It is also evident that for some species the calculated thermochemical parameters show very little variation with either the level of theory, or basis set, or treatment of vibrational modes — this renders the inclusion of such species in databases designed to validate new methods of limited value.<br></div>

scholarly journals Modeling organic aerosols in a megacity: comparison of simple and complex representations of the volatility basis set approach

2010 ◽  
Vol 10 (12) ◽  
pp. 30205-30277 ◽  
Author(s):  
M. Shrivastava ◽  
J. Fast ◽  
R. Easter ◽  
W. I. Gustafson ◽  
R. A. Zaveri ◽  
...  
Keyword(s):  
Gas Phase ◽  
Secondary Organic Aerosol ◽  
Computational Cost ◽  
Organic Aerosols ◽  
Field Measurements ◽  
Organic Aerosol ◽  
Basis Set ◽  
Aerosol Formation ◽  
Secondary Organic Aerosol Formation ◽  
The City

Abstract. The Weather Research and Forecasting model coupled with chemistry (WRF-Chem) is modified to include a volatility basis set (VBS) treatment of secondary organic aerosol formation. The VBS approach, coupled with SAPRC-99 gas-phase chemistry mechanism, is used to model gas-particle partitioning and multiple generations of gas-phase oxidation of organic vapors. In addition to the detailed 9-species VBS, a simplified mechanism using 2 volatility species (2-species VBS) is developed and tested for similarity to the 9-species VBS in terms of both mass and oxygen-to-carbon ratios of organic aerosols in the atmosphere. WRF-Chem results are evaluated against field measurements of organic aerosols collected during the MILAGRO 2006 campaign in the vicinity of Mexico City. The simplified 2-species mechanism reduces the computational cost by a factor of 2 as compared to 9-species VBS. Both ground site and aircraft measurements suggest that the 9-species and 2-species VBS predictions of total organic aerosol mass as well as individual organic aerosol components including primary, secondary, and biomass burning are comparable in magnitude. In addition, oxygen-to-carbon ratio predictions from both approaches agree within 25%, providing evidence that the 2-species VBS is well suited to represent the complex evolution of organic aerosols. Model sensitivity to amount of anthropogenic semi-volatile and intermediate volatility (S/IVOC) precursor emissions is also examined by doubling the default emissions. Both the emission cases significantly under-predict primary organic aerosols in the city center and along aircraft flight transects. Secondary organic aerosols are predicted reasonably well along flight tracks surrounding the city, but are consistently over-predicted downwind of the city. Also, oxygen-to-carbon ratio predictions are significantly improved compared to prior studies by adding 15% oxygen mass per generation of oxidation; however, all modeling cases still under-predict these ratios downwind as compared to measurements, suggesting a need to further improve chemistry parameterizations of secondary organic aerosol formation.

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