scholarly journals Improvements to the representation of BVOC chemistry–climate interactions in UKCA (v11.5) with the CRI-Strat 2 mechanism: incorporation and evaluation

2021 ◽  
Vol 14 (8) ◽  
pp. 5239-5268
Author(s):  
James Weber ◽  
Scott Archer-Nicholls ◽  
Nathan Luke Abraham ◽  
Youngsub M. Shin ◽  
Thomas J. Bannan ◽  
...  
Keyword(s):  
United Kingdom ◽  
Rate Constants ◽  
Inorganic Nitrogen ◽  
Peroxy Radical ◽  
Tropospheric Chemistry ◽  
Chemical Mechanism ◽  
Aerosol Formation ◽  
Reaction Rate Constants ◽  
Climate Interactions ◽  
The Impact

Abstract. We present the first incorporation of the Common Representative Intermediates version 2.2 tropospheric chemistry mechanism, CRI v2.2, combined with stratospheric chemistry, into the global chemistry–climate United Kingdom Chemistry and Aerosols (UKCA) model to give the CRI-Strat 2 mechanism. A rigorous comparison of CRI-Strat 2 with the earlier version, CRI-Strat, is performed in UKCA in addition to an evaluation of three mechanisms, CRI-Strat 2, CRI-Strat and the standard UKCA chemical mechanism, StratTrop v1.0, against a wide array of surface and airborne chemical data. CRI-Strat 2 comprises a state-of-the-art isoprene scheme, optimized against the Master Chemical Mechanism v3.3.1, which includes isoprene peroxy radical isomerization, HOx recycling through the addition of photolabile hydroperoxy aldehydes (HPALDs), and isoprene epoxy diol (IEPOX) formation. CRI-Strat 2 also features updates to several rate constants for the inorganic chemistry, including the reactions of inorganic nitrogen and O(1D). The update to the isoprene chemistry in CRI-Strat 2 increases OH over the lowest 500 m in tropical forested regions by 30 %–50 % relative to CRI-Strat, leading to an improvement in model–observation comparisons for surface OH and isoprene relative to CRI-Strat and StratTrop. Enhanced oxidants also cause a 25 % reduction in isoprene burden and an increase in oxidation fluxes of isoprene and other biogenic volatile organic compounds (BVOCs) at low altitudes with likely impacts on subsequent aerosol formation, atmospheric lifetime, and climate. By contrast, updates to the rate constants of O(1D) with its main reactants relative to CRI-Strat reduces OH in much of the free troposphere, producing a 2 % increase in the methane lifetime, and increases the tropospheric ozone burden by 8 %, primarily from reduced loss via O(1D)+H2O. The changes to inorganic nitrogen reaction rate constants increase the NOx burden by 4 % and shift the distribution of nitrated species closer to that simulated by StratTrop. CRI-Strat 2 is suitable for multi-decadal model integrations and the improved representation of isoprene chemistry provides an opportunity to explore the consequences of HOx recycling in the United Kingdom Earth System Model (UKESM1). This new mechanism will enable a re-evaluation of the impact of BVOCs on the chemical composition of the atmosphere and further probe the feedback between the biosphere and the climate.

scholarly journals Improvements to the representation of BVOC chemistry-climate interactions in UKCA (vn11.5) with the CRI-Strat 2 mechanism: Incorporation and Evaluation 

2021 ◽  
Author(s):  
James Weber ◽  
Scott Archer-Nicholls ◽  
Nathan Luke Abraham ◽  
Youngsub Matthew Shin ◽  
Thomas J. Bannan ◽  
...  
Keyword(s):  
United Kingdom ◽  
Rate Constants ◽  
Inorganic Nitrogen ◽  
Peroxy Radical ◽  
Tropospheric Chemistry ◽  
Chemical Mechanism ◽  
Aerosol Formation ◽  
Reaction Rate Constants ◽  
Climate Interactions ◽  
The Impact

Abstract. We present the first incorporation of the Common Representative Intermediates version 2.2 tropospheric chemistry mechanism, CRI v2.2, combined with stratospheric chemistry, into the global chemistry-climate United Kingdom Chemistry and Aerosols (UKCA) model to give the CRI-Strat 2 mechanism. A rigorous comparison of CRI-Strat 2 with the earlier version, CRI-Strat, is performed in UKCA in addition to an evaluation of three mechanisms, CRI-Strat 2, CRI-Strat and the standard UKCA chemical mechanism, StratTrop vn1.0, against a wide array of surface and airborne chemical data. CRI-Strat 2 comprises a state-of-the-art isoprene scheme, optimised against the MCM v3.3.1, which includes isoprene peroxy radical isomerisation, HOx-recycling through the addition of photolabile hydroperoxy aldehydes (HPALDs) and IEPOX formation. CRI-Strat 2 also features updates to several rate constants for the inorganic chemistry including the reactions of inorganic nitrogen and O(1D). The update to the isoprene chemistry in CRI-Strat 2 increases OH over the lowest 500 m in tropical forested regions by 30–50 %, relative to CRI-Strat, leading to an improvement in model-observation comparisons for surface OH and isoprene relative to CRI-Strat and StratTrop. Enhanced oxidants also cause a 25 % reduction in isoprene burden and an increase in oxidation fluxes of isoprene and other biogenic volatile organic compounds (BVOCs) at low altitudes with likely impacts on subsequent atmospheric lifetime, aerosol formation and climate. By contrast, updates to the rate constants of O(1D) with its main reactants relative to CRI-Strat reduces OH in much of the free troposphere, producing a 2 % increase in the methane lifetime, and increases the tropospheric ozone burden by 8 %, primarily from reduced loss via O(1D) + H2O. The changes to inorganic nitrogen reaction rate constants increase the NOx burden by 4 % and shift the distribution of nitrated species closer to that simulated by StratTrop. CRI-Strat 2 is suitable for multi-decadal model integrations and the improved representation of isoprene chemistry provides an opportunity to explore the consequences of HOx-recycling in the United Kingdom Earth System Model (UKESM1). This new mechanism will enable a re-evaluation of the impact of BVOCs on the chemical composition of the atmosphere and probe further the feedback between the biosphere and the climate.

scholarly journals Global simulations of monoterpene-derived peroxy radical fates and the distributions of highly oxygenated organic molecules (HOM) and accretion products

2021 ◽  
Author(s):  
Ruochong Xu ◽  
Joel A. Thornton ◽  
Ben H. Lee ◽  
Yanxu Zhang ◽  
Lyatt Jaeglé ◽  
...  
Keyword(s):  
Rate Constants ◽  
First Generation ◽  
Transport Model ◽  
Peroxy Radical ◽  
Organic Aerosol ◽  
Laboratory Studies ◽  
Chemical Transport Model ◽  
Cross Reactions ◽  
Formation Kinetics ◽  
The Impact

Abstract. We evaluate monoterpene-derived peroxy radical (MT-RO2) unimolecular autoxidation and self and cross reactions with other RO2 in the GEOS-Chem global chemical transport model. Formation of associated highly oxygenated organic molecule (HOM) and accretion products are tracked in competition with other bimolecular reactions. Autoxidation is the dominant fate up to 6–8 km for first-generation MT-RO2 which can undergo unimolecular H-shifts. Reaction with NO can be a more common fate for H-shift rate constants < 0.1 s−1 or at altitudes higher than 8 km due to the imposed Arrhenius temperature dependence of unimolecular H-shifts. For MT-derived HOM-RO2, generated by multi-step autoxidation of first-generation MT-RO2, reaction with other RO2 is predicted to be the major fate throughout most of the boreal and tropical forested regions, while reaction with NO dominates in temperate and subtropical forests of the Northern Hemisphere. The newly added reactions result in ~4 % global average decrease of HO2 and RO2 mainly due to faster self-/cross-reactions of MT-RO2, but the impact upon HO2/OH/NOx abundances is only important in the planetary boundary layer (PBL) over portions of tropical forests. Within the bounds of formation kinetics and HOM photochemical lifetime constraints from laboratory studies, predicted HOM concentrations in MT-rich regions and seasons reach 10 % or even exceed total organic aerosol as predicted by the standard GEOS-Chem model. Comparisons to observations reveal large uncertainties remain for key reaction parameters and processes, especially the photochemical lifetime of HOM and associated accretion products. Using the highest reported yields and H-shift rate constants of MT-RO2 that undergo autoxidation, HOM concentrations tend to exceed the limited set of observations. Similarly, we infer that RO2 cross reactions rate constants near the gas-kinetic limit with accretion product branching greater than ~0.25 are inconsistent with total organic aerosol unless there is rapid decomposition of accretion products, the accretion products have saturation vapor concentrations > > 1 μg m−3, or modeled MT emission rates are overestimated. This work suggests further observations and laboratory studies related to MT-RO2 derived HOM and gas-phase accretion product formation kinetics, and especially their atmospheric fate, such as gas-particle partitioning, multi-phase chemistry, and net SOA formation, are needed.

Incorporation and evaluation of the CRI v2.2 chemical mechanism in UKESM1: An alternative mechanism with updated isoprene chemistry for investigating the influence of BVOCs on atmospheric composition and climate. 

2021 ◽  
Author(s):  
James Weber ◽  
Scott Archer-Nicholls ◽  
N. Luke Abraham ◽  
Youngsub M. Shin ◽  
Thomas Bannan ◽  
...  
Keyword(s):  
Peroxy Radical ◽  
Tropospheric Chemistry ◽  
Chemical Mechanism ◽  
Atmospheric Composition ◽  
Radiation Budget ◽  
Alternative Mechanism ◽  
Mixing Ratios ◽  
The United Kingdom ◽  
Surface Mixing ◽  
Phase Chemistry

&lt;p&gt;We present the first incorporation and evaluation of the Common Representative Intermediates version 2.2 chemistry mechanism, CRI v2.2, for use in the United Kingdom Earth System Model (UKESM1). Tuned against the MCM v3.3.1, the CRI v2.2 mechanism builds on the previous CRI version, CRI v2.1, in UKESM1 (Archer-Nicholls et al., 2020) by updating isoprene chemistry and offers a more comprehensive description of tropospheric chemistry than the standard chemistry mechanism STRAT-TROP (ST).&lt;/p&gt;&lt;p&gt;&lt;span&gt;CRI v2.2 adds state-of-the-art isoprene chemistry with the introduction of HO&lt;/span&gt;&lt;sub&gt;&lt;span&gt;x&lt;/span&gt;&lt;/sub&gt;&lt;span&gt;-recycling via the isoprene peroxy radical isomerisation pathway, &lt;/span&gt;&lt;span&gt;making UKESM1 one of the first CMIP6 models to include this important chemistry. &lt;/span&gt;&lt;span&gt;HO&lt;/span&gt;&lt;sub&gt;&lt;span&gt;x&lt;/span&gt;&lt;/sub&gt;&lt;span&gt;-recycling has noticeable effects on oxidants in regions with large emissions of biogenic volatile organic compounds (BVOCs). Low altitude OH in tropical forested regions increases by 75-150% relative to ST, reducing the existing model low bias compared to observations. Consequently, isoprene surface mixing ratios decrease considerably (25-40%), significantly improving the model high bias relative to ST. Methane lifetime decreases by 2% and tropospheric ozone burden increases by 4%. &lt;/span&gt;&lt;/p&gt;&lt;p&gt;Aerosol processes also differ between CRI v2.2 and ST, resulting in changes to the size and number distributions. Relative to ST, CRI v2.2 simulates an 8% decrease in the sulphate aerosol burden with 20% decreases in the nucleation and Aitken modes. By contrast, the secondary organic aerosol (SOA) nucleation mode burden increases by 11%. Globally, the average nucleation and Aitken mode aerosol number concentrations decrease by 20%.&lt;/p&gt;&lt;p&gt;The differences in aerosol and gas phase chemistry between CRI v2.2 and ST are likely to have impacts on the radiation budget. We plan to use CRI v2.2 and ST to investigate the influence that the chemical mechanism has on the simulated chemistry-climate feedbacks from BVOCs. In addition, CRI v2.2 will serve as the basis for the addition of a scheme describing the formation of highly oxygenated organic molecules (HOMs) from BVOCs, facilitating a semi-explicit mechanism for new particle formation from organic species.&lt;/p&gt;

scholarly journals Air–snowpack exchange of bromine, ozone and mercury in the springtime Arctic simulated by the 1-D model PHANTAS – Part 2: Mercury and its speciation

2014 ◽  
Vol 14 (8) ◽  
pp. 4135-4167 ◽  
Author(s):  
K. Toyota ◽  
A. P. Dastoor ◽  
A. Ryzhkov
Keyword(s):  
Boundary Layer ◽  
Rate Constants ◽  
Ozone Depletion ◽  
Equilibrium Constants ◽  
Ambient Air ◽  
Reaction Rates ◽  
Chemical Mechanism ◽  
The Arctic ◽  
Trace Constituents ◽  
The Impact

Abstract. Atmospheric mercury depletion events (AMDEs) refer to a recurring depletion of mercury occurring in the springtime Arctic (and Antarctic) boundary layer, in general, concurrently with ozone depletion events (ODEs). To close some of the knowledge gaps in the physical and chemical mechanisms of AMDEs and ODEs, we have developed a one-dimensional model that simulates multiphase chemistry and transport of trace constituents throughout porous snowpack and in the overlying atmospheric boundary layer (ABL). This paper constitutes Part 2 of the study, describing the mercury component of the model and its application to the simulation of AMDEs. Building on model components reported in Part 1 ("In-snow bromine activation and its impact on ozone"), we have developed a chemical mechanism for the redox reactions of mercury in the gas and aqueous phases with temperature dependent reaction rates and equilibrium constants accounted for wherever possible. Thus the model allows us to study the chemical and physical processes taking place during ODEs and AMDEs within a single framework where two-way interactions between the snowpack and the atmosphere are simulated in a detailed, process-oriented manner. Model runs are conducted for meteorological and chemical conditions that represent the springtime Arctic ABL characterized by the presence of "haze" (sulfate aerosols) and the saline snowpack on sea ice. The oxidation of gaseous elemental mercury (GEM) is initiated via reaction with Br-atom to form HgBr, followed by competitions between its thermal decomposition and further reactions to give thermally stable Hg(II) products. To shed light on uncertain kinetics and mechanisms of this multi-step oxidation process, we have tested different combinations of their rate constants based on published laboratory and quantum mechanical studies. For some combinations of the rate constants, the model simulates roughly linear relationships between the gaseous mercury and ozone concentrations as observed during AMDEs/ODEs by including the reaction HgBr + BrO and assuming its rate constant to be the same as for the reaction HgBr + Br, while for other combinations the results are more realistic by neglecting the reaction HgBr + BrO. Speciation of gaseous oxidized mercury (GOM) changes significantly depending on whether or not BrO is assumed to react with HgBr to form Hg(OBr)Br. Similarly to ozone (reported in Part 1), GEM is depleted via bromine radical chemistry more vigorously in the snowpack interstitial air than in the ambient air. However, the impact of such in-snow sink of GEM is found to be often masked by the re-emissions of GEM from the snow following the photo-reduction of Hg(II) deposited from the atmosphere. GOM formed in the ambient air is found to undergo fast "dry deposition" to the snowpack by being trapped on the snow grains in the top ~1 mm layer. We hypothesize that liquid-like layers on the surface of snow grains are connected to create a network throughout the snowpack, thereby facilitating the vertical diffusion of trace constituents trapped on the snow grains at much greater rates than one would expect inside solid ice crystals. Nonetheless, on the timescale of a week simulated in this study, the signal of atmospheric deposition does not extend notably below the top 1 cm of the snowpack. We propose and show that particulate-bound mercury (PBM) is produced mainly as HgBr42− by taking up GOM into bromide-enriched aerosols after ozone is significantly depleted in the air mass. In the Arctic, "haze" aerosols may thus retain PBM in ozone-depleted air masses, allowing the airborne transport of oxidized mercury from the area of its production farther than in the form of GOM. Temperature dependence of thermodynamic constants calculated in this study for Henry's law and aqueous-phase halide complex formation of Hg(II) species is a critical factor for this proposition, calling for experimental verification. The proposed mechanism may explain observed changes in the GOM–PBM partitioning with seasons, air temperature and the concurrent progress of ozone depletion in the high Arctic. The net deposition of mercury to the surface snow is shown to increase with the thickness of the turbulent ABL and to correspond well with the column amount of BrO in the atmosphere.

scholarly journals The role of atom tunneling in gas-phase reactions in planet-forming disks

2019 ◽  
Vol 627 ◽  
pp. A45 ◽  
Author(s):  
J. Meisner ◽  
I. Kamp ◽  
W.-F. Thi ◽  
J. Kästner
Keyword(s):  
Gas Phase ◽  
Rate Constants ◽  
Reaction Rate ◽  
Tunneling Effect ◽  
Gas Phase Reactions ◽  
Disk Model ◽  
Reaction Rate Constants ◽  
T Tauri ◽  
Simple Molecules ◽  
The Impact

Context. Chemical Gas-phase reactions of simple molecules have been recently revised to include atom tunneling at very low temperatures. This paper investigates the impact of the increased reaction rate constant due to tunneling effects on planet-forming disks. Aims. Our aim is to quantify the astrophysical implications of atom tunneling for simple molecules that are frequently used to infer disk structure information or to define the initial conditions for planet (atmosphere) formation. Methods. We quantify the tunneling effect on reaction rate constants by using H2 + OH → H2O + H as a scholarly example in comparison to previous UMIST2012 rate constants. In a chemical network with 1299 reactions, we identify all chemical reactions that could show tunneling effects. We devise a simple formulation of reaction rate constants that overestimates tunneling and screen a standard T Tauri disk model for changes in species abundances. For those reactions found to be relevant, we find values of the most recent literature for the rate constants including tunneling and compare the resulting disk chemistry to the standard disk model(s), a T Tauri and a Herbig disk. Results. The rate constants in the UMIST2012 database in many cases already capture tunneling effects implicitly, as seen in the curvature of the Arrhenius plots of some reactions at low temperature. A rigorous screening procedure identified three neutral-neutral reactions where atom tunneling could change simple molecule abundances. However, by adopting recent values of the rate constants of these reactions and due to the layered structure of planet-forming disks, the effects are limited to a small region between the ion-molecule dominated regime and the ice reservoirs where cold (<250 K) neutral-neutral chemistry dominates. Abundances of water close to the midplane snowline can increase by a factor of two at most compared to previous results with UMIST2012 rates. Observables from the disk surface, such as high excitation (>500 K) water line fluxes, decrease by 60% at most when tunneling effects are explicitly excluded. On the other hand, disk midplane quantities relevant for planet formation such as the C-to-O ratio and also the ice-to-rock ratio are clearly affected by these gas-phase tunneling effects.

scholarly journals Comparison of tropospheric gas-phase chemistry schemes for use within global models

2009 ◽  
Vol 9 (5) ◽  
pp. 1831-1845 ◽  
Author(s):  
K. M. Emmerson ◽  
M. J. Evans
Keyword(s):  
Gas Phase ◽  
Transport Model ◽  
Regional Scale ◽  
Tropospheric Chemistry ◽  
Chemical Mechanism ◽  
Model Framework ◽  
Transport Models ◽  
Global Models ◽  
Calculated Concentration ◽  
The Impact

Abstract. Methane and ozone are two important climate gases with significant tropospheric chemistry. Within chemistry-climate and transport models this chemistry is simplified for computational expediency. We compare the state of the art Master Chemical Mechanism (MCM) with six tropospheric chemistry schemes (CRI-reduced, GEOS-CHEM and a GEOS-CHEM adduct, MOZART-2, TOMCAT and CBM-IV) that could be used within composition transport models. We test the schemes within a box model framework under conditions derived from a composition transport model and from field observations from a regional scale pollution event. We find that CRI-reduced provides much skill in simulating the full chemistry, yet with greatly reduced complexity. We find significant variations between the other chemical schemes, and reach the following conclusions. 1) The inclusion of a gas phase N2O5+H2O reaction in one scheme and not others is a large source of uncertainty in the inorganic chemistry. 2) There are significant variations in the calculated concentration of PAN between the schemes, which will affect the long range transport of reactive nitrogen in global models. 3) The representation of isoprene chemistry differs hugely between the schemes, leading to significant uncertainties on the impact of isoprene on composition. 4) Differences are found in NO3 concentrations in the nighttime chemistry. Resolving these four issues through further investigative laboratory studies will reduce the uncertainties within the chemical schemes of global tropospheric models.

scholarly journals Comparison of tropospheric chemistry schemes for use within global models

2008 ◽  
Vol 8 (6) ◽  
pp. 19957-19987
Author(s):  
K. M. Emmerson ◽  
M. J. Evans
Keyword(s):  
Transport Model ◽  
Regional Scale ◽  
Tropospheric Chemistry ◽  
Chemical Mechanism ◽  
Night Time ◽  
Model Framework ◽  
Transport Models ◽  
Global Models ◽  
Calculated Concentration ◽  
The Impact

Abstract. Methane and ozone are two important climate gases with significant tropospheric chemistry. Within chemistry-climate and transport models this chemistry is simplified for computational expediency. We compare the state of the art Master Chemical Mechanism (MCM) with six tropospheric chemistry schemes (CRI-reduced, GEOS-CHEM and a GEOS-CHEM adduct, MOZART, TOMCAT and CBM-IV) that could be used within composition transport models. We test the schemes within a box model framework under conditions derived from a composition transport model and from field observations from a regional scale pollution event. We find that CRI-reduced provides much skill in simulating the full chemistry, yet with greatly reduced complexity. We find significant variations between the other chemical schemes, and reach the following conclusions. 1) The inclusion of a gas phase N2O5+H2O reaction in some schemes and not others is a large source of uncertainty in the inorganic chemistry. 2) There are significant variations in the calculated concentration of PAN between the schemes, which will affect the long range transport of reactive nitrogen in global models. 3) The representation of isoprene chemistry differs hugely between the schemes, leading to significant uncertainties on the impact of isoprene on composition. 4) Night-time chemistry is badly represented with significant disagreements in the ratio of NO3 to NOx. Resolving these four issues through further investigative laboratory studies will reduce the uncertainties within the chemical schemes of global tropospheric models.

scholarly journals Influence of non-ideality on condensation to aerosol

2009 ◽  
Vol 9 (4) ◽  
pp. 1325-1337 ◽  
Author(s):  
S. Compernolle ◽  
K. Ceulemans ◽  
J.-F. Müller
Keyword(s):  
Activity Coefficient ◽  
Water Uptake ◽  
Organic Molecules ◽  
Complex Function ◽  
Complex Mixture ◽  
Chemical Mechanism ◽  
Solubility Parameters ◽  
Order Ideal ◽  
Aerosol Formation ◽  
The Impact

Abstract. Secondary organic aerosol (SOA) is a complex mixture of water and organic molecules. Its composition is determined by the presence of semi-volatile or non-volatile compounds, their saturation vapor pressure and activity coefficient. The activity coefficient is a non-ideality effect and is a complex function of SOA composition. In a previous publication, the detailed chemical mechanism (DCM) for α-pinene oxidation and subsequent aerosol formation BOREAM was presented. In this work, we investigate with this DCM the impact of non-ideality by simulating smog chamber experiments for α-pinene degradation and aerosol formation and taking the activity coefficient into account of all molecules in the aerosol phase. Several versions of the UNIFAC method are tested for this purpose, and missing parameters for e.g. hydroperoxides and nitrates are inferred from fittings to activity coefficient data generated using the SPARC model. Alternative approaches to deal with these missing parameters are also tested, as well as an activity coefficient calculation method based on Hansen solubility parameters (HSP). It turns out that for most experiments, non-ideality has only a limited impact on the interaction between the organic molecules, and therefore on SOA yields and composition, when water uptake is ignored. The reason is that often, the activity coefficient is on average close to 1 and, specifically for high-VOC experiments, partitioning is not very sensitive on the activity coefficient because the equilibrium is shifted strongly towards condensation. Still, for ozonolysis experiments with low amounts of volatile organic carbon (low-VOC), the UNIFAC parameterization of Raatikainen et al. leads to significantly higher SOA yields (by up to a factor 1.6) compared to the ideal case and to other parameterizations. Water uptake is model dependent, in the order: ideal > UNIFAC-Raatikainen > UNIFAC-Peng > UNIFAC-Hansen ≈ UNIFAC-Magnussen ≈ UNIFAC-Ming. In the absence of salt dissolution, phase splitting from pure SOA is unlikely.

Correlation and prediction of azo dye degradation by nonlinear least-square regression in combined ozonation and ultrasonolysis processes

2011 ◽  
Vol 46 (3) ◽  
pp. 250-258 ◽  
Author(s):  
Masroor Mohajerani ◽  
Mehrab Mehrvar ◽  
Farhad Ein-Mozaffari
Keyword(s):  
Azo Dyes ◽  
Rate Constants ◽  
Reaction Rate ◽  
Synergetic Effect ◽  
Operating Conditions ◽  
Least Square ◽  
Combined Processes ◽  
Reaction Rate Constants ◽  
Least Square Regression ◽  
The Impact

Correlative reaction kinetics based on nonlinear least square regression were obtained to predict the degradation of p-aminophenol (PAP), C.I. Reactive Yellow 84 (RY84), C.I. Reactive Blue 19 (RB19), and C.I. Direct Red 23 (DR23) in combined ultrasonolysis and ozonation. Effects of ultrasonolysis and ozonation as individual processes, as well as the synergetic effect for the degradation of azo dyes, were studied by linear and nonlinear regression methods. An initial dye concentration correlation index (φ) for each compound was developed to study the effects of initial concentrations of organics on their reaction rate constants. Reaction rate constants for the azo dyes’ degradation in ozonation and ultrasonolysis alone and their combination were obtained for different operating conditions. Results showed that ultrasonolysis alone was almost ineffective for decolorization and mineralization of azo dyes, but the combination of ozonation and ultrasonolysis had a significant effect on their degradation. Both ozone dose and ultrasonic density had a direct effect on the reaction rate constants, where the impact of ozone was greater with respect to that of the ultrasound. The synergetic effect of combined processes as a function of ozone concentration and ultrasound density varied from 0 to 5, 0 to 4, and 0 to 35 for RY84, RB19, and DR23, respectively.

scholarly journals Influence of non-ideality on aerosol growth

2008 ◽  
Vol 8 (5) ◽  
pp. 17061-17093
Author(s):  
S. Compernolle ◽  
K. Ceulemans ◽  
J.-F. Müller
Keyword(s):  
Activity Coefficient ◽  
Water Uptake ◽  
Organic Molecules ◽  
Complex Function ◽  
Complex Mixture ◽  
Chemical Mechanism ◽  
Order Ideal ◽  
Aerosol Formation ◽  
Volatile Organic Carbon ◽  
The Impact

Abstract. Secondary organic aerosol (SOA) is a complex mixture of water and organic molecules. Its composition is determined by the presence of semi-volatile or non-volatile compounds, their vapor pressure and activity coefficient. The activity coefficient is a non-ideality effect and is a complex function of SOA composition. In a previous publication, the detailed chemical mechanism (DCM) for α-pinene oxidation and subsequent aerosol formation BOREAM was presented. In this work, we investigate with this DCM the impact of non-ideality by simulating smog chamber experiments for α-pinene degradation and aerosol formation. Several versions of the UNIFAC method are tested for this purpose, and missing parameters for e.g. hydroperoxides and nitrates are inferred from fittings to activity coefficient data generated using the SPARC model. It turns out that for most experiments, non-ideality has only a limited impact on the interaction between the organic molecules, and therefore on SOA yields and composition, when water uptake is ignored. Still, for ozonolysis experiments with low amounts of volatile organic carbon (low-VOC), the UNIFAC parameterization of Raatikainen et al. leads to significantly higher SOA yields (by up to a factor 1.6) compared to the ideal case and to other parameterizations. Water uptake is model dependent, in the order: ideal>UNIFAC-Raatikainen>UNIFAC-Peng>UNIFAC-Hansen≈UNIFAC-Magnussen≈UNIFAC-Ming. In the absence of salt dissolution, phase splitting from pure SOA is unlikely.

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