scholarly journals Aqueous phase oxidation of sulphur dioxide by ozone in cloud droplets

2016 ◽  
Vol 16 (3) ◽  
pp. 1693-1712 ◽  
Author(s):  
C. R. Hoyle ◽  
C. Fuchs ◽  
E. Järvinen ◽  
H. Saathoff ◽  
A. Dias ◽  
...  
Keyword(s):  
Aqueous Phase ◽  
Rate Constants ◽  
Nuclear Research ◽  
Aqueous System ◽  
Cloud Droplets ◽  
European Organization ◽  
Reaction Rate Constants ◽  
Oxidation Rates ◽  
Phase Oxidation ◽  
Bulk Solutions

Abstract. The growth of aerosol due to the aqueous phase oxidation of sulfur dioxide by ozone was measured in laboratory-generated clouds created in the Cosmics Leaving OUtdoor Droplets (CLOUD) chamber at the European Organization for Nuclear Research (CERN). Experiments were performed at 10 and −10 °C, on acidic (sulfuric acid) and on partially to fully neutralised (ammonium sulfate) seed aerosol. Clouds were generated by performing an adiabatic expansion – pressurising the chamber to 220 hPa above atmospheric pressure, and then rapidly releasing the excess pressure, resulting in a cooling, condensation of water on the aerosol and a cloud lifetime of approximately 6 min. A model was developed to compare the observed aerosol growth with that predicted using oxidation rate constants previously measured in bulk solutions. The model captured the measured aerosol growth very well for experiments performed at 10 and −10 °C, indicating that, in contrast to some previous studies, the oxidation rates of SO2 in a dispersed aqueous system can be well represented by using accepted rate constants, based on bulk measurements. To the best of our knowledge, these are the first laboratory-based measurements of aqueous phase oxidation in a dispersed, super-cooled population of droplets. The measurements are therefore important in confirming that the extrapolation of currently accepted reaction rate constants to temperatures below 0 °C is correct.

scholarly journals Aqueous phase oxidation of sulphur dioxide by ozone in cloud droplets

2015 ◽  
Vol 15 (23) ◽  
pp. 33843-33896 ◽  
Author(s):  
C. R. Hoyle ◽  
C. Fuchs ◽  
E. Järvinen ◽  
H. Saathoff ◽  
A. Dias ◽  
...  
Keyword(s):  
Aqueous Phase ◽  
Atmospheric Pressure ◽  
Reaction Rates ◽  
Aqueous System ◽  
Excess Pressure ◽  
Cloud Droplets ◽  
Oxidation Rates ◽  
Phase Oxidation ◽  
Bulk Solutions ◽  
Seed Aerosol

Abstract. The growth of aerosol due to the aqueous phase oxidation of SO2 by O3 was measured in laboratory generated clouds created in the CLOUD chamber at CERN. Experiments were performed at 10 and −10 °C, on acidic (sulphuric acid) and on partially to fully neutralised (ammonium sulphate) seed aerosol. Clouds were generated by performing an adiabatic expansion – pressurising the chamber to 220 hPa above atmospheric pressure, and then rapidly releasing the excess pressure, resulting in a cooling, condensation of water on the aerosol and a cloud lifetime of approximately 6 min. A model was developed to compare the observed aerosol growth with that predicted by oxidation rates previously measured in bulk solutions. The model captured the measured aerosol growth very well for experiments performed at 10 and −10 °C, indicating that, in contrast to some previous studies, the oxidation rates of SO2 in a dispersed aqueous system are well represented by accepted rates, based on bulk measurements. To the best of our knowledge, these are the first laboratory based measurements of aqueous phase oxidation in a dispersed, super-cooled population of droplets. The measurements are therefore important in confirming that the extrapolation of currently accepted reaction rates to temperatures below 0 °C is correct.

scholarly journals Constraining condensed-phase formation kinetics of secondary organic aerosol components from isoprene epoxydiols

2016 ◽  
Vol 16 (3) ◽  
pp. 1245-1254 ◽  
Author(s):  
T. P. Riedel ◽  
Y.-H. Lin ◽  
Z. Zhang ◽  
K. Chu ◽  
J. A. Thornton ◽  
...  
Keyword(s):  
Aqueous Phase ◽  
Atmospheric Aerosols ◽  
Rate Constants ◽  
Reaction Rate ◽  
Secondary Organic Aerosol ◽  
Organic Aerosol ◽  
Heterogeneous Reactions ◽  
Model Calculations ◽  
Reaction Rate Constants ◽  
Aerosol Mass

Abstract. Isomeric epoxydiols from isoprene photooxidation (IEPOX) have been shown to produce substantial amounts of secondary organic aerosol (SOA) mass and are therefore considered a major isoprene-derived SOA precursor. Heterogeneous reactions of IEPOX on atmospheric aerosols form various aerosol-phase components or "tracers" that contribute to the SOA mass burden. A limited number of the reaction rate constants for these acid-catalyzed aqueous-phase tracer formation reactions have been constrained through bulk laboratory measurements. We have designed a chemical box model with multiple experimental constraints to explicitly simulate gas- and aqueous-phase reactions during chamber experiments of SOA growth from IEPOX uptake onto acidic sulfate aerosol. The model is constrained by measurements of the IEPOX reactive uptake coefficient, IEPOX and aerosol chamber wall losses, chamber-measured aerosol mass and surface area concentrations, aerosol thermodynamic model calculations, and offline filter-based measurements of SOA tracers. By requiring the model output to match the SOA growth and offline filter measurements collected during the chamber experiments, we derive estimates of the tracer formation reaction rate constants that have not yet been measured or estimated for bulk solutions.

scholarly journals Constraining condensed-phase formation kinetics of secondary organic aerosol components from isoprene epoxydiols

2015 ◽  
Vol 15 (20) ◽  
pp. 28289-28316 ◽  
Author(s):  
T. P. Riedel ◽  
Y.-H. Lin ◽  
Z. Zhang ◽  
K. Chu ◽  
J. A. Thornton ◽  
...  
Keyword(s):  
Aqueous Phase ◽  
Atmospheric Aerosols ◽  
Rate Constants ◽  
Reaction Rate ◽  
Secondary Organic Aerosol ◽  
Organic Aerosol ◽  
Heterogeneous Reactions ◽  
Model Calculations ◽  
Reaction Rate Constants ◽  
Aerosol Mass

Abstract. Isomeric epoxydiols from isoprene photooxidation (IEPOX) have been shown to produce substantial amounts of secondary organic aerosol (SOA) mass and are therefore considered a major isoprene-derived SOA precursor. Heterogeneous reactions of IEPOX on atmospheric aerosols form various aerosol-phase components or "tracers" that contribute to the SOA mass burden. A limited number of the reaction rate constants for these acid-catalyzed aqueous-phase tracer formation reactions have been constrained through bulk laboratory measurements. We have designed a chemical box model with multiple experimental constraints to explicitly simulate gas- and aqueous-phase reactions during chamber experiments of SOA growth from IEPOX uptake onto acidic sulfate aerosol. The model is constrained by measurements of the IEPOX reactive uptake coefficient, IEPOX and aerosol chamber wall-losses, chamber-measured aerosol mass and surface area concentrations, aerosol thermodynamic model calculations, and offline filter-based measurements of SOA tracers. By requiring the model output to match the SOA growth and offline filter measurements collected during the chamber experiments, we derive estimates of the tracer formation reaction rate constants that have not yet been measured or estimated for bulk solutions.

Kinetic features of gold cementation using dendritic zinc powders

2020 ◽  
pp. 36-43
Author(s):  
K. D. Naumov ◽  
V. G. Lobanov ◽  
E. B. Kolmachikhina
Keyword(s):  
Alkaline Solution ◽  
Rate Constants ◽  
Initial Period ◽  
Gold Content ◽  
Reaction Rate Constants ◽  
Oxidation Rates ◽  
Electrolytic Powder ◽  
Zinc Powders ◽  
Cyanide Solutions ◽  
Kinetic Features

The study covers kinetic features of gold cementation from cyanide solutions using two zinc powders of various origins. The first one was obtained by distillation and is currently applied in gold cementation from cyanide solutions (traditional powder). The second one was obtained by electrochemical reduction from the alkaline solution (experimental, electrolytic powder). The main distinguishing feature of these cementation powders is their specific surface area. This indicator for the electrolytic powder is 2.6 times higher than for the traditional one (3.02 m2 /g and 1.16 m2 /g, respectively) due to its dendritic form. The studies used a solution with a gold content of 50.8 μmol/dm3 and a sodium cyanide content of 0.04 mol/dm3 NaCN was taken. Cementation revealed a powder depassivation period associated with oxide film dissolution and overcoming diffusion difficulties. The traditional powder depassivation period (10–15 sec) exceeds that of the electrolytic powder (5–8 sec). Experimental rate constants of the cementation reaction were determined for the process involving both powders under study at different ratios of zinc and gold masses in the solution. Experimental reaction rate constants for the electrolytic powder under the studied conditions were 1.3– 1.6 times higher than that for the traditional powder. It was found that oxidation rates of zinc powders compared at different ratios of zinc and gold masses are virtually the same. At the same time, absolute rates of electrolytic powder dissolution in the initial period are nearly 2 times greater. As the powder reacts with the alkaline solution, absolute dissolution rates of electrolytic and traditional powders are equalized.

Estimation of Aqueous-Phase Reaction Rate Constants of Hydroxyl Radical with Phenols, Alkanes and Alcohols

2009 ◽  
Vol 28 (11-12) ◽  
pp. 1309-1316 ◽  
Author(s):  
Ya-nan Wang ◽  
Jingwen Chen ◽  
Xuehua Li ◽  
Siyu Zhang ◽  
Xianliang Qiao
Keyword(s):  
Hydroxyl Radical ◽  
Aqueous Phase ◽  
Rate Constants ◽  
Reaction Rate ◽  
Phase Reaction ◽  
Reaction Rate Constants

scholarly journals Aqueous phase oxidation of bisulfite influenced by nitrate photolysis

2020 ◽  
Author(s):  
Lu Chen ◽  
Lingdong Kong ◽  
Songying Tong ◽  
Kejing Yang ◽  
Shengyan Jin ◽  
...  
Keyword(s):  
Aqueous Phase ◽  
Cloud Droplets ◽  
Radical Chain ◽  
Sulfate Production ◽  
Halogen Chemistry ◽  
Phase Oxidation ◽  
Aqueous Oxidation ◽  
Insight Into ◽  
Solid Aerosol

Abstract. Nitrate aerosol is ubiquitous in the atmosphere, and it can exit in both solid aerosol particles and fog and cloud droplets. Nitrate in the aqueous and particulate phase can undergo photolysis to produce oxidizing active radicals, which will inevitably affect various atmospheric chemical processes. However, the role of nitrate aerosols in these atmospheric photochemical processes remains unclear. In this study, the effects of nitrate photolysis on the aqueous phase oxidation of bisulfite under different conditions were investigated. Results show that nitrate photolysis can significantly promote the oxidation of bisulfite to sulfate. It is found that pH plays a significant role in the reaction, and ammonium sulfate has significant impacts on regulating the pH of solution and the enhancement of sulfate production. We also found an apparent synergism among halogen chemistry, nitrate and its photochemistry and S(IV) aqueous oxidation, especially the oxidation of halide ions by the nitrate photolysis and by the intermediate peroxymonosulfuric acid (HSO5−) produced by the free radical chain oxidation of S(IV) in acidic solution leads to the coupling of the redox cycle of halogen with the oxidation of bisulfite, which promotes the continuous aqueous oxidation of bisulfite and the formation of sulfate. In addition, it is also found that O2 is of great significance on nitrate photolysis for the conversion of HSO3−, and H2O2 generation during the nitrate photolysis is verified. These results provide a new insight into the heterogeneous aqueous phase oxidation pathways and mechanisms of SO2 in cloud and fog droplets and haze particles.

scholarly journals Laboratory studies of the aqueous-phase oxidation of polyols: submicron particles vs. bulk aqueous solution

2014 ◽  
Vol 14 (9) ◽  
pp. 13649-13680 ◽  
Author(s):  
K. E. Daumit ◽  
A. J. Carrasquillo ◽  
J. F. Hunter ◽  
J. H. Kroll
Keyword(s):  
Aqueous Phase ◽  
Liquid Water ◽  
Water Soluble ◽  
Bulk Phase ◽  
Submicron Particles ◽  
Laboratory Studies ◽  
Cloud Droplets ◽  
Fenton Chemistry ◽  
Phase Oxidation ◽  
Aqueous Oxidation

Abstract. Oxidation in the atmospheric aqueous phase (cloud droplets and deliquesced particles) has received recent attention as a potential pathway for the formation of highly oxidized organic aerosol. Most laboratory studies of aqueous-phase oxidation, however, are carried out in bulk solutions rather than aqueous droplets. Here we describe experiments in which aqueous oxidation of polyols (water-soluble species with chemical formula CnH2n+2On) is carried out within submicron particles in an environmental chamber, allowing for significant gas-particle partitioning of reactants, intermediates, and products. Dark Fenton chemistry is used as a source of hydroxyl radicals, and oxidation is monitored using a high-resolution aerosol mass spectrometer (AMS). Aqueous oxidation is rapid, and results in the formation of particulate oxalate; this is accompanied by substantial loss of carbon to the gas phase, indicating the formation of volatile products. Results are compared to those from analogous oxidation reactions carried out in bulk solution. The bulk-phase chemistry is similar to that in the particles, but with substantially less carbon loss. This is likely due to differences in partitioning of early-generation products, which evaporate out of the aqueous phase under chamber conditions (in which liquid water content is low), but remain in solution for further aqueous processing in the bulk phase. This work suggests that the product distributions from oxidation in aqueous aerosol may be substantially different from those in bulk oxidation experiments. This highlights the need for aqueous oxidation studies to be carried out under atmospherically relevant partitioning conditions, with liquid water contents mimicking those of cloud droplets or aqueous aerosol.

scholarly journals libcloudph++ 1.1: aqueous phase chemistry extension of the Lagrangian cloud microphysics scheme

2018 ◽  
Author(s):  
Anna Jaruga ◽  
Hanna Pawlowska
Keyword(s):  
Programming Languages ◽  
Aqueous Phase ◽  
Numerical Models ◽  
Cloud Condensation Nuclei ◽  
Cloud Microphysics ◽  
Chemical Processes ◽  
Cloud Droplets ◽  
Microphysics Scheme ◽  
Phase Oxidation ◽  
Phase Chemistry

Abstract. This paper introduces a new scheme available in the library of algorithms for representing cloud microphysics in numerical models named libcloudph++. The scheme extends the Lagrangian microphysics scheme available in libcloudph++ to the aqueous phase chemical processes occurring within cloud droplets. The representation of chemical processes focuses on the aqueous phase oxidation of the dissolved SO2 by O3 and H2O2. The Lagrangian Microphysics and Chemistry (LMC) scheme allows tracking the changes in the cloud condensation nuclei (CCN) distribution caused by both collisions between cloud droplets and aqueous phase oxidation. The scheme is implemented in C++ and equipped with bindings to Python which allow reusing the created scheme from models implemented in other programming languages. The scheme can be used on either CPU or GPU, and is distributed under the GPL3 license. Here, the LMC scheme is tested in a simple 0-dimensional adiabatic parcel model and then used in a 2-dimensional prescribed flow framework. The results are discussed with the focus on changes to the CCN sizes and compared with other model simulations discussed in the literature.

scholarly journals libcloudph++ 2.0: aqueous-phase chemistry extension of the particle-based cloud microphysics scheme

2018 ◽  
Vol 11 (9) ◽  
pp. 3623-3645 ◽  
Author(s):  
Anna Jaruga ◽  
Hanna Pawlowska
Keyword(s):  
Aqueous Phase ◽  
Numerical Models ◽  
Cloud Condensation Nuclei ◽  
Cloud Microphysics ◽  
Chemical Processes ◽  
Cloud Droplets ◽  
Microphysics Scheme ◽  
Phase Oxidation ◽  
Phase Chemistry ◽  
Phase Chemical

Abstract. This paper introduces a new scheme available in the library of algorithms for representing cloud microphysics in numerical models named libcloudph++. The scheme extends the particle-based microphysics scheme with a Monte Carlo coalescence available in libcloudph++ to the aqueous-phase chemical processes occurring within cloud droplets. The representation of chemical processes focuses on the aqueous-phase oxidation of the dissolved SO2 by O3 and H2O2. The particle-based microphysics and chemistry scheme allows for tracking of the changes in the cloud condensation nuclei (CCN) distribution caused by both collisions between cloud droplets and aqueous-phase oxidation. The scheme is implemented in C++ and equipped with bindings to Python. The scheme can be used on either a CPU or a GPU, and is distributed under the GPLv3 license. Here, the particle-based microphysics and chemistry scheme is tested in a simple 0-dimensional adiabatic parcel model and then used in a 2-dimensional prescribed flow framework. The results are discussed with a focus on changes to the CCN sizes and comparison with other model simulations discussed in the literature.

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