Effect of surface–bulk partitioning on the heterogeneous oxidation of aqueous saccharide aerosols

Fan, Hanyu; Masaya, Tadini Wenyika; Goulay, Fabien

doi:10.1039/c8cp06785f

Cited by 6 publications

(23 citation statements)

References 44 publications

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“…The remaining sample flow was sent to a gas chromatograph with flame ionization detection (GC-FID) for monitoring the acetone loss. Figure 1 displays a schematic of the offline GC-MS experimental setup at WVU [46]. The saccharide particles were generated by nebulizing a 5 mg mL −1 saccharide aqueous solution using a constant output atomizer (TSI, model3076) with a 1.5 L min −1 N 2 flow.…”

Section: Methodsmentioning

confidence: 99%

“…Following the particle collection, the reactants and products were extracted from the PTFE filter by sonication using a mixture of ethanol and distilled water [46]. The samples were modified by silylation and analyzed by GC-MS.…”

Section: Methodsmentioning

confidence: 99%

“…The samples were modified by silylation and analyzed by GC-MS. Details of the extraction, silylation, and analysis procedures are given elsewhere [46]. All the samples were analyzed in triplicate.…”

Section: Methodsmentioning

confidence: 99%

“…The OH exposure (the time-integrated OH concentration) quantifications have been described previously [16,46]. The hexane (acetone in the case of the ALS experiments) tracer was injected into the bottom 1/5 of the flow tube through a 1/8 inch I.D Teflon tube in order to obtain a detectable tracer concentration.…”

Section: Methodsmentioning

confidence: 99%

“…In the present study, particles containing a monosaccharide, methyl-β-d-glucopyranoside (MGP, C 7 H 14 O 6 ), and a disaccharide, lactose (C 12 H 22 O 11 ) at a fixed water content were employed to investigate the effect of composition and viscosity on the OH-initiated oxidation of highly oxygenated atmospheric particles. In previous experiments [46], we investigated the heterogeneous transformation of liquid, mixed saccharide particles. In this case, diffusion was not the rate limiting step and partitioning between the bulk and the surface of the particle was found to play a significant role.…”

Section: Introductionmentioning

confidence: 99%

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Effect of Bulk Composition on the Heterogeneous Oxidation of Semi-Solid Atmospheric Aerosols

Fan

Goulay

2019

Atmosphere

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The OH-initiated heterogeneous oxidation of semi-solid saccharide particles with varying bulk compositions was investigated in an atmospheric pressure flow tube at 30% relative humidity. Reactive uptake coefficients were determined from the rate loss of the saccharide reactants measured by mass spectrometry at different monosaccharide (methyl-β-d-glucopyranoside, C7H14O6) and disaccharide (lactose, C12H22O11) molar ratios. The reactive uptake for the monosaccharide was found to decrease from 0.53 ± 0.10 to 0.05 ± 0.06 as the mono-to-disaccharide molar ratio changed from 8:1 to 1:1. A reaction–diffusion model was developed in order to determine the effect of chemical composition on the reactive uptake. The observed decays can be reproduced using a Vignes relationship to predict the composition dependence of the reactant diffusion coefficients. The experimental data and model results suggest that the addition of the disaccharide significantly increases the particle viscosity leading to slower mass transport phenomena from the bulk to the particle surface and to a decreased reactivity. These findings illustrate the impact of bulk composition on reactant bulk diffusivity which determines the rate-limiting step during the chemical transformation of semi-solid particles in the atmosphere.

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Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Effect of Bulk Composition on the Heterogeneous Oxidation of Semi-Solid Atmospheric Aerosols

Fan

Goulay

2019

Atmosphere

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A Molecular Dynamic Study of the Effects of Surface Partitioning on the OH Radical Interactions with Solutes in Multicomponent Aqueous Aerosols

Masaya

Goulay

2023

J. Phys. Chem. A

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The surface−bulk partitioning of small saccharide and amide molecules in aqueous droplets was investigated using molecular dynamics. The air−particle interface was modeled using a 80 Å cubic water box containing a series of organic molecules and surrounded by gaseous OH radicals. The properties of the organic solutes within the interface and the water bulk were examined at a molecular level using density profiles and radial pair distribution functions. Molecules containing only polar functional groups such as urea and glucose are found predominantly in the water bulk, forming an exclusion layer near the water surface. Substitution of a single polar group by an alkyl group in sugars and amides leads to the migration of the molecule toward the interface. Within the first 2 nm from the water surface, surface-active solutes lose their rotational freedom and adopt a preferred orientation with the alkyl group pointing toward the surface. The different packing within the interface leads to different solvation shell structures and enhanced interaction between the organic molecules and absorbed OH radicals. The simulations provide quantitative information about the dimension, composition, and organization of the air−water interface as well as about the nonreactive interaction of the OH radicals with the organic solutes. It suggests that increased concentrations, preferred orientations, and decreased solvation near the air−water surface may lead to differences in reactivities between surface-active and surface-inactive molecules. The results are important to explain how heterogeneous oxidation mechanisms and kinetics within interfaces may differ from those of the bulk.

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Chemical equilibria of aqueous ammonium–carboxylate systems in aqueous bulk, close to and at the water–air interface

Blanco

Topel

Bajnóczi

et al. 2019

Phys. Chem. Chem. Phys.

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Effect of surface–bulk partitioning on the heterogeneous oxidation of aqueous saccharide aerosols

Abstract: Experiments and simulations are employed to discuss the effect of surface partitioning on the heterogeneous kinetics.

Cited by 6 publications

References 44 publications

Effect of Bulk Composition on the Heterogeneous Oxidation of Semi-Solid Atmospheric Aerosols

Effect of Bulk Composition on the Heterogeneous Oxidation of Semi-Solid Atmospheric Aerosols

A Molecular Dynamic Study of the Effects of Surface Partitioning on the OH Radical Interactions with Solutes in Multicomponent Aqueous Aerosols

Chemical equilibria of aqueous ammonium–carboxylate systems in aqueous bulk, close to and at the water–air interface

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