Cloud Chemical Heterogeneity and Its Influence on Aqueous sulfur(IV) Oxidation

Differences in chemical composition among cloud and fog drops of diverse sizes were investigated at several locations across the United States. Chemical species including acidity, total sulfur (IV), hydrogen peroxide, formaldehyde, hydroxymethanesulfonate (HMS) and trace metals iron and manganese were measured. Samples were collected with three cloud samplers capable of partitioning the cloud drop size spectrum into two or three independent drop size fractions. Measurements of pH variations within natural cloud drop populations reveal that small drops are often more acidic than large drops. No obvious pattern of drop size-dependence of hydrogen peroxide concentrations was observed. Trace metal concentrations were found to vary with drop size in clouds and fogs sampled at a variety of U.S. locations. Iron speciation measurements in San Joaquin Valley fogs revealed that dissolved iron in small fog drops was present almost entirely as Fe(III). The observed size dependence of hydrogen ion and trace metal concentrations in cloud and fog drops is expected to influence in-cloud S(IV) oxidation rates. Effects of chemical heterogeneity on overall in-cloud S(IV) oxidation rates will largely depend on contributions of the different oxidation paths. About 84 percent of the samples are calculated to experience little enhancement in S(IV) oxidation, due to the dominance of the H$\sb2$O$\sb2$ path. Approximately 9 percent of the samples are calculated to experience oxidation rate enhancement between 10 and 30%, while 7 percent of the samples are calculated to experience oxidation rate enhancement of 30% or more. Effects of chemical heterogeneity on enhancements in sulfur oxidation rates are likely to be strong when (1) hydrogen peroxide concentrations are low, for example the radiation fog in California's San Joaquin Valley, where the calculated enhancement factors range from 1.10 to 1.65, or (2) the droplet pH is high enough to support rapid S(IV) oxidation by ozone and metal-catalyzed S(IV) autooxidation, for example in relatively pristine environments like Angora Pk., Oregon, where the calculated enhancement factors range from 1.02 to 2.0. We expect real clouds to contain more than two chemically distinct drop populations. A wide distribution of drop compositions can support even faster sulfur oxidation rates.

Name thesis:degree_name

Ph.D.

Level thesis:degree_level

Dissertation

Discipline thesis:degree_discipline

Civil Engineering

Grantor

University of Illinois at Urbana-Champaign

Year dc:date

2015

Author dc:creator

• Rao, Xin

Contributors dc:contributor

• J. Collett
• S. Larson

• Physics, Atmospheric Science

Language dc:language

eng

Identifier

(MiAaPQ)AAI9812745

OAI identifier oai:identifier

oai:www.ideals.illinois.edu:2142/83446