Multiphase Chemistry of Ozone on Fulvic Acids Solutions

Abstract

By means of a wetted-wall flow tube, we studied the multiphase chemistry of ozone on aqueous solutions containing fulvic acids (FA), taken as proxies for atmospheric "humic like substances", so-called HULIS. In these experiments, the loss of gaseous O3 was monitored by UV-visible absorption spectroscopy at the reactor outlet (i.e., after contact between the gaseous and liquid phases). Measurements are reported in terms of dimensionless uptake coefficients (gamma) in the range from 1.6 x 10(-7) to 1.3 x 10(-5) depending on ozone gas phase concentration (in the range from 6.6 to 34.4 x 10(11) molecules cm(-3)) and fulvic acid aqueous concentration (in the range from 0.25 to 2.5 mg L(-1)) and pH (in the range from 2.5 to 9.2). The measured kinetics were observed to follow a Langmuir-Hinshelwood type mechanism, in which O3 first adsorbs on the liquid surface and then reacts with the Fulvic Acid molecules. The reported uptake coefficients are greatly increased over those measured on pure water, demonstrating that the presence in solution of fulvic acids does greatly enhance the uptake kinetics. Accordingly, the chemical interactions of fulvic acids (or HULIS) may be a driving force for the uptake of ozone on liquid organic aerosols and can also represent an important mechanism for the O3 deposition to the rivers and lakes.