Theses and Dissertations

Issuing Body

Mississippi State University


Wang, Chuji

Committee Member

Dibble, Theodore S

Committee Member

Pierce, Donna M.

Committee Member

Pradhan, Prabhakar

Committee Member

Arnoldus, Henk F.

Date of Degree


Document Type

Dissertation - Campus Access Only


Applied Physics

Degree Name

Doctor of Philosophy (Ph.D)


James Worth Bagley College of Engineering


Department of Physics and Astronomy


The widespread pollution of mercury motivates research into its atmospheric chemistry and transport. Gaseous elemental mercury (Hg(0)) dominates mercury emission to the atmosphere, but the rate of its oxidation to mercury compound (Hg(II)) plays a significant role in controlling where and when mercury deposits to ecosystems. Atomic bromine is regarded as the main oxidant for Hg(0) oxidation, known to initiate the oxidation via a two-step process in the atmosphere – formation of BrHg (R1) and subsequent reactions of BrHg with abundant free radicals Y, i.e., NO2, HOO, etc. (R2), where the reaction of BrHg +Y could also lead to the reduction of Hg(I) to Hg(0) (R3). A different oxidation pathway of BrHg + O3 (R4) is currently regarded as the dominant Hg(II) oxidation pathway in the atmosphere. Hg + Br + M → BrHg + M (R1) BrHg + Y + M → BrHgY + M (R2) BrHg + Y → BrY +Hg (R3) BrHg + O3 → BrHgO + O2 (R4) While the rate constants of R1 have been experimentally measured a decade ago, this research focuses on the experimental kinetic studies on the reaction of R2-R4 to better assist the efforts to predict how emission reductions impact the spatial distribution of mercury entry into ecosystems. The kinetic studies of BrHg redox chemistry are conducted by utilizing laser photolysis-laser induced fluorescence-cavity ringdown spectroscopy (LP-LIF-CRDS) systems, where BrHg radicals are generated via laser photolysis and monitored in the reaction via LIF and CRDS measurements. We report mainly on our experimental kinetic studies of the redox reactions of BrHg with relatively abundant trace gases such as NO2, NO, O3, O2, and VOCs, especially on the temperature and pressure dependence of the reaction rate constants using our LP-LIF system. We present the development and the characterization of a novel LP-CRDS system, which is a powerful tool to study reactions during which fluorescence quenching interferes with LIF measurement, and to study the spectroscopy of Hg(I) and Hg(II) compounds.