Dr. Millero proposes to continue his study of how ionic interactions affect chemical processes in seawater and other natural waters. In the next two years he will examine how the major components of seawater affect the rates of oxidation of metals and nonmetals. Measurements of the rates of oxidation will be made in seawater as a function of pH, salinity and temperature. Kinetic measurents will also be made in mixed ionic solutions (Na-Mg-Ci, Na-Cl-SO4, NaC1-NaC104, etc.) at a constant ionic strength to elucidate the ionic interactions. Studies of the products and intermediates of the oxidation will be made in an attempt to elucidate the mechanisms of the reaction. During the next two years he also plans to continue measurements on the oxidation of Fe(II), Cu(I) and H2S with H2O2 in seawater and the major sea salts. New measurements will be initiated on the oxidation of H2SO3 with H2O2. Thermodynamic pK1 and pK2 measurements for the ionization of H2So3 in NaC1, NaMgC1, and KC1 will be completed as a function of temperature (0 to 50degrees C) and ionic strength (0 to 6m). These measurements will be used to examine the effect of pH on the oxidation of H2SO3. He will participate in field studies in the Black Sea (1988), direct measurements will be made on the oxidation of H2S in these waters to compare field measurements with laboratory results. Differences are expected due to the coupled oxidations of Fe(II) and Mn (II) and catalytic effects of micro-organisms. Laboratory measurements using metal saturated HS- solutions will be made to examine the catalytic effects that may occur in natural waters. The effect various parameters have on the formation of intermediates SO32- will also be examined.
