Combustion Aerosols: Factors Governing Their Size and Composition and Implications to Human Health

ABSTRACT

Particulate matter (PM) emissions from stationary combustion sources burning coal, fuel oil, biomass, and waste, and PM from internal combustion (IC) engines burning gasoline and diesel, are a significant source of primary particles smaller than 2.5 μm (PM_2.5) in urban areas. Combustion-generated particles are generally smaller than geologically produced dust and have unique chemical composition and morphology. The fundamental processes affecting formation of combustion PM and the emission characteristics of important applications are reviewed. Particles containing transition metals, ultrafine particles, and soot are emphasized because these types of particles have been studied extensively, and their emissions are controlled by the fuel composition and the oxidant-tem-perature-mixing history from the flame to the stack. There is a need for better integration of the combustion, air pollution control, atmospheric chemistry, and inhalation health research communities. Epidemiology has demonstrated that susceptible individuals are being harmed by ambient PM. Particle surface area, number of ultrafine particles, bioavailable transition metals, polycyclic aromatic hydrocarbons (PAH), and other particle-bound organic compounds are suspected to be more important than particle mass in determining the effects of air pollution. Time- and size-resolved PM measurements are needed for testing mechanistic toxicological hypotheses, for characterizing the relationship between combustion operating conditions and transient emissions, and for source apportionment studies to develop air quality plans. Citations are provided to more specialized reviews, and the concluding comments make suggestions for further research.     

Reaction of arsenic vapor species with fly ash compounds: kinetics and speciation of the reaction with calcium silicates

In coal combustion systems, the partitioning of arsenic between the vapor and solid phases is determined by the interaction of arsenic vapors with fly ash compounds under post-combustion conditions. This partitioning is affected by gas–solid reactions between the calcium components of the ash particles and arsenic vapors. In this study, bench scale experiments were conducted with calcium compounds typical of coal-derived fly ash to determine product formation, the extent of reaction and reaction rates when contacted by arsenic oxide vapors. Experiments conducted with arsenic trioxide (As₄O_6(g)) vapors in contact with calcium oxide, di-calcium silicate and mono-calcium silicate over the temperature range 600–1000 °C indicated that these solids were capable of reacting with arsenic vapor species in both air and nitrogen. Calcium arsenate was the observed reaction product in all the samples analyzed. Maximum capture of arsenic occurred at 1000 °C with calcium oxide being the most effective of the three solids over the range of temperatures studied. Using a shrinking core model for a first order reaction and the results from intrinsic kinetic experiments conducted in air, the reaction rate constants were found to be 1.4×10⁻³exp(−2776/T) m/s for calcium oxide particles, 7.2×10⁻³exp(−3367/T) m/s for di-calcium silicate particles and 5.5×10⁻³exp(−3607/T) m/s for mono-calcium silicate particles. These results therefore suggest that any calcium present in fly ash can react with arsenic vapor and capture the metal in water-insoluble forms of the less hazardous As(V) oxidation state.