A study is reported of surface segregation phenomena for fly ash and aluminosilicates representative of coal mineral matter during heating. The materials studied included a 20-..mu..m average diameter fly ash powder, a glass prepared from the fly ash, and Ca- and K-rich aluminosilicate minerals. The samples were heated both in air and under vacuum for extended periods at temperatures up to 1100/sup 0/C. XPS, Auger and SIMS methods were used to obtain relative surface elemental concentrations for major and minor components and depth profiles for some of the samples. Major differences were noted between samples heated in air (oxidizing) and those heated in vacuum (reducing) environments. For the fly ash glass heated in air Fe, Ti and Mg become enriched on the surfaces while heating in vacuum leads to Si surface segregation. Different trends upon heating were also observed for the Ca- and K-rich aluminosilicates. The results indicate two levels of surface enrichment upon the fly ash glass; a thin (< 500 A) layer and a thicker (1- to 2-..mu..m) layer most evident for heating in air where an Fe-rich layer is formed. The present results indicate that the rates of surface segregation may not be sufficiently fast on the time scale of fly ash formation to result in equilibrium surface segregation. It is concluded that condensation processes during fly ash formation probably play a major role in the observed fly ash surface enrichments.