Fly ash samples collected from two locations in the exhaust stream of a coal-fired power plant differ markedly with respect to the abundance of thin (approximate to 0.1 mu m) sulfur-rich surface coatings that are observable by scanning electron microscopy. The coatings, tentatively identified as an aluminum-potassium-sulfate phase, probably form upon reaction between condensed sulfuric acid aerosols and glass surfaces, and are preferentially concentrated on ash exposed to exhaust stream gases for longer. The coatings are highly soluble and if sufficiently abundant, can impart an acidic pH to solutions initially in contact with ash. These observations suggest that proposals for ash use and predictions of ash behavior during disposal should consider the transient, acid-generating potential of some ash fractions and the possible effects on initial ash leachability and alteration.