The oxygen and sulfur isotope compositions of sulfate, particularly the oxygen-17 anomaly, provide clues to the origin of sulfate. We report a variable oxygen-17 anomaly for water- and acid-leached sulfate from an Oligocene volcanic ash bed in the northern High Plains, U.S.A. We find no sulfate O-17 anomaly, however, in freshly collected ashes from recent eruptions around the world. The Oligocene paleoclimatic and sedimentary evidence argues against a hyperarid condition in the High Plains, thus a long-term background atmospheric sulfate accumulation is less likely the origin. Combining sulfur isotope data, we suggest that the anomalous sulfate was associated with volcanic eruptions in the west, but was not directly carried by ash-falls. Extreme dry-fog (sulfate haze) events resulting from tropospheric oxidation of volcanic sulfur gases might provide a viable explanation for the sulfates in the ash bed that carry the oxygen-17 anomaly.