The vent-hosted hydrothermal system of Ruapehu volcano is normally covered by a c. 10 million m 3 acidic crater lake where volcanic gases accumulate. Through analysis of eruption observations, granulometry, mineralogy and chemistry of volcanic ash from the 1995-1996 Ruapehu eruptions we report on the varying influences on environmental hazards associated with the deposits. All measured parameters are more dependent on the eruptive style than on distance from the vent. Early phreatic and phreatomagmatic eruption phases from crater lakes similar to that on Ruapehu are likely to contain the greatest concentrations of environmentally significant elements, especially sulphur and fluoride. These elements are contained within altered xenolithic material extracted from the hydrothermal system by steam explosions, as well as in residue hydrothermal fluids adsorbed on to particle surfaces. In particular, total F in the ash may be enriched by a factor of 6 relative to original magmatic contents, although immediately soluble F does not show such dramatic increases. Highly soluble NaF and CaSiF 6 phases, demonstrated to be the carriers of 'available' F in purely magmatic eruptive systems, are probably not dominant in the products of phreatomagmatic eruptions through hydrothermal systems. Instead, slowly soluble compounds such as CaF 2, AlF 3 and Ca 5(PO 4) 3F dominate. Fluoride in these phases is released over longer periods, where only one third is leached in a single 24-h water extraction. This implies that estimation of soluble F in such ashes based on a single leach leads to underestimation of the F impact, especially of a potential longer-term environmental hazard. In addition, a large proportion of the total F in the ash is apparently soluble in the digestive system of grazing animals. In the Ruapehu case this led to several thousand sheep deaths from fluorosis.