Groundwater geochemistry is controlled by chemical interactions with aquifer rocks, and offers a powerful geochemical exploration technique for locating concealed mineral- isation. Techniques are applied for identifying constituents of aquifers using the compositions of their groundwaters, collected from the surface through drill holes, water bores or springs. Even slowly moving groundwaters have passed through large volumes of rocks which surround any sample site. Products from these rock-water contacts modify the groundwater. By relating water composition to the minerals from which the dissolved species may have been derived, geochemical exploration information is obtained for a significantly larger zone than is represented by drill hole rock samples. In this paper we describe some solution chemical tech- niques we are applying in mineral exploration, particularly in areas of Australia where ground- waters are highly saline and contain enhanced concentrations of trace metals. EQUILIBRIUM MODELS FOR SALINE GROUNDWATERS Central to our technique is the assumption that in low rainfall regions, aquifer rocks and contained groundwaters are in chemical equili- brium. Solubility calculations then allow us to predict upper limits to the soluble products of groundwater interaction with aquifer rocks and to identify minerals with which the groundwater is saturated. Whilst equilibrium calculations require input of concentrations of all dissolved species, they are actually based on "activity" of dissolved species rather than the analysed concentrations. Unless waters have very low ionic strengths (a measure of total dissolved solids), activity of a solute is not equal to its analytical concentration but equals concentration multiplied by an "activity coefficent". Several methods exist for calculating mineral solubilities. The ion-association model, commonly used in programs such as WATEQ (Truesdell and Jones, 1974) and later deriv- atives such as MINTEQ, assume the formation of complex ions such as MgSO4(0), CaCl+, which are described by formation constants. Activity coefficients are obtained by the extended Debye