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In order to reveal the intra-annual variability of the major ion composition of the Pilcomayo river, a dryland river, and its relationship to discharge, water samples were taken at regular time intervals from May 1998 until February 1999 at the town of Villa Montes (Bolivia). Water chemistry of the Pilcomayo river was highly variable during the year and strongly influenced by differences in discharge between the wet and the dry season. Halite dissolution appeared to play an important role and both Cl and Na concentrations became very high (±10 mmol
L
−1) during the dry season. Pyrite weathering and dissolution of gypsum, dolomite and calcite determined Ca, Mg, CO
3 and SO
4 chemistry. At the onset of the rainy season `rinse out' effects occurred, resulting in marked concentration peaks especially for the least soluble ions. Possible effects on biota, such as consequences for trace metal toxicity, are discussed briefly.