Rain acidity may be ascribed to emissions from power station stacks, as well as emissions from other industry, biomass burning, maritime influences, agricultural influences, etc. Rain quality data are available for 30 sites in the South African interior, some from as early as 1985 for up to 14 rainfall seasons, while others only have relatively short records. The article examines trends over time in the raw and volume weighted concentrations of the parameters measured, separately for each of the sites for which sufficient data are available. The main thrust, however, is to examine the inter-relationship structure between the concentrations within each rain event (unweighted data), separately for each site, and to examine whether these inter-relationships have changed over time. The rain events at individual sites can be characterized by approximately eight combinations of rainfall parameters (or rain composition signatures), and these are common to all sites. Some sites will have more events from one signature than another, but there appear to be no signatures unique to a single site. Analysis via factor and cluster analysis, with a correspondence analysis of the results, also aid interpretation of the patterns. This spatio-temporal analysis, performed by pooling all rain event data, irrespective of site or time period, results in nine combinations of rainfall parameters being sufficient to characterize the rain events. The sites and rainfall seasons show patterns in these combinations of parameters, with some combinations appearing more frequently during certain rainfall seasons. In particular, the presence of the combination of low acetate and formate with high magnesium appears to be increasing in the later rainfall seasons, as does this combination together with calcium, sodium, chloride, potassium and fluoride. As expected, sites close together exhibit similar signatures. Copyright © 2002 John Wiley & Sons, Ltd.