The impact of elemental cycling and biological fractionation in the soil–vegetation system was investigated for 6 Red Brown Earth soil profiles (Xeralfs and Xerults) from South Australia by comparing geochemical and ⁸⁷Sr/⁸⁶Sr data from bulk soils, soil exchange pool, and vegetation (grapes). In all 6 soil profiles from 3 different sites, Ba/Ca ratios of vegetation, soil exchange pool, and bulk soils were found to be a more robust biological fractionation indicator than Sr/Ca ratios. In the base-poor soils of the Coonawarra–Padthaway area of South Australia, the degree of weathering of soil material, as estimated by titania and alumina contents, correlated very well with the biological fractionation indicator Ba/Ca. Soil horizons with greater clay and titania content also had higher degrees of biological fractionation. Similar Red Brown Earth soils 400 km north in the Clare Valley showed either no, or poor, biological fractionation signature in their bulk soil. The Clare Valley soils have a stronger colluvial component and are richer in base cations than the Coonawarra and Padthaway sites. The main source of bulk soil material in the base-poor soils of the Coonawarra–Padthaway areas is dust, which has greatly influenced the base cation concentration, Ba/Ca ratios, and the strontium isotope ratios. Soils from Clare Valley, by comparison, are less intensely weathered and are thus not as dependent on dust and biocycling for their base cations. Biological fractionation has not left a discernible signature on the composition of the bulk soil. The exchange pools at all 3 sites are dominated by wetfall–dryfall sources, which in this coastal area are dominated by marine sources. For the base-poor soils of the Coonawarra–Padthaway area, the most likely major source of aeolian detritus is Murray River mud. The fine-grained component of this mud, with its organic matter content, relatively high base cation concentrations, and low strontium isotope ratios (Douglas et al. 1995) appears to have overwhelmed other dust sources and caused a homogenisation of the geochemical signature of fine-grained bulk soils in this area. Subsequent in situ weathering and neoformation following dust deposition were strongly influenced by exchange phase concentrations and ratios and resulted in an enhanced biological fractionation signature of the soils.