The distribution of platinum-group elements (pGEs) has been investigated in matte and slag samples from Waterval Smelter (Rustenburg Platinum Mines). The study showed that a strong preference of PGEs for alloy phases in matte represents a concentration mechanism that commenced in the furnace but can be considered a continuum from natural processes. Metal losses to fayalite (converter) slag occur by matte entrainment due to the mechanical capture of liquid sulphide droplets from the matte layer, and the exsolution of dissolved metal sulphide resulting from changes in the oxidation state of the slag. The latter is comparable to immiscible sulphide in basic magmas. However, the observed distribution of PGEs shows enrichment in metal phases of the matte. A mechanism is proposed whereby naked PGEs in silicate melts coalesce to form clusters which are stabilised by surface attachment of sulphur atoms. This envelope acts to 'draw the cluster into sulphide melts. Small particle melting effects permit PGE clusters to remain as liquids at magmatic and smelter temperatures.