Water pollution events may arise rapidly, requiring a methodology that is easy to implement, fast to deploy, and sufficiently sensitive to detect the trace presence of hazardous contaminants. A cheap and easy to use silicone rubber (polydimethylsiloxane (PDMS)) miniature passive sampler is described. In order to test the methodology, pollutants were concentrated, in situ, from surface water in and around Pretoria, South Africa. The versatile sampler allowed for conventional and enhanced sensitivity, solvent-free analysis by comprehensive gas chromatography -time of flight mass spectrometry (GCxGC-TOFMS) and high resolution TOFMS (GC-HRT). Contaminants detected in surface water include caffeine, personal care products, pharmaceuticals, pesticides and polycyclic aromatic hydrocarbons.