Nafion-modified mercury thin film electrodes have been investigated for the analysis of trace metals in environmental samples of waters and effluent by batch injection analysis with square wave anodic stripping voltammetry. The method, involving injection over the detector electrode of untreated samples of volume of the order of 50 microlitres has fast response, blocking and fouling of the electrode is minimum as shown by studies with surface-active components. Comparison is made between glassy carbon substrate electrodes and carbon fibre microelectrode array substrates, the latter leading to a small sensitivity enhancement. Application to analysis of river water and industrial effluent for labile zinc, cadmium, lead and copper ions is demonstrated in collected samples and after acid digestion.