An on-line preconcentration procedure using solid phase extraction (SPE) for the determination of copper in different water samples by inductively coupled plasma optical emission spectrometry (ICP-OES) is proposed. The copper was retained on a minicolumn filled with ethyl vinyl acetate (EVA) at pH 8.0 without using any complexing reagent. The experimental optimization step was performed using a two-level full factorial design. The results showed that pH, sample loading flow rate, and their interaction (at the tested levels) were statistically significant. In order to determine the best conditions for preconcentration and determination of copper, a final optimization of the significant factors was carried out using a central composite design (CCD). The calibration graph was linear with a regression coefficient of 0.995 at levels near the detection limit up to at least 300 mu g L-1. An enrichment factor (EF) of 54 with a preconcentration time of 187.5 s was obtained. The limit of detection (3 sigma) was 0.26 mu g L-1. The sampling frequency for the developed methodology was about 15 samples/h. The relative standard deviation (RSD) for six replicates containing 50 mu g L-1 of copper was 3.76%. The methodology was successfully applied to the determination of Cu in tap, mineral, river water samples, and in a certified VKI standard reference material. (C) 2010 Elsevier B.V. All rights reserved.