A simple analytical scheme for the detection and quantification of amitrol and triazine herbicides (atrazine, ametryn and atraton) and degradation product (2-hydroxyatrazine) in environmental water samples by CZE is reported. On-column preconcentration of analytes from untreated water samples (mineral, spring, tap and river water) is accomplished by introducing an acid plug (200 mM citrate of pH 2.0) after the sample and then proceeding with the CZE separation, using 100 mM formiate buffer of pH 3.5 as running buffer and 25.0 KV as separation voltage. UV detection at 200 nm provides LODs from 50 to 300 nM in untreated samples and they were lowered tenfold by sample preconcentration by evaporation. Calculated recoveries were typically higher than 90%. Minimal detectable concentration of the electroactive amitrol could be decreased about 20-fold when electrochemical detection was employed by monitoring the amperometric signal at +800 mV using a carbon paste electrode (LOD of 9.6 nM, 0.81 mu g/L, versus 170 nM, 14.3 mu g/L, using amperometric and UV detection, respectively) in untreated water samples.