Conventional positive-ion and negative-ion modes (PI and NI ,respectively), the use of ammonium acetate and ammonium formate and the addition of 2% chloroacetonitrile in the liquid chromatographic eluent using filament-on thermospray LC-MS have been applied for the determination of selected herbicides. By using acetonitrile-water and 0.05 M ammonium acetate mixtures, the chlorotriazine herbicides showed [M + (CH 3 CN)H] + and [M -H] -ions as base peaks in PI and NI modes, respectively. When ammonium formate and ammonium acetate were added to methanol-water eluent, the phenylurea herbicides exhibited in PI mode a relevant peak between 50-70% relative intensity corresponding to [M + (CH 3 OH)NH 4 ] +
and [M + (CH 3 COOH)NH 4 ]+, respectively, whereas the base peak was [M + NH 4 ] + in both cases. The formation of [M + HCOOHNH 4 ] + was incidently observed in PI when ammonium formate was used. With this ionizing additive and NI the chlorinated phenoxyacid herbicides exhibited [M + HCOO] -as base peak, thus allowing a complementary structural information to [M + CH 3 COO] -, a typical ion obtained whenammonium acetate was added as ionizing additive. The addition of 2% chloroacetonitrile to acetonitrile-water eluent showed in NI mode a [M + Cl] -ion as base peak instead of [M + CH 3 COO] -or [M + HCCO] -ions in combination with other main ions which were assigned to [M -H] -and [M + H] -. Applications are reported for the determination of phenylurea and chlorinated phenoxyacid herbicides in spiked water samples by using PI and NI modes, respectively.