The possibility of analysing 33 carbamate pesticides and 14 of their transformation products was investigated utilizing Ñow injection particle beam/mass spectrometry (PBMS) with electron impact (EI) ionization and ammonia and methane positive and negative chemical ionization (CI). Optimum operating conditions of the interface and mass spectrometer in each mode were determined, with special attention given to spectrum quality ; variables investigated included ion source temperature and ion source pressure in CI experiments. Ammonia, as a reagent gas, provided less fragmentation and better quantitative results than methane. The CI response was generally higher with positive ion detection (PCI) than with negative ion detection (NCI), but NCI was found to be highly selective for compounds such as aminocarb, asulam and thiophanate-methyl. As regards analyte detectability, EI performed best for most compounds, with the spectra providing relevant structure information. The response of more polar degradation products is generally larger by 2-3 orders of magnitude compared with the parent compounds. When analysing real samples, the combined use of CI for molecular mass determination and EI for structure elucidation is required. The spectral information from this study and additional chromatographic data were used for the determination of low-and sub-lg l~1 levels of the test carbamates in surface water.