In order to detect highly polar organic compounds in water using membrane inlet mass spectrometry (MIMS), we designed a desorption chemical ionization ion source with a tubular polyacrylonitrile membrane positioned in the center of the chemical ionization (Cl) ion plasma. With this system we have for the first time been able to detect dicarboxylic acids (malonic and succinic acid) in aqueous samples with a MIMS system. The dicarboxylic acids were detected with both standard MIMS and trap-and-release MIMS methods. The trap-and-release MIMS method gave the best signal to noise ratio spectra with detection limits down to 50 mg/L. Although the results presented are very preliminary, they suggest that rapid detection or even on-line monitoring of this important group of biological metabolites might be possible with a MIMS system. Copyright # 1999 John Wiley & Sons, Ltd. Received 25 January 1999; Revised 18 February 1999; Accepted 19 February 1999 In the standard version of membrane inlet mass spectrometry (MIMS) a polymer membrane (silicone) is used as the only separation between a liquid sample and the mass spectrometer. Volatile organic compounds dissolve in the membrane, diffuse through it and evaporate into the ion source of the mass spectrometer, where they are ionized and analyzed. This transport process, called pervaporation, is highly specific and favors hydrophobic compounds. For example, hydrophobic compounds, such as the typical industrial solvents trichloroethene and toluene, can be measured at extremely low levels (parts-per-trillion), 1 whereas hydrophilic compounds like small carboxylic acid can only be detected at parts-per-million levels.2 Besides the preference for hydrophobic compounds, the standard MIMS method is useful only for determination of volatile compounds (boiling point below 200°C).Several researchers have worked on an expansion of the MIMS technique to include detection of less volatile and/or hydrophilic compounds.3 Thus far only the trap-and-release MIMS (T&R-MIMS) system 4,5 has successfully been used to detect compounds of both low volatility and relatively high polarity, such as acetylsalicylic acid, caffeine and pentachlorophenol. However, new and very promising techniques are under development at other laboratories. For example, Soni et al.6 developed a MIMS system using laser-stimulated desorption to assist the evaporation of nonvolatile hydrophobic compounds like indeno[1,2,3,-cd]pyrene (b.p. 530°C) from the membrane surface, and Yakovlev et al.7 developed a MIMS system using high electric fields to draw ions from solution through the membrane and into the mass spectrometer. In this paper we present the first results obtained with a system in which T&R-MIMS was combined with desorption chemical ionization (DCI). Desorption chemical ionization was developed in 1973 by Baldwin and McLafferty 8 as a method for the detection of involatile compounds (oligopeptides). In their experiments the sample was deposited as a dilute solution on the surface of the extended tip of a conventio...