Recent advances in membrane introduction mass spectrometry (MIMS) are revie
wed. On-line monitoring is treated by focusing on critical variables, inclu
ding the nature and dimensions of the membrane, and the analyte vapor press
ure, diffusivity, and solubility in the membrane barrier Sample introductio
n by MIMS is applied in (i) on-line monitoring of chemical and biological r
eactors, (ii) analysis of volatile organic compounds in environmental matri
ces, including ail; water and soil, and (iii) in more fundamental studies,
such as measurements of thermochemical properties, reaction mechanisms, and
kinetics.
New semipermeable membranes are discussed, including those consisting of th
in polymers, low vapor pressure liquids, and zeolites. These membranes have
been used to monitor polar compounds, selectively differentiate compounds
through affinity-binding, and provide isomer differentiation based on molec
ular size. Measurements at high spatial resolution, for example, using sili
cone-capped hypodermic needle inlets, are also covered, as is electrically
driven sampling through microporous membranes. Other variations on the basi
c MIMS experiment include analyte preconcentration through cryotrapping (CT
-MIMS) or trapping in the membrane (trap-and-release), as well as different
ial thermal release methods and reverse phase (i.e., organic solvent) MMS.
Method limitations center on semivolatile compounds and complex mixture ana
lysis, and novel solutions are discussed. Semivolatile compounds have been
monitored with thermally assisted desorption, ultrathin membranes and deriv
atization techniques. Taking advantage of the differences in time of membra
ne permeation, mixtures of structurally similar compounds have been differe
ntiated by using sample modulation techniques and by temperature-programmed
desorption from a membrane interface. Selective ionization techniques that
increase instrument sensitivity towards polar compounds are also described
, and comparisons are made with other direct sampling (nonchromatographic)
methods that are useful in mixture analysis. (C) 2000 John Wiley & Sons, In
c.