Direct analysis of samples using atmospheric pressure ionization (API) provides a more rapid method for analysis of volatile and semivolatile compounds than vacuum solids probe methods and can be accomplished on commercial API mass spectrometers. With only a simple modification to either an electrospray (ESI) or atmospheric pressure chemical ionization (APCI) source, solid as well as liquid samples can be analyzed in seconds. The method acts as a fast solids/liquid probe introduction as well as an alternative to the new direct analysis in real time (DART) and desorption electrospray ionization (DESI) methods for many compound types. Vaporization of materials occurs in the hot nitrogen gas stream flowing from an ESI or APCI probe. Ionization of the thermally induced vapors occurs by corona discharge under standard APCI conditions. Accurate mass and mass-selected fragmentation are demonstrated as is the ability to obtain ions from biological tissue, currency, and other objects placed in the path of the hot nitrogen stream.

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Modification of commercial LC/MS instrumentation to allow both atmospheric pressure (AP) LC/MS and GC/MS is described. Advantages of this additional capability versus LC/MS alone include higher chromatographic resolution in the GC versus LC mode, greater peak capacity for complex mixture analysis, higher sensitivity for a variety of volatile compounds, and the ability to observe compounds of low polarity that are not readily observed in LC/MS. Advantages over conventional GC/MS include the ability to use higher carrier gas flow and shorter columns for passing less volatile materials through the gas chromatograph, selective ionization, and rapid switching between positive and negative ion modes. Other advantages include application of the enhanced capabilities of LC/MS instrumentation to GC/MS analyses such as cone voltage fragmentation, MS n , high mass resolution, and accurate mass measurement. Limitations of APGC/MS include the inability to observe saturated hydrocarbon and certain other highly nonpolar compounds and less odd-electron fragmentation for computer aided library searching. For some analyses, the limitation related to ionization of highly nonpolar compounds is advantageous, as is the simplified mass spectrum and easy molecular weight identification that results from less fragmentation observed in the AP ionization mode. (J Am Soc Mass Spectrom 2005, 16, 1730 -1738