Real-time analysis of methanol in air and water by membrane introduction mass spectrometry.

We present results for the near-real-time, on-line detection of methanol in both air and water using membrane introduction mass spectrometry (MIMS). In these experiments, we compare the sensitivity of a poly(dimethylsiloxane) (PDMS) membrane and an allyl alcohol (AA) membrane to the detection of methanol. In MIMS, the membrane serves as the interface between the sample and the vacuum of the mass spectrometer. Membrane-diffused water was used as the reagent ion (H3O+) for chemical ionization of methanol in an ion trap mass spectrometer. Linear calibration curves have been obtained for methanol using both PDMS and AA membranes. For PDMS, detection limits of methanol are 14 ppmv and 5 ppm in air and water, respectively. For AA, detection limits are 3.3 ppmv and 2 ppm in air and water, respectively. We demonstrate that the sensitivity of the analysis can be altered by the chemistry of the membrane. When the AA membrane is used, the sensitivity of MIMS is enhanced over that of PDMS by a factor of 8.5 for methanol in air and by a factor of 23.4 for methanol in water.

Membrane introduction mass spectrometry: trends and applications.

Recent advances in membrane introduction mass spectrometry (MIMS) are reviewed. On-line monitoring is treated by focusing on critical variables, including the nature and dimensions of the membrane, and the analyte vapor pressure, diffusivity, and solubility in the membrane barrier. Sample introduction by MIMS is applied in (i) on-line monitoring of chemical and biological reactors, (ii) analysis of volatile organic compounds in environmental matrices, including air, 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 thin 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 molecular size. Measurements at high spatial resolution, for example, using silicone-capped hypodermic needle inlets, are also covered, as is electrically driven sampling through microporous membranes. Other variations on the basic MIMS experiment include analyte preconcentration through cryotrapping (CT-MIMS) or trapping in the membrane (trap-and-release), as well as differential thermal release methods and reverse phase (i.e., organic solvent) MIMS. Method limitations center on semivolatile compounds and complex mixture analysis, and novel solutions are discussed. Semivolatile compounds have been monitored with thermally assisted desorption, ultrathin membranes and derivatization techniques. Taking advantage of the differences in time of membrane permeation, mixtures of structurally similar compounds have been differentiated 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.

Analysis of polar organic compounds using charge exchange ionization and membrane introduction mass spectrometry.

Charge exchange ionization in conjunction with membrane introduction mass spectrometry provides a sensitive method for the detection of polar volatile organic compounds and semivolatile compounds in air. Sample introduction into an ion trap mass spectrometer was accomplished with a hollow fiber silicone membrane assembly. Atmospheric oxygen, which diffuses through the membrane, was used as the charge exchange reagent. Chemical ionization parameters were optimized using methyl ethyl ketone (2-butanone) standards in air. Several other oxygen-containing compounds, including acetone (2-propanone), methyl isobutyl ketone (4-methyl-2-pentanone), propanal, isopropyl alcohol (2-propanol), cyclohexanol, dimethyl sulfoxide (sulfinylbismethane), 2-(diethylamino)ethanol, and dimethyl methylphosphonate were analyzed with this technique. This method was used to obtain mass spectra for a variety of classes of compounds and produced a 4-20-fold improvement in response for all of the polar compounds we examined when compared to signal obtained from electron ionization.

Air analysis using tenax collection with jet-separator enrichment and ion trap mass spectrometric analysis.

A dual adsorbent trap inlet system has been developed for an ion trap mass spectrometer (ITMS) to provide a rapid and sensitive system for screening of volatile organic compounds in air. The system employs three stages of concentration: preconcentration on an adsorbent Tenax trap, focusing in a cryogenic collection trap, and jet separator enrichment immediately prior to analysis by ITMS. Ten minute integrated samples are collected and analyzed immediately. The detection limit is 0. 9 parts-per-trillion by volume (pptrv) based on toluene as the analyte, and the reproducibility is 2% or better. Ambient air was analyzed for toluene on April 4, 1996 in Los Alamos, New Mexico, and concentrations ranged from 11-158 pptrv.

A method of increasing the sensitivity for laser desorption in an ion trap mass spectrometer.

Laser desorption in an ion trap mass spectrometer shows significant promise for both qualitative and trace analysis. In this work, we explore various combinations of time-varying DC and radiofrequency (RF) fields in order to optimize laser-generated signals. By judicious choice of timing between the laser desorption pulse and the rise in the applied RF trapping potential, we observed over an order of magnitude enhancement in the trapped ion signal. This new method for laser desorption has enabled us to observe mass spectra of many compounds (e.g., pyrene, dichlorobenzene, and ferrocene) that are barely detectable using previous laser desorption methods. Effects of laser timing and the magnitude of the steady-state RF potential are discussed.