Fast, high temperature and thermolabile GC—MS in supersonic molecular beams

Abstract

This work describes and evaluates the coupling of a fast gas chromatograph (GC) based on a short column and high carrier gas flow rate to a supersonic molecular beam mass spectrometer (MS). A 50 cm long megabore column serves for fast GC separation and connects the injector to the supersonic nozzle source. Sampling is achieved with a conventional syringe based splitless sample injection. The injector contains no septum and is open to the atmosphere. The linear velocity of the carrier gas is controlled by a by-pass (make-up) gas flow introduced after the column and prior to the supersonic nozzle. The supersonic expansion serves as a jet separator and the skimmed supersonic molecular beam (SMB) is highly enriched with the heavier organic molecules. The supersonic molecular beam constituents are ionized either by electron impact (EI) or hyperthermal surface ionization (HSI) and mass analyzed. A 1 s fast GC—MS of four aromatic molecules in methanol is demonstrated and some fundamental aspects of fast GC—MS with time limit constraints are outlined. The flow control (programming) of the speed of analysis is shown and the analysis of thermolabile and relatively non-volatile molecules is demonstrated and discussed. The tail-free, fast GC—MS of several mixtures is shown and peak tailing of caffeine is compared with that of conventional GC—MS. The improvement of the peak shapes with the SMB—MS is analyzed with the respect to the elimination of thermal vacuum chamber background. The extrapolated minimum detected amount was about 400 ag of anthracence- d 10, with an elution time which was shorter than 2s. Repetitive injections could be performed within less than 10 s. The fast GC—MS in SMB seems to be ideal for fast target compound analysis even in real world, complex mixtures. The few seconds GC—MS separation and quantification of lead (as tetraethyllead) in gasoline, caffeine in coffee, and codeine in a drug is demonstrated. Controlled HSI selectivity is demonstrated in the range of 10 1 to 10 4 anthracene/decane which helped to simplify the selective analysis of aromatic molecules in gasoline. The contribution of SMB to the operation of the fast GC—MS is summarized and the compatibility with conventional GC having a megabore column is shown. Splitless injections of 100 μL sample solutions for trace level concentration detection is also presented (with a conventional GC).