5.1 Introduction and History

The earliest forms of mass spectrometry go back to the observation of canal rays by Goldstein in 1886 and again by Wien in 1899. Thompson’s later discovery of the electron also used one of the simplest mass spectrometers to bend the path of the cathode rays (electrons) and determine their charge to mass ratio. Later, in 1928, the first isotopic measurements were made by Aston. These basic experiments and instruments were presented to most readers in first-year general chemistry. More modern aspects of mass spectrometry are attributed to Arthur Jeffrey Dempster and F.W. Aston in 1918 and 1919. Since this time there has been a flurry of activity [not only concerning minor advances in components of mass spectrometers such as different types of instrument interfaces (direct injection, GC, and HPLC)] to different ionization sources (electron and chemical ionization) but also new types of ion separators. For example, double focusing magnetic sector mass filters were developed by Mattauch and Herzog in 1934 (and recently revised into a new type of mass filter), time of flight MS by Stephens in 1946, ion cyclotron resonance MS by Hipple and Thomas in 1949, quadrupole MS by Steinwedel in 1953, and ion trap MS by Paul and Dehmelt in the 1960s.

Mass spectrometry was first coupled with GC as a means of sample introduction in 1956 by Golhke et al. and with HPLC via electro-spray ionization in the mid 1980s (Blakely and Vestal, 1983; Yamashita and Fenn, 1984). New methods of mass spectrometry are constantly under development and even as recent as 1985, Hillenkamp and Michael Karas developed the MALDI technique (a laser-based sample introduction device) that radically advanced the analysis of protein structures and more types of mass analyzers will certainly be developed. This chapter will deal only with basic mass spectrometer instruments used in the analysis of organic chemicals exiting GC and HPLC systems, and is also applicable to effluents from ion chromatographic systems. One of the most comprehensive Internet summaries of the history of mass spectrometry can be found at http://masspec.scripps.edu/mshistory/timeline/timeline.php.

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