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The development in recent years of ionization techniques in which the sample is introduced in solution has greatly expanded the analytical capabilities of mass spectrometry. Fast atom bombardment produces steady currents of ions with masses in excess of 10,000 Daltons, and also permits analysis of organic salts and zwitterions. Thermospray offers the potential for interfacing liquid chromatography with mass spectrometry, using aqueous buffered elution solvents. In these and other solution-based ionization techniques, ions can be produced by solution chemistry, and controlled by controlling pH, inorganic salt content, etc. Principles and operation of these two techniques will be reviewed and examples …