An electrokinetic pump can be used to deliver calibrant (“lock mass”) ions to a mass spectrometer for calibration of a mass spectrometry system. Electrokinetically controlled calibrant delivery can help to eliminate the need for the more cumbersome mechanisms that are often used for ion delivery. In addition, electrokinetically controlled calibrant delivery can provide for a more user-friendly system in which a calibrant solution can be packaged into a disposable cartridge. Furthermore, when implemented in a microfluidic format, electrokinetically controlled calibrant delivery can be coupled with an electrokinetically controlled separation system, such as capillary electrophoresis (CE), to allow efficient solid-state switching between analytical and calibrant sprays.