The invention provides a method and apparatus for trapping, releasing and/or separating sample components in solution passing through a channel with or without packing material present by passing ion current through the channel driven by an electric field. A portion of the ion current comprises cation and/or anion species generated from second solution flows separated from the sample solution flow path by semipermeable membranes. Cation and/or Anion ion species generated in the second solution flow regions are transferred into the sample solution flow path through ion selective semipermeable membranes. Ion current moving along the sample solution flow path is controlled by varying the composition of the second solutions and/or changing the voltage between membrane sections for a given sample solution composition. The sample composition may also be varied separately or in parallel to enhance trapping, release and/or separation efficiency and range. The invention when interfaced to an Atmospheric Pressure Ion Source, that may include Electrospray Ionization, with mass spectrometric analysis enables independent control of the on-line sample separation process and the Atmospheric Pressure Ion Source or Electrospray ionization processes.