The invention provides for efficient collection of analyte ions and neutral molecules from surfaces for their subsequent analysis with spectrometry. In an embodiment of the invention, a ‘multiple desorption ionization source’ includes a tube which can contain ions for subsequent sampling within a defined spatial resolution from desorption ionization at or near atmospheric pressures. In an embodiment, electrostatic fields are used to direct ions a plurality of tubes positioned in close proximity to the surface of the sample being analyzed. In an embodiment of the present invention, either narrow inside diameter capillary tubes or wide diameter tubes can be used in combination with a vacuum inlet to draw ions and neutrals into the spectrometer for analysis. In an embodiment of the invention, a dopant is introduced into a tube to analyze the sample. In an embodiment of the invention, a plurality of ionization sources is used to analyze the sample.