Certain configurations of an ionization source comprising a multipolar rod assembly are described. In some examples, the multipolar rod assembly can be configured to provide a magnetic field and a radio frequency field into an ion volume formed by a substantially parallel arrangement of rods of the multipolar rod assembly. The ionization source may also comprise an electron source configured to provide electrons into the ion volume of the multipolar rod assembly to ionize analyte introduced into the ion volume. Systems and methods using the ionization source are also described.