An electrokinetic method and apparatus for discretely collecting ionic contaminants from a variety of media, with an ionic current there across in which an ion collection compartment has been positioned. Each compartment preferably compromises of an anion or cation exchange membrane and a solution that provides an accumulation zone for ions that permeate into the compartment. After the collection period, the solution is extracted from the compartment, and the concentration of ionic contaminants is determined using standard analytical methods. The preferred apparatus embodiment for use in conjunction with such a method has a direct-push probe configuration. The apparatus can be used (a) to detect low concentrations of ionic contaminants, (b) to evaluate cleanup efficiencies, and (c) to monitor the transport of ionic contaminants.