Transformation processes of nitroaromatic compounds (NAC) are described that lead to polar and highly hydrophilic metabolites in ammunition waste water. For the identification of proposed metabolites, several analytical methods for the separation and determination of these compounds were developed and applied to the investigation of a former ammunition plant and its surroundings. The compound classes which were investigated include nitro and amino substituted toluenesulfonic acids, nitrobenzoic acids, aminobenzoic acids and nitromethylphenols. Method development was usually done with high performance liquid chromatography and ion pairing or ion suppression techniques. In the leachate water of a disposal site of a former ammunition plant in Stadtallendorf, Germany, 15 compounds from the above-mentioned categories have been found to be present in concentrations up to a few hundred microgram/L. The presence of so many polar compounds suggest that current and future surveying programs should include representative analytes of the investigated categories.