The properties of iron (Fe) complexes and compounds in the environment influence several central processes, e.g., iron uptake, adsorption/desorption of contaminants and nutrients, and redox transformations, as well as the fate of of natural organic matter (NOM). It is thus important to characterize Fe species in environmental samples. Synchrotron-based extended X-ray absorption fine structure (EXAFS) spectroscopy has been used in several studies on soils and sediments, but literature is scarce on investigations of natural waters because of low Fe concentrations. In this study we have described a gentle and noninvasive preconcentration method, based on electrostatic adsorption onto ion-exchange resins, suitable for EXA.FS analysis of Fe species in dilute stream water samples. The EXAFS results of metal organic model complexes showed that no significant local structural distortions were induced by the method. We also demonstrated the feasibility for an 8 mu M Fe stream water sample. The Fe heterogeneity in this stream water was investigated via a gradient series at 28%, 42%, 77%, 84%, and 100% adsorption of total iron. The EXAFS results showed that Fe(III) in this stream water was divided into Fe(III)-NOM complexes and Fe(III) (oxyhydr)oxides associated with NOM, and that each class consisted of several subspecies.