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An experimental speciation scheme consisting of ultra-filtration (1 kD), cation and anion exchange has been developed. Parallel calculations of the ion balances are performed using the computer routine MINTEQA2. The experimental and computed ion balances suffer from non-equilibrium conditions, incalculability of metal-binding colloids or sub-colloids, inaccurate Eh measurements and analytical errors. In most samples colloidal or sub-colloidal structures of Fe oxy-hydroxides and/or gypsum influence the behavior of many trace elements. The comparison of theory and experiment has to be restricted to acid waters (pH < 5) where colloids (≥1–450 nm) and non-filterable colloids or sub-colloids (<1 nm) play a minor role. Yet, only a few transition metals such as Mn, Fe, Co, Ni, Cu, Zn, or Cd remain more or less free of colloidal influence in low pH waters. The effect of DOC on Al may be estimated by model substances like citrate.