Chromium in its various oxidation states has been characterized by variable toxicity with as yet unclear molecular traits. In an effort to comprehend the molecular basis of chromium toxicity we embarked on research activities probing the structural speciation of Cr(III) in the presence of physiological substrates unlike those present n human and plant fluids. The results point to species of distinct structural and chemical reactivity characteristics that shed light on the molecular basis of Cr(III) reactivity in biologically relevant fluids.