Several metal or metalloid ions exist in multiple oxidation states and can undergo electron transfer reactions that are important in biological and environmental systems. There are endogenous metal ions such as iron, copper, and cobalt that participate in oxidation-reduction reactions with species of oxygen like molecular dioxygen, superoxide, and hydrogen peroxide. These reactions may be modulated by endogenous reducing agents such as glutathione, ascorbate, and tocopherol. The reactions can be described in terms of thermodynamics through the use of standard electrode potentials. A favorable reaction will depend on the concentrations of the reactants and may depend on the pH and/or on the presence of organic ligands that form complexes with the metal or metalloid. Arsenate (As(V)) can react with glutathione in buffered aqueous solutions to produce arsenite (As(III)) and oxidized glutathione. This reaction may be important in the methylation reactions of arsenic. Arsenic species can decrease the red blood cell levels of reduced glutathione, but the products of oxidation and the mechanism of oxidation are more complex than those found in water alone. Chromium (VI) is thought to interact with DNA after first reacting with a reducing agent such as glutathione to form lower oxidation states of chromium. These examples illustrate the importance of oxidation-reduction reactions for toxic metals and metalloids.