Oxidation/Reduction
The number of electrons associated with an element dictates its oxidation state.
Elements can exist in several oxidation states. For example, iron commonly exists in the +2
or +3 state, arsenic as +3 or +5, and chromium as +3 or +6. Oxidation-reduction (redox)
reactions involve a transfer of electrons and, therefore, a change in the oxidation state of
elements. Redox reactions are important to studies of subsurface contamination because the
chemical properties for the elements can change substantially with changes in the oxidation
state. For example, in slightly acidic to alkaline environments, Fe(III) is fairly insoluble and
precipitates as a solid phase (hydrous ferric oxide) that has a large adsorption capacity for
metal ions. In contrast, Fe(II) is fairly soluble and its oxides have a much lower adsorption
capacity. As the Fe(III) solid phase is reduced, not only is the Fe(II) brought into solution but
so are any contaminants that may have been adsorbed onto it.
Chromium is a naturally occurring element that primarily exists in three states
Chromium-0, Chromium III and Chromium VI (Hexavalent Chromium). Chromium-0 is
metallic and is used in the production of steel. Chromium III readily forms many different
compounds and is an essential human dietary element. However it is Chromium VI that is the
most hazardous form of the element. Hexavalent chromium, Cr(VI), exists in ground water as
the relatively mobile and toxic anions HCrO4 -
and CrO-4
2 . The reduced form of chromium,
Cr(III), is a cation that under slightly acidic to alkaline conditions is fairly insoluble, readily
adsorbed, and much less toxic than Cr(VI). Selenium also undergoes important redox
transformations. Selenate (Se(VI)) is more mobile and less toxic than selenite (Se(IV)).