4.3.1 Chemical Speciation
Speciation is of the major importance to provide the qualitative information on their
reactivity under changing conditions and crucial information about ecotoxicity characteristics
(reactivity, bioavailability, toxicity) of contaminants. Speciation of the metal ions in the soil
solution may play a significant role in its bioavailability. The behavior of the elements in the
environment cannot predict on the basis of their total concentration because it overlooks the
fact that not all of the metal may be labile or available for uptake due to the different and
complex distribution patterns of metals among various chemical species of solid phases. The
total metal content of a soil is distributed among all possible chemical forms (speciation) in
the solid, liquid or the biotic phases. Use of total concentration as a criterion to assess the
potential risks may be misleading as the risks may be over-estimated, implies that all forms of
a given metal have an equal impact on the environment. Despite this, the bioavailability of
metals and the toxicity of metals are more closely related to bioavailable metal, rather than
total metal concentrations in soil. Knowing the distribution and transformation of metals
under changing condition of environment is therefore very useful to understand the processes
whereby metals are held in soil and the condition under which they can be released.
4.3.2 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