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13  Phytoremediation Towards the Future: Focus on Bioavailable Contaminants  277

            13.2.1.6  Iron and Manganese Oxides

            Hydrous Fe and Mn oxides are particularly effective in influencing metal solubility
            in relatively oxidizing conditions. They are important in reducing metal
            concentrations in soil solutions by both specific adsorption reactions and precipita-
            tion. Although Mn oxides are typically less abundant in soils than Fe oxides, they
            are particularly involved in sorption reactions with heavy metals. Mn oxides also
            adsorb heavy metals more strongly, thus reducing their mobility and thus reducing
            phytoextraction efficiency. Under reduced conditions, on the other hand, the disso-
            lution of Fe and Mn oxides/hydroxides can release adsorbed Arsenic, and
            phytoextraction is promoted (Fitz and Wenzel 2002). When a chelating agent
            such as EDTA is used to increase metal solubility (Pb), this can also promote the
            dissolution of oxy-hydroxides, thus also promoting the uptake of different inorganic
            elements such as arsenic (Pedron et al. 2010).



            13.2.1.7  Other Factors

            There are a number of other factors that may affect the solubility of metals in soils
            and in turn phytoextraction efficiency. Temperature, which influences the decom-
            position of organic matter, can modify the mobilization of organometal complexes
            and consequently plant uptake. An increase in the ionic strength of soil solutions
            reduces the sorption of heavy metals by soil surfaces, due to the increased compe-
            tition from alkaline metals (Petruzzelli and Pezzarossa 2003). Similar effects also
            derive from the simultaneous presence of many heavy metals in soil solutions, and
            these metals compete for the same sorption sites. This increases mobility in
            contaminated soils due to the saturation of adsorption sites. The living phase of
            soil is also of great importance in determining metal solubility, which is dependent
            to some extent both on microbial and on root activity. In the rhizosphere, microbial
            consortia are able to mobilize metals by changes in the rhizosphere pH. Plants can
            increase metal solubility following the release in the exudates both of protons,
            which increase the acidity, and of organic substances which act as complexing
            agents. Microbial biomass may promote the removal of heavy metals from soil
            solutions by precipitation as sulfides and by sorption processes on new available
            surfaces characterized by organic functional groups (Wenzel 2009).




            13.3  Bioavailability with a View to Phytoextraction


            Depending on the soil’s properties, metals are distributed in soil in different pools
            of availability to plants. In phytoextraction, only metals in soil solutions will be
            available for plant uptake. This amount should be considered in terms of both
            intensity and capacity. Intensity identifies the concentration of metals in a soil
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