Accumulation and mobilization of arsenate by Fe(III) polyions trapped in a Ca-polygalacturonate network.

The role of Fe(III) stored at the soil-root interface in the accumulation of arsenate and the influence of citric acid on the As(V) mobility were investigated by using Ca-polygalacturonate networks (PGA). The results indicate that in the 2.5-6.2 pH range Fe(III) interacts with As(V) leading to the sorption of As(V) on Fe(III) precipitates or Fe-As coprecipitates. The FT-IR analysis of these precipitates evidenced that the interaction produces Fe(III)-As(V) inner-sphere complexes with either monodentate or bidentate binuclear attachment of As(V) depending on pH. In the 3.0-6.0 pH range, As(V) diffuses freely through the polysaccharidic matrix that was found to exert a negligible reducing action towards As(V). At pH 6.0 citric acid is able to mobilize arsenate from the As-Fe-PGA network through the complexation of the Fe(III) polyions that leads to the release of As(V).

Oxidation of caffeic acid by Fe(III) trapped in a Ca-polygalacturonate network.

With the aim to verify if Fe(III) ions accumulated in a network of Ca-polygalacturonate (PGA) may promote the oxidation of caffeic acid (CAF) the interaction at pH 5.0 between CAF and Fe(III) ions trapped in a PGA was studied. The sorption kinetics evidenced a great affinity of CAF towards the Fe-PGA matrix. Chromatographic tests showed that the interaction leads to the formation of products which can be considered as CAF oligomers characterized by FT-IR spectra similar to those of natural humic acids. Tests carried out under nitrogen suggest that at pH 5.0 oxygen does not affect the nature of these oxidation products. Oxygen was hypothesized to exert a direct action on the redox process by oxidizing the Fe(II) ions, produced by oxidation of CAF, to Fe(III) thus regenerating oxidizing sites. A possible mechanism of formation of the polymers was proposed that implies that the CAF oxidation leads to highly reactive species such as semiquinones which give rise, by an oxidative coupling reaction, to the formation of oligomers that can aggregate through secondary bonds to produce more complex structures as those that characterize humic acids.

Possible role of the polyuronic components in accumulation and mobilization of iron and phosphate at the soil--root interface.

With the aim to investigate the role of the polyuronic components in the accumulation of iron and phosphate at the soil-root interface, the interactions of Ca-polygalacturonates (PGAs) with Fe(III) and P ions and of Fe(III)-Ca-polygalacturonates (Fe-PGAs) with P ions were studied at pH 4.7. The role of citric, malic and pyruvic acids in the mobilization of Fe(III) and P, in the presence and absence of Ca(II) 2.5mM, was also investigated. The sorption kinetics evidenced that P diffuses freely through the calcium polysaccharidic matrix whereas Fe(III) accumulates as an hydroxypolymer. The sorption kinetics of P by the Fe-PGA indicated that the amount of P sorbed increases with increasing its initial concentration up to a constant value equal to 0.98micromol/3.87micromolmg(-1) of Fe(III)-polymer trapped. The FT-IR spectra of the P-Fe-PGA systems, show bands attributable to P-O(H) stretching vibrations. The study of systems with a constant initial P amount and varying Fe(III) amounts allowed to hypothesize that phosphate settles down inside holes formed by the carboxylate groups of galacturonic units. Citric and malic acids showed to be active in the mobilization of both Fe and P whereas pyruvic acid appeared inactive.

Reduction of Cr(VI) by caffeic acid.

In the soil-plant system, the Cr(VI) toxicity can be moderated through redox reactions involving phenolic substances. In such a context, we report the reducing activity of caffeic acid (CAF) towards Cr(VI) in aqueous phase. The redox reaction between Cr(VI) and CAF was studied as a function of both time and pH at different initial metal concentrations. The reaction was particularly effective at pH 2.5. The kinetic data indicate that the reaction proceeds through two steps: the first is faster and involves four electrons, the latter, which is slower, five electrons. The chromatograms evidence the formation of oxidation products (OP) with a different redox activity towards Cr(VI). A yield of Cr(III) equal to that obtained at pH 2.5 and pH 3.1 in about 7 and 25 h, respectively, was reached at pH 4.2 only after a much longer reaction time (50h). At pH>4.2 the reaction occurred even more slowly, and its kinetic trend was more and more difficult to study at pH values higher than 5.0 due to the formation of precipitates. Other phenolics investigated (o-, m-, p-coumaric acids) showed a reducing activity negligible compared to that of CAF: about 30% of p-coumaric acid was oxidized at pH 2.5 only after two months of reaction.