Sb(V) adsorption and desorption onto ferrihydrite: influence of pH and competing organic and inorganic anions.

In this study, we investigated the Sb(V) adsorption on ferrihydrite (Fh) at different pH values, in the presence and absence of common competing anions in soil such as phosphate (P(V)) and arsenate (As(V)). Batch adsorption experiments, carried out at pH 4.5, 6.0, and 7.0, showed a greater affinity of Fh towards P(V) and As(V) with respect to Sb(V), especially at higher pH values, while the opposite was true at acidic pH. The capacity of Fh to accumulate greater amounts of phosphate and arsenate in the 6.0-7.0 pH range was mainly linked to the different acid properties of P(V), As(V), and Sb(V) oxyanions. The Sb(V) adsorption on Fh was highly pH-dependent and followed the following order: pH 4.5 (0.957 mmol·g-1 Fh) > pH 6.0 (0.701 mmol·g-1 Fh) > pH 7.0 (0.583 mmol·g-1 Fh). Desorption of antimonate from Sb(V)-saturated Fh, treated with citric and malic acid solutions, was ~equal to 55, 68, and 76% of that sorbed at pH 4.5, 6.0, and 7.0, respectively, while phosphate, arsenate, and sulfate were able to release significantly lower Sb(V) amounts. The FT-IR spectra revealed substantial absorbance shifts related to the surface hydroxyl groups of Fh, which were attributed to the formation of Fe-O-Sb(V) bonds and supported the formation of inner-sphere bonding between Sb(V) and Fh.

Municipal solid waste compost as a novel sorbent for antimony(V): adsorption and release trials at acidic pH.

The ability of two municipal solid waste composts (MSW-Cs) to sorb antimony(V) in acidic conditions (pH 4.5) was investigated. Sorption isotherms and kinetics showed that both MSW-Cs could sorb antimony(V), even if in different amounts (~ 0.18 and 0.24 mmol g-1 of Sb(V) by MSW-C1 and MSW-C2, respectively). These differences were ascribed to the chemical composition of composts, as well as to the total acidity of their humic substances. The Sb(V) sorption by both MSW-Cs followed a pseudo-second-order kinetic model, while the sorption isotherms data fitted the Freundlich model better than the Langmuir one. The humic acids extracted from composts contributed to 4.26 and 8.24% of Sb(V) sorption by MSW-C1 and MSW-C2 respectively. SEM-EDX spectra of the MSW-C+Sb(V) systems showed a certain association of Ca(II) with Sb(V), while sequential extraction procedures indicated that more than 80% of the Sb(V) sorbed was strongly retained by MSW-Cs. On the other hand, treatment with oxalic acid at pH 4.5 favored the release of more than 98 and 65% of the Sb(V) sorbed by MSW-C1 and MSW-C2 respectively, supporting a possible role of calcium in Sb(V) retention. The results from this study suggest that MSW-Cs could be used as amendments for the in-situ immobilization of Sb(V) in acidic-polluted soils.

Detoxification Processes from Vanadate at the Root Apoplasm Activated by Caffeic and Polygalacturonic Acids.

In the root apoplasm, V(V) and V(IV) toxicity can be alleviated through redox and complexation reactions involving phenolic substances and the polyuronic components. In such context we report the role of polygalacturonic acid (PGA) on the reducing activity of caffeic acid (CAF) towards V(V). The redox reaction was particularly effective at pH 2.8 leading to the formation of oxidation products with redox activity towards V(V). An o-quinone was identified as the first product of the reaction which is further involved in the formation of CAF dimers. At pH ≥ 3.6 the redox activity decreased and a yield in V(IV) equal to 38, 31, 21 and 14% was found at pH 3.6, 4.0. 5.0 and 6.0 respectively compared with that obtained at pH 2.8. The redox reaction was faster in the presence of PGA and a higher yield of V(IV) was found in the 4.0-6.0 pH range with respect to the CAF-V(V) binary system. The higher efficiency of the redox reaction in the presence of PGA was related with the ability of PGA to bind V(IV). The biological significance of the redox reaction between CAF and V(V), as well as the role of PGA in such reaction, was established "in vivo" using triticale plants. Results showed that PGA reduced significantly the phytotoxic effects of the V(V)-CAF system.