Antonio De Martino

Retention of arsenic on hydrous ferric oxides generated by electrochemical peroxidation

Electrochemical peroxidation (ECP), an emerging remediation technology, with direct electric current applied to steel electrode and small addition of H2O2, was used to remove As(III) from contaminated aqueous solutions. Bench scale experiments were conducted to evaluate the sorption and distribution of arsenic between the soluble and solid state hydrous ferric oxides (HFO) formed as part of the ECP process. ECP was effective in removing arsenic from the aqueous solution, with >98% of the applied As(III) adsorbed on HFO. Removal was complete within 3 min of ECP treatment and apparently independent of the initial pH of the water (3.5-9.5). In the absence of H2O2 more As(III) was adsorbed by solid state iron at pH 9.5 than at 3.5 (2600 vs. 1750 microg l(-1)). Thus H2O2 was crucial to oxidize As(III) to As(V) which is more strongly retained by HFO. Removal of As was not significantly affected by the concentration of H2O2 or by current processing time. The optimal operating conditions were pH < 6.5, H2O2 concentration of 10 mg l(-1) and current process time not exceeding 3 min. X-ray diffraction (XRD), diffuse-reflectance infrared Fourier transform (DRIFT) spectroscopy and transmission electron microscopy (TEM) were applied to study the HFO deposits. The XRD data indicated the prevalence of poorly ordered Fe minerals in the suspended ECP solids with a dominance of 5 line ferrihydrite in the absence of H2O2. At pH 3.5 and with 100 mg H2O2 l(-1), akaganeite was formed, whereas an incipient hematitic phase, reflection at 0.39 nm, occurred at pH 6.5. DRIFT data indicate that both As(III) and As(V) were specifically adsorbed onto HFO at acid and neutral pH. TEM observations indicated the presence of spherical shape ferrihydrite and provided evidence for possible formation of subrounded hematite and acicular shape goethite.

Removal of 4-chloro-2-methylphenoxyacetic acid from water by sorption on carbon nanotubes and metal oxide nanoparticles

A comparative study was performed on the sorption capacity of the phenoxy acid herbicide (4-chloro-2-methylphenoxyacetic acid), also known as MCPA, on a single-walled carbon nanotube (SWCNT), three multi-walled carbon nanotubes with average outer diameters of 15, 30 and 50 nm (MWCNT15, MWCNT30 and MWCNT50), and nanoscale metal oxides (Al2O3, TiO2 and ZnO). The most efficient sorbent was the SWCNT, followed by the three MWCNTs. The metal oxide nanoparticles showed a much lower sorption capacity. The herbicide bound to the tested carbon nanotubes, by a combination of electron donor–acceptor (π–π EDA) interactions and hydrogen bonds. On the contrary, MCPA bound to the considered metal oxide nanoparticles by electrostatic interactions occurring between the carboxylate anions of the same herbicide and OH2+ of the sorbent. Experiments of cyclic sorption showed the pesticides to be totally removed by only two sorption cycles on the SWCNT and MWCNT15, whereas the same waste water was purified after four cycles on nano Al2O3. Finally, desorption studies carried out in ethanol showed a potential re-use of the SWCNT.

Synthesis, characterization, and sorption capacity of layered double hydroxides and their complexes with polymerin.

Mg-Al layered double hydroxides (LDHs) containing chloride (LDH-Cl) or carbonate (LDH-CO(3)) in the interlayer were obtained at room temperature and after calcitation at 450 degrees C (LDH-Cl-450 and LDH-CO(3)-450) and were characterized by X-ray diffraction and Fourier transform infrared analyses. Sorption isotherms of a humic acidlike fraction naturally occurring in olive oil mill waste waters, named polymerin, on these LDH minerals were carried out. Because LDH-CO(3) showed the highest capacity to sorb polymerin among the four LDH minerals synthesized, two organo-mineral complexes named LDH-CO(3)-LP (low polymerin) and LDH-CO(3)-HP (high polymerin) were prepared by coprecipitation (LDH-CO(3)-LP) and sorption onto a preformed LDH-CO(3) mineral (LDH-CO(3)-HP). These complexes were characterized chemically and physicochemically, and their stability to pH and after thermal treatment at 80 degrees C were evaluated. The diffuse reflectance infrared Fourier transform and X-ray analysis of the complexes indicated that polymerin was sorbed only on the external surfaces of LDH-CO(3) and no intercalation occurred. The LDH-polymerin complexes appeared to be more stable than LDH-CO(3) at pH 4.0 and showed that they were able to sorb both As(V) and Zn. Because the waste waters are usually contaminated with mixtures of pollutants in cationic and anionic forms, the LDH-polymerin complexes appear more suitable than the sorbents in a potential water remediation process.

Polymerin and lignimerin, as humic acid-like sorbents from vegetable waste, for the potential remediation of waters contaminated with heavy metals, herbicides, or polycyclic aromatic hydrocarbons.

Polymerin is a humic acid-like polymer, which we previously recovered for the first time from olive oil mill waste waters (OMWW) only, and chemically and physicochemically characterized. We also previously investigated its versatile sorption capacity for toxic inorganic and organic compounds. Therefore, a review is presented on the removal, from simulated polluted waters, of cationic heavy metals [Cu(II), Zn, Cr(III)] and anionic ones [Cr(VI)) and As(V)] by sorption on this natural organic sorbent in comparison with its synthetic derivatives, K-polymerin, a ferrihydrite-polymerin complex and with ferrihydrite. An overview is also performed of the removal of ionic herbicides (2,4-D, paraquat, MCPA, simazine, and cyhalofop) by sorption on polymerin, ferrihydrite, and their complex and of the removal of phenanthrene, as a representative of polycyclic aromatic hydrocarbons, by sorption on this sorbent and its complexes with micro- or nanoparticles of aluminum oxide, pointing out the employment of all these sorbents in biobed systems, which might allow the remediation of water and protection of surface and groundwater. In addition, a short review is also given on the removal of Cu(II) and Zn from simulated contaminated waters, by sorption on the humic acid-like organic fraction, named lignimerin, which we previously isolated for the first time, in collaboration with a Chilean group, from cellulose mill Kraft waste waters (KCMWW) only. More specifically, the production methods and the characterization of the two natural sorbents (polymerin and lignimerin) and their derivatives (K-polymerin ferrihydrite-polymerin, polymerin-microAl(2)O(3) and -nanoAl(2)O(3), and H-lignimerin, respectively) as well as their sorption data and mechanism are reviewed. Published and original results obtained by the cyclic sorption on all of the considered sorbents for the removal of the above-mentioned toxic compounds from simulated waste waters are also reported. Moreover, sorption capacity and mechanism of the considered compounds on polymerins and lignimerins are evaluated in comparison with other known natural sorbents, especially of humic acid nature and other organic matter. Some of their technical aspects and relative costs are also considered. Finally, the possible large-scale application of the considered sorption systems for water remediation is briefly discussed.

Sustainable sorption strategies for removing Cr3+ from tannery process wastewater

Two different strategies for the removal of trivalent chromium (Cr(3+)) from contaminated water are reported. The first one is based on the sorption process on an organo-mineral complex, named LDH-HP, obtained in turn by sorption of polymerin, the humic acid-like fraction occurring in olive oil mill wastewater, on a layered double hydroxide (LDH) of magnesium and aluminium with carbonate in the interlayer. This sorption process is preliminary developed on simulated wastewater (SW) as theoretical model and successively applied on tannery process wastewaters (TPWs) natively containing Cr(3+). The removal of Cr(3+) from TPW is lower than that observed for SW, because of the large compositional variability of TPW. The second one is based on the direct production of a LDH of magnesium and chromium (Cr(3+)), using as starting material TPW, naming LDH-TPW the complex produced. This process allows the complete removal of Cr(3+) from TPW and also the abatement of chemical oxygen demand, indicating to be a very promising purification process for an industrial application.

Comparative study on the sorption capacity of cyhalofop Acid on polymerin, ferrihydrite, and on a ferrihydrite-polymerin complex.

A comparative study was performed on the sorption capacity of the phenoxy acid herbicide cyhalofop on polymerin (from olive oil mill effluents), ferrihydrite, and a ferrihydrite-polymerin complex, by using a batch equilibrium method. The most efficient sorbent showed to be ferrihydrite followed by the ferrihydrite-polymerin complex and polymerin. Cyhalofop acid bound to ferrihydrite by a combination of ionic and ion-dipole bonding, whereas the same herbicide bound to the ferrihydrite-polymerin complex by ionic bonding and to polymerin by hydrogen bonding. Simulated wastewaters contaminated with cyhalofop acid were completely purified by two sorption cycles on ferrihydrite and five cycles on the ferrihydrite-polymerin complex, whereas the same wastewaters maintained a constant residue even after five sorption cycles on polymerin. For the first time, the possible use of a mineral (ferrihydrite) and an organo-mineral complex (ferrihydrite-polymerin) as a filter for the control of the herbicide contamination in point sources is proposed and briefly discussed.