Margherita Silvetti

XRD, FTIR, AND THERMAL ANALYSIS OF BAUXITE ORE-PROCESSING WASTE (RED MUD) EXCHANGED WITH HEAVY METALS

The present work shows the results of X-ray diffraction (XRD), Fourier transform infrared (FTIR), and thermal analysis of untreated (RMnt) and acid-treated red mud (RMa), a bauxite ore-processing waste, exchanged with Pb2+, Cd2+, and Zn2+ cations. These studies were performed in order to investigate the changes in the sorbent structure caused by the exchange with metals of different ionic radii.The XRD pattern of RMnt, analyzed according to the Rietveld method, showed a mixture of eight different phases. However, just three phases made up 78 wt.% of the RMnt: cancrinite (33 wt.%), hematite (29 wt.%), and sodalite (16 wt.%). X-ray diffraction patterns of RMnt exchanged with Pb2+ and Cd2+ cations revealed two additional phases, namely hydrocerussite [Pb3(CO3)2(OH)2 (10 wt.%))] and octavite [CdCO3 (8 wt.%)].These two phases probably originated from the carbonate precipitation processes which were due to the decarbonation of cancrinite. Hydrocerussite and octavite were not found in the case of acid-treated red mud samples.In the FTIR spectra, the introduction of cations caused a distinct shift to higher wavenumbers in the peak at ∼1100 cm−1, which is attributed to the asymmetric stretch of Si-O-Al. This effect may be associated with the Pb2+, Cd2+, and Zn2+ adsorbed by the red muds which caused a deformation of the initial structure.Thermal analysis data of the red mud samples were obtained by thermogravimetric/differential thermogravimetric analysis, and these methods were employed to evaluate the desorption behavior of water and to clarify the thermal stability of the chemical phases of the different red mud samples. The loss of metal-bound water in the red mud samples was found to depend on the size of non-framework cations and water loss consistently followed the order: Zn2+>Cd2+>Pb2+.

Study of sorption processes and FT-IR analysis of arsenate sorbed onto red muds (a bauxite ore processing waste)

In this study we evaluated the arsenate adsorption capacity of red muds (RM), wastes tailing from the alumina production, at different pH values (4, 7, and 10). RM samples were artificially enriched in batch tests with solutions containing increasing concentrations of As(V). The pH of the solution significantly affected the adsorption, which increased with the decrease of pH. Moreover a sequential extraction procedure [H(2)O; (NH(4))(2)SO(4); NH(4)H(2)PO(4); NH(4)(+)-oxalate; NH(4)(+)-oxalate+ascorbic acid] was applied to RM samples exchanged with arsenate. Using this approach it was shown that low concentrations of arsenate sorbed in RM were present as water soluble and exchangeable fractions, while NH(4)(+)-oxalate and NH(4)(+)-oxalate+ascorbic acid extracted most of the adsorbed arsenate from RM at different pH values. Besides, FT-IR spectroscopy was used to better understand the nature of RM surface configuration after As(V) sorption. In the FT-IR spectra the presence of As(V) species was highlighted by a well resolved band at 865 cm(-1). The intensity and broadness of this band increased at the decreasing of pH. This band could be related to nu(As-O) vibration of an inner-sphere Al-O-As complex and/or due to As-O bonds of the adsorbed As(V) species on Fe oxides of RM samples.

Copper(II) and lead(II) removal from aqueous solution by water treatment residues

In this study, we investigated the ability of Fe- and Al-based water treatment residues (Fe- and Al-WTR) to accumulate Pb(II) and Cu(II) at pH 4.5. The role of the inorganic and organic fractions of WTRs in metals sorption was also assessed. Sorption isotherms showed a higher sorption of Pb(II) by both WTRs with respect to Cu(II) (e.g. 0.105 and 0.089 mmol g(-1) of Pb(II) and Cu(II) respectively sorbed by Fe-WTR). Fe-WTR revealed a stronger sorbent for both metals than Al-WTR. The amount of Pb(II) and Cu(II) sorbed by Fe-WTR was about the 69% and 63% higher than that sorbed by the Al-WTR. The organic matter of Fe- and Al-WTR contributed to about 26% and 8.5% respectively in the sorption of both metals. The sequential extraction procedure showed that the greatest amount of metals sorbed by both WTRs were tightly bound and not extractable, and this was particularly apparent for Cu(II). The FT-IR spectra indicated the formation of inner-sphere complexes between the Fe(Al)-O nucleus and Pb(II) and Cu(II). Moreover, the FT-IR spectra also suggested that the humic fraction of WTRs interacted, through the carboxylate groups, with Cu(II) and Pb(II) by forming mainly monodentate and bidentate complexes, respectively.

Water treatment residues as accumulators of oxoanions in soil. Sorption of arsenate and phosphate anions from an aqueous solution

Here we report a survey addressed to determine, at different pH values (pH 4.0, 7.0 and 9.0), the ability of two different water treatment residues, a Fe-based (Fe-WTR) and an Al-based (Al-WTR), to accumulate arsenate and phosphate anions from an aqueous solution and to define the mechanism which regulate the sorption of these anions. Fe-WTR showed a greater As(V) and P(V) sorption capacity respect to Al-WTR at all the pH values investigated, in particular at pH 4.0. The greater capacity of the Fe-WTR to accumulate phosphate at pH 4.0 seems to be linked to the higher content of manganese ions compared to Al-WTR, which can give rise, with phosphate ions, to the formation of MnHPO4 precipitates. Sequential extraction of As(V)- or P(V)-WTRs suggested that the main mechanism governing the sorption of both two anions likely involve the formation of inner-sphere surface complexes [Fe/Al-O-As(P)]. Such a coordination mode was supported by the FT-IR spectra that exhibit well resolved band at 865cm(-1) and 1040cm(-1) attributable to ν(As-O) or ν(P-O) stretching vibration, respectively.

Influence of lead in the sorption of arsenate by municipal solid waste composts: metal(loid) retention, desorption and phytotoxicity

The ability of two municipal solid waste composts (MSW-C) to sorb As(V) in the presence of Pb(II) and in acidic conditions was investigated. Sorption isotherms and kinetics showed that both MSW-C were able to sorb As(V) in a similar way (∼0.24mmolg-1 MSW-C), but only when Pb(II) was present (0.45mmolL-1). The concomitant sorption of Pb(II) by both MSW-C (∼0.40mmolg-1) suggested that the metal cation was likely acting as bridging element between the negatively charged functional groups of composts and As(V). SEM-EDX analysis of the MSW-C+Pb(II)+As(V) systems supported the association between Pb(II) and As(V), while sequential extraction procedures and organic acids treatment showed that As(V) was strongly retained by MSW-C+Pb(II) and suggested the presence of different interaction types between As(V) and Pb(II). Plant growth experiments highlighted the key role of Pb(II) in the reduction of As(V)-phytotoxicity for triticale plants (×Triticosecale Wittm.) in the presence of MSW-C.

Arsenic mobilization by citrate and malate from a red mud-treated contaminated soil.

The mobility and bioavailability of As in the soil-plant system can be affected by a number of organic acids that originate from the activity of plants and microorganisms. In this study we evaluated the ability of citrate and malate anions to mobilize As in a polluted subacidic soil (UP soil) treated with red mud (RM soil). Both anions promoted the mobilization of As from UP and RM soils, with citrate being more effective than malate. The RM treatment induced a greater mobility of As. The amounts of As released in RM and UP soils treated with 3.0 mmol L citric acid solution were 2.78 and 1.83 μmol g respectively, whereas an amount equal to 1.73 and 1.06 μmol g was found after the treatment with a 3.0 mmol L malic acid solution. The release of As in both soils increased with increasing concentration of organic acids, and the co-release of Al and Fe in solution also increased. The sequential extraction showed that Fe/Al (oxi)hydroxides in RM were the main phases involved in As binding in RM soil. Two possible mechanisms could be responsible for As solubilization: (i) competition of the organic anions for As adsorption sites and (ii) partial dissolution of the adsorbents (e.g., dissolution of iron and aluminum oxi-hydroxides) induced by citrate or malate and formation of complexes between dissolved Fe and Al and organic anions. This is the first report on the effect of malate and citrate on the As mobility in a polluted soil treated with RM.

X-RAY DIFFRACTION AND THERMAL ANALYSIS OF BAUXITE ORE-PROCESSING WASTE (RED MUD) EXCHANGED WITH ARSENATE AND PHOSPHATE

The use of waste materials from mineral ore processing has much potential for immobilizing pollutants such as arsenic (As) in natural soils and waters. The purpose of the present study was to investigate red mud (RM, a finely textured bauxite-ore residue) as a sequestering agent for arsenate and phosphate, including characterization of the types of surface complexes formed. The mineralogical and structural changes occurring in RM were investigated after exchange with arsenate [As(V)-RM] and phosphate [P(V)-RM] anions at pH 4.0, 7.0, and 10.0. Eight different phases were present in the untreated red mud (RMnt), though 80 wt.% of the crystalline phase consisted of sodalite, hematite, gibbsite, and boehmite. The X-ray diffraction (XRD) data for As(V)-RM revealed an anion-promoted dissolution of the gibbsite, suggesting that this phase was the most active for As(V) sequestration. In addition, the lattice parameters of cancrinite were different in As(V)-RM at pH 7.0 and 10.0 from those in RMnt. The changes may be related to the incorporation of arsenate in the cancrinite cages. X-ray diffraction patterns of P(V)-RM at pH 4.0 and 7.0 revealed the dissolution of sodalite, hematite, and gibbsite, and the formation of a novel phase, berlinite [(α,β)AlPO4]. The new phases detected through XRD and thermal (TG/DTG) analysis in P(V)-RM probably originated through an initial phosphate-promoted dissolution of some RM phases, followed by a precipitation reaction between the phosphate and Al/Fe ions. The results obtained suggest that phosphate and arsenate, though with different reactivities, were strongly bound to some RM phases, such as gibbsite, cancrinite, sodalite, and hematite through mechanisms such as chemical sorption and coprecipitation reactions. The knowledge acquired will be helpful in selecting alternative materials such as red muds, which currently pose critical economic and environmental challenges related to their disposal, for the decontamination of soils and waters polluted with As.