Xanthate-modified alginates for the removal of Pb(II) and Ni(II) from aqueous solutions: A brief analysis of alginate xanthation.

Mining is the most common activity that introduces heavy metal ions into aquatic ecosystems, especially in low income-developing nations where governments are implementing stricter regulations for industrial wastewater. In this context, this work is focused on the application of xanthate-modified alginates for the removal of Pb(II) and Ni(II) from aqueous solutions. In order to confirm the presence of xanthate groups alongside alginate chains, characterization by second-derivative FT-IR was carried out and significance evidence attributed to xanthate groups was found at around 1062-1079 cm-1, 829-845 cm-1 and 620-602 cm-1. In addition to this, thermogravimetric analysis and differential scanning calorimetry were employed to explore thermal properties of modified alginates. According to these results, enthalpy changes (∆H) characteristic of dehydration and collapse of biopolymeric structure were estimated as +11.41 J/g and -6.83 J/g, respectively. Furthermore, the presence of S element was confirmed by EDS mapping technique, whereas FESEM image showed a cracked and homogeneous surface distribution. On the other hand, the effect of important parameters such as pH, dosage, initial concentration as well as Langmuir and Freundlich isotherm were deeply discussed. Finally, rheological measurements were performed aiming to investigate the gel-like viscoelastic features associated to nickel xanthate compound.

Xanthation of alginate for heavy metal ions removal. Characterization of xanthate-modified alginates and its metal derivatives.

Xanthates are widely used in mining industry as collectors for its high affinity towards metal sulfides and precious metal ores. The possibility of using alginate for xanthation has not been explored yet despite the feasibility by the presence of hydroxyl groups alongside the polymeric chains. Therefore, this work aims to evaluate the alginate as a matrix for xanthation and its application on heavy metal ions removal. In order to obtain green materials, important pararmeter were explored such as the effect of reaction time (4-12 h), type of base (NaOH/KOH) and amount of carbon disulfide (2-10%v/v). Xanthated alginates were analyzed by NMR techniques and evidence of ß-elimination was detected at 5.45 ppm. Furthermore, the presence of S element was confirmed by EDS mapping technique, while XRD showed a semi-crystalline structure. On the other hand, the chemical shifts of δ(C=S) and ν(C=S) bands were found around 863-805 cm-1 and 662-602 cm-1 respectively. Also, a shoulder at 182 ppm is appreciated by NMR in solid state attributed to CS group. According to FESEM analyses, morphology of xanthated alginates is affected by interaction with heavy metal ions. Finally, suitable materials for the removal of heavy metal ions were established at optimum pH values.

Chemical modification of alginate with cysteine and its application for the removal of Pb(II) from aqueous solutions.

It has been synthesized, characterized and tested a new biomaterial AlgS (sodium alginate functionalized with cysteine) to remove Pb(II) in aqueous media. The maximum Pb(II)-sorption capacity of AlgS (Qmax = 770 mg·g-1) is between almost two and nine times higher than other alginate-materials reported in the literature. Techniques, such as TGA/DSC, SEM/EDS, BET, FTIR, UV-Vis, XRD and 13C solid state-NMR have been used to study the chemical-modification of alginate at oxidation and aminofication stages. The formation of the imine intermediate (C=N), after 24 h of reaction was identified by a UV band at 348 nm. Typical IR-bands of AlgS were identified at 2970, 955, 949 and 1253 cm-1 which are associated to CH, SPb, SH and CN stretching vibrations, respectively. 13C solid state-NMR spectra of AlgS, show peaks at 33-38 ppm and 55-60 ppm associate to δ (HS-CH2-) of cysteine and δ (CN) respectively. The ΔH° and ΔG° negative values for Pb(II) sorption indicate that it is an exothermic process and occur spontaneously. Finally, it was found that the Pb(II) sorption on AlgS is significantly affected by the presence of cationic (Na+, Mg2+ and Al3+) and anionic (Cl-, NO3-) co-ions.

Chemical modification of sodium alginate with thiosemicarbazide for the removal of Pb(II) and Cd(II) from aqueous solutions.

A new material (AlgOx-TSC), based on alginate (Alg) chemically modified with thiosemicarbazide (TSC), has been synthesized and tested as an effective biomaterial to remove Pb(II) and Cd(II) ions in aqueous solutions. The synthesis was carried out by controlling the following steps, i/partial oxidation process of alginate in NaIO4 to obtain AlgOx, ii/reacting of AlgOx, at 40-45 °C, with TSC in NaBH4. AlgOx-TSC has been characterized by Field Emission Scanning Electron Microscopy (FESEM/EDS), Fourier Transform Infrared Spectroscopy (ATR-IR), solid state 13C NMR spectroscopy and Point of Zero Charge (pHPZC) measuremenmts. In order to enhance the sorption process, the effect of contact time, sorbent dosage, initial concentration and reusability of the novel sorbent were investigated becoming the AlgOx-TSC a promising material capable of removing high concentrations of heavy metal ions such as Pb(II) (up to 950 mg/g at pH 3) and Cd(II) (up to 300 mg/g at pH 7) in aqueous solutions.