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Biosorption of heavy metals from aqueous solutions using keratin biomaterials

    Student thesis: Doctoral thesis

    Abstract

    Biosorption is an effective technique for the removal of heavy metals from wastewaters resulting from human and industrial activities. Waste biomaterials are considered ideal alternatives as novel biosorbents due to the low relatively cost-effective ratio and the high efficient adsorption capacities for heavy metals. A vast array of low-cost waste biomaterials from large-scales industrial operations have been successfully employed as biosorbents for the removal of heavy metals from wastewaters. As a kind of abundant biological resources, keratin biomaterials are investigated currently for this purpose, which show high capacity of biosorption of heavy metals due to their high contents of carboxyl, hydroxyl, amino and sulfur-containing functional groups. This thesis is concerned with the use of keratin biomaterials, specifically human hair, dog hair, chicken feathers and degreased wool, as biosorbents for the removal of heavy metals from aqueous solutions._x000D_ First of all, the removal of heavy metals from aqueous solutions by different kinds of human hair was investigated. It was found that the bleached and dyed hair showed the best biosorption capacities for all checked heavy metal ions. Based on these preliminary results, two human hair samples including native hair (H1) and bleached-dyed hair (H2) were selected to do further study. A systematic comparison of biosorption performance for removing Cr(III), Ni(II), Co(II), Mn(II), Cu(II), Zn(II), Cd(II) and Pb(II) ions from aqueous solution under different conditions, was provided. The H2 (bleached-dyed hair) showed better biosorption capacity than H1 (in native). It could be attributed to the higher surface area and more number of sulfonate groups, which is confirmed by the SEM and FT-IR analysis, respectively. The biosorption capacities of heavy metals followed the order Cu(II) > Pb(II) > Cr(III) > Zn(II) > Cd(II) > Ni(II) > Co(II) > Mn(II) for H2, and Cu(II) > Cr(III) > Pb(II) for H1, and the biosorption of the rest of the heavy metals for H1 was not significant. The pseudo-second order kinetic model is more likely to predict kinetic behavior of the metal biosorption process for whole contact time range, with the chemical sorption being the rate-controlling step. The maximum biosorption capacity of H1 and H2 for_x000D_ Pb(II) by Langmuir isotherm model were 1.7×10-5 and 23.2×10-5 mol/g at 295 K, respectively. The effect of sulfonate groups on the human hair surface can enhance the biosorption capacity of human hair as well as the elution efficiency of EDTA solution as eluent. The regenerated human hair samples with EDTA and rinsing later with water, showed good biosorption capacities of their reuse. So, the human hair is considered as a potential biosorbent for the removal of heavy metals from aqueous solutions._x000D_ Based on the above results, we can confirm that H2 (bleached-dyed hair) shows the best biosorption capacity, which inspire us to properly chemically modify the human hair to enhance its biosorption capacity. So, native human hair was treated by a proper oxidation method, and its biosorption performance was evaluated and compared with the native one. The chemical composition and morphology of human hair were analyzed by FR-IR and SEM respectively, after the oxidation treatment as well as after the metal biosorption process. The treated human hair showed better biosorption capacity for heavy metals comparing with the untreated one, as expected, due to the higher surface area after the treatment, and more sulfonate groups present on the surface, which have been formed through the oxidation reaction. The parameters affecting the biosorption of heavy metals, such as contact time, initial aqueous pH value, biosorbent dosage and initial metal concentration have been investigated. According to the kinetics and isotherm studies, the rate limiting step of the biosorption process might be the chemical sorption due to the formation of chemical bonds between the metal ions and the functional groups of the treated human hair in monolayer coverage. The maximum biosorption capacity of the treated human hair for Cr(III), Cu(II), Cd(II) and Pb(II) by Langmuir isotherm model at 295 K are 9.47×10-5, 5.57×10-5, 3.77×10-5, 3.61×10-5 mol/g, respectively. Negative standard Gibb’s energy indicates that the heavy metal biosorption process is thermodynamically feasible and spontaneous nature. The sulfonate groups on the treated human hair formed in the oxidation treatment, not only enhance the biosorption capacity, but also assist the desorption of metal ions by using EDTA. In addition, the elution using EDTA is beneficial to its reuse. Thus, the human hair treated by the oxidation method exhibits satisfactory biosorption capacity and can be used as an effective biosorbent for the removal of heavy metals from aqueous solutions._x000D_ Four common waste keratin biomaterials including human hair, dog hair, chicken feathers and degreased wool were used as biosorbents for the removal of heavy metals from aqueous solutions. The biosorption process was carried out under different conditions. The total biosorption capacity of the four biosorbents generally followed the order degreased wool > chicken feathers > human hair > dog hair. This is probably due to the partial oxidation of the degreased wool and the high surface area of chicken feathers, which are confirmed by FT-IR and SEM, respectively. Kinetic results indicated that chemical sorption is the basic mechanism in the biosorption processes. The experimental data fitted very well to the Langmuir isotherm model and the biosorption process is thermodynamically feasible and spontaneous nature, as indicated previously with the human hair case. These four keratin biomaterials regenerated with EDTA and rinsed with deionized water exhibit good biosorption capacity, especially for the chicken feathers (low cystine content) and the degreased wool (oxidized keratin fiber). The four waste keratin biomaterials, being cheap and easily available materials, could be an alternative to more costly adsorbents used nowadays for the heavy metals removal in wastewaters treatment processes._x000D_ Based on these results, it can be said that keratin biomaterials can be used as potential biosorbents for the removal of heavy metals, and that the human hair treated with an oxidation procedure can enhance its biosorption capacity. Therefore, the other keratin biomaterials including dog hair, chicken feathers and degreased wool were also treated by using the same chemical modification method. The treated dog hair shows better biosorption capacity than the native one, with similar behavior to the treated human hair. However, the biosorption capacities of chicken feathers and degreased wool are not improved by this method, which is probably due to the condition of modification (especially for the wool that has been degreased previously) and the properties of the keratin biomaterials themselves. Therefore, further characterization of the treated dog hair is followed. Corresponding biosorption experiments with the treated dog hair were carried out to investigate the effect of different parameters, such as contact time, pH of the solution and biosorbent dosage, as in the previous cases of study. Kinetic and isotherm models were also used to fit the experimental data, the results indicate that the_x000D_ chemical sorption is the rate limiting step in the biosorption process. The maximum biosorption capacity of the treated dog hair for Pb(II) by the Langmuir isotherm model is 5.79×10-5 mol/g at 295 K. The treated dog hair shows a good reusability after simple elution with EDTA and rinsing with deionized water._x000D_ In conclusion, the waste keratin biomaterials can be used as low-cost and effective biosorbents to remove heavy metals from aqueous solutions. In general, the oxidation treatment can significantly enhance the biosorption capacities of the keratin biomaterials. But the different conditions of the oxidation treatment for each keratin biomaterial should be considered for the proper modification in each case. These kinds of keratin biomaterials are expected to be applied in large scale to deal with the industrial wastewaters in near future.
    Date of Award22 Jul 2014
    Original languageEnglish
    SupervisorCristina Palet Ballus (Director)

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