Abstract
This study presents the application of a safe, cost effective, environmental friendly, and efficient technology for the removal of trivalent chromium ions from aqueous solutions, based on the valorisation of a renewable resource, Laminaria digitata seaweed. Insights into trivalent chromium speciation in solution and interaction with the active sites present in the surface of the brown algae were studied. Carboxyl and hydroxyl groups were identified as the major binding sites present in the surface of the biosorbent, in concentrations (Q max) of 2.06 ± 0.01 and 1.4 ± 0.7 mmol g−1, and with proton binding parameters (pK) of 3.28 ± 0.01 and 11 ± 1, respectively. Trivalent chromium uptake at equilibrium conditions was well described at different acidic pH conditions and chromium concentrations, using a model which incorporates trivalent chromium hydrolysis reactions in the aqueous phase and its chemical interactions with the available active sites (carboxyl groups) present in the surface of biosorbent. The distribution profile of trivalent chromium species present in the solution as well as at the binding sites indicated that Cr3+ and CrOH2+ exhibit different affinities for the carboxyl groups present in the surface of the biomass according to the pH. A mass transfer kinetics model was applied to describe the kinetics at batch system, being possible to obtain the distribution of CrOH2+ and Cr3+ species in solution and at the binding sites.
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Abbreviations
- a p :
-
Specific area of the particle (cm−1)
- B :
-
Representative of the functional group in the biomass
- B T or Q max :
-
Total number of binding sites B per unit mass of biomass (mmol g−1)
- C i :
-
Concentration of species i in the fluid phase (mmol L−1)
- C H :
-
Proton concentration in the solution (mmol L−1)
- D h,i :
-
Coefficient of homogeneous diffusion inside the particle for each species i (cm2 s−1)
- F obj-a :
-
Objective function
- i :
-
Experimental sample number
- k :
-
Reaction rate constant (s−1)
- k p,i :
-
Overall mass transfer coefficient of species i (cm s−1)
- \( K^{\prime}_{\text{H}} \) :
-
Average of the affinity distribution of hydrogen ions
- K int i,H :
-
The intrinsic proton affinity constant at each binding site i
- K H :
-
Dissociation constant of functional group (mol L−1)
- K M1 :
-
Binding constant of Cr3+ to functional group (L mol−1)
- K M2 :
-
Binding constant of CrOH2+ to functional group (L mol−1)
- K s :
-
Thermodynamic equilibrium constant (mol L−1)
- m H :
-
Width of the Sips distribution
- n :
-
Number of samples
- q :
-
Concentration of species i in the solid phase (mmol g−1)
- 〈q i 〉:
-
Average concentration of species i in the solid phase (mmol g−1)
- \( q_{i}^{ * } \) :
-
Equilibrium concentration of species i in the solid phase (mmol g−1)
- Q H :
-
Weighted sum of the charge contributions of each active site (mmol g−1)
- Q expH,i :
-
Experimental charge of an acidic surface (mmol g−1)
- Q estH,i :
-
Estimated charge of an acidic surface (mmol g−1)
- R :
-
Half of the thin plate thickness (cm)
- V :
-
Volume of the liquid in the reactor (L)
- W :
-
Algal mass (g)
- t :
-
Time (s)
- z :
-
Distance to the symmetry plane (cm)
- τd,i :
-
Time constant for diffusion of ionic species into the particle (s)
- r i :
-
Kinetic rate (mmol L−1 s−1)
- θ T,H :
-
Total degree of protonation
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Acknowledgments
The authors are grateful to the project of International Cooperation, Edital-CGCI-010/2009, Projeto CAPES/FCT no. 279/2010, financed by CAPES-Brazil and FCT-Portugal. This work was also partially supported by project PEst-C/EQB/LA0020/2011, financed by FEDER through COMPETE—Programa Operacional Factores de Competitividade and by FCT—Fundação para a Ciência e a Tecnologia. Ingrid M. Dittert also acknowledges her Doctoral fellowship provided by CAPES. V.J.P. Vilar acknowledges financial support from Programme Ciência 2008 (FCT).
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Dittert, I.M., Vilar, V.J.P., da Silva, E.A.B. et al. Turning Laminaria digitata seaweed into a resource for sustainable and ecological removal of trivalent chromium ions from aqueous solutions. Clean Techn Environ Policy 15, 955–965 (2013). https://doi.org/10.1007/s10098-012-0565-3
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DOI: https://doi.org/10.1007/s10098-012-0565-3