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Frontiers of Environmental Science & Engineering

ISSN 2095-2201

ISSN 2095-221X(Online)

CN 10-1013/X

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Front. Environ. Sci. Eng.    2015, Vol. 9 Issue (3) : 385-393    https://doi.org/10.1007/s11783-014-0648-y
RESEARCH ARTICLE
Comparing the adsorption behaviors of Cd, Cu and Pb from water onto Fe-Mn binary oxide, MnO2 and FeOOH
Wei XU1,2,Huachun LAN1,Hongjie WANG3,Hongming LIU1,Jiuhui QU1,*()
1. Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085, China
2. Graduate University of Chinese Academy of Sciences, Beijing 100039, China
3. College of Environmental Science and Engineering, Beijing Forestry University, Beijing 100083, China
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Abstract

The adsorption potential of FMBO, FeOOH, MnO2 for the removal of Cd2+, Cu2+ and Pb2+ in aqueous systems was investigated in this study. Comparing to FMBO and FeOOH, MnO2 offered a much higher removal capacity towards the three metal ions. The maximal adsorption capacity of MnO2 for Cd2+, Cu2+ and Pb2+ were 1.23, 2.25 and 2.60 mmol·g-1, respectively. And that for FMBO were 0.37, 1.13, and 1.18 mmol·g-1 and for FeOOH were 0.11, 0.86 and 0.48 mmol·g-1, respectively. The adsorption behaviors of the three metal ions on the three adsorbents were all significantly affected by pH values and heavy metal removal efficiency increased with pH increased. The Langmuir and Freundlich adsorption models were used to describe the adsorption equilibrium of the three metal ions onto the three adsorbents. Results showed that the adsorption equilibrium data fitted well to Langmuir isotherm and this indicated that adsorption of metal ions occurred on the three metal oxides adsorbents limited to the formation of a monolayer. More negative charged of MnO2 surface than that of FMBO and FeOOH could be ascribed by lower pHiep of MnO2 than that of FMBO and FeOOH and this could contribute to more binding sites on MnO2 surface than that of FMBO and FeOOH. The higher metal ions uptake by MnO2 than FMBO and FeOOH could be well explained by the surface charge mechanism.
Keywords heavy metals      Fe-Mn binary oxide      manganese dioxide      ferric hydroxide      adsorption     
Corresponding Author(s): Jiuhui QU   
Online First Date: 18 February 2014    Issue Date: 30 April 2015
 Cite this article:   
Wei XU,Huachun LAN,Hongjie WANG, et al. Comparing the adsorption behaviors of Cd, Cu and Pb from water onto Fe-Mn binary oxide, MnO2 and FeOOH[J]. Front. Environ. Sci. Eng., 2015, 9(3): 385-393.
 URL:  
https://academic.hep.com.cn/fese/EN/10.1007/s11783-014-0648-y
https://academic.hep.com.cn/fese/EN/Y2015/V9/I3/385
kinetic model equation parameters
Pseudo-first-order equation qt = qmax-exp(ln(qmax)-kt) qt is the amount of heavy metal desorbed at time tqmax is the maximum amount of heavy metal desorbed at equilibriumk and a are constants
Elovich qt=a+klnt
Parabolic diffusion qt = a+kt0.5
power function qt = atk
Pseudo-second-order qt=qmax+qmax/(kqmaxt-1)
Tab.1  Kinetic equations tested to describe time-dependent Cd, Cu and Pb adsorption to MnO2, FMBO, and FeOOH
kinetic model equation parameters
Langmuir qe = qmaxKLCe/(1+KLCe) qe is the amount of heavy metal adsorbed on the adsorbents (mmol·g-1). Ce is the equilibrium heavy metal concentration in solution phase (mmol·L-1). KL is the equilibrium adsorption constant related to the affinity of binding sites (L·mmol-1) and qmax is the maximum amount of heavy metal per unit weight of adsorbent for complete monolayer coverage
Freundlich q e = K F C e n qe and Ce are previously denoted. KF is roughly an indicator of the adsorption capacity and n is the heterogeneity factor which has a lower value for more heterogeneous surfaces
Tab.2  Langmuir and Freundlich isotherm equations for Cd, Cu and Pb adsorption by MnO2, FMBO, and FeOOH
Fig.1  XRD diffraction pattern of FMBO, FeOOH and MnO2
Fig.2  Zeta potential of FMBO, FeOOH and MnO2
Fig.3  Kinetics of Cd (a), Cu (b) and Pb (c) removal by FMBO, FeOOH and MnO2. Adsorbents concentration was 200 mg·L-1 for Cd and Cu and 100 mg·L-1 for Pb. pH was 6.0±0.1 for Cu and Pb and 8.0±0.1 for Cd. Initial Cd and Pb concentration was 0.2 mmol·L-1 and Cu concentrations was 0.5 mmol·L-1
Condition Pseudo-first-order equation Elovich Parabolic diffusion Power function Pseudo-second-order
qmax/(mmol·g-1) k/(mmol·g-1·h-1) R2 k R2 k R2 k R2 qmax k R2
Cd MnO2 1.35 1.52 0.75 0.18 0.94 0.14 0.66 0.15 0.88 1.45 1.67 0.91
FMBO 0.89 0.46 0.95 0.15 0.93 0.12 0.72 0.24 086 0.98 0.65 0.97
FeOOH 0.56 0.45 0.99 0.11 0.92 0.08 0.65 0.26 0.80 0.63 0.93 0.98
Cu MnO2 1.51 1.44 0.46 0.18 0.97 0.15 0.75 0.12 0.94 1.66 0.63 0.75
FMBO 0.96 0.33 0.87 0.16 0.96 0.13 0.74 0.22 0.90 1.05 0.23 0.95
FeOOH 0.71 0.33 0.84 0.11 0.95 0.18 0.75 0.21 0.90 0.76 0.33 0.92
Pb MnO2 1.86 4.85 0.56 0.14 0.73 0.95 0.36 0.075 0.67 1.95 4.27 0.84
FMBO 0.91 0.77 0.94 0.15 0.89 0.11 0.61 0.20 0.80 0.99 1.11 0.96
FeOOH 0.58 0.18 0.97 0.11 0.93 0.10 0.91 0.39 0.94 0.67 0.31 0.99
Tab.3  The kinetic model parameters for the adsorption of Cd on FMBO, FeOOH, MnO2 at pH 8.0 and T= 20±1°C and for the adsorption of Cu and Pb on FMBO, FeOOH, MnO2 at pH 6.0 and T= 20±1°C
Fig.4  Effects of pH on Cd, Cu, and Pb removal at fixed initial heavy metal concentration (0.4 mmol·L-1) (200 mg·L-1 suspension)
Fig.5  Adsorption isotherms for Cd2+(a), Cu2+(b) and Pb2+(c) by FMBO, FeOOH and MnO2 in a 200 mg·L-1 suspension at pH 7.0±0.1 for Cd and 6.0±0.1 for Cu and Pb
Adsorbent Langmuir model Freundlich model
qm/(mmol·g-1) KL/(L·mg-1) R2 KF n R2
Cd MnO2 1.23 122.5 0.87 1.86 4.5 0.82
FMBO 0.37 14.2 0.91 0.48 2.7 0.80
FeOOH 0.11 8.9 0.96 0.13 2.4 0.88
Cu MnO2 2.25 189.8 0.928 3.59 4.22 0.837
FMBO 1.13 55.4 0.940 1.53 4.10 0.844
FeOOH 0.86 14.0 0.929 1.14 2.54 0.877
Pb MnO2 2.60 195.1 0.490 4.07 4.45 0.470
FMBO 1.18 234.4 0.944 1.82 4.06 0.940
FeOOH 0.48 43.5 0.806 0.63 4.04 0.712
Tab.4  Langmuir and Freundlich isotherm constants for Cd adsorption by FMBO, FeOOH and MnO2 at pH 7.0 and T = 20±1°C and for Cu and Pb adsorption at pH 6.0 and T = 20±1°C
Fig.6  FTIR spectra of (a) MnO2, MnO2 + Cd, MnO2 + Cu and MnO2 + Pb; (b) FMBO, FMBO+ Cd, FMBO+ Cu, and FMBO+ Pb; (c) FeOOH, FeOOH+ Cd, FeOOH+ Cu, and FeOOH+ Pb. Initial Cd, Cu, and Pb concentration was 0.5 mmol·L-1 and adsorbents concentration of 200 mg·L-1 was used. Solution pH was maintained as 6.0 by intermittent addition of dilute HNO3 or KOH
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