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Adsorption of Cu(II) on humic acids derived from different organic materials |
LI Cui-lan, JI Fan, WANG Shuai, ZHANG Jin-jing, GAO Qiang, WU Jing-gui, ZHAO Lan-po, WANG Li-chun, ZHENG Li-rong |
1、College of Resource and Environmental Science, Jilin Agricultural University, Changchun 130118, P.R.China
2、Institute of Plant Science, Jilin Agricultural Science and Technology College, Jilin 132101, P.R.China
3、Institute of Agricultural Resources and Environments, Jilin Academy of Agricultural Sciences, Changchun 130124, P.R.China
4、Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049, P.R.China |
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摘要 The adsorption of Cu(II) from aqueous solution onto humic acid (HA) which was isolated from cattle manure (CHA), peat (PHA), and leaf litter (LHA) as a function of contact time, pH, ion strength, and initial concentration was studied using the batch method. X-ray absorption spectroscopy (XAS) was used to examine the coordination environment of the Cu(II) adsorbed by HA at a molecular level. Moreover, the chemical compositions of the isolated HA were characterized by elemental analysis and solid-state 13C nuclear magnetic resonance spectroscopy (NMR). The kinetic data showed that the adsorption equilibrium can be achieved within 8 h. The adsorption kinetics followed the pseudo-second-order equation. The adsorption isotherms could be well fitted by the Langmuir model, and the maximum adsorption capacities of Cu(II) on CHA, PHA, and LHA were 229.4, 210.4, and 197.7 mg g–1, respectively. The adsorption of Cu(II) on HA increased with the increase in pH from 2 to 7, and maintained a high level at pH>7. The adsorption of Cu(II) was also strongly influenced by the low ionic strength of 0.01 to 0.2 mol L–1 NaNO3, but was weakly influenced by high ionic strength of 0.4 to 1 mol L–1 NaNO3. The Cu(II) adsorption on HA may be mainly attributed to ion exchange and surface complexation. XAS results revealed that the binding site and oxidation state of Cu adsorbed on HA surface did not change at the initial Cu(II) concentrations of 15 to 40 mg L–1. For all the Cu(II) adsorption samples, each Cu atom was surrounded by 4 O/N atoms at a bond distance of 1.95 Å in the first coordination shell. The presence of the higher Cu coordination shells proved that Cu(II) was adsorbed via an inner-sphere covalent bond onto the HA surface. Among the three HA samples, the adsorption capacity and affinity of CHA for Cu(II) was the greatest, followed by that of PHA and LHA. All the three HA samples exhibited similar types of elemental and functional groups, but different contents of elemental and functional groups. CHA contained larger proportions of methoxyl C, phenolic C and carbonyl C, and smaller proportions of alkyl C and carbohydrate C than PHA and LHA. The structural differences of the three HA samples are responsible for their distinct adsorption capacity and affinity toward Cu(II). These results are important to achieve better understanding of the behavior of Cu(II) in soil and water bodies in the presence of organic materials.
Abstract The adsorption of Cu(II) from aqueous solution onto humic acid (HA) which was isolated from cattle manure (CHA), peat (PHA), and leaf litter (LHA) as a function of contact time, pH, ion strength, and initial concentration was studied using the batch method. X-ray absorption spectroscopy (XAS) was used to examine the coordination environment of the Cu(II) adsorbed by HA at a molecular level. Moreover, the chemical compositions of the isolated HA were characterized by elemental analysis and solid-state 13C nuclear magnetic resonance spectroscopy (NMR). The kinetic data showed that the adsorption equilibrium can be achieved within 8 h. The adsorption kinetics followed the pseudo-second-order equation. The adsorption isotherms could be well fitted by the Langmuir model, and the maximum adsorption capacities of Cu(II) on CHA, PHA, and LHA were 229.4, 210.4, and 197.7 mg g–1, respectively. The adsorption of Cu(II) on HA increased with the increase in pH from 2 to 7, and maintained a high level at pH>7. The adsorption of Cu(II) was also strongly influenced by the low ionic strength of 0.01 to 0.2 mol L–1 NaNO3, but was weakly influenced by high ionic strength of 0.4 to 1 mol L–1 NaNO3. The Cu(II) adsorption on HA may be mainly attributed to ion exchange and surface complexation. XAS results revealed that the binding site and oxidation state of Cu adsorbed on HA surface did not change at the initial Cu(II) concentrations of 15 to 40 mg L–1. For all the Cu(II) adsorption samples, each Cu atom was surrounded by 4 O/N atoms at a bond distance of 1.95 Å in the first coordination shell. The presence of the higher Cu coordination shells proved that Cu(II) was adsorbed via an inner-sphere covalent bond onto the HA surface. Among the three HA samples, the adsorption capacity and affinity of CHA for Cu(II) was the greatest, followed by that of PHA and LHA. All the three HA samples exhibited similar types of elemental and functional groups, but different contents of elemental and functional groups. CHA contained larger proportions of methoxyl C, phenolic C and carbonyl C, and smaller proportions of alkyl C and carbohydrate C than PHA and LHA. The structural differences of the three HA samples are responsible for their distinct adsorption capacity and affinity toward Cu(II). These results are important to achieve better understanding of the behavior of Cu(II) in soil and water bodies in the presence of organic materials.
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Received: 22 August 2013
Accepted:
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Fund: This work was supported by the Key Technologies R&D Program of China (2013BAD07B02 and 2013BAC09B01), the Special Fund for Agro-Scientific Research in the Public Interest of China (201103003), the Postdoctoral Project of Jilin Province, China (01912), and the Doctoral Initiative Foundation of Jilin Agricultural University, China (201216). Valuable comments by three anonymous reviewers greatly improved the manuscript. |
Corresponding Authors:
ZHANG Jin-jing, Tel: +86-431-84532955,E-mail: zhangjinjing@126.com; ZHENG Li-rong, Tel: +86-10-88235980, E-mail: zhenglr@ihep.ac.cn
E-mail: zhangjinjing@126.com; zhenglr@ihep.ac.cn
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Cite this article:
LI Cui-lan, JI Fan, WANG Shuai, ZHANG Jin-jing, GAO Qiang, WU Jing-gui, ZHAO Lan-po, WANG Li-chun, ZHENG Li-rong.
2015.
Adsorption of Cu(II) on humic acids derived from different organic materials. Journal of Integrative Agriculture, 14(1): 168-177.
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Alvarez-Puebla R A, Valenzuela-Calahorro C, Garrido J J. 2004.Cu(II) retention on a humic substance. Journal of Colloidand Interface Science, 270, 47-55Arias M, Barral M T, Mejuto J C. 2002. Enhancement of copperand cadmium adsorption on kaolin by the presence of humicacids. Chemosphere, 48, 1081-1088Ashley J T F. 1996. Adsorption of Cu(II) and Zn(II) by estuarine,riverine and terrestrial humic acids. Chemosphere, 33,2175-2187Brunetti G, Plaza C, Clapp C E, Senesi N. 2007. Compositionaland functional features of humic acids from organicamendments and amended soils in Minnesota, USA. SoilBiology and Biochemistry, 39, 1355-1365Cheah S F, Brown Jr G E, Parks G A. 1998. XAFS spectroscopystudy of Cu(II) sorption on amorphous SiO2 and γ-Al2O3:Effect of substrate and time on sorption complexes. Journalof Colloid and Interface Science, 208, 110-128Cheah S F, Brown Jr G E, Parks G A. 2000. XAFS studyof Cu model compounds and Cu2+ sorption productson amorphous SiO2, γ-Al2O3, and anatase. AmericanMineralogist, 85, 118-132Davies G, Ghabbour E A. 1998. Humic Substances: Structures,Properties and Uses. Royal Society of Chemistry,Cambridge.Fang L, Zhou C, Cai P, Chen W, Rong X, Dai K, Liang W, GuJ D, Huang Q. 2011. Binding characteristics of copper andcadmium by cyanobacterium Spirulina platensis. Journalof Hazardous Materials, 190, 810-815Gardea-Torresdey J L, Tang L, Salvador J M. 1996. Copperadsorption by esterified and unesterified fractions ofSphagnum peat moss and its different humic substances.Journal of Hazardous Materials, 48, 191-206Ginder-Vogel M, Sparks D L. 2010. The impacts of X-rayabsorption spectroscopy on understanding soil processesand reaction mechanisms. Developments in Soil Science,34, 1-26Hur J, Jung K Y, Schlautman M A. 2011. Altering thecharacteristics of a leaf litter-derived humic substance byadsorptive fractionation versus simulated solar irradiation.Water Research, 45, 6217-6226Ippolito J A, Strawn D G, Scheckel K G. 2013. Investigationof copper sorption by sugar beet processing lime waste.Journal of Environmental Quality, 42, 919-924Johnson C S, Kropf A J. 2002. In situ XAFS analysis of theLixNi0.8Co0.2O2 cathode during cycling in lithium batteries.Electrochimica Acta, 47, 3187-3194Khalil M I, Hossain M B, Schmidhalter U. 2005. Carbon andnitrogen mineralization in different upland soils of thesubtropics treated with organic materials. Soil Biology andBiochemistry, 37, 1507-1518Karlsson T, Persson P, Skyllberg U. 2006. Complexation ofcopper(II) in organic soils and in dissolved organic matter-EXAFS evidence for chelatering structures. EnvironmentalScience and Technology, 40, 2623-2628Karlsson T. 2005. Complexation of cadmium, copper and methylmercury to functional groups in natural organic matter.Studied by X-ray absorption spectroscopy and bindingaffinity experiments. Ph D thesis, Swedish University ofAgricultural Sciences, Swedish.Li J, Hu J, Sheng G, Zhao G, Huang Q. 2009. Effect of pH, ionicstrength, foreign ions and temperature on the adsorption ofCu(II) from aqueous solution to GMZ bentonite. Colloids andSurfaces (A: Physicochemical and Engineering Aspects),349, 195-201Li J, Wu J. 2013. Compositional and structural difference offulvic acid from black soil applied with different organicmaterials: Assessment after three years. Journal ofIntegrative Agriculture, 12, 1865-1871Li Y, Yue Q, Gao B. 2010. Adsorption kinetics and desorptionof Cu(II) and Zn(II) from aqueous solution onto humic acid.Journal of Hazardous Materials, 178, 455-461Liang X, Xu Y, Wang L, Sun Y, Lin D, Sun Y, Qin X, Wan Q.2013. Sorption of Pb2+ on mercapto functionalized sepiolite.Chemosphere, 90, 548-555Newville M. 2001. IFEFFIT: Interactive XAFS analysis andFEFF fitting. Journal of Synchrotron Radiation, 8, 324-332Nierop K G J, Buurman P, de Leeuw J W. 1999. Effectof vegetation on chemical composition of H horizonsin incipient podzols as characterized by 13C NMR andpyrolysis-GC/MS. Geoderma, 90, 111-129Ribeiro J S, Ok S S, Garrigues S, de la Guardia M. 2001. FTIRtentative characterization of humic acids extracted fromorganic materials. Spectroscopy Letters, 34, 179-190Rice J A, MacCarthy P. 1991. Statistical evaluation of theelemental composition of humic substances. OrganicGeochemistry, 17, 635-648Simpson A J, McNally D J, Simpson M J. 2011. NMRspectroscopy in environmental research: From molecularinteractions to global processes. Progress in NuclearMagnetic Resonance Spectroscopy, 58, 97-175Stevenson F J. 1994. Humus Chemistry: Genesis, Composition,and Reactions. John Wiley & Sons, New York.Strawn D G, Baker L L. 2008. Speciation of Cu in a contaminatedagricultural soil measured by XAFS, μ-XAFS, and μ-XRF.Environmental Science and Technology, 42, 37-42Strawn D G, Baker L L. 2009. Molecular characterizationof copper in soils using X-ray absorption spectroscopy.Environmental Pollution, 157, 2813-2821Tan X, Chang P, Fan Q, Zhou X, Yu S, Wu W, Wang X. 2008.Sorption of Pb(II) on Na-rectorite: Effects of pH, ionicstrength, temperature, soil humic acid and fulvic acid.Colloids and Surfaces (A: Physicochemical and EngineeringAspects), 328, 8-14Theng B K G. 2012. Humic substances. Developments in ClayScience, 4, 391-456Unsal T, Ok S S. 2001. Description of characteristics of humicsubstances from different waste materials. BioresourceTechnology, 78, 239-242Wang S, Hu J, Li J, Dong Y. 2009. Influence of pH, soilhumic/fulvic acid, ionic strength, foreign ions and addition sequences on adsorption of Pb(II) onto GMZ bentonite.Journal of Hazardous Materials, 167, 44-51Wright D A, Welbourn P. 2002. Environmental Toxicology.Cambridge University Press, UK.Xia K, Bleam W, Helmke P A. 1997. Studies of the nature of Cu2+and Pb2+ binding sites in soil humic substances using X-rayabsorption spectroscopy. Geochimica et CosmochimicaActa, 61, 2211-2221Xing B, Liu J, Liu X, Han X. 2005. Extraction and characterizationof humic acids and humin fractions from a black soil ofChina. Pedosphere, 15, 1-8Xu J, Huang P. 2010. Molecular Environmental Soil Scienceat the Interfaces in the Earth’s Critical Zone. ZhejiangUniversity Press, Hangzhou and Springer-Verlag, BerlinHeidelberg.Xu P, Zeng G, Huang D, Lai C, Zhao M, Wei Z, Li N, Huang C,Xie G. 2012. Adsorption of Pb(II) by iron oxide nanoparticlesimmobilized Phanerochaete chrysosporium: Equilibrium,kinetic, thermodynamic and mechanisms analysis.Chemical Engineering Journal, 203, 423-431Yan C. 1988. Research Methods of Soil Fertility. AgriculturePress, Beijing, China. (in Chinese)Zabinsky S I, Rehr J J, Ankudinov A, Albers R C, Eller M. 1995.Multiple-scattering calculations of X-ray-absorption spectra.Physical Review (B), 52, 2995-3009Zhang J, Hu F, Li H, Gao Q, Song X, Ke X, Wang L. 2011.Effects of earthworm activity on humus compositionand humic acid characteristics of soil in a maize residueamended rice-wheat rotation agroecosystem. Applied SoilEcology, 51, 1-8Zhang J, Wang L, Li C. 2010. Humus Characteristics after maizeresidues degradation in soil amended with different copperconcentrations. Plant, Soil and Environment, 56, 120-124Zhang J, Wang S, Wang Q, Wang N, Li C, Wang L. 2013. Firstdetermination of Cu adsorption on soil humin. EnvironmentalChemistry Letters, 11, 41-46Zhao W, Tan W, Feng X, Liu F, Xie Y, Xie Z. 2011. XAFSstudies on surface coordination of Pb2+ on birnessites withdifferent average oxidation states. Colloids and Surfaces (A:Physicochemical and Engineering Aspects), 379, 86-92 |
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