Abstract
The concentrations and protonation constants of the functional groups like carboxyl and phenolic hydroxyl groups in spruce bark were determined by a potentiometric acid–base titration method. The non-cellulosic carbohydrates in spruce bark were also characterized by acid methanolysis and GC, including determination of the uronic acid units, which are the key units involved in metal sorption. Sorption of metal ions to bark takes place by ion exchange, mainly by complexation to these functional groups. The sorption equilibrium time, studied by using a batch method, was approximately 5 min. The metal sorption capacity of spruce bark and the affinity order of metal ions were studied with four different metal ion mixtures using a column chromatographic method. Because a method of competition was used, concentration of metal ions adsorbed to bark depends on the metal ions present in the mixtures studied. In the sorption experiments with same metal ion mixtures, inner bark of spruce exhibited higher sorption capacity than outer bark. By combination of the results from several experiments, the following affinity order was obtained Fe3+ ≫ Pb2+ ≫ Cu2+ ≫ Cd2+ > Zn2+ > Ni2+ > Ba2+ > Ca2+ > Sr2+ > Mn2+ > Mg2+ ≫ K+ ~ Na+ ~ Li+. Bark has a great potential as an effective and inexpensive sorbent for removal of metal ions from, e.g., waste water.
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References
Argun ME, Dursun S, Karatas M (2009) Removal of Cd(II), Pb(II), Cu(II) and Ni(II) from water using modified pine bark. Desalination 249(2):519–527
Dorfner K (ed) (1991) Ion exchangers. Walter de Gruyter, Berlin
Evans PD, Michell AJ, Schmalzl KJ (1992) Studies of the degradation and protection of wood surfaces. Wood Sci Technol 26(2):151–163
Fengel D, Wegener G (1989) Constituents of bark. In: Fengel D, Wegener G (eds) Wood: chemistry, ultrastructure, reactions. Walter de Gruyter, Berlin, pp 241–267
Granholm K, Su P, Harju L, Ivaska A (2009) Study on desorption of Mn, Fe, and Mg from TMP and evaluation of the complexing strength of different chelating agents using side reaction coefficients. Holzforschung 63(6):785–790
Gundogdu A, Ozdes D, Duran C, Bulut VN, Soylak M, Senturk HB (2009) Biosorption of Pb(II) ions from aqueous solution by pine bark (Pinus brutia Ten.). Chem Eng J 153(1–3):62–69
Harju L, Saarela K-E, Rajander J, Lill J-O, Lindroos A, Heselius S-J (2002) Environmental monitoring of trace elements in bark of Scots pine by thick-target PIXE. Nucl Instrum Methods Phys Res B 189:303–309
Harkin JM, Rowe JW (1971) Bark and its possible uses. Forest Products Laboratory, Forest Service U.S. Department of Agriculture, Madison, WI
Herbelin A, Westall JC (1999) FITEQL: a computer program for determination of chemical equilibrium constants from experimental data [computer program], v. 4.0. Department of Chemistry, Oregon State University, Corvallis, OR
Hubbe MA, Hasan SH, Ducoste JJ (2011) Cellulosic substrates for removal of pollutants from aqueous systems: a review. 1. Metals. Bioresources 6(2):2161–2287
Krogell J, Holmbom B, Pranovich A, Hemming J, Willför S (2012) Extraction and chemical characterization of Norway spruce inner and outer bark. Nord Pulp Pap Res J 27(1):6–17
Miranda I, Gominho J, Mirra I, Pereira H (2012) Chemical characterization of barks from Picea abies and Pinus sylvestris after fractioning into different particle sizes. Ind Crops Prod 36(1):395–400
Mun S, Ku C, Kim J (2010) Adsorption of metal and uranyl ions onto amidoximated Pinus densiflora bark. Wood Sci Technol 44(2):283–299
Munagapati VS, Yarramuthi V, Nadavala SK, Alla SR, Abburi K (2010) Biosorption of Cu(II), Cd(II) and Pb(II) by Acacia leucocephala bark powder: kinetics, equilibrium and thermodynamics. Chem Eng J 157(2–3):357–365
Naiya TK, Chowdhury P, Bhattacharya AK, Das SK (2009) Saw dust and neem bark as low-cost natural biosorbent for adsorptive removal of Zn(II) and Cd(II) ions from aqueous solutions. Chem Eng J 148(1):68–79
Patnukao P, Kongsuwan A, Pavasant P (2008) Batch studies of adsorption of copper and lead on activated carbon from Eucalyptus camaldulensis Dehn. bark. J Environ Sci 20(9):1028–1034
Pranovich AV, Sundberg KE, Holmbom BR (2003) Chemical changes in thermomechanical pulp at alkaline conditions. J Wood Chem Technol 23(1):89–112
Reddy DHK, Seshaiah K, Reddy AV, Rao MM, Wang MC (2010) Biosorption of Pb2+ from aqueous solutions by Moringa oleifera bark: equilibrium and kinetic studies. J Hazard Mater 174(1–3):831–838
Reddy DHK, Ramana DKV, Seshaiah K, Reddy AVR (2011) Biosorption of Ni(II) from aqueous phase by Moringa oleifera bark, a low cost biosorbent. Desalination 268(1–3):150–157
Sarin V, Pant KK (2006) Removal of chromium from industrial waste by using eucalyptus bark. Biores Technol 97(1):15–20
Shin EW, Karthikeyan KG, Tshabalala MA (2007) Adsorption mechanism of cadmium on juniper bark and wood. Biores Technol 98(3):588–594
Södö M, Su P, Granholm K, Harju L, Ivaska A (2007) Study on metal ion affinities to oxygen delignified hardwood kraft pulp by a column chromatographic method. Nord Pulp Pap Res J 22(4):462–467
Su P, Granholm K, Harju L, Ivaska A (2010a) Study of metal ion binding to unbleached softwood kraft pulp by column chromatography. Appita J 63(2):143–149
Su P, Granholm K, Pranovich A, Harju L, Holmbom B, Ivaska A (2010b) Sorption of metal ions to untreated, alkali-treated and peroxide-bleached TMP. Cellulose 17(5):1033–1044
Su P, Granholm K, Harju L, Ivaska A (2011) Binding affinities of different metal ions to unbleached hardwood kraft pulp. Holzforschung 65(4):619–622
Su P, Granholm K, Pranovich A, Harju L, Holmbom B, Ivaska A (2012) Metal ion sorption to birch and spruce wood. BioResouces 7(2):2141–2155
Subbaiah MV, Vijaya Y, Kumar NS, Reddy AS, Krishnaiah A (2009) Biosorption of nickel from aqueous solutions by Acacia leucocephala bark: kinetics and equilibrium studies. Colloids Surf B Biointerfaces 74(1):260–265
Sundberg A, Sundberg K, Lillandt C, Holmbom B (1996) Determination of hemicelluloses and pectins in wood and pulp fibres by acid methanolysis and gas chromatography. Nord Pulp Pap Res J 11(4):216–219
Willför S, Pranovich A, Tamminen T, Puls J, Laine C, Suurnäkki A, Saake B, Uotila K, Simolin H, Hemming J, Holmbom B (2009) Carbohydrate analysis of plant materials with uronic acid-containing polysaccharides—a comparison between different hydrolysis and subsequent chromatographic analytical techniques. Ind Crops Prod 29(2–3):571–580
Acknowledgments
This work is a part of the activities at Åbo Akademi Process Chemistry Centre within the Finnish Center of Excellence Program (2000–2011) by the Academy of Finland. Financial support from the Research Institute of Åbo Akademi Foundation is gratefully acknowledged. We also thank M.Sc. Jesús Arroyo for performing a part of the column sorption experiments.
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Su, P., Granholm, K., Pranovich, A. et al. Sorption of metal ions from aqueous solution to spruce bark. Wood Sci Technol 47, 1083–1097 (2013). https://doi.org/10.1007/s00226-013-0562-7
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DOI: https://doi.org/10.1007/s00226-013-0562-7