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Frontiers of Environmental Science & Engineering

ISSN 2095-2201

ISSN 2095-221X(Online)

CN 10-1013/X

Postal Subscription Code 80-973

2018 Impact Factor: 3.883

Front. Environ. Sci. Eng.    2017, Vol. 11 Issue (1) : 7
Interactions between metal ions and the biopolymer in activated sludge: quantification and effects of system pH value
Yun Zhou1,2,Siqing Xia1,Binh T. Nguyen2,Min Long1,Jiao Zhang3,Zhiqiang Zhang1()
1. State Key Laboratory of Pollution Control and Resource Reuse, College of Environmental Science and Engineering, Tongji University, Shanghai 200092, China
2. Biodesign Swette Center for Environmental Biotechnology, Arizona State University, Tempe, AZ 85287-5701, USA
3. School of Civil Engineering and Transportation, Shanghai Urban Construction Vocational College, Shanghai 200432, China
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The biopolymer showed two protein-like fluorescence peaks (peaks A and B).

Interactions of Pb(II) and biopolymer were quantified at various system pH values.

System pH values significantly affect the quenching constant values for both peaks.

Peak B plays a more important role in the interactions than peak A.

Removal mechanism of metal ions by activated sludge system was further disclosed.

The quantification and effects of system pH value on the interactions between Pb(II) and the biopolymer from activated sludge were investigated. The biopolymer had two protein-like fluorescence peaks (Ex/Em= 280 nm/326–338 nm for peak A; Ex/Em= 220–230 nm/324–338 nm for peak B). The fluorescence intensities of peak B were higher than those of peak A. The fluorophores of both peaks could be largely quenched by Pb(II), and the quencher dose for peak B was about half of that for peak A. The modified Stern-Volmer equation well depicted the fluorescence quenching titration. The quenching constant (Ka) values for both peaks decreased with rising system pH value, and then sharply decreased under alkaline conditions. It could be attributed to that the alkaline conditions caused the reduction of available Pb(II) due to the occurrence of Pb(OH)2 sediments. The Ka values of peak B were bigger than those for peak A at the same system pH values. Accordingly, the aromatic protein (peak B) plays the key role in the interactions between metal ions and the biopolymer.

Keywords Metal ions      Biopolymer      Activated sludge      Three-dimensional excitation emission matrix (3D-EEM)      Fluorescence regional integration (FRI) technique      Quantification     
Corresponding Authors: Zhiqiang Zhang   
Issue Date: 09 January 2017
 Cite this article:   
Yun Zhou,Siqing Xia,Binh T. Nguyen, et al. Interactions between metal ions and the biopolymer in activated sludge: quantification and effects of system pH value[J]. Front. Environ. Sci. Eng., 2017, 11(1): 7.
Fig.1  The 3D-EEM fluorescence spectra of biopolymer (a) before and (b) after binding 40 mg·L1 Pb(II) at the system pH value of 6.0
Fig.2  Effect of the system pH value on the fluorescence intensities of (a) peak A and (b) peak B before and after adsorbing 40.0 mg·L1 Pb(II)
Fig.3  The fluorescence intensities of (a) peak A and (b) peak B in the biopolymer titrated by the noted Pb(II) concentrations under various system pH values
Fig.4  Distribution of FRI in the biopolymer titrated by the noted Pb(II) concentrations under various system pH values
system pH value peak A peak B
KSV( × 103 L·mol1) kq( × 1011 L·(mol·s)1) R2 KSV( × 103 L·mol1) kq( × 1011 L·(mol·s)1) R2
4.0 4.56 4.56 0.9847 0.79 0.79 0.7131
6.0 5.53 5.53 0.9886 1.23 1.23 0.7442
8.0 1.51 1.51 0.9783 0.34 0.34 0.7992
Tab.1  Stern-Volmer quenching constants for binding Pb(II) to peaks A and B in the biopolymer at various system pH values
Fig.5  Stern-Volmer plots of fluorescence emission quenching of biopolymer titrated with increasing Pb(II) concentration under various system pH value conditions at (a) peak A and (b) peak B
Fig.6  Modified Stern-Volmer plots of fluorescence emission quenching of biopolymer titrated with increasing Pb(II) concentration under various system pH value conditions at (a) peak A and (b) peak B
system pH value peak A peak B
Ka ( × 102) fa R2 Ka ( × 102) fa R2
4.0 2.14 1.21 0.9927 7.62 1.54 0.9977
6.0 2.27 1.46 0.9997 9.60 1.94 0.9949
8.0 0.61 1.14 0.9967 3.83 1.34 0.9923
Tab.2  Modified Stern-Volmer quenching constants for binding Pb(II) to peaks A and B in the biopolymer at various system pH values
1 Li W W, Yu H Q. Insight into the roles of microbial extracellular polymer substances in metal biosorption. Bioresource Technology, 2014, 160: 15–23 pmid: 24345430
2 Morgan J W, Forster C F, Evison L. A comparative study of the nature of biopolymers extracted from anaerobic and activated sludges. Water Research, 1990, 24(6): 743–750
3 Sheng G P, Yu H Q, Li X Y. Extracellular polymeric substances (EPS) of microbial aggregates in biological wastewater treatment systems: a review. Biotechnology Advances, 2010, 28(6): 882–894 pmid: 20705128
4 Liu H, Fang H H P. Characterization of electrostatic binding sites of extracellular polymers by linear programming analysis of titration data. Biotechnology and Bioengineering, 2002, 80(7): 806–811 pmid: 12402326
5 Sheng G P, Yu H Q. Characterization of extracellular polymeric substances of aerobic and anaerobic sludge using three-dimensional excitation and emission matrix fluorescence spectroscopy. Water Research, 2006, 40(6): 1233–1239 pmid: 16513156
6 Sheng G P, Xu J, Luo H W, Li W W, Li W H, Yu H Q, Xie Z, Wei S Q, Hu F C. Thermodynamic analysis on the binding of heavy metals onto extracellular polymeric substances (EPS) of activated sludge. Water Research, 2013, 47(2): 607–614 pmid: 23159005
7 Zhang D, Pan X, Mostofa K M G, Chen X, Mu G, Wu F, Liu J, Song W, Yang J, Liu Y, Fu Q. Complexation between Hg(II) and biofilm extracellular polymeric substances: an application of fluorescence spectroscopy. Journal of Hazardous Materials, 2010, 175(1-3): 359–365 pmid: 19889498
8 Sheng G P, Xu J, Li W H, Yu H Q. Quantification of the interactions between Ca2+, Hg2+ and extracellular polymeric substances (EPS) of sludge. Chemosphere, 2013, 93(7): 1436–1441 pmid: 24012141
9 Braissant O, Decho A W, Dupraz C, Glunk C, Przekop K M, Visscher P T. Exopolymeric substances of sulfate-reducing bacteria: interactions with calcium at alkaline pH and implication for formation of carbonate minerals. Geobiology, 2007, 5(4): 401–411
10 Salehizadeh H, Shojaosadati S A. Extracellular biopolymeric flocculants: recent trends and biotechnological importance. Biotechnology Advances, 2001, 19(5): 371–385 pmid: 14538073
11 Wang L L, Wang L F, Ren X M, Ye X D, Li W W, Yuan S J, Sun M, Sheng G P, Yu H Q, Wang X K. pH dependence of structure and surface properties of microbial EPS. Environmental Science & Technology, 2012, 46(2): 737–744 pmid: 22191521
12 Zhou Y, Xia S Q, Zhang J, Nguyen B T, Zhang Z Q. Insight into the influences of pH value on Pb(II) removal by the biopolymer extracted from activated sludge. Chemical Engineering Journal, 2017, 308(15): 1098–1104
13 Zhou Y, Xia S Q, Zhang J, Zhang Z Q, Hermanowicz S W. Adsorption characterizations of biosorbent extracted from waste activated sludge for Pb(II) and Zn(II). Desalination and Water Treatment, 2016, 57(20): 9343–9353
14 Zhou Y, Zhang Z, Zhang J, Xia S. New insight into adsorption characteristics and mechanisms of the biosorbent from waste activated sludge for heavy metals. Journal of Environmental Sciences (China), 2016, 45: 248–256 pmid: 27372140
15 Chen W, Westerhoff P, Leenheer J A, Booksh K. Fluorescence excitation-emission matrix regional integration to quantify spectra for dissolved organic matter. Environmental Science & Technology, 2003, 37(24): 5701–5710 pmid: 14717183
16 Cai X L, Liu G X, Zhao X, Hao Y X, Zhao Y C. Fluorescence excitation–emission matrix combined with regional integration analysis to characterize the composition and transformation of humic and fulvic acids from landfill at different stabilization stages. Waste management, 2012, 32(3):438–447
17 Pan X, Liu J, Zhang D. Binding of phenanthrene to extracellular polymeric substances (EPS) from aerobic activated sludge: a fluorescence study. Colloids and Surfaces. B, Biointerfaces, 2010, 80(1): 103–106 pmid: 20561771
18 Papadopoulou A, Green R J, Frazier R A. Interaction of flavonoids with bovine serum albumin: a fluorescence quenching study. Journal of Agricultural and Food Chemistry, 2005, 53(1): 158–163 pmid: 15631523
19 Gauthier T D, Shane E C, Guerin W F, Seitz W R, Grant C L. Fluorescence quenching method for determining equilibrium constants for polycyclic aromatic hydrocarbons binding to dissolved humic materials. Environmental Science & Technology, 1986, 20(11): 1162–1166
20 Lu X, Jaffe R. Interaction between Hg(II) and natural dissolved organic matter: a fluorescence spectroscopy based study. Water Research, 2001, 35(7): 1793–1803 pmid: 11329682
21 Hu Y J, Liu Y, Zhang L X, Zhao R M, Qu S S. Studies of interaction between colchicine and bovine serum albumin by fluorescence quenching method. Journal of Molecular Structure, 2005, 750(1): 174–178
22 American Public Health A, American Water Works A, Water Pollution Control F, Water Environment F. Standard Methods for the Examination of Water and Wastewater: American Public Health Association, 1915
23 Frølund B, Palmgren R, Keiding K, Nielsen P H. Extraction of extracellular polymers from activated sludge using a cation exchange resin. Water Research, 1996, 30(8): 1749–1758
24 Yamashita Y, Tanoue E. Chemical characterization of protein-like fluorophores in DOM in relation to aromatic amino acids. Marine Chemistry, 2003, 82(3): 255–271
25 Laane R. Influence of pH on the fluorescence of dissolved organic matter. Marine Chemistry, 1982, 11(4): 395–401
26 Ghosh K, Schnitzer M. Fluorescence excitation spectra of humic substances. Canadian Journal of Soil Science, 1980, 60(2): 373–379
27 Comte S, Guibaud G, Baudu M. Biosorption properties of extracellular polymeric substances (EPS) towards Cd, Cu and Pb for different pH values. Journal of Hazardous Materials, 2008, 151(1): 185–193 pmid: 17611021
28 Zhou Y, Zhang Z Q, Zhang J, Xia S Q. Understanding key constituents and feature of the biopolymer in activated sludge responsible for binding heavy metals. Chemical Engineering Journal, 2016, 304(15): 527–532
29 Borisover M, Laor Y, Bukhanovsky N, Saadi I. Fluorescence-based evidence for adsorptive binding of pyrene to effluent dissolved organic matter. Chemosphere, 2006, 65(11): 1925–1934 pmid: 16934851
30 Guibaud G, Comte S, Bordas F, Dupuy S, Baudu M. Comparison of the complexation potential of extracellular polymeric substances (EPS), extracted from activated sludges and produced by pure bacteria strains, for cadmium, lead and nickel. Chemosphere, 2005, 59(5): 629–638 pmid: 15792660
31 Brown M J, Lester J N. Role of bacterial extracellular polymers in metal uptake in pure bacterial culture and activated sludge-II Effects of mean cell retention time. Water Research, 1982, 16(11): 1549–1560
32 Merroun M L, Selenska-Pobell S. Bacterial interactions with uranium: an environmental perspective. Journal of Contaminant Hydrology, 2008, 102(3-4): 285–295 pmid: 19008016
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