Removal of clofibric acid from aqueous solution by polyethylenimine-modified chitosan beads

doi:10.1007/s11783-013-0622-0

Front. Environ. Sci. Eng.

2014, Vol. 8

Issue (5) : 675-682 https://doi.org/10.1007/s11783-013-0622-0

RESEARCH ARTICLE

Removal of clofibric acid from aqueous solution by polyethylenimine-modified chitosan beads

Yao NIE¹, Shubo DENG^1,²(

), Bin WANG¹, Jun HUANG^1,², Gang YU^1,²

¹. POPs Research Center, School of Environment, Tsinghua University, Beijing 100084, China
². State Key Joint Laboratory of Environment Simulation and Pollution Control, Tsinghua University, Beijing 100084, China

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Abstract

Polyethylenimine (PEI)-modified chitosan was prepared and used to remove clofibric acid (CA) from aqueous solution. PEI was chemically grafted on the porous chitosan through a crosslinking reaction, and the effects of PEI concentration and reaction time in the preparation on the adsorption of clofibric acid were optimized. Scanning electron microscopy (SEM) showed that PEI macromolecules were uniformly grafted on the porous chitosan, and the analysis of pore size distribution indicated that more mesopores were formed due to the crosslinking of PEI molecules in the macropores of chitosan. The PEI-modified chitosan had fast adsorption for CA within the initial 5 h, while this adsorbent exhibited an adsorption capacity of 349 mg·g⁻¹ for CA at pH 5.0 according to the Langmuir fitting, higher than 213 mg·g⁻¹ on the porous chitosan. The CA adsorption on the PEI-modified chitosan was pH-dependent, and the maximum adsorption was achieved at pH 4.0. Based on the surface charge analysis and comparison of different pharmaceuticals adsorption, electrostatic interaction dominated the sorption of CA on the PEI-modified chitosan. The PEI-modified chitosan has a potential application for the removal of some anionic micropollutants from water or wastewater.

Keywords clofibric acid PEI-modified chitosan adsorption capacity adsorption mechanism electrostatic interaction

Corresponding Author(s): Shubo DENG

Issue Date: 20 June 2014

Cite this article:

Yao NIE,Shubo DENG,Bin WANG, et al. Removal of clofibric acid from aqueous solution by polyethylenimine-modified chitosan beads[J]. Front. Environ. Sci. Eng., 2014, 8(5): 675-682.

URL:

https://academic.hep.com.cn/fese/EN/10.1007/s11783-013-0622-0
https://academic.hep.com.cn/fese/EN/Y2014/V8/I5/675

compounds	molecular formula	molecular weight	log K_ow	pK_a	molecular size/nm
clofibric acid (CA)	$C 10 H 11 C l O 3$	214.66	2.57	2.9 [29,30]	0.94
bezafibrate (BF)	$C 19 H 20 C l N O 4$	361.82	4.25	3.6 [29,31]	1.66
caffeine (CF)	$C 8 H 10 N 4 O 2$	194.19	−0.07	10.4 [29]	0.83
sulpiride (SP)	$C 15 H 23 N 3 O 4 S$	341.43	1.10	9.1,10.0 [31]	1.13

Tab.1 Properties of four PPCPs used in this study

Fig.1 Effects of PEI concentration (a) and crosslinking reaction time (b) in the adsorbent preparation on the removal of CA

Fig.2 SEM images of crosslinked chitosan before (a) and after (b) PEI modification

Fig.3 Mesopore size distribution of the crosslinked chitosan and PEI-modified chitosan

Fig.4 Sorption kinetics of clofibric acid on the crosslinked chitosan and PEI-modified chitosan at pH 5.0

Tab.2 Calculated parameters for the Langmuir and Freundlich equations for the adsorption of CA on the two kinds of chitosan

Fig.5 Adsorption isotherms of clofibric acid on the crosslinked chitosan and PEI-modified chitosan at pH 5.0 as well as the modeling using the Langmuir and Freundlich equations. (a) adsorbed amounts were expressed by the unit of mg·g⁻¹ adsorbent; (b) adsorbed amounts were expressed by the unit of mg·g⁻¹ chitosan

Fig.6 Effect of solution pH on the sorption of CA on the crosslinked chitosan and PEI-modified chitosan

Fig.7 Zeta potentials of the crosslinked chitosan and PEI-modified chitosan at different solution pH

Fig.8 Removal of different PPCPs on the PEI-modified chitosan beads at pH 5.0

1	D Fatta-Kassinos, S Meric, A Nikolaou. Pharmaceutical residues in environmental waters and wastewater: current state of knowledge and future research. Analytical and Bioanalytical Chemistry, 2011, 399(1): 251–275 https://doi.org/10.1007/s00216-010-4300-9 pmid: 21063687
2	W Z Li, Q Sui, S G Lu, Z F Qiu, K F Lin. Identification and ecotoxicity assessment of intermediates generated during the degradation of clofibric acid by advanced oxidation processes. Frontiers of Environmental Science & Engineering, 2012, 6(4): 445–454 https://doi.org/10.1016/j.chemosphere.2005.01.032 pmid: 15993150
3	C Tixier, H P Singer, S Oellers, S R Müller. Occurrence and fate of carbamazepine, clofibric acid, diclofenac, ibuprofen, ketoprofen, and naproxen in surface waters. Environmental Science and Technology, 2003, 37(6): 1061–1068 doi:10.1021/es025834r pmid: 12680655
4	G R Boyd, H Reemtsma, D A Grimm, S Mitra. Pharmaceuticals and personal care products (PPCPs) in surface and treated waters of Louisiana, USA and Ontario, Canada. The Science of the Total Environment, 2003, 311(1–3): 135–149 https://doi.org/10.1016/S0048-9697(03)00138-4 pmid: 12826389
5	W H Xu, G Zhang, S C Zou, X D Li, Y C Liu. Determination of selected antibiotics in the Victoria Harbour and the Pearl River, South China using high-performance liquid chromatography-electrospray ionization tandem mass spectrometry. Environmental Pollution, 2007, 145(3): 672–679 https://doi.org/10.1016/j.envpol.2006.05.038 pmid: 16996177
6	B Kasprzyk-Hordern, R M Dinsdale, A J Guwy. The effect of signal suppression and mobile phase composition on the simultaneous analysis of multiple classes of acidic/neutral pharmaceuticals and personal care products in surface water by solid-phase extraction and ultra performance liquid chromatography-negative electrospray tandem mass spectrometry. Talanta, 2008, 74(5): 1299–1312 https://doi.org/10.1016/j.talanta.2007.08.037 pmid: 18371783
7	O A H Jones, N Voulvoulis, J N Lester. Aquatic environmental assessment of the top 25 English prescription pharmaceuticals. Water Research, 2002, 36(20): 5013–5022 https://doi.org/10.1016/S0043-1354(02)00227-0 pmid: 12448549
8	S Weigel, J Kuhlmann, H Hühnerfuss. Drugs and personal care products as ubiquitous pollutants: occurrence and distribution of clofibric acid, caffeine and DEET in the North Sea. The Science of the Total Environment, 2002, 295(1–3): 131–141 https://doi.org/10.1016/S0048-9697(02)00064-5 pmid: 12186282
9	K V Thomas, M J Hilton. The occurrence of selected human pharmaceutical compounds in UK estuaries. Marine Pollution Bulletin, 2004, 49(5–6): 436–444 https://doi.org/10.1016/j.marpolbul.2004.02.028 pmid: 15325211
10	K K Barnes, D W Kolpin, E T Furlong, S D Zaugg, M T Meyer, L B Barber. A national reconnaissance of pharmaceuticals and other organic wastewater contaminants in the United States−I) groundwater. The Science of the Total Environment, 2008, 402(2–3): 192–200 https://doi.org/10.1016/j.scitotenv.2008.04.028 pmid: 18556047
11	F Gagné, C Blaise, C André. Occurrence of pharmaceutical products in a municipal effluent and toxicity to rainbow trout (Oncorhynchus mykiss) hepatocytes. Ecotoxicology and Environmental Safety, 2006, 64(3): 329–336 PMID:15923035 https://doi.org/10.1016/j.ecoenv.2005.04.004
12	M Nassef, S Matsumoto, M Seki, F Khalil, I J Kang, Y Shimasaki, Y Oshima, T Honjo. Acute effects of triclosan, diclofenac and carbamazepine on feeding performance of Japanese medaka fish (Oryzias latipes). Chemosphere, 2010, 80(9): 1095–1100 https://doi.org/10.1016/j.chemosphere.2010.04.073 pmid: 20537681
13	P Pfluger, D R Dietrich. Effects on pharmaceuticals in the environment–an overview and principle considerations. In: K Kummerer, ed. Pharmaceuticals in the Environment. Heidelberg: Springer, 2011, 11–17
14	S K Khetan, T J Collins. Human pharmaceuticals in the aquatic environment: a challenge to Green Chemistry. Chemical Reviews, 2007, 107(6): 2319–2364 https://doi.org/10.1021/cr020441w pmid: 17530905
15	T Heberer. Occurrence, fate, and removal of pharmaceutical residues in the aquatic environment: a review of recent research data. Toxicology Letters, 2002, 131(1–2): 5–17 https://doi.org/10.1016/S0378-4274(02)00041-3 pmid: 11988354
16	T A Ternes. Occurrence of drugs in German sewage treatment plants and rivers. Water Research, 1998, 32(11): 3245–3260 https://doi.org/10.1016/S0043-1354(98)00099-2
17	B Nunes, A R Gaio, F Carvalho, L Guilhermino. Behaviour and biomarkers of oxidative stress in Gambusia holbrooki after acute exposure to widely used pharmaceuticals and a detergent. Ecotoxicology and Environmental Safety, 2008, 71(2): 341– 354 https://doi.org/10.1016/j.ecoenv.2007.12.006 pmid: 18243307
18	T Heberer. Tracking persistent pharmaceutical residues from municipal sewage to drinking water. Journal of Hazardous Materials, 2002, 266(3–4): 175–189
19	V Matamoros, J García, J M Bayona. Organic micropollutant removal in a full-scale surface flow constructed wetland fed with secondary effluent. Water Research, 2008, 42(3): 653–660 https://doi.org/10.1016/j.watres.2007.08.016 pmid: 17826819
20	A S Mestre, M L Pinto, J Pires, J M F Nogueira, A P Carvalho. Effect of solution pH on the removal of clofibric acid by cork-based activated carbon. Carbon, 2010, 48(4): 92–980 https://doi.org/10.1016/j.carbon.2009.11.013
21	D Simazaki, J Fujiwara, S Manabe, M Matsuda, M Asami, S Kunikane. Removal of selected pharmaceuticals by chlorination, coagulation-sedimentation and powdered activated carbon treatment. Water Science and Technology, 2008, 58(5): 1129–1135 https://doi.org/10.2166/wst.2008.472 pmid: 18824814
22	Z Hasan, J Jeon, S H Jhung. Adsorptive removal of naproxen and clofibric acid from water using metal-organic frameworks. Journal of Hazardous Materials, 2012, 209–210(30): 151–157 https://doi.org/10.1016/j.jhazmat.2012.01.005 pmid: 22277335
23	T X Bui, H Choi. Adsorptive removal of selected pharmaceuticals by mesoporous silica SBA-15. Journal of Hazardous Materials, 2009, 168(2–3): 602–608 https://doi.org/10.1016/j.jhazmat.2009.02.072 pmid: 19327889
24	H R Wei, S B Deng, Q Huang, Y Nie, B Wang, J Huang, G Yu. Regenerable granular carbon nano tubes/ alumina hybrid adsorbents for diclofenac sodium and carbamazepine removal from aqueous solution. Water Research, 2013, 47(12): 4139–4147 https://doi.org/10.1016/j.biortech.2008.01.053 pmid: 18342504
25	S Chatterjee, D S Lee, M W Lee, S H Woo. Enhanced adsorption of congo red from aqueous solutions by chitosan hydrogel beads impregnated with cetyl trimethyl ammonium bromide. Bioresource Technology, 2009, 100(11): 2803–2809 https://doi.org/10.1016/j.biortech.2008.12.035 pmid: 19208471
26	R R Navarro, K Sumi, N Fujii, M Matsumura. Mercury removal from wastewater using porous cellulose carrier modified with polyethyleneimine. Water Research, 1996, 30(10): 2488–2494 https://doi.org/10.1016/0043-1354(96)00143-1
27	S Deng, Y P Ting. Polyethylenimine-modified fungal biomass as a high-capacity adsorbent for chromium anion removal. Environmental Science and Technology, 2005, 39(21): 8490–8496 https://doi.org/10.1021/es050697u pmid: 16294892
28	S Deng, R Ma, Q Yu, J Huang, G Yu. Enhanced removal of pentachlorophenol and 2,4-D from aqueous solution by an aminated biosorbent. Journal of Hazardous Materials, 2009, 165(1–3): 408–414 https://doi.org/10.1016/j.jhazmat.2008.10.029 pmid: 19013710
29	United States National Library of Medicine (USNLM). Toxicology Data Network. .
30	C Nebot, S W Gibb, K G Boyd. Quantification of human pharmaceuticals in water samples by high performance liquid chromatography-tandem mass spectrometry. Analytica Chimica Acta, 2007, 598(1): 87–94 https://doi.org/10.1016/j.aca.2007.07.029 pmid: 17693311
31	E Yamamoto, T Sakaguchi, T Kajima, N Mano, N Asakawa. Novel methylcellulose-immobilized cation-exchange precolumn for on-line enrichment of cationic drugs in plasma. Journal of Chromatography. B, Analytical Technologies in the Biomedical and Life Sciences, 2004, 807(2): 327–334 https://doi.org/10.1016/j.jchromb.2004.04.028 pmid: 15203047
32	Q Yu, S B Deng, G Yu. Selective removal of perfluorooctane sulfonate from aqueous solution using chitosan-based molecularly imprinted polymer adsorbents. Water Research, 2008, 42(12): 3089–3097 https://doi.org/10.1016/j.watres.2008.02.024 pmid: 18374386
33	Q Y Zhang, S B Deng, G Yu, J Huang. Removal of perfluorooctane sulfonate from aqueous solution by crosslinked chitosan beads: sorption kinetics and uptake mechanism. Bioresource Technology, 2011, 102(3): 2265–2271 https://doi.org/10.1016/j.biortech.2010.10.040 pmid: 21044835
34	Y H Gao, M A Deshusses. Adsorption of clofibric acid and ketoprofen onto powdered activated carbon: effect of natural organic matter. Environmental Technology, 2011, 33(15–16): 1719–1727 https://doi.org/10.1080/09593330.2011.554888 pmid: 22439557
35	N Lindqvist, T Tuhkanen, L Kronberg. Occurrence of acidic pharmaceuticals in raw and treated sewages and in receiving waters. Water Research, 2005, 39(11): 2219–2228 https://doi.org/10.1016/j.watres.2005.04.003 pmid: 15935437

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