Abstract
As an alternative to traditional adsorbents, mesoporous magnetic polypyrrole (MMPPy) was first used as an adsorbent for the removal of acid, neutral, and basic pharmaceutical compounds considered aqueous pollutants. Ibuprofen (IBU, acid), caffeine (CAF, neutral), and bupropion (BUP, basic) were chosen as adsorbates and applied in adsorption studies. They proved to be pH dependent of the aqueous solution and the best results were found at pH 4 for IBU and CAF and pH 7 for BUP and 60 mg was the optimal amount of adsorbent to be used in the studies. Adsorption was extremely fast and the equilibrium was reached up to 180 s. The adsorption data of all analytes could be well interpreted by the pseudo second-order kinetic model and the dual-site Langmuir-Freundlich isotherm model. The adsorption capacities obtained by the dual-site Langmuir-Freundlich model were 53.67 mg g−1, 16.74 mg g−1, and 24.72 mg g−1 for IBU, CAF, and BUP, respectively. Thermodynamic parameters revealed that IBU adsorption becomes spontaneous as temperature increases and CAF and BUP adsorption occurs through a non-spontaneous process. In addition, this study shows endothermic nature of the adsorption process. Analytes were desorbed using an aqueous solution at pH 10 for IBU, pH 7 for CAF, and pH 4 for BUP and then the material was regenerated successfully. The results suggest that MMPPy can be efficiently used in the removal of different organic analytes found in contaminated water.





Similar content being viewed by others
Data availability
Data used to support the findings of this study are available from the corresponding author upon request.
References
Acero JL, Benitez FJ, Real FJ, Teva F (2012) Coupling of adsorption, coagulation, and ultrafiltration processes for the removal of emerging contaminants in a secondary effluent. Chem Eng J 210:1–8. https://doi.org/10.1016/j.cej.2012.08.043
Akpa OM, Unuabonah EI (2011) Small-sample corrected Akaike information criterion: an appropriate statistical tool for ranking of adsorption isotherm models. Desalination 272:20–26. https://doi.org/10.1016/j.desal.2010.12.057
Ali I, AL-Othmanb ZA, Alwarthan A (2016) Synthesis of composite iron nano adsorbent and removal of ibuprofen drug residue from water. J Mol Liq 219:858–864. https://doi.org/10.1016/j.molliq.2016.04.031
Anacleto SS, de Oliveira HL, da Silva ATM, do Nascimento TA, Borges KB (2017) Preparation of an organic–inorganic hybrid molecularly imprinted polymer for effective removal of albendazole sulfoxide enantiomers from aqueous medium. J Environ Chem Eng 5:6179–6187. https://doi.org/10.1016/j.jece.2017.11.049
Asuquo ED, Martin AD (2016) Sorption of cadmium (II) ion from aqueous solution onto sweet potato (Ipomoea batatas L.) peel adsorbent: characterisation, kinetic and isotherm studies. J Environ Chem Eng 4:4207–4228. https://doi.org/10.1016/j.jece.2016.09.024
Ayawei N, Ebelegi AN, Wankasi D (2017) Modelling and interpretation of adsorption isotherms. J Chem 2017:1–11. https://doi.org/10.1155/2017/3039817
Babalola JO, Koiki BA, Eniayewu Y, Salimonu A, Olowoyo JO, Oninla VO, Alabi HA, Ofomaja AE, Omorogie MO (2016) Adsorption efficacy of Cedrela odorata seed waste for dyes: non linear fractal kinetics and non linear equilibrium studies. J Environ Chem Eng 4:3527–3536. https://doi.org/10.1016/j.jece.2016.07.027
Beltrame KK, Cazetta AL, de Souza PSC, Spessato L, Silva TL, Almeida VC (2018) Adsorption of caffeine on mesoporous activated carbon fibers prepared from pineapple plant leaves. Ecotoxicol Environ Saf 147:64–71. https://doi.org/10.1016/j.ecoenv.2017.08.034
Bhushan R, Batra S (2013) Direct enantiomeric resolution of (±)-bupropion using chiral liquid chromatography. JPC 26:491–495. https://doi.org/10.1556/JPC.26.2013.6.6
Boparai HK, Joseph M, O’Carroll DM (2011) Kinetics and thermodynamics of cadmium ion removal by adsorption onto nano zerovalent iron particles. J Hazard Mater 186:458–465. https://doi.org/10.1016/j.jhazmat.2010.11.029
Bui TX, Choi H (2009) Adsorptive removal of selected pharmaceuticals by mesoporous silica SBA-15. J Hazard Mater 168:602–608. https://doi.org/10.1016/j.jhazmat.2009.02.072
Chakraborty P, Banerjee S, Kumar S, Sadhukhan S, Halder G (2018a) Elucidation of ibuprofen uptake capability of raw and steam activated biochar of Aegle marmelos shell: isotherm, kinetics, thermodynamics and cost estimation. Process Saf Environ Prot 118:10–23. https://doi.org/10.1016/j.psep.2018.06.015
Chakraborty P, Show S, Banerjee S, Halder G (2018b) Mechanistic insight into sorptive elimination of ibuprofen employing bidirectional-activated biochar from sugarcane bagasse: performance evaluation and cost estimation. J Environ Chem Eng 6:5287–5300. https://doi.org/10.1016/j.jece.2018.08.017
Chávez-Guajardo AE, Medina-Llamas JC, Maqueira L, Andrade CAS, Alves KGB, de Melo CP (2015) Efficient removal of Cr (VI) and Cu (II) ions from aqueous media by use of polypyrrole/maghemite and polyaniline/maghemite magnetic nanocomposites. Chem Eng J 281:826–836. https://doi.org/10.1016/j.cej.2015.07.008
Chemicalize (2019) http://www.chemicalize.org, 2019. Accessed 22 Jan 2019
Cui X, Mao S, Liu M, Yuan H, Du Y (2008) Mechanism of surfactant micelle formation. Langmuir 19:10771–10775. https://doi.org/10.1021/la801705y
Davaran S, Alimirzalu S, Nejati-Koshki K, Nasrabadi HT, Akbarzadeh A, Khandaghi AA, Abbasian M, Alimohammadi S (2014) Physicochemical characteristics of fe3o4 magnetic nanocomposites based on poly(N-isopropylacrylamide) for anti-cancer drug delivery. Asian Pac J Cancer Prev 15:49–54. https://doi.org/10.7314/APJCP.2014.15.1.49
Dubey SP, Dwivedi AD, Sillanpaa M, Gopal K (2010) Artemisia vulgaris-derived mesoporous honeycomb-shaped activated carbon for ibuprofen adsorption. Chem Eng J 165:537–544. https://doi.org/10.1016/j.cej.2010.09.068
Dutra FVA, Pires BC, Nascimento TA, Mano V, Borges KB (2017) Polyaniline deposited cellulose fiber composite prepared via in situ polymerization: enhancing adsorption properties for removal of meloxicam from aqueous media. RSC Adv 7:12639–12649. https://doi.org/10.1039/c6ra27019k
Dutra FVA, Pires BC, Nascimento TA, Borges KB (2018) Functional polyaniline/multiwalled carbon nanotube composite as an efficient adsorbent material for removing pharmaceuticals from aqueous media. J Environ Manag 221:28–37. https://doi.org/10.1016/j.jenvman.2018.05.051
Feng J, Sun N, Wu D, Yang H, Xu H, Yan W (2017) Preparation of Fe3O4/TiO2/polypyrrole ternary magnetic composite and using as adsorbent for the removal of acid red G. J Polym Environ 25:781–791. https://doi.org/10.1007/s10924-016-0839-7
Fu J, Chen Z, Wang M, Liu S, Zhang J, Zhang J, Han R, Xu Q (2015) Adsorption of methylene blue by a high-efficiency adsorbent (polydopamine microspheres): kinetics, isotherm, thermodynamics and mechanism analysis. Chem Eng J 259:53–61. https://doi.org/10.1016/j.cej.2014.07.101
Galunin E, Ferreti J, Zapelini I, Vieira I, Tarley CRT, Abrão T, Santos MJ (2014) Cadmium mobility in sediments and soils from a coal mining area on Tibagi River watershed: environmental risk assessment. J Hazard Mater 265:280–287. https://doi.org/10.1016/j.jhazmat.2013.11.010
Gholitabar S, Tahermansouri H (2017) Kinetic and multi-parameter isotherm studies of picric acid removal from aqueous solutions by carboxylated multi-walled carbon nanotubes in the presence and absence of ultrasound. Carbon Lett 22:14–24. https://doi.org/10.5714/CL.2017.22.014
Gil A, Santamaria L, Korili AS (2018) Removal of caffeine and diclofenac from aqueous solution by adsorption on multiwalled carbon nanotubes. Colloid Interf Sci Commun 22:25–28. https://doi.org/10.1016/j.colcom.2017.11.007
Guo X, Du B, Wei Q, Yang J, Hu L, Yan L, Xu W (2014) Synthesis of amino functionalized magnetic graphenes composite material and its application to remove Cr(VI), Pb(II), Hg(II), Cd(II) and Ni(II) from contaminated water. J Hazard Mater 278:211–220. https://doi.org/10.1016/j.jhazmat.2014.05.075
Hameed BH, Ahmad AA (2009) Batch adsorption of methylene blue from aqueous solution by garlic peel, an agricultural waste biomass. J Hazard Mater 164:870–875. https://doi.org/10.1016/j.jhazmat.2008.08.084
Jiao Z, Bai Y, Zeng Y, Lv S, Fan H, Huang W (2017) Fabrication of polypyrrole-coated magnetic particles for quinone extraction from fine atmospheric particulate matter. Anal Methods 9:345–351. https://doi.org/10.1039/C6AY03071H
Kashanian F, Kokkinis G, Bernardi J, Zand MR, Shamloo A, Giouroudi I (2018) A novel magnetic microfluidic platform for on-chip separation of 3 types of silica coated magnetic nanoparticles (Fe3O4@SiO2). Sens Actuators A 270:223–230. https://doi.org/10.1016/j.sna.2017.12.047
Largitte L, Pasquier R (2016) A review of the kinetics adsorption models and their application to the adsorption of lead by an activated carbon. Chem Eng Res Des 109:495–504. https://doi.org/10.1016/j.cherd.2016.02.006
Lee YR, Tian M, Kim SN, Ahn WS, Row KH (2014) Adsorption isotherms of caffeine and theophylline on metal-organic frameworks. Adsorpt Sci Technol 32:724–735. https://doi.org/10.1260/0263-6174.32.9.725
Liu X, Zhang L (2015) Removal of phosphate anions using the modified chitosan beads: adsorption kinetic, isotherm and mechanism studies. Powder Technol 277:112–119. https://doi.org/10.1016/j.powtec.2015.02.055
Mall ID, Srivastava VC, Agarwal NK, Mishra IM (2005) Adsorptive removal of malachite green dye from aqueous solution by bagasse fly ash and activated carbon-kinetic study and equilibrium isotherm analyses. Colloids Surf A Physicochem Eng Asp 264:17–28. https://doi.org/10.1016/j.colsurfa.2005.03.027
Milonjić SK (2007) A consideration of the correct calculation of thermodynamic parameters of adsorption. J Serb Chem Soc 72:1363–1367. https://doi.org/10.2298/JSC0712363M
Mohammeda NAS, Abu-Zurayka RA, Hamadnehb I, Al-Dujailia AH (2018) Phenol adsorption on biochar prepared from the pine fruit shells: equilibrium, kinetic and thermodynamics studies. J Environ Manag 226:377–385. https://doi.org/10.1016/j.jenvman.2018.08.033
Nascimento TA, Dutra FVA, Pires BC, Borges KB (2018) Efficient removal of anti-inflammatory phenylbutazone from an aqueous solution employing a composite material based on poly(aniline-co-pyrrole)/multi-walled carbon nanotubes. New J Chem 42:7030–7042. https://doi.org/10.1039/C8NJ00861B
Nasreen S, Urooj A, Rafique U, Ehrman S (2016) Functionalized mesoporous silica: absorbents for water purification. Desalin Water Treat 57:29352–29362. https://doi.org/10.1080/19443994.2016.1185744
Nayak AK, Pal A (2018) Rapid and high-performance adsorptive removal of hazardous acridine orange from aqueous environment using Abelmoschus esculentus seed powder: single- and multi-parameter optimization studies. J Environ Manag 217:573–591. https://doi.org/10.1016/j.jenvman.2018.03.137
Ncibi MC, Sillanpaa M (2017) Optimizing the removal of pharmaceutical drugs carbamazepine and dorzolamide from aqueous solutions using mesoporous activated carbons and multi-walled carbon nanotubes. J Mol Liq 238:379–388. https://doi.org/10.1016/j.molliq.2017.05.028
Özer ET, Sarikaya AG, Osman B (2016) Adsorption and removal of diethyl phthalate from aqueous media with poly(hydroxyethyl methacrylate) nanobeads. Desalin Water Treat 57:28864–28874. https://doi.org/10.1080/19443994.2016.1186568
Pires BC, Dutra FVA, Nascimento TA, Borges KB (2017) Preparation of PPy/cellulose fibre as an effective potassium diclofenac adsorbent. React Funct Polym 113:40–49. https://doi.org/10.1016/j.reactfunctpolym.2017.02.002
Rafati L, Ehrampoush MH, Rafati AA, Mokhtari M, Mahvi AH (2018) Removal of ibuprofen from aqueous solution by functionalized strong nano-clay composite adsorbent: kinetic and equilibrium isotherm studies. Int J Environ Sci Technol 15:513–524. https://doi.org/10.1007/s13762-017-1393-0
Raji C, Anirudhan TS (1998) Batch Cr(VI) removal by polyacrylamide- grafted sawdust: kinetics and thermodynamics. Water Res 32:3772–3780. https://doi.org/10.1016/S0043-1354(98)00150-X
Santaeufemia S, Torres E, Abalde J (2018) Biosorption of ibuprofen from aqueous solution using living and dead biomass of the microalga Phaeodactylum tricornutum. J Appl Phycol 30:471–482. https://doi.org/10.1007/s10811-017-1273-5
Shahri EE, Eshaghi Z (2015) Superparamagnetic Fe3O4@SiO2 core–shell composite nanoparticles for the mixed hemimicelle solid-phase extraction of benzodiazepines from hair and wastewater samples before high-performance liquid chromatography analysis. J Sep Sci 38:4095–4104. https://doi.org/10.1002/jssc.201500743
Shahri FB, Niazi A, Akrami A (2018) Application of full factorial design for removal of polycyclic aromatic dye from aqueous solution using 4A zeolite: adsorption isotherms, thermodynamic and kinetic studies. Polycycl Aromat Compd 38:141–156. https://doi.org/10.1080/10406638.2016.1173074
Shao P, Duanb X, Xu J, Tiana J, Shi W, Gao S, Xu M, Cui F, Wang S (2017) Heterogeneous activation of peroxymonosulfate by amorphous boron for degradation of bisphenol S. J Hazard Mater 322:532–539 https://doi-org.ez32.periodicos.capes.gov.br/10.1016/j.jhazmat.2016.10.020
Shao P, Tian J, Yang F, Duan X, Gao S, Shi W, Luo X, Cui F, Luo S, Wang S (2018) Identification and regulation of active sites on nanodiamonds: establishing a highly efficient catalytic system for oxidation of organic contaminants. Adv Funct Mater 28:1705295 https://doi-org.ez32.periodicos.capes.gov.br/10.1002/adfm.201705295
Shao P, Ding L, Luo J, Luo Y, You D, Zhang Q, Luo X (2019) Lattice-defect-enhanced adsorption of arsenic on zirconia nanospheres: a combined experimental and theoretical study. ACS Appl Mater 11:929736–929745. https://doi.org/10.1021/acsami.9b06041
Sun W, Zhou Y, Su Q, Chen L, Wang Y, Liu J, Sun Y, Ma H (2017) Removal of chromium(VI) from aqueous solutions using polypyrrole-based magnetic composites. Polym Bull 74:1157–1174. https://doi.org/10.1007/s00289-016-1769-1
Syafiuddin A, Salmiati S, Jonbi J, Fulazzaky MA (2018) Application of the kinetic and isotherm models for better understanding of the behaviors of silver nanoparticles adsorption onto different adsorbents. J Environ Manag 218:59–70. https://doi.org/10.1016/j.jenvman.2018.03.066
Tahmasebi E, Yamini Y, Seidi S, Rezazadeh M (2013) Extraction of three nitrophenols using polypyrrole-coated magnetic nanoparticles based on anion exchange process. J Chromatogr A 1314:15–23. https://doi.org/10.1016/j.chroma.2013.09.012
Tang S, Lan Q, Liang J, Chen S, Liu C, Zhao J, Cheng Q, Cao YC, Liu J (2017) Facile synthesis of Fe3O4@PPy core-shell magnetic nanoparticles and their enhanced dispersity and acid stability. Mater Des 121:47–50. https://doi.org/10.1016/j.matdes.2017.02.049
Vijayaraghavan K, Padmesh TVN, Palanivelu K, Velan M (2006) Biosorption of nickel(II) ions onto Sargassum wightii: application of two-parameter and three-parameter isotherm models. J Hazard Mater B 133:304–308. https://doi.org/10.1016/j.jhazmat.2005.10.016
Wang B, Hua Y, Ye Y, Chen R, Li Z (2017) Transparent superhydrophobic solar glass prepared by fabricating groove-shaped arrays on the surface. Appl Surf Sci 426:957–964. https://doi.org/10.1016/j.apsusc.2017.07.169
Yan L, Qin L, Yu H, Li S, Shan R, Du B (2015) Adsorption of acid dyes from aqueous solution by CTMAB modified bentonite: kinetic and isotherm modeling. J Mol Liq 211:1074–1781. https://doi.org/10.1016/j.molliq.2015.08.032
Yang GCC, Tang PL (2016) Removal of phthalates and pharmaceuticals from municipal wastewater by graphene adsorption process. Water Sci Technol 73:2268–2274. https://doi.org/10.2166/wst.2016.006
Yin X, Shao P, Ding L, Xi Y, Zhang K, Zang L, Shia H, Luo X (2019) Protonation of rhodanine polymers for enhancing the capture and recovery of Ag+ from highly acidic wastewater. Environ Sci Nano. https://doi.org/10.1039/C9EN00833K
Zhang L, Shao HP, Zheng H, Lin T, Guo ZM (2016) Synthesis and characterization of Fe3O4@SiO2 magnetic composite nanoparticles by a one-pot process. Int J Miner Metall Mater 23:1112–1118. https://doi.org/10.1007/s12613-016-1329-6
Zhao R, Yan Y, Li M, Yan H (2008) Selective adsorption of tea polyphenols from aqueous solution of the mixture with caffeine on macroporous crosslinked poly(N-vinyl-2-pyrrolidinone). React Funct Polym 68:768–774. https://doi.org/10.1016/j.reactfunctpolym.2007.11.016
Żółtowska-Aksamitowska S, Bartczak P, Zembrzuska J, Jesionowski T (2018) Removal of hazardous non-steroidal anti-inflammatory drugs from aqueous solutions by biosorbent based on chitin and lignin. Sci Total Environ 612:1223–1233. https://doi.org/10.1016/j.scitotenv.2017.09.037
Acknowledgments
Some Brazilian agencies contributed to this work, and the authors thank for their support: CNPq (Conselho Nacional de Desenvolvimento Científico e Tecnológico), FAPEMIG (Fundação de Amparo à Pesquisa do Estado de Minas Gerais), Rede Mineira de Química (RQ-MG) supported by FAPEMIG (Project: REDE-113/10; Project: CEX-RED-0010-14), and Universidade Federal de Juiz de Fora (UFJF).
Funding
This study was also financed in part by the Coordenação de Aperfeiçoamento de Pessoal de Nível Superior-Brasil (CAPES)-Finance Code 001.
Author information
Authors and Affiliations
Corresponding author
Ethics declarations
Conflict of interest
The authors declare that they have no conflicts of interest.
Additional information
Responsible editor: Tito Roberto Cadaval Jr
Publisher’s note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Electronic supplementary material
ESM 1
(DOCX 217 kb)
Rights and permissions
About this article
Cite this article
Pires, B.C., Dutra, F.V.A. & Borges, K.B. Synthesis of mesoporous magnetic polypyrrole and its application in studies of removal of acidic, neutral, and basic pharmaceuticals from aqueous medium. Environ Sci Pollut Res 27, 6488–6504 (2020). https://doi.org/10.1007/s11356-019-07207-2
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11356-019-07207-2


