Advertisement

Environmental Science and Pollution Research

, Volume 25, Issue 36, pp 36724–36735 | Cite as

Synthesis of a molecularly imprinted polymer and its application in selective extraction of fenoprofen from wastewater

  • Zama Emmaculate Mbhele
  • Somandla Ncube
  • Lawrence Mzukisi Madikizela
Research Article
  • 102 Downloads

Abstract

The presence of various classes of pharmaceutical drugs in different environmental compartments has been reported worldwide. In South Africa, the detection of pharmaceuticals especially the non-steroidal anti-inflammatory drugs is recent, and more studies are being done in order to fully understand their fate in the aquatic environment. With considerations for the need of better sample preparation techniques, this study synthesized a molecularly imprinted polymer for the selective extraction of a non-steroidal anti-inflammatory drug, fenoprofen in aqueous environmental samples. Batch adsorption studies showed that adsorption of fenoprofen onto the cavities of the polymer followed a Langmuir isotherm as well as a pseudo second order model implying formation of a monolayer on the surface through chemisorption. The polymer had a maximum adsorption capacity of 38.8 mg g−1 and a Langmuir surface area of 1607 m2 g−1. The imprinted polymer was then used as the selective sorbent for solid phase extraction in the analysis of fenoprofen from wastewater followed by chromatographic determination. The analytical method gave a detection limit of 0.64 ng mL−1 and recovery of 99.6%. The concentration of fenoprofen detected in influent and effluent samples from two wastewater treatment plants ranged from 24 to 58 ng mL−1. The ability of the treatment plants to remove fenoprofen during wastewater processing based on the difference in concentrations in influent and effluent samples was found to be 41%. This work has shown that there is a possibility of release of fenoprofen from wastewater treatment plants into surface water sources.

Keywords

Molecularly imprinted polymer Fenoprofen Wastewater Selective solid-phase extraction 

Abbreviations

EGDMA

ethylene glycol dimethacrylate

MISPE

molecularly imprinted solid-phase extraction

MIP

molecularly imprinted polymer

NIP

non-imprinted polymer

NSAIDs

non-steroidal anti-inflammatory drugs

SPE

solid-phase extraction

WWTP

wastewater treatment plant

Notes

Funding

This work was financially supported by National Research Foundation of South Africa (Grant Number: 114415).

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.

References

  1. Agunbiade FO, Moodley B (2014) Pharmaceuticals as emerging organic contaminants in Umgeni River water system, KwaZulu-Natal, South Africa. Environ Monit Assess 186:7273–7291.  https://doi.org/10.1007/s10661-014-3926-z CrossRefGoogle Scholar
  2. Agunbiade FO, Moodley B (2016) Occurrence and distribution pattern of acidic pharmaceuticals in surface water, wastewater, and sediment of the Msunduzi River, Kwazulu-Natal, South Africa. Environ Toxicol Chem 35:36–46.  https://doi.org/10.1002/etc.3144 CrossRefGoogle Scholar
  3. Amdany R, Chimuka L, Cukrowska E (2014) Determination of naproxen, ibuprofen and triclosan in wastewater using the polar organic chemical integrative sampler (POCIS): a laboratory calibration and field application. Water SA 40:407–414.  https://doi.org/10.4314/wsa.v40i3.3 CrossRefGoogle Scholar
  4. Amdany R, Moya A, Cukrowska E, Chimuka L (2015) Optimization of the temperature for the extraction of pharmaceuticals from wastewater by a hollow fiber silicone membrane. Anal Lett 48:2343–2356.  https://doi.org/10.1080/00032719.2015.1033722 CrossRefGoogle Scholar
  5. Ashfaq M, Li Y, Wang Y, Chen W, Wang H, Chen X, Wu W, Huang Z, Yu CP, Sun Q (2017) Occurrence, fate, and mass balance of different classes of pharmaceuticals and personal care products in an anaerobic-anoxic-oxic wastewater treatment plant in Xiamen, China. Water Res 123:655–667.  https://doi.org/10.1016/j.watres.2017.07.014 CrossRefGoogle Scholar
  6. Biel-Maeso M, Corada-Fernández C, Lara-Martín PA (2017) Determining the distribution of pharmaceutically active compounds (PhACs) in soils and sediments by pressurized hot water extraction (PHWE). Chemosphere 185:1001–1010.  https://doi.org/10.1016/j.chemosphere.2017.07.094 CrossRefGoogle Scholar
  7. Bolster CH, Hornberger GM (2007) On the use of linearized Langmuir equations. Soil Sci Soc Am J 71:1796–1806.  https://doi.org/10.2136/sssaj2006.0304 CrossRefGoogle Scholar
  8. Byun H-S, Youn Y-N, Yun Y-H, Yoon S-D (2010) Selective separation of aspirin using molecularly imprinted polymers. Sep Purif Technol 74:144–153.  https://doi.org/10.1016/j.seppur.2010.05.017 CrossRefGoogle Scholar
  9. Chen L, Xu S, Li J (2011) Recent advances in molecular imprinting technology: current status, challenges and highlighted applications. Chem Soc Rev Chem Soc Rev 40:2922–2942.  https://doi.org/10.1039/c0cs00084a CrossRefGoogle Scholar
  10. Dai CM, Zhou XF, Zhang YL, Liu SG, Zhang J (2011) Synthesis by precipitation polymerization of molecularly imprinted polymer for the selective extraction of diclofenac from water samples. J Hazard Mater 198:175–181.  https://doi.org/10.1016/j.jhazmat.2011.10.027 CrossRefGoogle Scholar
  11. Dawod M, Breadmore MC, Guijt RM, Haddad PR (2008) Electrokinetic supercharging for on-line preconcentration of seven non-steroidal anti-inflammatory drugs in water samples. J Chromatogr A 1189:278–284.  https://doi.org/10.1016/j.chroma.2007.12.056 CrossRefGoogle Scholar
  12. Dorne JLCM, Ragas AMJ, Frampton GK, Spurgeon DS, Lewis DF (2007) Trends in human risk assessment of pharmaceuticals. Anal Bioanal Chem 387:1167–1172.  https://doi.org/10.1007/s00216-006-0961-9 CrossRefGoogle Scholar
  13. Duan YP, Dai CM, Zhang YL, Ling-Chen (2013) Selective trace enrichment of acidic pharmaceuticals in real water and sediment samples based on solid-phase extraction using multi-templates molecularly imprinted polymers. Anal Chim Acta 758:93–100.  https://doi.org/10.1016/j.aca.2012.11.010 CrossRefGoogle Scholar
  14. Farrington K, Regan F (2007) Investigation of the nature of MIP recognition: the development and characterisation of a MIP for ibuprofen. Biosens Bioelectron 22:1138–1146.  https://doi.org/10.1016/j.bios.2006.06.025 CrossRefGoogle Scholar
  15. Figueiredo L, Erny GL, Santos L, Alves A (2016) Applications of molecularly imprinted polymers to the analysis and removal of personal care products: a review. Talanta 146:754–765.  https://doi.org/10.1016/j.talanta.2015.06.027 CrossRefGoogle Scholar
  16. Foguel MV, Pedro NTB, Wong A, Khan S, Zanoni MVB, Sotomayor MPT (2017) Synthesis and evaluation of a molecularly imprinted polymer for selective adsorption and quantification of acid green 16 textile dye in water samples. Talanta 170:244–251.  https://doi.org/10.1016/j.talanta.2017.04.013 CrossRefGoogle Scholar
  17. Gama MR, Bottoli CBG (2017) Molecularly imprinted polymers for bioanalytical sample preparation. J Chromatogr B 1043:107–121.  https://doi.org/10.1016/j.jchromb.2016.09.045 CrossRefGoogle Scholar
  18. Gilart N, Marcé RM, Fontanals N, Borrull F (2013) A rapid determination of acidic pharmaceuticals in environmental waters by molecularly imprinted solid-phase extraction coupled to tandem mass spectrometry without chromatography. Talanta 110:196–201.  https://doi.org/10.1016/j.talanta.2013.02.039 CrossRefGoogle Scholar
  19. Gumbi BP, Moodley B, Birungi G, Ndungu PG (2017) Detection and quantification of acidic drug residues in South African surface water using gas chromatography-mass spectrometry. Chemosphere 168:1042–1050.  https://doi.org/10.1016/j.chemosphere.2016.10.105 CrossRefGoogle Scholar
  20. He C, Long Y, Pan J, Li K, Liu F (2007) Application of molecularly imprinted polymers to solid-phase extraction of analytes from real samples. J Biochem Biophys Methods 70:133–150.  https://doi.org/10.1016/j.jbbm.2006.07.005 CrossRefGoogle Scholar
  21. Hoshina K, Horiyama S, Matsunaga H, Haginaka J (2011) Simultaneous determination of non-steroidal anti-inflammatory drugs in river water samples by liquid chromatography-tandem mass spectrometry using molecularly imprinted polymers as a pretreatment column. J Pharm Biomed Anal 55:916–922.  https://doi.org/10.1016/j.jpba.2011.03.014 CrossRefGoogle Scholar
  22. Jux U, Baginski RM, Arnold H-G, Krönke M, Seng PN (2002) Detection of pharmaceutical contaminations of river, pond, and tap water from Cologne (Germany) and surroundings. Int J Hyg Environ Health 205:393–398.  https://doi.org/10.1078/1438-4639-00166 CrossRefGoogle Scholar
  23. Kolodzik JM, Eilers MA, Angelos MG (1990) Nonsteroidal anti-inflammatory drugs and coma: a case report of fenoprofen overdose. Ann Emerg Med 19:378–381.  https://doi.org/10.1016/S0196-0644(05)82339-X CrossRefGoogle Scholar
  24. Kubo T, Otsuka K (2016) Recent progress for the selective pharmaceutical analyses using molecularly imprinted adsorbents and their related techniques: a review. J Pharm Biomed Anal 130:68–80.  https://doi.org/10.1016/j.jpba.2016.05.044 CrossRefGoogle Scholar
  25. Li WC (2014) Occurrence, sources, and fate of pharmaceuticals in aquatic environment and soil. Environ Pollut 187:193–201.  https://doi.org/10.1016/j.envpol.2014.01.015 CrossRefGoogle Scholar
  26. Madikizela LM, Chimuka L (2016) Determination of ibuprofen, naproxen and diclofenac in aqueous samples using a multi-template molecularly imprinted polymer as selective adsorbent for solid-phase extraction. J Pharm Biomed Anal 128:210–215.  https://doi.org/10.1016/j.jpba.2016.05.037 CrossRefGoogle Scholar
  27. Madikizela LM, Chimuka L (2017a) Simultaneous determination of naproxen, ibuprofen and diclofenac in wastewater using solid-phase extraction with high performance liquid chromatography. Water SA 43:264–274.  https://doi.org/10.4314/wsa.v43i2.10 CrossRefGoogle Scholar
  28. Madikizela LM, Chimuka L (2017b) Occurrence of naproxen, ibuprofen, and diclofenac residues in wastewater and river water of KwaZulu-Natal Province in South Africa. Environ Monit Assess 189:348.  https://doi.org/10.1007/s10661-017-6069-1 CrossRefGoogle Scholar
  29. Madikizela LM, Muthwa SF, Chimuka L (2014) Determination of triclosan and ketoprofen in river water and wastewater by solid phase extraction and high performance liquid chromatography. S Afr J Chem 67:143–150Google Scholar
  30. Madikizela LM, Tavengwa NT, Chimuka L (2017) Status of pharmaceuticals in African water bodies: occurrence, removal and analytical methods. J Environ Manag 193:211–220.  https://doi.org/10.1016/j.jenvman.2017.02.022 CrossRefGoogle Scholar
  31. Madikizela LM, Tavengwa NT, Chimuka L (2018) Applications of molecularly imprinted polymers for solid-phase extraction of non-steroidal anti-inflammatory drugs and analgesics from environmental waters and biological samples. J Pharm Biomed Anal 147:624–633CrossRefGoogle Scholar
  32. Manzo V, Ulisse K, Rodríguez I, Pereira E, Richter P (2015) A molecularly imprinted polymer as the sorptive phase immobilized in a rotating disk extraction device for the determination of diclofenac and mefenamic acid in wastewater. Anal Chim Acta 889:130–137.  https://doi.org/10.1016/j.aca.2015.07.038 CrossRefGoogle Scholar
  33. Marchese D, Perret D, Gentili A, Curini RPF (2003) Determination of non-steroidal anti-inflammatory drugs in surface water and wastewater by liquid chromatography-tandem mass spectrometry. Chromatographia 58:263–269.  https://doi.org/10.1365/s10337-003-0052-4 CrossRefGoogle Scholar
  34. Martinez-Sena T, Armenta S, de la Guardia M, Esteve-Turrillas FA (2016) Determination of non-steroidal anti-inflammatory drugs in water and urine using selective molecular imprinted polymer extraction and liquid chromatography. J Pharm Biomed Anal 131:48–53.  https://doi.org/10.1016/j.jpba.2016.08.006 CrossRefGoogle Scholar
  35. Matongo S, Birungi G, Moodley B, Ndungu P (2015a) Occurrence of selected pharmaceuticals in water and sediment of Umgeni River, KwaZulu-Natal, South Africa. Environ Sci Pollut Res 22:10298–10308.  https://doi.org/10.1007/s11356-015-4217-0 CrossRefGoogle Scholar
  36. Matongo S, Birungi G, Moodley B, Ndungu P (2015b) Pharmaceutical residues in water and sediment of Msunduzi River, KwaZulu-Natal, South Africa. Chemosphere 134:133–140.  https://doi.org/10.1016/j.chemosphere.2015.03.093 CrossRefGoogle Scholar
  37. Meischl F, Schemeth D, Harder M, Köpfle N, Tessadri R, Rainer M (2016) Synthesis and evaluation of a novel molecularly imprinted polymer for the selective isolation of acetylsalicylic acid from aqueous solutions. J Environ Chem Eng 4:4083–4090.  https://doi.org/10.1016/j.jece.2016.09.013 CrossRefGoogle Scholar
  38. Miao X-S, Koenig BG, Metcalfe CD (2002) Analysis of acidic drugs in the effluents of sewage treatment plants using liquid chromatography–electrospray ionization tandem mass spectrometry. J Chromatogr A 952:139–147.  https://doi.org/10.1016/S0021-9673(02)00088-2 CrossRefGoogle Scholar
  39. Nakada N, Tanishima T, Shinohara H, Kiri K, Takada H (2006) Pharmaceutical chemicals and endocrine disrupters in municipal wastewater in Tokyo and their removal during activated sludge treatment. Water Res 40:3297–3303.  https://doi.org/10.1016/j.watres.2006.06.039 CrossRefGoogle Scholar
  40. Ncube S, Kunene P, Tavengwa NT, Tutu H, Richards H, Cukrowska E, Chimuka L (2017) Synthesis and characterization of a molecularly imprinted polymer for the isolation of the 16 US-EPA priority polycyclic aromatic hydrocarbons (PAHs) in solution. J Environ Manag 199:192–200.  https://doi.org/10.1016/j.jenvman.2017.05.041 CrossRefGoogle Scholar
  41. Patrolecco L, Ademollo N, Grenni P, Tolomei A, Barra Caracciolo A, Capri S (2013) Simultaneous determination of human pharmaceuticals in water samples by solid phase extraction and HPLC with UV-fluorescence detection. Microchem J 107:165–171.  https://doi.org/10.1016/j.microc.2012.05.035 CrossRefGoogle Scholar
  42. Patsias J, Papadopoulou-Mourkidou E (2000) Development of an automated on-line solid-phase extraction-high-performance liquid chromatographic method for the analysis of aniline, phenol, caffeine and various selected substituted aniline and phenol compounds in aqueous matrices. J Chromatogr A 904:171–188.  https://doi.org/10.1016/S0021-9673(00)00927-4 CrossRefGoogle Scholar
  43. Qiao F, Sun H, Yan H, Row KH (2006) Molecularly imprinted polymers for solid phase extraction. Chromatographia 64:625–634.  https://doi.org/10.1365/s10337-006-0097-2 CrossRefGoogle Scholar
  44. Quintana JB, Rodil R, Reemtsma T (2004) Suitability of hollow fibre liquid-phase microextraction for the determination of acidic pharmaceuticals in wastewater by liquid chromatography-electrospray tandem mass spectrometry without matrix effects. J Chromatogr A 1061:19–26.  https://doi.org/10.1016/j.chroma.2004.10.090 CrossRefGoogle Scholar
  45. Quintana JB, Rodil R, Muniategui-Lorenzo S, López-Mahía P, Prada-Rodríguez D (2007) Multiresidue analysis of acidic and polar organic contaminants in water samples by stir-bar sorptive extraction-liquid desorption-gas chromatography-mass spectrometry. J Chromatogr A 1174:27–39.  https://doi.org/10.1016/j.chroma.2007.07.088 CrossRefGoogle Scholar
  46. Rodil R, Quintana JB, López-Mahía P, Muniategui-Lorenzo S, Prada-Rodríguez D (2009) Multi-residue analytical method for the determination of emerging pollutants in water by solid-phase extraction and liquid chromatography-tandem mass spectrometry. J Chromatogr A 1216:2958–2969.  https://doi.org/10.1016/j.chroma.2008.09.041 CrossRefGoogle Scholar
  47. Simazaki D, Fujiwara J, Manabe S et al (2008) Removal of selected pharmaceuticals by chlorination, coagulation–sedimentation and powdered activated carbon treatment. Water Sci Technol 58:1129 LP–1121135CrossRefGoogle Scholar
  48. Song YP, Li N, Zhang HC, Wang GN, Liu JX, Liu J, Wang JP (2017) Dummy template molecularly imprinted polymer for solid phase extraction of phenothiazines in meat based on computational simulation. Food Chem 233:422–428.  https://doi.org/10.1016/j.foodchem.2017.04.146 CrossRefGoogle Scholar
  49. Sun Z, Schüssler W, Sengl M, Niessner R, Knopp D (2008) Selective trace analysis of diclofenac in surface and wastewater samples using solid-phase extraction with a new molecularly imprinted polymer. Anal Chim Acta 620:73–81.  https://doi.org/10.1016/j.aca.2008.05.020 CrossRefGoogle Scholar
  50. Sun Q, Lv M, Hu A, Yang X, Yu CP (2014) Seasonal variation in the occurrence and removal of pharmaceuticals and personal care products in a wastewater treatment plant in Xiamen, China. J Hazard Mater 277:69–75.  https://doi.org/10.1016/j.jhazmat.2013.11.056 CrossRefGoogle Scholar
  51. Sun Q, Li Y, Li M, Ashfaq M, Lv M, Wang H, Hu A, Yu CP (2016) PPCPs in Jiulong River estuary (China): spatiotemporal distributions, fate, and their use as chemical markers of wastewater. Chemosphere 150:596–604.  https://doi.org/10.1016/j.chemosphere.2016.02.036 CrossRefGoogle Scholar
  52. Tahmasebi Z, Davarani SSH, Asgharinezhad AA (2016) An efficient approach to selective electromembrane extraction of naproxen by means of molecularly imprinted polymer-coated multi-walled carbon nanotubes-reinforced hollow fibers. J Chromatogr A 1470:19–26.  https://doi.org/10.1016/j.chroma.2016.09.067 CrossRefGoogle Scholar
  53. Tran NH, Gin KYH (2017) Occurrence and removal of pharmaceuticals, hormones, personal care products, and endocrine disrupters in a full-scale water reclamation plant. Sci Total Environ 599–600:1503–1516.  https://doi.org/10.1016/j.scitotenv.2017.05.097 CrossRefGoogle Scholar
  54. Tran NH, Hu J, Ong SL (2013) Simultaneous determination of PPCPs, EDCs, and artificial sweeteners in environmental water samples using a single-step SPE coupled with HPLC-MS/MS and isotope dilution. Talanta 113:82–92.  https://doi.org/10.1016/j.talanta.2013.03.072 CrossRefGoogle Scholar
  55. Tran NH, You S, Hosseini-bandegharaei A, Chao H-P (2017) Mistakes and inconsistencies regarding adsorption of contaminants from aqueous solutions: a critical review. Water Res 120:88–116.  https://doi.org/10.1016/j.watres.2017.04.014 CrossRefGoogle Scholar
  56. Urase T, Kagawa C, Kikuta T (2005) Factors affecting removal of pharmaceutical substances and estrogens in membrane separation bioreactors. Desalination 178:107–113.  https://doi.org/10.1016/j.desal.2004.11.031 CrossRefGoogle Scholar
  57. Verenitch SS, Lowe CJ, Mazumder A (2006) Determination of acidic drugs and caffeine in municipal wastewaters and receiving waters by gas chromatography-ion trap tandem mass spectrometry. J Chromatogr A 1116:193–203.  https://doi.org/10.1016/j.chroma.2006.03.005 CrossRefGoogle Scholar
  58. Yang Y, Ok YS, Kim K-H, Kwon EE, Tsang YF (2017) Occurrences and removal of pharmaceuticals and personal care products (PPCPs) in drinking water and water/sewage treatment plants: a review. Sci Total Environ 596–597:303–320.  https://doi.org/10.1016/j.scitotenv.2017.04.102 CrossRefGoogle Scholar
  59. Zhang J, Li F, Wang XH, Xu D, Huang YP, Liu ZS (2016) Preparation and characterization of dual-template molecularly imprinted monolith with metal ion as pivot. Eur Polym J 80:134–144.  https://doi.org/10.1016/j.eurpolymj.2016.05.009 CrossRefGoogle Scholar
  60. Zhao L, Ban L, Zhang QW, Huang YP, Liu ZS (2011) Preparation and characterization of imprinted monolith with metal ion as pivot. J Chromatogr A 1218:9071–9079.  https://doi.org/10.1016/j.chroma.2011.10.027 CrossRefGoogle Scholar
  61. Zhu H, Xu J, Varlashkin P, Long S, Kidd C (2001) Dehydration, hydration behavior, and structural analysis of fenoprofen calcium. J Pharm Sci 90:845–859.  https://doi.org/10.1002/jps.1038 CrossRefGoogle Scholar
  62. Zorita S, Boyd B, Jönsson S, Yilmaz E, Svensson C, Mathiasson L, Bergström S (2008) Selective determination of acidic pharmaceuticals in wastewater using molecularly imprinted solid-phase extraction. Anal Chim Acta 626:147–154.  https://doi.org/10.1016/j.aca.2008.07.051 CrossRefGoogle Scholar
  63. Zorita S, Mårtensson L, Mathiasson L (2009) Occurrence and removal of pharmaceuticals in a municipal sewage treatment system in the south of Sweden. Sci Total Environ 407:2760–2770.  https://doi.org/10.1016/j.scitotenv.2008.12.030 CrossRefGoogle Scholar
  64. Zunngu SS, Madikizela LM, Chimuka L, Mdluli PS (2017) Synthesis and application of a molecularly imprinted polymer in the solid-phase extraction of ketoprofen from wastewater. C R Chim 20:585–591.  https://doi.org/10.1016/j.crci.2016.09.006 CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  • Zama Emmaculate Mbhele
    • 1
  • Somandla Ncube
    • 2
  • Lawrence Mzukisi Madikizela
    • 1
  1. 1.Department of ChemistryDurban University of TechnologyDurbanSouth Africa
  2. 2.Department of ChemistryUniversity of South AfricaFloridaSouth Africa

Personalised recommendations