Analytical and Bioanalytical Chemistry

, Volume 410, Issue 25, pp 6643–6651 | Cite as

Application of polyethyleneimine-modified attapulgite for the solid-phase extraction of chlorophenols at trace levels in environmental water samples

  • Mengsa Chai
  • Yihui Chen
  • Rongrong Xuan
  • Junfeng Ma
  • Zhenfeng Jin
  • Tingting WangEmail author
  • Dan Qiu
  • Lihua Zhang
  • Yukui Zhang
Research Paper


A polyethyleneimine (PEI)-modified attapulgite was employed as a new adsorbent for solid-phase extraction (SPE) of chlorophenols (CPs) from environmental water samples. Key factors pivotal to extraction efficiency, such as organic additive, pH, salt, sample loading volume, elution volume, and sample loading flow rate, were investigated. The maximum adsorption capacity of CPs reached 38 mg/g, and the adsorption behavior could be described with the Langmuir isotherm model. The developed SPE procedure was then tested on river water samples. Of this cartridge, 0.4 g could be used to treat up to 100 mL of the water sample, with high recoveries achieved. The limit of detection (S/N = 3) and the limit of quantification (S/N = 10) were in range of 0.08–0.56 and 0.27–1.88 ng/mL, respectively. The mean recoveries of CPs spiked in river water samples ranged from 84.4 to 96.8% with relative standard deviations for the intra-day and inter-day less than 6.30%. The developed SPE method exhibited high sensitivity, high selectivity, excellent accuracy, and good repeatability to the analysis of trace CPs in complicated aqueous matrices.

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Attapulgite Chlorophenols Environmental water samples Solid-phase extraction 



The project is supported by the National Natural Science Foundation of China (21405085), the Public Applied Research Programs of Technology of Zhejiang Province (2015C37015, LGN18B060002), the Zhejiang Provincial Natural Science Foundation of China (LQ12B05001), and the Key Laboratory of Separation Sciences for Analytical Chemistry, Dalian Institute of Chemical Physics, Chinese Academy of Sciences (KL-1701).

Compliance with ethical standards

Conflict of interest

The authors declare that they have no competing interests.


  1. 1.
    Yuan SF, Liu ZH, Lian HX, Yang CT, Lin Q, Yin H, et al. Fast trace determination of nine odorant and estrogenic chloro and bromo-phenolic compounds in real water samples through automated solid-phase extraction coupled with liquid chromatography tandem mass spectrometry. Environ Sci Pollut Res. 2018;25(4):3813–22.CrossRefGoogle Scholar
  2. 2.
    Santana CM, Padrón ME, Ferrera ZS, Rodríguez JJ. Development of a solid-phase microextraction method with micellar desorption for the determination of chlorophenols in water samples. Comparison with conventional solid-phase microextraction method. J Chromatogr A. 2007;1140(1–2):13–20.CrossRefPubMedGoogle Scholar
  3. 3.
    Michałowicz J, Duda W. Phenols-sources and toxicity. Pol J Environ Stud. 2007;16(3):347–62.Google Scholar
  4. 4.
    Guo F, Liu Q, Shi JB, Wei FS, Jiang GB. Direct analysis of eight chlorophenols in urine by large volume injection online turbulent flow solid-phase extraction liquid chromatography with multiple wavelength ultraviolet detection. Talanta. 2014;119:396–400.CrossRefPubMedGoogle Scholar
  5. 5.
    Crespin MA, Gallego M, Valcarcel M. Solid-phase extraction method for the determination of free and conjugated phenol compounds in human urine. J Chromatogr B. 2002;773(2):89–96.CrossRefGoogle Scholar
  6. 6.
    Ben Hassine S, Hammami B, Touil S, Driss MR. Determination of chlorophenols in water samples using solid-phase extraction enrichment procedure and gas chromatography analysis. Bull Environ Contam Toxicol. 2015;95(5):654–60.CrossRefPubMedGoogle Scholar
  7. 7.
    Insa S, Salvadó V, Antió E. Development of solid-phase extraction and solid-phase microextraction methods for the determination of chlorophenols in cork macerate and wine samples. J Chromatogr A. 2004;1047(1):15–20.CrossRefPubMedGoogle Scholar
  8. 8.
    Luo YB, Zhu GT, Li XS, Yuan BF, Feng YQ. Facile fabrication of reduced graphene oxide-encapsulated silica: a sorbent for solid-phase extraction. J Chromatogr A. 2013;1299:10–7.CrossRefPubMedGoogle Scholar
  9. 9.
    Cai YQ, Cai YE, Mou SF, Lu YQ. Multi-walled carbon nanotubes as a solid-phase extraction adsorbent for the determination of chlorophenols in environmental water samples. J Chromatogr A. 2005;1081(2):245–7.CrossRefPubMedGoogle Scholar
  10. 10.
    Fattahi N, Assadi Y, Hosseini MR, Jahromi EZ. Determination of chlorophenols in water samples using simultaneous dispersive liquid-liquid microextraction and derivatization followed by gas chromatography-electron-capture detection. J Chromatogr A. 2007;1157(1–2):23–9.CrossRefPubMedGoogle Scholar
  11. 11.
    Moradi M, Yamini Y, Esrafili A, Seidi S. Application of surfactant assisted dispersive liquid-liquid microextraction for sample preparation of chlorophenols in water samples. Talanta. 2010;82(5):1864–9.CrossRefPubMedGoogle Scholar
  12. 12.
    Meng WK, Liu L, Wang X, Zhao RS, Wang ML, Lin JM. Polyphenylene core-conjugated microporous polymer coating for highly sensitive solid-phase microextraction of polar phenol compounds in water samples. Anal Chim Acta. 2018;1015:27–34.CrossRefPubMedGoogle Scholar
  13. 13.
    Li QL, Huang F, Wang XL, Wang X, Zhao RS. Multiple-helix cobalt(II)-based metal-organic nanotubes on stainless steel fibers for solid-phase microextraction of chlorophenol and nitrophenols from water samples. Microchim Acta. 2017;184(6):1817–25.CrossRefGoogle Scholar
  14. 14.
    Gong SX, Wang X, Chen Y, Cheng CG, Wang ML, Zhao RS. Carboxylated solid carbon spheres as a novel solid-phase microextraction coating for sensitive determination of phenols in environmental water samples. J Chromatogr A. 2015;1401:17–23.CrossRefPubMedGoogle Scholar
  15. 15.
    Wang X, Wang H, Huang P, Ma X, Lu X. Du X. Preparation of three-dimensional mesoporous polymer in situ polymerization solid phase microextraction fiber and its application to the determination of seven chlorophenols. J Chromatogr A. 2017;1479:40–7.CrossRefPubMedGoogle Scholar
  16. 16.
    Cheng Q, Qu F, Li NB, Luo HQ. Mixed hemimicelles solid-phase extraction of chlorophenols in environmental water samples with 1-hexadecyl-3- methylimidazolium bromide-coated Fe3O4 magnetic nanoparticles with high-performance liquid chromatographic analysis. Anal Chim Acta. 2012;715:113–9.CrossRefPubMedGoogle Scholar
  17. 17.
    Rouvière F, Buleté A, Cren-Olivé C, Arnaudguilhem C. Multiresidue analysis of aromatic organochlorines in soil by gas chromatography-mass spectrometry and QuEChERS extraction based on water/dichloromethane partitioning. Comparison with accelerated solvent extraction. Talanta. 2012;93:336–44.CrossRefPubMedGoogle Scholar
  18. 18.
    Lu W, Ming W, Zhang X, Chen L. Molecularly imprinted polymers for dispersive solid-phase extraction of phenolic compounds in aqueous samples coupled with capillary electrophoresis. Electrophoresis. 2016;37(19):2487–95.CrossRefPubMedGoogle Scholar
  19. 19.
    Feng QZ, Zhao LX, Yan W, Lin JM, Zheng ZX. Molecularly imprinted solid-phase extraction combined with high performance liquid chromatography for analysis of phenolic compounds from environmental water samples. J Hazard Mater. 2009;167(1–3):282–8.CrossRefPubMedGoogle Scholar
  20. 20.
    Sirvent G, Hidalgo M, Salvadó V. Evaluation of a new solid-phase cartridge for the preconcentration of phenolic compounds in water. J Sep Sci. 2004;27(7–8):613–8.CrossRefPubMedGoogle Scholar
  21. 21.
    Lu W, Wang X, Wu X, Liu D, Li J, Chen L, et al. Multi-template imprinted polymers for simultaneous selective solid-phase extraction of six phenolic compounds in water samples followed by determination using capillary electrophoresis. J Chromatogr A. 2017;1483:30–9.CrossRefPubMedGoogle Scholar
  22. 22.
    Liu Q, Shi J, Zeng L, Wang T, Cai Y, Jiang G. Evaluation of graphene as an advantageous adsorbent for solid-phase extraction with chlorophenols as model analytes. J Chromatogr A. 2011;1218(2):197–204.CrossRefPubMedGoogle Scholar
  23. 23.
    Liu Q, Shi J, Sun J, Wang T, Zeng L, Jiang G. Graphene and graphene oxide sheets supported on silica as versatile and high-performance adsorbents for solid-phase extraction. Angew Chem. 2011;50(26):5913–7.CrossRefGoogle Scholar
  24. 24.
    Alvarez-Ayuso E, García-Sánchez A. Removal of cadmium from aqueous solutions by palygorskite. J Hazard Mater. 2007;147(1–2):594–600.CrossRefPubMedGoogle Scholar
  25. 25.
    Chang Y, Liu HW, Zha F, Chen HK, Ren XN, Lei ZQ. Adsorption of Pb(II) by N-methylimidazole modified palygorskite. Chem Eng J. 2011;167(1):183–9.CrossRefGoogle Scholar
  26. 26.
    Wang H, Wang X, Ma J, Xia P, Zhao J. Removal of cadmium (II) from aqueous solution: a comparative study of raw attapulgite clay and a reusable waste-struvite/attapulgite obtained from nutrient-rich wastewater. J Hazard Mater. 2017;329:66–76.CrossRefPubMedGoogle Scholar
  27. 27.
    Xue A, Zhou S, Zhao Y, Lu X, Han P. Effective NH2-grafting on attapulgite surfaces for adsorption of reactive dyes. J Hazard Mater. 2011;194:7–14.CrossRefPubMedGoogle Scholar
  28. 28.
    Huang J, Liu Y, Wang X. Selective adsorption of tannin from flavonoids by organically modified attapulgite clay. J Hazard Mater. 2008;160(2–3):382–7.CrossRefPubMedGoogle Scholar
  29. 29.
    Yang M, Xi X, Wu X, Lu R, Zhou W, Zhang S, et al. Vortex-assisted magnetic β-cyclodextrin/attapulgite-linked ionic liquid dispersive liquid-liquid microextraction coupled with high-performance liquid chromatography for the fast determination of four fungicides in water samples. J Chromatogr A. 2015;1381:37–47.CrossRefPubMedGoogle Scholar
  30. 30.
    Cui X, Zhang P, Yang X, Yang M, Zhou W, Zhang S, et al. β-CD/ATP composite materials for use in dispersive solid-phase extraction to measure (fluoro)quinolone antibiotics in honey samples. Anal Chim Acta. 2015;878:131–9.CrossRefPubMedGoogle Scholar
  31. 31.
    Chu G, Cai W, Shao X. Preparation of 4-butylaniline-bonded attapulgite for pre-concentration of bisphenol A in trace quantity. Talanta. 2015;136:29–34.CrossRefPubMedGoogle Scholar
  32. 32.
    Wang TT, Chen YH, Ma JF, Jin ZF, Chai MS, Xiao XW, et al. A polyethyleneimine-modified attapulgite as a novel solid support in matrix solid-phase dispersion for the extraction of cadmium traces in seafood products. Talanta. 2018;180:254–9.CrossRefPubMedGoogle Scholar
  33. 33.
    Wang TT, Xuan RR, Ma JF, Tan Y, Jin ZF, Chen YH, et al. Using activated attapulgite as sorbent for solid-phase extraction of melamine in milk formula samples. Anal Bioanal Chem. 2016;408(24):6671–7.CrossRefPubMedGoogle Scholar
  34. 34.
    Jandera P. Stationary and mobile phases in hydrophilic interaction chromatography: a review. Anal Chim Acta. 2011;692:1–2): 1–25.CrossRefPubMedGoogle Scholar
  35. 35.
    Frenich AG, Romero-González R, Gómez-Pérez ML, Martínez Vidal JL. Multi-mycotoxin analysis in eggs using a QuEChERS-based extraction procedure and ultra-high-pressure liquid chromatography coupled to triple quadrupole mass spectrometry. J Chromatogr A. 2011;1218(28):4349–56.CrossRefPubMedGoogle Scholar
  36. 36.
    Basheer C, Chong HG, Hii TM, Lee HK. Application of porous membrane-protected micro-solid-phase extraction combined with HPLC for the analysis of acidic drugs in wastewater. Anal Chem. 2007;79(17):6845–50.CrossRefPubMedGoogle Scholar

Copyright information

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

Authors and Affiliations

  • Mengsa Chai
    • 1
  • Yihui Chen
    • 2
  • Rongrong Xuan
    • 3
  • Junfeng Ma
    • 4
  • Zhenfeng Jin
    • 1
  • Tingting Wang
    • 1
    Email author
  • Dan Qiu
    • 1
  • Lihua Zhang
    • 5
  • Yukui Zhang
    • 5
  1. 1.School of Materials and Chemical EngineeringNingbo University of TechnologyNingboChina
  2. 2.Xiangshan Entry-Exit Inspection and Quarantine BureauXiangshanChina
  3. 3.Obstetrical DepartmentAffiliated Hospital of Medical School Ningbo University and Ningbo City Third HospitalNingboChina
  4. 4.Proteomics and Metabolomics Shared ResourceGeorgetown University Medical CenterWashingtonUSA
  5. 5.Key Laboratory of Separation Science for Analytical Chemistry, National Chromatographic Research and Analysis Center, Dalian Institute of Chemical PhysicsChinese Academy of SciencesDalianChina

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