Skip to main content
SpringerLink
Log in

Using activated attapulgite as sorbent for solid-phase extraction of melamine in milk formula samples

  • Research Paper
  • Published:
Analytical and Bioanalytical Chemistry Aims and scope Submit manuscript

Abstract

In this study, a simple solid-phase extraction (SPE) approach by using activated attapulgite as sorbent was successfully developed for the determination of melamine in milk formula samples. Crucial factors impacting the extraction efficiency, including sample solvent, elution solvent, and sample loading volume, were investigated. Under the optimal extraction conditions, the sample loading volume was up to 200 mL and the adsorption capacity of the melamine gave rise to 1154 μg g−1. Excellent linear calibration curves (r 2 > 0.999) were achieved, and then the limit of detection (S/N = 3) and the limit of quantification (S/N = 10) were found to be 0.15 and 0.5 ng mL−1, respectively. The recoveries of the melamine spiked in four milk formula samples at three concentration levels ranged from 83.5 to 111.0 % with relative standard deviations (RSDs) less than 10.2 %. Furthermore, RSDs of batch to batch (n = 4) of the acidified attapulgite used in this developed method were in the range of 2.3∼7.3 %. In comparison to the commercial Oasis MCX, the acidified attapulgite sorbent even outperformed (at least in terms of reproducibility) for melamine analysis in real food samples. Because of its simplicity, the newly developed SPE method based on acidified attapulgite nanoparticles should provide a promising tool for daily monitoring of doped melamine in milk formula or other complex matrices.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5

Similar content being viewed by others

References

  1. Xu XM, Ren YP, Zhu Y, Cai ZX, Han JL, Huang BF, et al. Direct determination of melamine in dairy products by gas chromatography/mass spectrometry with coupled column separation. Anal Chim Acta. 2009;650:39–43.

    Article  CAS  Google Scholar 

  2. Xia X, Ding S, Li X, Gong X, Zhang S, Jiang H, et al. Validation of a confirmatory method for the determination of melamine in egg by gas chromatography-mass spectrometry and ultra-performance liquid chromatography-tandem mass spectrometry. Anal Chim Acta. 2009;651:196–00.

    Article  CAS  Google Scholar 

  3. Sun H, Wang L, Ai L, Liang S, Wu H. A sensitive and validated method for determination of melamine residue in liquid milk by reversed phase high-performance liquid chromatography with solid-phase extraction. Food Control. 2010;21:686–91.

    Article  CAS  Google Scholar 

  4. Zhang H, Zhang Z, Hu Y, Yang X, Yao S. Synthesis of a novel composite imprinted material based on multiwalled carbon nanotubes as a selective melamine absorbent. J Agric Food Chem. 2011;59:1063–71.

    Article  CAS  Google Scholar 

  5. Cheng W, Liu Z, Wang Y. Preparation and application of surface molecularly imprinted silica gel for selective extraction of melamine from milk samples. Talanta. 2013;116:396–02.

    Article  CAS  Google Scholar 

  6. He L, Su Y, Zheng Y, Huang X, Wu L, Liu Y, et al. Novel cyromazine imprinted polymer applied to the solid-phase extraction of melamine from feed and milk samples. J Chromatogr A. 2009;1216:6196–03.

    Article  CAS  Google Scholar 

  7. Wang T, Zhu Y, Ma J, Xuan R, Gao H, Liang Z, et al. Hydrophilic solid-phase extraction of melamine with ampholine-modified hybrid organic-inorganic silica material. J Sep Sci. 2015;38:87–92.

    Article  Google Scholar 

  8. Zhang Y, Lin S, Jiang P, Zhu X, Ling J, Zhang W, et al. Determination of melamine and cyromazine in milk by high performance liquid chromatography coupled with online solid-phase extraction using a novel cation-exchange restricted access material synthesized by surface initiated atom transfer radical polymerization. J Chromatogr A. 2014;1337:17–21.

    Article  CAS  Google Scholar 

  9. Chen L, Liang H, Lu Y, Cui C, Yu S. Synthesis of an attapulgite clay@carbon nanocomposite adsorbent by a hydrothermal carbonization process and their application in the removal of toxic metal ions from water. Langmuir. 2011;27:8998–04.

    Article  CAS  Google Scholar 

  10. Fan Q, Shao D, Lu Y, Wu W, Wang X. Effect of pH, ionic strength, temperature and humic substances on the sorption of Ni(II) to Na-attapulgite. Chem Eng J. 2009;150:188–95.

    Article  CAS  Google Scholar 

  11. Chen H, Zhao Y, Wang A. Removal of Cu(II) from aqueous solution by adsorption onto acid-activated palygorskite. J Hazard Mater. 2007;149:346–54.

    Article  CAS  Google Scholar 

  12. 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.

    Article  CAS  Google Scholar 

  13. Zhao Y, Chen Y, Li M, Zhou S, Xue A, Xing W. Adsorption of Hg2+ from aqueous solution onto polyacrylamide/attapulgite. J Hazard Mater. 2009;171:640–6.

    Article  CAS  Google Scholar 

  14. Zhao C, Zhao T, Liu X, Zhang H. A novel molecularly imprinted polymer for simultaneous extraction and determination of sudan dyes by on-line solid phase extraction and high performance liquid chromatography. J Chromatogr A. 2010;1217:6995–02.

    Article  CAS  Google Scholar 

  15. Zhao C, Guan X, Liu X, Zhang H. Synthesis of molecularly imprinted polymer using attapulgite as matrix by ultrasonic irradiation for simultaneous on-line solid phase extraction and high performance liquid chromatography determination of four estrogens. J Chromatogr A. 2012;1229:72–8.

    Article  CAS  Google Scholar 

  16. 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.

    Article  CAS  Google Scholar 

  17. Zhang L, Li Z, Hu Z, Chang X. Solid phase extraction of gold(III) on attapulgite modified with triocarbohydrazide prior to its determination in environmental samples by ICP-OES. Spectrochim Acta A Mol Biomol Spectrosc. 2011;79:1234–9.

    Article  CAS  Google Scholar 

  18. Zang Z, Li Z, Zhang L, Li R, Hu Z, Chang X, et al. Chemically modified attapulgite with asparagine for selective solid-phase extraction and preconcentration of Fe(III) from environmental samples. Anal Chim Acta. 2010;663:213–7.

    Article  CAS  Google Scholar 

  19. Myriam M, Suárez M, Martín-Pozas JM. Structural and textural modifications of palygorskite and sepiolite under acid treatment. Clays Clay Miner. 1998;46:225–31.

    Article  CAS  Google Scholar 

  20. Wang W, Chen H, Wang A. Adsorption characteristics of Cd(II) from aqueous solution onto activated palygorskite. Sep Purif Technol. 2007;55:157–64.

    Article  CAS  Google Scholar 

  21. Wang T, Chen Y, Ma J, Qian Q, Jin Z, Zhang L, et al. Attapulgite nanoparticles-modified monolithic column for hydrophilic in-tube solid-phase microextraction of cyromazine and melamine. Anal Chem. 2016;88:1535–41.

    Article  CAS  Google Scholar 

  22. Jandera P. Stationary and mobile phases in hydrophilic interaction chromatography: a review. Anal Chim Acta. 2011;692:1–25.

    Article  CAS  Google Scholar 

  23. Guo Y, Gaiki S. Retention behavior of small polar compounds on polar stationary phases in hydrophilic interaction chromatography. J Chromatogr A. 2005;1074:71–80.

    Article  CAS  Google Scholar 

  24. Horvath J, Dolník V. Polymer wall coating for capillary electrophoresis. Electrophoresis. 2001;22:644–55.

    Article  CAS  Google Scholar 

  25. Dai H, Shi Y, Wang Y, Sun Y, Hu J, Ni P, et al. A carbon dot based biosensor for melamine detection by fluorescence resonance energy transfer. Sensor Actuat B-Chem. 2014;202:201–8.

    Article  CAS  Google Scholar 

  26. Boudriche L, Calvet R, Chamayou A, Hamdi B, Balard H. Removal of lead(II) from aqueous solution using modified palygorskite, contribution of inverse gas chromatography. J Chromatogr A. 2015;1408:207–16.

    Article  CAS  Google Scholar 

  27. Tian M, Bi W, Row KH. Molecular imprinting in ionic liquid-modified porous polymer for recognitive separation of three tanshinones from Salvia miltiorrhiza Bunge. Anal Bioanal Chem. 2011;399:2495–02.

    Article  CAS  Google Scholar 

  28. Su R, Wang X, Xu X, Wang Z, Li D, Zhao X, et al. Application of multiwall carbon nanotubes-based matrix solid phase dispersion extraction for determination of hormones in butter by gas chromatography mass spectrometry. J Chromatogr A. 2011;1218:5047–54.

    Article  CAS  Google Scholar 

  29. 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 waste water. Anal Chem. 2007;79:6845–50.

    Article  CAS  Google Scholar 

Download references

Acknowledgments

The project is supported by the National Natural Science Foundation of China (21405085), the Public Applied Research Programs of Technology of Zhejiang Province (2015C37015), the Zhejiang Provincial Natural Science Foundation of China (LQ12B05001), and Ningbo Natural Science Foundation of China (2012A610091).

Author information

Authors and Affiliations

  1. School of Materials and Chemical Engineering/School of Safety Engineering, Ningbo University of Technology, Ningbo, Zhèjiāng, 315016, China

    Ting-Ting Wang & Zhen-Feng Jin

  2. Key Laboratory of Separation Science for Analytical Chemistry, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, Dalian, Liaoning, 116023, China

    Li-Hua Zhang & Yu-Kui Zhang

  3. Department of Biological Chemistry, The Johns Hopkins University School of Medicine, 25 N. Wolfe Street, Baltimore, MD, 21205-2185, USA

    Jun-Feng Ma

  4. Ningbo Entry-Exit Inspection and Quarantine Bureau, Ningbo, Zhèjiāng, 315016, China

    Yao Tan & Yi-Hui Chen

  5. Obstetrical Department, Affiliated Hospital of Ningbo University School of Medicine, Ningbo, Zhèjiāng, 315016, China

    Rong-Rong Xuan

Authors
  1. Ting-Ting Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Rong-Rong Xuan
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Jun-Feng Ma
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Yao Tan
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Zhen-Feng Jin
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Yi-Hui Chen
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Li-Hua Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Yu-Kui Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Ting-Ting Wang.

Ethics declarations

Conflict of interest

The authors declare that they have no competing interests.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Wang, TT., Xuan, RR., Ma, JF. et al. Using activated attapulgite as sorbent for solid-phase extraction of melamine in milk formula samples. Anal Bioanal Chem 408, 6671–6677 (2016). https://doi.org/10.1007/s00216-016-9779-2

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00216-016-9779-2

Keywords

Search

Navigation