Microchimica Acta

, 186:400 | Cite as

Simultaneous extraction and preconcentration of monomethylmercury and inorganic mercury using magnetic cellulose nanoparticles

  • Feras Abujaber
  • María Jiménez-Moreno
  • Francisco Javier Guzmán Bernardo
  • Rosa C. Rodríguez Martín-DoimeadiosEmail author
Original Paper


Magnetite (Fe3O4) nanoparticles were modified with nanocellulose and are showed to be a useful sorbent for magnetic solid-phase extraction of mercury species. Speciation analysis was performed by using gas chromatography coupled to atomic fluorescence detection (GC-pyro-AFS). The magnetic properties of the sorbent make this approach simple and rapid, and the use of a renewable and biodegradable nanomaterial (nanocellulose) makes it environmentally friendly. The factors that affect adsorption (pH value, amount of nanomaterial, time, volume of sample) and desorption (solvent, time) have been optimized. Both desorption and derivatization of mercury species were performed in a single step. This reduces considerably the sample preparation time. Under the optimized conditions, the limits of detection are 4.0 pg mL−1 for monomethylmercury and 5.6 pg mL−1 for inorganic mercury. The repeatability and reproducibility are satisfactory. The method enables inorganic mercury and monomethylmercury to be simultaneously extracted, with preconcentration factors up to 300. The potential interferences of organic matter and/or co-existing ions were also investigated using synthetic waters. The procedure was applied to the analysis of tap water and river water samples with different characteristics from a mercury polluted area (Almadén, Spain). The extraction recoveries ranged from 81 to 98% regardless of the type of water, which demonstrates the applicability of the method. This is the first time that this kind of sorbent is used for trace metal speciation.

Graphical abstract

Schematic representation of the new composite material (made of Fe3O4 magnetic nanoparticles and cellulose fibers, MCNPs) for the simultaneous extraction and preconcentration of mercury species taking advantage of the magnetic properties of this eco-friendly sorbent.


Nanocellulose Magnetic solid phase extraction Monomethylmercury Inorganic mercury Water samples 



The authors thank the Spanish Ministry of Economy and Competitiveness for the financial support (Project CTQ2016-78793-P) to this work.

Compliance with ethical standards

The authors declare that they have no competing interests.

Supplementary material

604_2019_3492_MOESM1_ESM.docx (34 kb)
ESM 1 (DOCX 33 kb)


  1. 1.
    Płotka-Wasylka J, Szczepańska N, de la Guardia M, Namieśnik J (2016) Modern trends in solid phase extraction: new sorbent media. TrAC - Trends Anal Chem 77:23–43. CrossRefGoogle Scholar
  2. 2.
    Buszewski B, Szultka M (2012) Past, present, and future of solid phase extraction: a review. Crit Rev Anal Chem 42:198–213. CrossRefGoogle Scholar
  3. 3.
    Zhang S, Fu R, Wang S, Gu Y, Chen S (2017) Novel nanocellulose/conducting polymer composite nanorod films with improved electrochromic performances. Mater Lett 202:127–130. CrossRefGoogle Scholar
  4. 4.
    Dufresne A (2013) Nanocellulose: a new ageless bionanomaterial. Mater Today 16:220–227. CrossRefGoogle Scholar
  5. 5.
    Ruiz-Palomero C, Soriano ML, Valcárcel M (2017) Nanocellulose as analyte and analytical tool: opportunities and challenges. TrAC - Trends Anal Chem 87:1–18. CrossRefGoogle Scholar
  6. 6.
    Chisvert A, Cárdenas S, Lucena R (2019) Dispersive micro-solid phase extraction. TrAC Trends Anal Chem 112:226–233. CrossRefGoogle Scholar
  7. 7.
    Giakisikli G, Anthemidis AN (2013) Magnetic materials as sorbents for metal/metalloid preconcentration and/or separation. A review. Anal Chim Acta 789:1–16. CrossRefPubMedGoogle Scholar
  8. 8.
    Faraji M (2016) Recent analytical applications of magnetic nanoparticles. Nano Res 1:264–290. CrossRefGoogle Scholar
  9. 9.
    Xie L, Jiang R, Zhu F, Liu H, Ouyang G (2014) Application of functionalized magnetic nanoparticles in sample preparation. Anal Bioanal Chem 406:377–399. CrossRefPubMedGoogle Scholar
  10. 10.
    Chang PR, Yu J, Ma X, Anderson DP (2011) Polysaccharides as stabilizers for the synthesis of magnetic nanoparticles. Carbohydr Polym 83:640–644. CrossRefGoogle Scholar
  11. 11.
    Donia AM, Atia AA, Abouzayed FI (2012) Preparation and characterization of nano-magnetic cellulose with fast kinetic properties towards the adsorption of some metal ions. Chem Eng J 191:22–30. CrossRefGoogle Scholar
  12. 12.
    Sun X, Yang L, Li Q, Zhao J, Li X, Wang X, Liu H (2014) Amino-functionalized magnetic cellulose nanocomposite as adsorbent for removal of Cr(VI): synthesis and adsorption studies. Chem Eng J 241:175–183. CrossRefGoogle Scholar
  13. 13.
    Zarei S, Niad M, Raanaei H (2018) The removal of mercury ion pollution by using Fe3O4-nanocellulose: synthesis, characterizations and DFT studies. J Hazard Mater 25:22060–22074. CrossRefGoogle Scholar
  14. 14.
    Wei J, Yang Z, Sun Y, Wang C, Fan J, Kang G, Zhang R, Dong X, Li Y (2019) Nanocellulose-based magnetic hybrid aerogel for adsorption of heavy metal ions from water. J Mater Sci 54:6709–6718. CrossRefGoogle Scholar
  15. 15.
    Adelantado C, Ríos Á, Zougagh M (2018) Magnetic nanocellulose hybrid nanoparticles and ionic liquid for extraction of neonicotinoid insecticides from milk samples prior to determination by liquid chromatography-mass spectrometry. Food Addit Contam Part A 35:1755–1766. CrossRefGoogle Scholar
  16. 16.
    Abujaber F, Guzmán Bernardo FJ, Rodríguez Martín-Doimeadios RC (2019) Magnetic cellulose nanoparticles as sorbents for stir bar-sorptive dispersive microextraction of polychlorinated biphenyls in juice samples. Talanta 201:266–270. CrossRefPubMedGoogle Scholar
  17. 17.
    Abujaber F, Zougagh M, Jodeh S, Ríos Á, Guzmán Bernardo FJ, Rodríguez Martín-Doimeadios RC (2018) Magnetic cellulose nanoparticles coated with ionic liquid as a new material for the simple and fast monitoring of emerging pollutants in waters by magnetic solid phase extraction. Microchem J 137:490–495. CrossRefGoogle Scholar
  18. 18.
    Karimi MA, Ghasemi MH, Aghagoli MJ, Beyki MH (2016) Preconcentration of cobalt ions by a melamine-modified cellulose@MWCNT nanohybrid. Microchim Acta 183:2949–2955. CrossRefGoogle Scholar
  19. 19.
    Ma S, He M, Chen B, Deng W, Zheng Q, Hu B (2016) Magnetic solid phase extraction coupled with inductively coupled plasma mass spectrometry for the speciation of mercury in environmental water and human hair samples. Talanta 146:93–99. CrossRefPubMedGoogle Scholar
  20. 20.
    Zhang S, Luo H, Zhang Y, Li X, Liu J, Xu Q, Wang Z (2016) In situ rapid magnetic solid-phase extraction coupled with HPLC-ICP-MS for mercury speciation in environmental water. Microchem J 126:25–31. CrossRefGoogle Scholar
  21. 21.
    Zhu S, Chen B, He M, Huang T, Hu B (2017) Speciation of mercury in water and fish samples by HPLC-ICP-MS after magnetic solid phase extraction. Talanta 171:213–219. CrossRefPubMedGoogle Scholar
  22. 22.
    Lopez-Garcia I, Vicente-Martinez Y, Hernandez-Cordoba M (2015) Determination of ultratraces of mercury species using separation with magnetic core-modified silver nanoparticles and electrothermal atomic absorption spectrometry. J Anal At Spectrom 30:1980–1987. CrossRefGoogle Scholar
  23. 23.
    Faraji M, Yamini Y, Rezaee M (2010) Extraction of trace amounts of mercury with sodium dodecyle sulphate-coated magnetite nanoparticles and its determination by flow injection inductively coupled plasma-optical emission spectrometry. Talanta 81:831–836. CrossRefPubMedGoogle Scholar
  24. 24.
    Li G, Liu M, Zhang Z, Geng C, Wu Z, Zhao X (2014) Extraction of methylmercury and ethylmercury from aqueous solution using surface sulfhydryl-functionalized magnetic mesoporous silica nanoparticles. J Colloid Interface Sci 424:124–131. CrossRefPubMedGoogle Scholar
  25. 25.
    Corps Ricardo AI, Sánchez-Cachero A, Jiménez-Moreno M, Guzmán Bernardo FJ, Rodríguez Martín-Doimeadios RC, Ríos Á (2017) Carbon nanotubes magnetic hybrid nanocomposites for a rapid and selective preconcentration and clean-up of mercury species in water samples. Talanta 179:442–447. CrossRefPubMedGoogle Scholar
  26. 26.
    Jiang W, Jin X, Yu X, Wu W, Xu LJ, Fu FF (2017) Ion-imprinted magnetic nanoparticles for specific separation and concentration of ultra-trace methyl mercury from aqueous sample. J Chromatogr A 1496:167–173. CrossRefPubMedGoogle Scholar
  27. 27.
    Xiang G, Li L, Jiang X, He L, Fan L (2013) Thiol-modified magnetic silica sorbent for the determination of trace mercury in environmental water samples coupled with cold vapor atomic absorption spectrometry. Anal Lett 46:706–716. CrossRefGoogle Scholar
  28. 28.
    Zhai Y, Duan S, He Q et al (2010) Solid phase extraction and preconcentration of trace mercury(II) from aqueous solution using magnetic nanoparticles doped with 1,5-diphenylcarbazide. Microchim Acta 169:353–360. CrossRefGoogle Scholar
  29. 29.
    Zhang W, Sun C, Yang X (2014) Magnetic solid-phase extraction combined with in situ slurry cold vapor generation atomic fluorescence spectrometry for preconcentration and determination of ultratrace mercury. Anal Methods 6:2876–2882. CrossRefGoogle Scholar
  30. 30.
    Ziaei E, Mehdinia A, Jabbari A (2014) A novel hierarchical nanobiocomposite of graphene oxide-magnetic chitosan grafted with mercapto as a solid phase extraction sorbent for the determination of mercury ions in environmental water samples. Anal Chim Acta 850:49–56. CrossRefPubMedGoogle Scholar
  31. 31.
    Li W, Zhao X, Liu S (2013) Preparation of entangled nanocellulose fibers from APMP and its magnetic functional property as matrix. Carbohydr Polym 94:278–285. CrossRefPubMedGoogle Scholar
  32. 32.
    Jiménez-Moreno M, Lominchar MÁ, Sierra MJ, Millán R, Martín-Doimeadios RCR (2018) Fast method for the simultaneous determination of monomethylmercury and inorganic mercury in rice and aquatic plants. Talanta 176:102–107. CrossRefPubMedGoogle Scholar
  33. 33.
    Terán-Baamonde J, Bouchet S, Tessier E, Amouroux D (2018) Development of a large volume injection method using a programmed temperature vaporization injector – gas chromatography hyphenated to ICP-MS for the simultaneous determination of mercury, tin and lead species at ultra-trace levels in natural waters. J Chromatogr A 1547:77–85. CrossRefPubMedGoogle Scholar
  34. 34.
    Casado-Carmona FA, Alcudia-León MC, Lucena R, Cárdenas S, Valcárcel M (2016) Magnetic nanoparticles coated with ionic liquid for the extraction of endocrine disrupting compounds from waters. Microchem J 128:347–353. CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Austria, part of Springer Nature 2019

Authors and Affiliations

  1. 1.Environmental Sciences Institute (ICAM), Department of Analytical Chemistry and Food TechnologyUniversity of Castilla-La ManchaToledoSpain

Personalised recommendations