Elsevier

Food Chemistry

Volume 232, 1 October 2017, Pages 98-104
Food Chemistry

Analytical Methods
A simple and sensitive vortex-assisted ionic liquid-dispersive microextraction and spectrophotometric determination of selenium in food samples

https://doi.org/10.1016/j.foodchem.2017.03.104Get rights and content

Highlights

  • An environmentally friendly extraction method was developed for the determination of Se.

  • The proposed method consumes less organic solvent.

  • The proposed method was applied to different food samples and to the standard reference material, NIST SRM 2976 mussel tissue.

Abstract

In the present study, a novel and eco-friendly vortex-assisted ionic liquid-based microextraction method was developed for the determination of selenium in food. The microextraction method is based on the liberation of iodine in the presence of selenium; the liberated iodine reacts with I to form I3. Anionic I3 reacts with cationic crystal violet dye, and the product is extracted into 1-hexyl-3-methylimidazolium hexafluorophosphate phase in the presence of Triton X-114. The proposed method is linear in the range of 2.0–70 µg L−1 and has a detection limit of 9.8 × 10−2 µg L−1. Relative standard deviations were 3.67% and 2.89% for the five replicate measurements of 14 and 35 µg L−1 Se(IV), respectively. The proposed method was successfully applied to different food samples (NIST SRM 2976 mussel tissue, pepper, ginger, wheat flour, red lentil, traditional soup, cornflour, cornstarch, and garlic) after microwave digestion.

Introduction

Selenium is an essential element for human metabolism, but a high intake of selenium is toxic. It is a part of many antioxidant enzymes and has a unique role in converting hydrogen peroxide to a nontoxic compound (Ohki, Nakajima, Hirakawa, Hayashi, & Takanashi, 2015). Selenium deficiency is associated with reduced immune function and cognitive decline (Rybínová, Václav Červený, Hraníček, & Rychlovský, 2016). There is some important evidence for a negative correlation between the levels of selenium and the types of cancer, such as colon and prostate (Niedzielski et al., 2016). According to the World Health Organization (WHO), the maximum concentration of selenium in drinking water should not exceed 10 µg L−1 (Segura et al., 2015). The maximum limit for daily intake is established to be 400 µg day−1 (Food & Nutrition Board & Institute of Medicine, 2000).

Determination of selenium in different matrices is an important task in analytical chemistry. The toxic and deficiency levels of selenium for metabolism are rather narrow (Serra, Estela, Coulomb, Boudenne, & Cerdà, 2010). There are hundreds of research articles existing in the literature on the development of new analytical methods for the quantitative extraction of selenium (Latorre, García, Martín, & Crecente, 2013). Different sophisticated instrumental analytical techniques such as inductively coupled plasma atomic emission spectrometry (Awual, Yaita, Suzuki, & Shiwaku, 2015), inductively coupled plasma mass spectrometry (Khan et al., 2013), hydride generation atomic fluorescence spectrometry (Zhang, Fu, Fang, Feng, & Ke, 2011), ETAAS (Izgi, Gucer, & Jaćimović, 2006), liquid chromatography with tandem mass spectrometry (Zembrzuska, Matusiewicz, Polkowska-Motrenko, & Chajduk, 2014), high-performance liquid chromatography–inductively coupled plasma mass spectrometry (Jagtap and Maher, 2016, Yu-Pin et al., 2015), sequential injection analysis–chemiluminescence (Ezoe, Ohyama, Hashem, Ohira, & Toda, 2015), and spectrophotometry (Wen, Zhang, Li, Fang, & Zhang, 2014) are used for the detection of trace and ultratrace amounts of selenium and its species (Tuzen & Pekiner, 2015). In many cases, a sample pretreatment prior to analysis is necessary for preconcentration and/or separation of analytes. For selenium, different types of extraction processes have been developed. Vrines et al. successfully extracted volatile-alcylated selenium and sulfur compounds by using solid-phase microextraction (Vriens, Mathis, Winkel, & Berg, 2015). Escudero et al. developed a method on the basis of extraction and preconcentration of selenium with a PVC column and coprecipitation with lanthanum hydroxide, La(OH)3 (Escudero, Pacheco, Gasquez, & Salonia, 2015). Another method developed by Kocot et al. is based on using graphene as solid adsorbents in energy-dispersive X-ray fluorescence spectrometric determination of selenium (Kocot, Leardi, Walczak, & Sitko, 2015). There also exist well-designed, interesting studies on headspace solid-phase microextraction of selenium conducted by different research groups (Shahdousti and Alizadeh, 2011, Tyburska et al., 2011).

Spectrophotometric techniques are generally preferred for the determination of analytes because of their simplicity and low cost. The determination of analytes at trace levels can be achieved using a suitable complexing agent. The main drawback of the spectrophotometric method is its poor selectivity. The complex matrix components generally interfere to a large extent; therefore, in most cases, the masking of the interfering species is unavoidable (Agrawal, Patel, & Shrivas, 2009). In addition, the elimination of matrix effects and the determination of analytes present at trace and ultra-trace levels are generally performed using different separation and extraction methods. Despite the large number of studies on solid-phase extraction of selenium, liquid–liquid extraction methods are relatively simpler alternatives. Because of high consumption of organic reagents in “conventional liquid–liquid” extraction, miniaturized forms of the extraction methodologies are very popular among analytical chemists. Miniaturized extraction techniques such as liquid–liquid microextraction, cloud-point extraction, and ionic liquid (IL)-based microextraction are the comparatively new techniques for the quantitative extraction of analytes into small volumes. In microextraction techniques, only microliters of extraction reagents are used. In cloud-point extraction, generally nonionic surfactants are used, and in IL-based microextraction, ILs are used as the extraction medium. These techniques are considered to be more “eco benign”, and because of the low vapor pressures of the reagents, they are much safer than the conventional extraction techniques (Rajabi, Asemipour, Barfi, Jamali, & Behzad, 2014).

In the present study, trace determination of selenium was performed on the basis of the formation of iodine in the presence of selenium. The liberated iodine reacted with crystal violet forming the reaction product. The formed complex was extracted into 1-hexyl-3-methylimidazolium hexafluorophosphate (IL), and Triton X-114 was used as the antisticking agent. The dispersion of phases was achieved by vortexing. A simple, rapid, selective, sensitive, and eco-friendly vortex-assisted ionic liquid-based microextraction (VA-IL-DLLME) method was used for the first time to determine selenium concentration in food samples.

Section snippets

Reagents and instrumentation

Twenty-five milligrams of crystal violet (Merck, Darmstadt, Germany) was diluted to approximately 25 mL, and 3.0 mL of orthophosphoric acid was added to this diluted solution. The solution was diluted to 100 mL and mixed until the crystal violet and orthophosphoric acid were completely dissolved. The stock (1000 mg/L) Se (IV) (Sigma-Aldrich, St. Louis, MO, USA) solution was prepared by the dissolution of SeO2. Triton X-114 (2%) was prepared and used as the antisticking agent. A KI (Merck) solution

Results and discussion

In strongly acidic medium, selenium oxidizes iodide to iodine, which immediately reacts with iodide to form tri-iodide. The tri-iodide ion forms an ion-associated complex with cationic compounds, such as crystal violet (Agrawal et al., 1998, Agrawal et al., 2009). The ion-associated species can be extracted using an IL phase, such as 1-hexyl-3-methylimidazolium hexafluorophosphate, and the product can be strongly absorbed at 329 nm. The absorbance value is directly proportional to the

Conclusion

The proposed VA-IL-DLLME method uses a vortex shaker system for the formation of vortex stream that accelerates the selenium complex extraction into the IL phase. A simple spectrophotometric technique for the accurate determination of selenium was proposed. The method was based on the liberation of iodine in the presence of selenium; the liberated iodine reacted with iodide to form tri-iodide ion, and the tri-iodide ion formed the ion-associated species, with the cationic crystal violet causing

Acknowledgment

The authors are grateful for the financial support from the Unit of the Scientific Research Projects of Cumhuriyet University, Cumhuriyet University Advanced Technology Research Center (CÜTAM) and the Unit of Scientific Research Projects of Gaziosmanpasa University. Dr. Mustafa Tuzen thank the Turkish Academy of Sciences for its financial support. The authors also thank Dr. Tulay Oymak for providing the standard reference material and for her help in microwave digestion experiments.

References (41)

  • I. Lavilla et al.

    Ultrasound-assisted extraction technique for establishing selenium contents in breast cancer biopsies by Zeeman electrothermal atomic absorption spectrometry using multi-injection

    Analytica Chimica Acta

    (2006)
  • Y. Li et al.

    Simultaneous speciation of inorganic selenium and antimony in water samples by electrothermal vaporization inductively coupled plasma mass spectrometry following selective cloud point extraction

    Water Research

    (2008)
  • C. Moscoso-Pérez et al.

    Pressurized liquid extraction followed by high performance liquid chromatography coupled to hydride generation atomic fluorescence spectrometry for arsenic and selenium speciation in atmospheric particulate matter

    Journal of Chromatography A

    (2008)
  • N.M. Najafi et al.

    Comparison of ultrasound-assisted emulsification and dispersive liquid–liquid microextraction methods for the speciation of inorganic selenium in environmental water samples using low density extraction solvents

    Analytica Chimica Acta

    (2012)
  • P. Niedzielski et al.

    Selenium species in selenium fortified dietary supplements

    Food Chemistry

    (2016)
  • H. Peng et al.

    Simultaneous speciation analysis of inorganic arsenic, chromium and seleniumin environmental waters by 3-(2- aminoethylamino) propyltrimethoxysilane modified multi-wall carbon nanotubes packed microcolumn solid phase extraction and ICP-MS

    Talanta

    (2015)
  • M. Rajabi et al.

    Ultrasound-assisted ionic liquid based dispersive liquid–liquid microextraction and flame atomic absorption spectrometry of cobalt, copper, and zinc in environmental water samples

    Journal of Molecular Liquids

    (2014)
  • M. Rybínová et al.

    UV-photochemical vapor generation with quartz furnace atomic absorption spectrometry for simple and sensitive determination of selenium in dietary supplements

    Microchemical Journal

    (2016)
  • B.M. Sargar et al.

    Sequential separation of selenium(IV) from tellurium(IV) by solvent extraction with N-n-octylaniline: Analysis of real samples

    Journal of Saudi Chemical Society

    (2011)
  • K.O. Saygi et al.

    Speciation of selenium(IV) and selenium(VI) in environmental samples by the combination of graphite furnace atomic absorption spectrometric determination and solid phase extraction on Diaion HP-2MG

    Talanta

    (2007)
  • Cited by (36)

    • Fast sequential multi element analysis of lead and cadmium in canned food samples using effervescent tablet-assisted switchable solvent based liquid phase microextraction (EA-SS-LPME) coupled with high-resolution continuum source flame atomic absorption spectrometry (HR-CS-FAAS)

      2022, Food Chemistry
      Citation Excerpt :

      In recent versions of SS-LPME, the method is coupled with assisted-techniques to create new versions such as the ultrasonic assisted switchable solvent based liquid phase microextraction (UA-SS-LPME) (Habibiyan, Ezoddin, Lamei, Abdi, Amini, & Ghazi-khansari, 2017), air assisted liquid phase microextraction based switchable-hydrophilicity solvent (AA-SHS-LPME) (Ezoddin, Abdi, & Lamei, 2016), vortex-assisted switchable solvent based green liquid phase microextraction (VA-SSLPME) (Memon, Yilmaz, & Soylak, 2017), effervescence assisted emulsification microextraction with switchable solvent (EA-EME-SS) (Hemmati & Rajabi, 2019), and CO2-effervescence assisted-extraction (Arpa, Albayati, & Yahya, 2018; Jing, Zhang, Zhu, Chen, Yi, & Wang, 2018; Lasarte-Aragones, Lucena, Cardenas, & Valcarcel, 2014; Li et al., 2019; Wang et al., 2018). The most widely used spectrometric methods for the determination of trace heavy metals are voltammetry (Rajawat, Kumar, & Satsangee, 2014), UV/Vis spectrophotometry (Aydin, Yilmaz, & Soylak, 2018; Bagda & Tuzen, 2017), colorimetry (Ratnarathorn, Chailapakul, Henry, & Dungchai, 2012), and inductively coupled plasma mass spectrometry (ICP-MS) (Ohki, Nakajima, Hirakawa, Hayashi, & Takanashi, 2016) as well as inductively coupled plasma-optical emission spectrometry (ICP-OES) (Gugushe, Mpupa, & Nomngongo, 2019). In the present study, atomic absorption spectrometry (AAS), both electro thermal atomic absorption spectrometry (GFAAS) (Zounr, Tuzen, Deligonul, & Khuhawar, 2018) and flame atomic absorption spectrometry (FAAS) (Memon et al., 2017), were selected for the evaluation and determination of Pb and Cd.

    • Innovative approach for obtaining phenolic compounds from guava (Psidium guajava L.) coproduct using ionic liquid ultrasound-assisted extraction (IL-UAE)

      2021, Biocatalysis and Agricultural Biotechnology
      Citation Excerpt :

      It is expected an income of US $ 39.6 million by the end of 2021 with the use of ILs (Claus et al., 2018; Hwang et al., 2018). Metal extraction in food samples (Bağda and Tüzen, 2017; Tuzen et al., 2018); organic synthesis (Berthod et al., 2017); processing of cellulosic biomass (Fort et al., 2007); and the extraction of PC from propolis (Cao et al., 2017), and seaweed (Vo Dinh et al., 2018) using ILs have been reported in the literature. [BMIM][Cl] and [BMIM][BF4] (Fig. 2), have been reported in the literature for extraction of PC (Ma et al., 2010; Martins et al., 2017). [

    • Optimization of vortex-assisted ionic liquid dispersive liquid–liquid microextraction by experimental design prior to hydride generation atomic absorption spectrometry for determination of selenium species in food, beverage and water samples

      2021, Journal of Food Composition and Analysis
      Citation Excerpt :

      Microextraction is one of the most widely used preconcentration procedure reported in the literature. It involves different analytical methods such as liquid–liquid extraction (LLE) (Zam et al., 2019; Messaoudi et al., 2020), ultrasound-assisted liquid phase microextraction (UALPME) based on deep eutectic solvent (DES) (Panhwar et al., 2017), magnetic effervescent tablet-assisted ionic liquid dispersive liquid-liquid microextraction (MEA-IL-DLLME) (Wang et al., 2016), vortex-assisted ionic liquid-dispersive microextraction (VA-ILDME) (Bağda and Tüzen, 2017), ultrasound assisted extraction (UAE) (Altunay et al., 2016), alcohol-DES based vortex assisted homogenous liquid-liquid microextraction (DES-VA-HLLME) (Altunay et al., 2020) and dual-cloud point extraction (d-CPE) (Wang et al., 2017). In recent years, researchers begin to use the room temperature ionic liquids (RTILs).

    • Determination of selenium in food and environmental samples using a gold nanocages/fluorinated graphene nanocomposite modified electrode

      2020, Journal of Food Composition and Analysis
      Citation Excerpt :

      The ingestion of selenium from food and environment is a major way of having selenium level in the human body because few organs can store selenium for a long time. Selenium as an important antioxidant and active ingredient of the human immune system (Bagda and Tuzen, 2017), it can scavenge free radicals, improve the immunity and inhibit cancers (Capriotti et al., 2018; Grijalba et al., 2017). However, either deficiency of selenium (< 40 μg/day) or excess ingestion of selenium (> 400 μg/day) will cause serious issues for human health (Jevtic et al., 2014).

    View all citing articles on Scopus
    View full text