Abstract
This article describes the synthesis and application of a novel sorbent for Cr(III) and Cr(VI) speciation prior to their quantitation by inductively coupled plasma mass spectrometry. The sorbent consists of polystyrene-divinyl benzene microbeads that were graft-coated with poly(oligo (ethylene glycol) methacrylate)-block-poly(glycidyl methacrylate). The particles were finally modified with phosphomethylated triethylene tetramine. The resulting microbeads are shown to be a viable sorbent for Cr(VI). The total concentration of chromium was determined after oxidation of Cr(III) to Cr(VI) with KMnO4 using the novel sorbent. The Cr(III) amount was then calculated by subtracting the concentration of Cr(VI) from that of total chromium. The optimum conditions for batch type sorption were established. Under optimal conditions, the limit of detection and quantification are 0.015 μg L−1 and 0.050 μg L−1, respectively. The kinetics and isotherms of the sorption of Cr(VI) were investigated. Following desorption with 0.1 M hydroxylamine hydrochloride, the method was successfully applied to spiked real water samples and a certified reference material.

Schematic presentation of a method for the sorption and speciation of chromium using amino methyl phosphonic acid functional brushes on polystyrene-divinyl benzene microspheres.
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Peng H, Zhang N, He M, Chen B, Hu B (2015) Simultaneous speciation analysis of inorganic arsenic, chromium and selenium in environmental waters by 3-(2-aminoethylamino) propyltrimethoxysilane modified multi-wall carbon nanotubes packed microcolumn solid phase extraction and ICP-MS. Talanta 131:266–272. https://doi.org/10.1016/j.talanta.2014.07.054
Yilmaz E, Soylak M (2016) Ultrasound assisted-deep eutectic solvent based on emulsification liquid phase microextraction combined with microsample injection flame atomic absorption spectrometry for valence speciation of chromium(III/VI) in environmental samples. Talanta 160:680–685. https://doi.org/10.1016/j.talanta.2016.08.001
Habila M, Unsal YE, Alothman ZA, Shabaka A, Tüzen M, Soylak M (2015) Speciation of chromium in natural waters, tea, and soil with membrane filtration flame atomic absorption spectrometry. Anal Lett 48:2258–2271. https://doi.org/10.1080/00032719.2015.1025278
Comber S, Gardner M (2003) Chromium redox speciation in natural waters. J Environ Monit 5:410–413. https://doi.org/10.1039/B302827E
Apte AD, Tare V, Bose P (2006) Extent of oxidation of Cr(III) to Cr(VI) under various conditions pertaining to natural environment. J Hazard Mater 128:164–174. https://doi.org/10.1016/j.jhazmat.2005.07.057
Karatepe A, Korkmaz E, Soylak M, Elci L (2010) Development of a coprecipitation system for the speciation/preconcentration of chromium in tap waters. J Hazard Mater 173:433–437. https://doi.org/10.1016/j.jhazmat.2009.08.098
Ying LY, Jiang HL, Zhou S, Zhou Y (2011) Ionic liquid as a complexation and extraction medium combined with high-performance liquid chromatography in the evaluation of chromium(VI) and chromium(III) speciation in wastewater samples. Microchem J 98:200–203. https://doi.org/10.1016/j.microc.2011.01.010
Li Y, Hu B, Jiang Z, Wu Y (2006) Speciation of chromium in water samples by cloud point extraction combined with low temperature electrothermal vaporization ICP-OES. Anal Lett 39:809–822. https://doi.org/10.1080/00032710600611574
Yayayürük AE, Yayayürük O (2017) Sorption characteristics of Cr(III) onto Florisil: kinetics, thermodynamics and equilibrium studies. Celal Bayar University Journal of Science 13:635–642. https://doi.org/10.18466/cbayarfbe.339318
El-Hefny NE (2009) Comparison of liquid–liquid extraction of Cr(VI) from acidic and alkaline solutions by two different amine extractants. Sep Purif Technol 67:44–49. https://doi.org/10.1016/j.seppur.2009.03.004
Dinker MK, Kulkarni PS (2015) Recent advances in silica-based materials for the removal of hexavalent chromium: a review. J Chem Eng Data 60:2521–2540. https://doi.org/10.1021/acs.jced.5b00292
Szala B, Bajda T, Jeleń A (2016) Removal of chromium (VI) from aqueous solutions using zeolites modified with HDTMA and ODTMA surfactants. Clay Miner 50:103–116. https://doi.org/10.1180/claymin.2015.050.1.10
Lapwanit S, Trakulsujaritchok T, Nongkhai PN (2016) Chelating magnetic copolymer composite modified by click reaction for removal of heavy metal ions from aqueous solution. Chem Eng J 289:286–295. https://doi.org/10.1016/j.cej.2015.12.073
Unuabonah EI, Olu-Owolabi BI, Adebowale KO (2016) Competitive adsorption of metal ions onto goethite–humic acid-modified kaolinite clay. Int J Environ Sci Technol 13:1043–1054. https://doi.org/10.1007/s13762-016-0938-y
Peng H, Zhang N, He M, Chen B, Hu B (2015) Simultaneous speciation analysis of inorganic arsenic, chromium and selenium in environmental waters by 3-(2-aminoethylamino) propyltrimethoxysilane modified multi-wall carbon nanotubes packed microcolumn solid phase extraction and ICP-MS. Talanta 131:266–272
Munonde T S, Maxakato NW, Nomngongo PN (2017) Preconcentration and speciation of chromium species using ICP-OES after ultrasound-assisted magnetic solid phase extraction with an amino-modified magnetic nanocomposite prepared from Fe3O4, MnO2 and Al2O3. Microchim Acta 184(4):1223–1232
Islam A, Ahmad H, Zaidi N, Kumar S (2016) A graphene oxide decorated with triethylenetetramine-modified magnetite for separation of chromium species prior to their sequential speciation and determination via FAAS. Microchim Acta 183(1):289–296
Vergili I, Gonder ZB, Kaya Y, Gürdag G, Cavus S (2017) Lead removal from battery wastewater using synthesized poly(ethyleneglycol dimethacrylate-methacrylic acid) gel bead and poly(methacrylic acid) hydrogel. Polym Bull 74:2605–2624. https://doi.org/10.1007/s00289-016-1855-4
Maatar W, Bouf S (2015) Poly(methacylic acid-co-maleic acid) grafted nanofibrillated cellulose as a reusable novel heavy metal ions adsorbent. Carbohydr Polym 126:199–207. https://doi.org/10.1016/j.carbpol.2015.03.015
Acar MH, Bicak N (2003) Synthesis of Hexylated Triethylenetetramine:new ligand for homogeneous atom transfer radical polymerization. J Polym Sci Part A: Polym Chem 41:1677–1680. https://doi.org/10.1002/pola.10716
Bicak N, Gazi M, Galli G, Chiellini E (2006) Polystyrene microspheres having epoxy functional dangling chains linked by hydrolytically stable bonds via ATRP. J Polym Sci Part A: Polym Chem 44:6708–6716. https://doi.org/10.1002/pola.21756
Ozer O, Ince A, Karagoz B, Bicak N (2013) Crosslinked PS-DVB microspheres with sulfonated polystyrene brushes as new generation of ion exchange resins. Desalination 309:141–147. https://doi.org/10.1016/j.desal.2012.09.024
Yayayürük O, Yayayürük AE (2016) Removal of Cu(II) from water samples using glycidyl methacrylate-based polymer functionalized with diethylenetriamine tetraacetic acid: investigation of adsorption characteristics. Water Air Soil Pollut 227:244–255. https://doi.org/10.1007/s11270-016-2943-7
Ince A, Tukenmez E, Bicak N, Karagoz B (2019) Cobalt-chelated polyamine brushes on solid microspheres for rapid binding and chemical storage of molecular oxygen. Ind Eng Chem 58:7769–7777
Alexandratos SD, Zhu X (2015) The role of polarizability in determining metal ion affinities in polymer-supported reagents: monoprotic phosphates and the effect of hydrogen bonding. New J Chem 39:5366–5373
Rakhunde R, Deshpande L, Juneja HD (2012) Chemical speciation of chromium in water: a review. Crit Rev Environ Sci Technol 42:776–810. https://doi.org/10.1080/10643389.2010.534029
Hadi M, Samarghandi MR, McKay G (2010) Equilibrium two-parameter isotherms of acid dyes sorption by activated carbons: study of residual errors. Chem Eng J 160:408–416. https://doi.org/10.1016/j.cej.2010.03.016
Han I, Schlautman MA, Batchelor B (2000) Removal of hexavalent chromium from groundwater by granular activated carbon. Water Environ Res 72:9–39
Rezvani M, Asgharinezhad AA, Ebrahimzadeh H, Shekari N (2014) A polyaniline-magnetite nanocomposite as an anion exchange sorbent for solid-phase extraction of chromium(VI) ions. Microchim Acta 181:1887–1895
Shirkhanloo H, Khaligh A, Golbabaei F, Sadeghi Z, Vahid A, Rashidi A (2015) On-line micro column preconcentration system based on amino bimodal mesoporous silica nanoparticles as a novel adsorbent for removal and speciation of chromium (III, VI) in environmental samples. J Environ Heal Sci Eng 13:47–59
Idris SA, Alotaibi K, Peshkur TA, Anderson P, Gibson LP (2012) Preconcentration and selective extraction of chromium species in water samples using amino modified mesoporous silica. J Colloid Interf Sci 386:344–349
Janik P, Zawisza B, Talik E, Sitko R (2018) Selective adsorption and determination of hexavalent chromium ions using graphene oxide modified with amino silanes. Microchim Acta 185:117–124
Corazza MZ, Ribeiro ES, Segatelli MG, Tarley CRT (2014) Study of cross-linked poly(methacrylic acid) and polyvinylimidazole as selective adsorbents for on-line preconcentration and redox speciation of chromium with flame atomic absorption spectrometry determination. Microchem J 117:18–26
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The authors gratefully acknowledge the financial support received from Ege University Research Fund (Project No: 2018 Fen 040).
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Erdem Yayayürük, A., Yayayürük, O., Tukenmez, E. et al. Polystyrene-divinyl benzene microspheres with amino methyl phosphonic acid functional hairy brushes for the sorption and speciation of chromium prior to inductively coupled plasma mass spectrometric determination. Microchim Acta 186, 571 (2019). https://doi.org/10.1007/s00604-019-3635-y
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DOI: https://doi.org/10.1007/s00604-019-3635-y