Speciation Analysis Of Chromium In Water Samples Through Sequential Combination Of Dispersive Magnetic Solid Phase Extraction Using Mesoporous Amino-functionalized Fe<inf>3</inf>o<inf>4</inf>/sio<inf>2</inf> Nanoparticles And Cloud Point Extraction

The present paper describes the sequential combination of dispersive magnetic solid phase extraction (DMSPE) with cloud point extraction (CPE) as a new nonchromatographic approach for preconcentration/redox speciation of chromium with FAAS detection. The method is based on sequential preconcentration of Cr(VI) at pH5.0 onto mesoporous amino-functionalized Fe3O4/SiO2 nanoparticles followed by cloud point extraction of Cr(III) as metallic complex with 4-(2-thiazolylazo)resorcinol (TAR). The variables that play an important role on the performance of both preconcentration methods were thoroughly optimized by means of factorial design. Under optimized condition, an aliquot of 45.0mL of sample was preconcentrated onto 25mg of magnetic nanoparticles during 1min following the elution with 0.5mL of 2.5molL-1 HCl. The supernatant containing Cr(III) was then subjected to CPE procedure, which was accomplished by using thermostatic bath at 90°C during 45min, 5.8×10-4molL-1 TAR and 0.3% (v/v) Triton X-114. The method provided preconcentration factors of 16 and 12 times yielding limits of detection (LOD) and quantification (LOQ) of 1.1 and 3.6μgL-1 for Cr(VI) and 3.2 and 10.5μgL-1 for Cr(III), respectively. A high tolerance toward potentially interfering ions (cations and anions) and humic acid was observed for the method. Precision (n=10) of the procedure determined as relative standard deviation (RSD) were, 5.8 and 3.7% for Cr(III) using solutions at 15.0 and 165.0μgL-1 and 5.5 and 3.0% for Cr(VI) using solutions at 15.0 and 75.0μgL-1 concentrations, respectively. The applicability of method was attested by analysis of water samples yielding good recovery values (91.4-103.5%). The accuracy of method was also checked for biological samples using a certified reference material DORM-3 (Fish Protein Certified Reference Material for Trace Metals). © 2015 Elsevier B.V.123185195Hashemin, P., Borounmand, J., Fat'hi, M.R., A dual column system using agarose-based adsorbents for preconcentration and speciation of chromium in water (2004) Talanta, 64, pp. 578-583Resolution number 430/2011, , http://www.mma.gov.br/port/conama/legiabre.cfm?codlegi=646, (accessed 05/13/2015)(2015) National Primary Drinking Water Standards, Maximum Contaminant Level, , http://water.epa.gov/drink/contaminants/index.cfm#List, United States Environmental Protection Agency Office of Water, (accessed 20/02/2015)Chromium in drinking-water, guidelines for drinking-water quality (1996) Health Criteria and Other Supporting Information, , fourth edition, World Health Organization, GenevaSumida, T., Ikenoue, T., Hamada, K., Sabarudin, A., Oshima, M., Motomizu, S., On-line using dual mini-columns for the speciation of chromium(III) and chromium(VI) and its application to water samples as studied by inductively coupled plasma-atomic emission spectrometry (2005) Talanta, 68, pp. 388-393Ferreira, S.L.C., de Andrade, J.B., Korn, M.G.A., Pereira, M.G., Lemos, V.A., dos Santos, W.N.L., Rodrigues, F.M., da Silva, E.G.P., Review of procedures involving separation and preconcentration for the determination of cadmium using spectrometric techniques (2007) J. Hazard. Mater., 145, pp. 358-367Maltez, H.F., Carasek, E., Chromium speciation and preconcentration using zirconium (IV) and zirconium (IV) phosphate chemically immobilized onto silica gel surface using a flow system and FAAS (2005) Talanta, 65, pp. 537-542Li, Y., Hu, B., Jiang, Z., Wu, Y., Speciation of chromium in water samples by cloud point extraction combined with low temperature electrothermal vaporization ICP-OES (2006) Anal. Lett., 39, pp. 809-822López-García, I., Vicente-Martinez, Y., Hernández-Córdoba, M., Determination of very low amounts of chromium(III) and (VI) using dispersive liquid-liquid microextraction by in situ formation of an ionic liquid followed by electrothermal atomic absorption spectrometry (2012) J. Anal. At. Spectrom., 27, pp. 874-880Tarley, C.R.T., Lima, G.F., Nascimento, D.R., Assis, A.R.S., Ribeiro, E.S., Diniz, K.M., Bezerra, M.A., Segatelli, M.G., Novel on-line sequential preconcentration system of Cr(III) and Cr(VI) hyphenated with flame atomic absorption spectrometry exploiting sorbents based on chemically modified silica (2012) Talanta, 100, pp. 71-79Furusho, Y., Sabarudin, A., Hakim, L., Oshita, K., Oshima, M., Motomizu, S., Automated pretreatment system for the speciation of Cr(III) and Cr(VI) using dual mini-columns packed with newly synthesized chitosan resin and ME-03 resin (2009) Anal. Sci., 25, pp. 51-56Zou, A.-M., Tang, X.-Y., Chen, M.-L., Wang, J.-H., Preconcentration and speciation of chromium in a sequential injection system incorporating dual mini-columns coupled with electrothermal atomic absorption spectrometry (2008) Spectrochim. Acta Part B, 63, pp. 607-611Corazza, M.Z., Ribeiro, E.S., Segatelli, M.G., Tarley, C.R.T., 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 (2014) Microchem. J., 117, pp. 18-26Sahan, S., Saçmaci, S., Kartal, S., Saçmaci, M., Sahin, U., Ülgen, A., Development of a new on-line system for the sequential speciation and determination of chromium species in various samples using a combination of chelating and ion exchange resins (2014) Talanta, 120, pp. 391-397Meeravali, N.N., Janjusha, R., Kumar, S.J., A novel non-chromatographic strategy for the sequential/simultaneous extraction and analysis of chromium species by eletrothermal atomic absorption spectrometry in effluents and different water sources (2014) J. Anal. At. Spectrom., 29, pp. 2168-2175Safaríková, M., Safarik, I., Magnetic solid-phase extraction (1999) J. Magn. Magn. Mater., 194, pp. 108-112Zhao, X., Cai, Y., Wu, F., Pan, Y., Liao, H., Xu, B., Determination of perfluorinated compounds in environmental water samples by high-performance liquid chromatography-electrospray tandem mass spectrometry using surfactant-coated Fe3O4 magnetic nanoparticles as adsorbents (2011) Microchem. J., 98, pp. 207-214Giakisikli, G., Anthemidis, A.N., Magnetic materials as sorbents of metal /metalloid preconcentration and/or separation. A review (2013) Anal. Chim. Acta, 789, pp. 1-16Wang, L., Sum, Y., Wang, J., Wang, J., Yu, A., Zhang, H., Song, D., Preparation of surface plasmon resonance biosensor based on magnetic core/shell Fe3O4/SiO2 and Fe3O4/Ag/SiO2 nanoparticles (2011) Colloids Surf. B, 84, pp. 484-490Yuan, Q., Li, N., Chi, Y., Geng, W., Yan, W., Zhao, Y., Li, X., Dong, B., Effect of large pore size of multifunctional mesoporous microsphere on removal of heavy metal ions (2013) J. Hazard. Mater., pp. 157-165Fan, H.-T., Fan, X., Li, J., Guo, M., Zhang, D., Yan, F., Sun, T., Selective removal of arsenic(V) from aqueous solution using a surface-ion-imprinted amine-functionalized silica gel sorbent (2012) Ind. Eng. Chem. Res., 51, pp. 5216-5223Cunha, C., Panseri, S., Iannazzo, D., Piperno, A., Pistone, A., Fazio, M., Russo, A., Galvagno, S., Hybrid composites made of multiwalled carbon nanotubes functionalized with Fe3O4 nanoparticles for tissue engineering applications (2012) Nanotechnology, 23, p. 465102Aronne, A., Marenna, E., Califano, V., Fanelli, E., Pernice, P., Trifuoggi, M., Vergara, A., Sol-gel synthesis and structural characterization of niobium-silicon mixed-oxide nanocomposites (2007) J. Sol-Gel Sci. Technol., 43, pp. 193-204Lima, G.F., Ohara, M.O., Clausen, D.N., Nascimento, D.R., Ribeiro, E.S., Segatelli, M.G., Bezerra, M.A., Tarley, C.R.T., Flow injection on-line minicolumn preconcentration and determination of trace copper ions using an alumina/titanium oxide grafted silica matrix and FAAS (2012) Microchim. Acta, 178, pp. 61-70Kung, K.-H.S., Hayes, K.F., Fourier transform infrared spectroscopy study of the adsorption of cetyltrimethylammonium bromide and cetylpyridinium chloride on silica (1993) Langmuir, 9, pp. 263-267Bois, L., Bonhommé, A., Ribes, A., Pais, B., Raffin, G., Tessier, F., Functionalized silica for heavy metal ions adsorption (2003) Colloids Surf. A Physicochem. Eng. Asp., 221, pp. 221-230Zhang, Y.-X., Yu, X.-Y., Jin, Z., Ji, Y., Xu, W.-H., Luo, T., Zhu, B.-J., Huang, X.-J., Ultra high adsorption capacity of fried egg jellyfish-like g-AlOOH(Boehmite) at SiO2/Fe3O4 porous magnetic microspheres for aqueous Pb(II) removal (2011) J. Mater. Chem., 21, pp. 16550-16557Lima, G.F., Ferreira, V.S., Godoy, N.V., Medeiros, R.F., Garrido, F.M.S., Ribeiro, E.S., Nakagaki, S., Tarley, C.R.T., Study of silica-manganese oxide hybrid material as a new solid phase for on-line continuous flow enrichment of Cd(II) ions coupled to flame atomic absorption spectrometry (2013) Microchem. J., 109, pp. 98-105de Oliveira, F.M., Somera, B.F., Ribeiro, E.S., Segatelli, M.G., Yabe, M.J.S., Galunin, E., Tarley, C.R.T., Kinetic and isotherm studies of Ni2+ adsorption on poly(methacrylic acid) synthesized through a hierarchical double-imprinting method using a Ni2+ ion and cationic surfactant as templates (2013) Ind. Eng. Chem. Res., 52, pp. 8550-8557Corma, A., From microporous to mesoporous molecular sieve materials and their use in catalysis (1997) Chem. Rev., 97, pp. 2373-2419Wang, J., Zheng, S., Shao, Y., Liu, J., Xu, Z., Zhu, D., Amino-functionalized Fe3O4 at SiO2 core-shell magnetic nanomaterial as a novel adsorbent for aqueous heavy metals removal (2010) J. Colloid Interface Sci., 349, pp. 293-299Boyaci, E., Çagir, A., Shahwan, T., Eroglu, A.E., Synthesis, characterization and application of a novel mercapto-and-amine-bifuncionalized silica for speciation/sorption of inorganic arsenic prior to inductively coupled plasma mass spectrometric determination (2011) Talanta, 85, pp. 1517-1525Tarley, C.R.T., Fernandes, F.F., Luccas, P.O., Segatelli, M.G., Enhanced selectivity and sensitivity for flow injection spectrophotometric determination of cobalt using solid phase extraction with a 2D ion-imprinted adsorbent (2011) Anal. Lett., 44, pp. 216-231de Carvalho, L.D., Costa, A.C.S., Ferreira, S.L.C., Teixeira, L.S.G., Spectrophotometric determination of chromium in steel with 4-(2-thiazolylazo)-resorcinol (TAR) using microwave radiation (2004) J. Braz. Chem. Soc., 15, pp. 153-157Subrahmanyam, B., Eshwar, M.C., Spectrophotometric determination of chromium(III) with 4-(2-thiazolylazo)-resorcinol (1976) Microchim. Acta, 2, pp. 579-584Tarley, C.R.T., Silveira, G., dos Santos, W.N.L., Matos, G.D., da Silva, E.G.P., Bezerra, M.A., Miró, M.A., Ferreira, S.L.C., Chemometric tools in electroanalytical chemistry: methods for optimization based on factorial design and response surface methodology (2009) Microchem. J., 92, pp. 58-67Montgomery, D.C., (2010) Design and Analysis of Experiments, , Wiley, New YorkResolution number 357/2005, , http://www.mma.gov.br/port/conama/legiabre.cfm?codlegi=459, (accessed 05/13/2015)de Wuilloud, J.C.A., Wuilloud, R.G., Sadi, B.B.M., Caruso, J.A., Trace humic and fulvic acid determination in natural water by cloud point extraction/preconcentration using non-ionic and cationic surfactants with FI-UV detection (2003) Analyst, 128, pp. 453-458Long, G.L., Winefordner, J.D., Limit of detection, a closer look at the IUPAC definition (1983) Anal. Chem., 55, pp. 712-724Wu, Y.-W., Zhang, J., Li, J.-F., Deng, Z.-L., Han, M.-X., We, X.-S., Fe3O4 at ZrO2 nanoparticles magnetic solid phase extraction coupled with flame atomic absorption spectrometry for chromium(III) speciation in environmental and biological samples (2012) Appl. Surf. Sci., 258, pp. 6772-6776Chamjangali, M.A., Goudarzi, N., Mirheidari, M., Bahramian, B., Sequential eluent injection technique as a new approach for the on-line enrichment and speciation of Cr(III) and Cr(VI) species on a single column with FAAS detection (2011) J. Hazard. Mater., 192, pp. 813-821Sun, Z., Liang, P., Determination of Cr(III) and total chromium in water samples by cloud point extraction and flame atomic absorption spectrometry (2008) Microchim. Acta, 162, pp. 121-125Saygi, K.O., Tuzen, M., Soylak, M., Elci, L., Chromium speciation by solid phase extraction on Dowex M 4195 chelating resin and determination by atomic absorption spectrometry (2008) J. Hazard. Mater., 153, pp. 1009-1014Tunçeli, A., Turker, A., Rehber, A., Speciation of Cr(III) and Cr(VI) in water after preconcentration of its 1, 5-diphenylcarbazone complex on amberlite XAD-16 resin and determination by FAAS (2002) Talanta, 57, pp. 1199-1204Uluozlu, O.D., Tuzen, M., Soylak, M., Speciation and separation of Cr(VI) and Cr(III) using coprecipitation with Ni2+/2-Nitroso-1-naphthol-4-sulfonic acid and determination by FAAS in water and food samples (2009) Food Chem. Toxicol., 47, pp. 2601-2605Balarama Krishna, M.V., Chandrasekaran, K., Rao, S.V., Karunasagar, D., Arunachalam, J., Speciation of Cr(III) and Cr(VI) in waters using immobilized moss and determination by ICP-MS and FAAS (2005) Talanta, 65, pp. 135-143Memon, J.-R., Memon, S.Q., Bhanger, M.I., Khuhawar, M.Y., Use of modified sorbent for the separation and preconcentration of chromium species from industrial waste water (2009) J. Hazard. Mater., 163, pp. 511-516Alves, V.N., Coelho, N.M.M., Selective extraction and preconcentration of chromium using Moringa oleifera husks as biosorbent and flame atomic absorption spectrometry (2013) Microchem. J., 109, pp. 16-2