ISC, DOAJ, CAS, Google Scholar......

Document Type : Review


1 Department of Food Science and Technology, Faculty of Agriculture, Kermanshah Branch, Islamic Azad University, Kermanshah, Iran.

2 Department of Chemistry, Faculty of Pharmaceutical Chemistry, Tehran Medical Sciences, Islamic Azad University, Tehran, Iran.


Nanoparticle-based magnetic solid phase microextraction (MSPME) has advanced in heavy metal ion concentration and speciation in recent years. This comprehensive review covers the latest developments in this field and their application to complex food samples. The review begins with conventional MSPE methods' challenges and constraints, then examines off-line and online MSPE formats. Later sections of the review examine solid phase extraction’s (SPE) use of magnetized inorganic nanomaterials. These include magnetic silica, alumina, titania, and layered double oxides. Magnetized carbonaceous nanomaterials, such as magnetic graphene and/or graphene oxides, carbon nanotubes, and carbon nitrides, also belong to this study. The study describes how magnetized organic polymers-non-imprinted and ion-imprinted improved SPE. Magnetized metal-organic frameworks (MOF), ionic liquids, and biosorbents are also covered briefly. Each section carefully examines nanomaterials' selectivity, sorption capacity, mechanisms of sorption, and synthesis routes. Nanomaterials are becoming key sorbents for toxic heavy metal extraction from food samples. Carbon nanomaterials (CNMs), magnetic nanoparticles (MNPs), nano-imprinted polymers (NIPs), nano-based metal-organic frameworks (N-MOFs), and silica nanoparticles (SiNPs) are leading preconcentration methods due to their high surface area, selectivity, rapid adsorption kinetics, and food contamination capture efficiency. The review emphasizes the importance of SPE and SPME, enhanced by nanomaterial sorbents and summarizes nanomaterial-infused solid phase extraction strategies and their impact on heavy metal extraction from food matrices. The review examines a variety of nanomaterials and their complex use to improve selectivity, extraction efficiency, and future research in this crucial area.


Main Subjects

[1] Altunay N, Tuzen M, Hazer B, Elik A: Usage of the newly synthesized poly (3-hydroxy butyrate)-b-poly (vinyl benzyl xanthate) block copolymer for vortex-assisted solid-phase microextraction of cobalt (II) and nickel (II) in canned foodstuffs. Food chemistry, 321:126690, (2020).
[2] Tuzen M, Soylak M, Citak D, Ferreira HS, Korn MG, Bezerra MA: A preconcentration system for determination of copper and nickel in water and food samples employing flame atomic absorption spectrometry. Journal of Hazardous materials,162(2-3):1041-1045, (2009).
[3] Ghorbani-Kalhor E: A metal-organic framework nanocomposite made from functionalized magnetite nanoparticles and HKUST-1 (MOF-199) for preconcentration of Cd (II), Pb (II), and Ni (II). Microchimica Acta, 183:2639-2647, (2016).
[4] Arthur CL, Pawliszyn J: Solid phase microextraction with thermal desorption using fused silica optical fibers. Analytical chemistry, 62(19):2145-2148, (1990).
[5] Li J, Wang Y-B, Li K-Y, Cao Y-Q, Wu S, Wu L: Advances in different configurations of solid-phase microextraction and their applications in food and environmental analysis. TrAC Trends in Analytical Chemistry, 72:141-152, (2015).
[6] Hou X, Tang S, Wang J: Recent advances and applications of graphene-based extraction materials in food safety. TrAC Trends in Analytical Chemistry,119:115603, (2019).
[7] Khalifehzadeh E, Ahmadi S, Beigmohammadi F: Magnetic dispersive solid phase extraction of ZEAralenone using Fe3O4@ hydroxy propyl methyl cellulose nanocomposite from wheat flour samples prior to fluorescence determination: Multivariate optimization by Taguchi design. Microchemical Journal, 170:106682, (2021).
[8]        Wen Y, Chen L, Li J, Liu D, Chen L: Recent advances in solid-phase sorbents for sample preparation prior to chromatographic analysis. TrAC Trends in Analytical Chemistry, 59:26-41, (2014).
[9]        Soares da Silva Burato J, Vargas Medina DA, de Toffoli AL, Vasconcelos Soares Maciel E, Mauro Lanças F: Recent advances and trends in miniaturized sample preparation techniques. Journal of separation science, 43(1):202-225, (2020).
[10] Xu S, Lu H, Zheng X, Chen L: Stimuli-responsive molecularly imprinted polymers: versatile functional materials. Journal of Materials Chemistry C, 1(29):4406-4422, (2013).
[11] Xu S, Li J, Song X, Liu J, Lu H, Chen L: Photonic and magnetic dual responsive molecularly imprinted polymers: preparation, recognition characteristics and properties as a novel sorbent for caffeine in complicated samples. Analytical Methods, 5(1):124-133, (2013).
[12] Klekotka U, Wińska E, Zambrzycka-Szelewa E, Satuła D, Kalska-Szostko B: Magnetic Nanoparticles as Effective Heavy Ion Adsorbers in Natural Samples. Sensors, 22(9):3297, (2022).
[13] Esmaeili Lashkarian E, Ahmadi S, Beigmohammadi F: Ultrasound-Assisted Dispersive Magnetic Solid-Phase Extraction Using Fe3O4@Hydroxypropyl Methylcellulose Combined with Flame Atomic Absorption Spectrometry for Determination of Cadmium(II) in Food Samples. Arabian Journal for Science and Engineering, 49(1):209-219, (2024).
[14] Wu P, Xu Z: Silanation of nanostructured mesoporous magnetic particles for heavy metal recovery. Industrial & engineering chemistry research, 44(4):816-824, (2005).
[15] Zhai Y, Duan Se, He Q, Yang X, Han Q: Solid phase extraction and preconcentration of trace mercury (II) from aqueous solution using magnetic nanoparticles doped with 1, 5-diphenylcarbazide. Microchimica Acta,169:353-360, (2010).
[16] Mandil A, Idrissi L, Amine A: Stripping voltammetric determination of mercury (II) and lead (II) using screen-printed electrodes modified with gold films, and metal ion preconcentration with thiol-modified magnetic particles. Microchimica Acta, 170:299-305, (2010).
[17] Huang C, Xie W, Li X, Zhang J: Speciation of inorganic arsenic in environmental waters using magnetic solid phase extraction and preconcentration followed by ICP-MS. Microchimica Acta, 173:165-172, (2011).
[18] Wang Y, Tian T, Wang L, Hu X: Solid-phase preconcentration of cadmium (II) using amino-functionalized magnetic-core silica-shell nanoparticles, and its determination by hydride generation atomic fluorescence spectrometry. Microchimica Acta, 180:235-242, (2013).
[19] Wierucka M, Biziuk M: Application of magnetic nanoparticles for magnetic solid-phase extraction in preparing biological, environmental and food samples. TrAC Trends in Analytical Chemistry, 59:50-58, (2014).
[20] Zhang N, Peng H, Wang S, Hu B: Fast and selective magnetic solid phase extraction of trace Cd, Mn and Pb in environmental and biological samples and their determination by ICP-MS. Microchimica Acta,175:121-128, (2011).
[21] Suleiman JS, Hu B, Peng H, Huang C: Separation/preconcentration of trace amounts of Cr, Cu and Pb in environmental samples by magnetic solid-phase extraction with Bismuthiol-II-immobilized magnetic nanoparticles and their determination by ICP-OES. Talanta, 77(5):1579-1583, (2009).
[22] Giakisikli G, Anthemidis AN: Magnetic materials as sorbents for metal/metalloid preconcentration and/or separation. A review. Analytica chimica acta, 789:1-16, (2013).
[23] Tobiasz A, Walas S: Solid-phase-extraction procedures for atomic spectrometry determination of copper. TrAC Trends in Analytical Chemistry, 62:106-122, (2014).
[24] Cohen P, Privman E: The social supergene dates back to the speciation time of two Solenopsis fire ant species. Scientific Reports, 10(1):11538, (2020).
[25] Escudero LB, Maniero MÁ, Agostini E, Smichowski PN: Biological substrates: Green alternatives in trace elemental preconcentration and speciation analysis. TrAC Trends in Analytical Chemistry, 80:531-546, (2016).
[26] He M, Huang L, Zhao B, Chen B, Hu B: Advanced functional materials in solid phase extraction for ICP-MS determination of trace elements and their species-A review. Analytica Chimica Acta, 973:1-24, (2017).
[27] Majedi SM, Lee HK: Recent advances in the separation and quantification of metallic nanoparticles and ions in the environment. TrAC Trends in Analytical Chemistry, 75:183-196, (2016).
[28] Molaei K, Bagheri H, Asgharinezhad AA, Ebrahimzadeh H, Shamsipur M: SiO2-coated magnetic graphene oxide modified with polypyrrole–polythiophene: a novel and efficient nanocomposite for solid phase extraction of trace amounts of heavy metals. Talanta, 167:607-616, (2017).
[29] Wang L, Hang X, Chen Y, Wang Y, Feng X: Determination of cadmium by magnetic multiwalled carbon nanotube flow injection preconcentration and graphite furnace atomic absorption spectrometry. Analytical Letters, 49(6):818-830, (2016).
[30] Sun L, Zhang C, Chen L, Liu J, Jin H, Xu H, Ding L: Preparation of alumina-coated magnetite nanoparticle for extraction of trimethoprim from environmental water samples based on mixed hemimicelles solid-phase extraction. Anal Chim Acta, 638(2):162-168, (2009).
[31] Nyaba L, Matong JM, Nomngongo PN: Nanoparticles consisting of magnetite and Al 2 O 3 for ligandless ultrasound-assisted dispersive solid phase microextraction of Sb, Mo and V prior to their determination by ICP-OES. Microchimica Acta, 183:1289-1297, (2016).
[32] Munonde T, Maxakato N, Nomngongo P: 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. Microchimica Acta, 184, (2017).
[33] Zhang N, Peng H, Hu B: Light-induced pH change and its application to solid phase extraction of trace heavy metals by high-magnetization Fe3O4@SiO2@TiO2 nanoparticles followed by inductively coupled plasma mass spectrometry detection. Talanta, 94:278-283, (2012).
[34] Khezeli T, Daneshfar A: Development of dispersive micro-solid phase extraction based on micro and nano sorbents. TrAC Trends in Analytical Chemistry, 89:99-118, (2017).
[35] Abdolmohammad-Zadeh H, Talleb Z: Speciation of As(III)/As(V) in water samples by a magnetic solid phase extraction based on Fe3O4/Mg–Al layered double hydroxide nano-hybrid followed by chemiluminescence detection. Talanta, 128:147–155, (2014).
[36] Kardar ZS, Beyki MH, Shemirani F: Takovite-aluminosilicate@ MnFe2O4 nanocomposite, a novel magnetic adsorbent for efficient preconcentration of lead ions in food samples. Food Chemistry, 209:241-247, (2016).
[37] Nata IF, Salim GW, Lee C-K: Facile preparation of magnetic carbonaceous nanoparticles for Pb2+ ions removal. Journal of hazardous materials, 183(1-3):853-858, (2010).
[38] Gong J, Wang X, Shao X, Yuan S, Yang C, Hu X: Adsorption of heavy metal ions by hierarchically structured magnetite-carbonaceous spheres. Talanta, 101:45-52, (2012).
[39] Habila MA, ALOthman ZA, El-Toni AM, Al-Tamrah SA, Soylak M, Labis JP: Carbon-coated Fe 3 O 4 nanoparticles with surface amido groups for magnetic solid phase extraction of Cr (III), Co (II), Cd (II), Zn (II) and Pb (II) prior to their quantitation by ICP-MS. Microchimica Acta, 184:2645-2651, (2017).
[40] Ghiasi T, Ahmadi S, Ahmadi E, Bavil Olyai MRT, Khodadadi Z: Novel electrochemical sensor based on modified glassy carbon electrode with graphene quantum dots, chitosan and nickel molybdate nanocomposites for diazinon and optimal design by the Taguchi method. Microchemical Journal, 160:105628, (2021).
[41] Azizi-Lalabadi M, Hashemi H, Feng J, Jafari SM: Carbon nanomaterials against pathogens; the antimicrobial activity of carbon nanotubes, graphene/graphene oxide, fullerenes, and their nanocomposites. Advances in Colloid and Interface Science, 284:102250, (2020).
[42] Li Z, Liu Z, Sun H, Gao C: Superstructured assembly of nanocarbons: fullerenes, nanotubes, and graphene. Chemical reviews, 115(15):7046-7117, (2015).
[43] Chandran DG, Muruganandam L, Biswas R: A review on adsorption of heavy metals from wastewater using carbon nanotube and graphene-based nanomaterials. Environmental Science and Pollution Research, 30(51):110010-110046, (2023).
[44] Krishna RH, Chandraprabha M, Samrat K, Murthy TK, Manjunatha C, Kumar SG: Carbon nanotubes and graphene-based materials for adsorptive removal of metal ions–a review on surface functionalization and related adsorption mechanism. Applied Surface Science Advances, 16:100431, (2023).
[45] Feng Y, Su X, Chen Y, Liu Y, Zhao X, Lu C, Ma Y, Lu G, Ma M: Research progress of graphene oxide-based magnetic composites in adsorption and photocatalytic degradation of pollutants: A review. Materials Research Bulletin,112207, (2023).
[46] Molaei MJ: Magnetic graphene, synthesis, and applications: a review. Materials Science and Engineering, 272:115325, (2021).
[47] Ghaemi F, Ali M, Yunus R, Othman RN: Synthesis of carbon nanomaterials using catalytic chemical vapor deposition technique. In: Synthesis, technology and applications of carbon nanomaterials. Elsevier, 1-27, (2019).
[48] Manawi YM, Ihsanullah, Samara A, Al-Ansari T, Atieh MA: A review of carbon nanomaterials’ synthesis via the chemical vapor deposition (CVD) method. Materials, 11(5):822, (2018).
[49] Kumar M, Ando Y: Chemical vapor deposition of carbon nanotubes: a review on growth mechanism and mass production. Journal of nanoscience and nanotechnology, 10(6):3739-3758, (2010).
[50] Tang T, Liu F, Liu Y, Li X, Xu Q, Feng Q, Tang N, Du Y: Identifying the magnetic properties of graphene oxide. Applied Physics Letters, 104(12) ,(2014).
[51] Sarkar S, Raul K, Pradhan S, Basu S, Nayak A: Magnetic properties of graphite oxide and reduced graphene oxide. Physica E: Low-dimensional Systems and Nanostructures, 64:78-82, (2014).
[52] Jiang X, Pan W, Chen M, Yuan Y, Zhao L: The fabrication of a thiol-modified chitosan magnetic graphene oxide nanocomposite and its adsorption performance towards the illegal drug clenbuterol in pork samples. Dalton Transactions, 49(18):6097-6107, (2020).
[53] Kazemi A, Bahramifar N, Heydari A, Olsen SI: Synthesis and sustainable assessment of thiol-functionalization of magnetic graphene oxide and superparamagnetic Fe3O4@ SiO2 for Hg (II) removal from aqueous solution and petrochemical wastewater. Journal of the Taiwan Institute of Chemical Engineers, 95:78-93, (2019).
[54] Yari M, Norouzi M, Mahvi AH, Rajabi M, Yari A, Moradi O, Tyagi I, Gupta VK: Removal of Pb (II) ion from aqueous solution by graphene oxide and functionalized graphene oxide-thiol: effect of cysteamine concentration on the bonding constant. Desalination and Water Treatment, 57(24):11195-11210, (2016).
[55] Shulaker MM, Hills G, Patil N, Wei H, Chen H-Y, Wong H-SP, Mitra S: Carbon nanotube computer. Nature, 501(7468):526-530, (2013).
[56] Baddour CE, Briens C: Carbon nanotube synthesis: a review. International journal of chemical reactor engineering, 3(1) , (2005).
[57] Dai H: Carbon nanotubes: synthesis, integration, and properties. Accounts of chemical research, 35(12):1035-1044, (2002).
[58] Kılınç E: γ-Fe2O3 magnetic nanoparticle functionalized with carboxylated multi walled carbon nanotube: synthesis, characterization, analytical and biomedical application. Journal of Magnetism and Magnetic Materials, 401:949-955, (2016).
[59] Wang H, Yan N, Li Y, Zhou X, Chen J, Yu B, Gong M, Chen Q: Fe nanoparticle-functionalized multi-walled carbon nanotubes: one-pot synthesis and their applications in magnetic removal of heavy metal ions. Journal of Materials Chemistry, 22(18):9230-9236, (2012).
[60] Guo J, Jiang H, Teng Y, Xiong Y, Chen Z, You L, Xiao D: Recent advances in magnetic carbon nanotubes: synthesis, challenges and highlighted applications. Journal of Materials Chemistry B, 9(44):9076-9099, (2021).
[61] Guo S, Duan N, Dan Z, Chen G, Shi F, Gao W: g-C3N4 modified magnetic Fe3O4 adsorbent: preparation, characterization, and performance of Zn (II), Pb (II) and Cd (II) removal from aqueous solution. Journal of Molecular Liquids, 258:225-234, (2018).
[62] Fahimirad B, Asghari A, Rajabi M: Magnetic graphitic carbon nitride nanoparticles covalently modified with an ethylenediamine for dispersive solid-phase extraction of lead (II) and cadmium (II) prior to their quantitation by FAAS. Microchimica Acta, 184:3027-3035, (2017).
[63] Asghari A: A magnetic graphitic carbon nitride as a new adsorbent for simple separation of Ni (II) ion from foodstuff by ultrasound-assisted magnetic dispersive micro solid-phase extraction method. Analytical Methods in Environmental Chemistry Journal, 1(01):47-56, (2018).
[64] Liao Q, Pan W, Zou D, Shen R, Sheng G, Li X, Zhu Y, Dong L, Asiri AM, Alamry KA: Using of g-C3N4 nanosheets for the highly efficient scavenging of heavy metals at environmental relevant concentrations. Journal of Molecular Liquids, 261:32-40, (2018).
[65] Chouhan RS, Gačnik J, Živković I, Nair SV, Van de Velde N, Vesel A, Šket P, Gandhi S, Jerman I, Horvat M: Green synthesis of a magnetite/graphitic carbon nitride 2D nanocomposite for efficient Hg 2+ remediation. Environmental Science: Nano, 10(10):2658-2671, (2023).
[66] Rajca A, Wongsriratanakul J, Rajca S: Magnetic ordering in an organic polymer. Science, 294(5546):1503-1505, (2001).
[67] Taghizadeh A, Taghizadeh M, Jouyandeh M, Yazdi MK, Zarrintaj P, Saeb MR, Lima EC, Gupta VK: Conductive polymers in water treatment: A review. Journal of Molecular Liquids, 312:113447, (2020).
[68] Rubio-Giménez V, Tatay S, Martí-Gastaldo C: Electrical conductivity and magnetic bistability in metal–organic frameworks and coordination polymers: charge transport and spin crossover at the nanoscale. Chemical Society Reviews, 49(15):5601-5638, (2020).
[69] Kumar R, Travas-Sejdic J, Padhye LP: Conducting polymers-based photocatalysis for treatment of organic contaminants in water. Chemical Engineering Journal Advances, 4:100047, (2020).
[70] Kitagawa S: Metal–organic frameworks (MOFs). Chemical Society Reviews, 43(16):5415-5418, (2014).
[71] Maya F, Cabello CP, Frizzarin RM, Estela JM, Palomino GT, Cerda V: Magnetic solid-phase extraction using metal-organic frameworks (MOFs) and their derived carbons. TrAC Trends in Analytical Chemistry, 90:142-152, (2017).
[72] Wu Y, Ma Y, Xu G, Wei F, Ma Y, Song Q, Wang X, Tang T, Song Y, Shi M: Metal-organic framework coated Fe3O4 magnetic nanoparticles with peroxidase-like activity for colorimetric sensing of cholesterol. Sensors and Actuators B: Chemical, 249:195-202, (2017).
[73] Dong X, Gao X, Song J, Zhao L: A novel dispersive magnetic solid phase microextraction using ionic liquid-coated amino silanized magnetic graphene oxide nanocomposite for high efficient separation/preconcentration of toxic ions from shellfish samples. Food Chemistry, 360:130023, (2021).
[74] Rofouei MK, Jamshidi S, Seidi S, Saleh A: A bucky gel consisting of Fe3O4 nanoparticles, graphene oxide and ionic liquid as an efficient sorbent for extraction of heavy metal ions from water prior to their determination by ICP-OES. Microchimica Acta, 184(9):3425-3432, (2017).
[75] Sahebi H, Massoud Bahrololoomi Fard S, Rahimi F, Jannat B, Sadeghi N: Ultrasound-assisted dispersive magnetic solid-phase extraction of cadmium, lead and copper ions from water and fruit juice samples using DABCO-based poly (ionic liquid) functionalized magnetic nanoparticles. Food Chemistry, 396:133637, (2022).
[76] Chen S, Qin X, Gu W, Zhu X: Speciation analysis of Mn(II)/Mn(VII) using Fe3O4@ionic liquids-β-cyclodextrin polymer magnetic solid phase extraction coupled with ICP-OES. Talanta, 161:325-332, (2016).
[77] Mehdinia A, Shegefti S, Shemirani F: A novel nanomagnetic task specific ionic liquid as a selective sorbent for the trace determination of cadmium in water and fruit samples. Talanta, 144:1266-1272, (2015).
[78] Chen R, Qiao X, Liu F: Ionic liquid-based magnetic nanoparticles for magnetic dispersive solid-phase extraction: A review. Analytica Chimica Acta, 1201:339632, (2022).
[79] Hemmati M, Rajabi M, Asghari A: Magnetic nanoparticle based solid-phase extraction of heavy metal ions: a review on recent advances. Microchimica Acta, 185:1-32, (2018).
[80] Lotfi Z, Mousavi HZ, Sajjadi SM: Covalently bonded double-charged ionic liquid on magnetic graphene oxide as a novel, efficient, magnetically separable and reusable sorbent for extraction of heavy metals from medicine capsules. Rsc Advances, 6(93):90360-90370, (2016).
[81] Esmaeili N, Rakhtshah J, Kolvari E, Shirkhanloo H: Ultrasound assisted-dispersive-modification solid-phase extraction using task-specific ionic liquid immobilized on multiwall carbon nanotubes for speciation and determination mercury in water samples. Microchemical Journal, 154:104632, (2020).
[82] Bagheri H, Afkhami A, Khoshsafar H, Rezaei M, Shirzadmehr A: Simultaneous electrochemical determination of heavy metals using a triphenylphosphine/MWCNTs composite carbon ionic liquid electrode. Sensors and Actuators B: Chemical, 186:451-460, (2013).
[83] Jiang Q, Zhang S, Sun M: Recent advances on graphene and graphene oxide as extraction materials in solid-phase (micro)extraction. TrAC Trends in Analytical Chemistry, 168:117283, (2023).
[84] Bagheri AR, Aramesh N, Lee HK: Chitosan-and/or cellulose-based materials in analytical extraction processes: A review. TrAC Trends in Analytical Chemistry, 116770, (2022).
[85] Azarova YA, Pestov A, Bratskaya SY: Application of chitosan and its derivatives for solid-phase extraction of metal and metalloid ions: a mini-review. Cellulose, 23(4):2273-2289, (2016).
[86] Sajid M: Chitosan-based adsorbents for analytical sample preparation and removal of pollutants from aqueous media: A review. Trends in Environmental Analytical Chemistry ,e00185, (2022).
[87] Pacheco PH, Gil RA, Cerutti SE, Smichowski P, Martinez LD: Biosorption: A new rise for elemental solid phase extraction methods. Talanta, 85(5):2290-2300,( 2011).