An insight into the fate of Cu²⁺ and zero-valent iron during removal of Cu²⁺ by nanoscale zero-valent iron

Abstract

Aim: The transformation of zero-valent iron (Fe⁰) and Cu²⁺ during Cu²⁺ removal by nanoscale zero-valent iron (nZVI) has not been properly investigated using modern analytical techniques, despite its importance in environmental toxicology and surface chemistry associated with wastewater treatment/groundwater remediation. This study critically examines the phenomenon using a variety of modern instruments that characterize the physical and chemical properties of materials and provides extensive comprehension of the subject.

Methods: As-prepared nZVI was used to remove Cu²⁺ in 5 mmol/L CuSO₄. The morphological and structural characteristics of the Cu²⁺ and nZVI after removal were investigated with the aid of scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD) and X-ray photoelectron spectrometry (XPS).

Results: Complete removal of Cu²⁺ by the nZVI was achieved within 60 min and remained constant till 120 min. The Cu²⁺ got reduced into cuprite (Cu₂O) and copper metal (Cu⁰) (the crystals of both transformation products were cubic), while the Fe⁰ nanoparticles transformed into lath-like lepidocrocite (γ-FeOOH) and twin-rod goethite (α-FeOOH). The mechanism of Fe⁰ transformation was that the Fe²⁺ produced by Fe⁰ corrosion and oxidation by Cu²⁺ was hydrolyzed and oxidized to form hydropyrite, which was later converted into lepidocrocite and goethite with the assistance of Fe²⁺. The transformation of Cu²⁺ was due to the strong reduction property of Fe⁰. The toxicity and bioavailability of the transformed products were lower than those of Cu²⁺ and Fe⁰ nanoparticles.

Conclusion: The findings are critical in understanding the fate of Fe⁰ nanoparticles and Cu²⁺ during Cu²⁺ removal by nZVI and can provide guidance for the application of nZVI technology.

Keywords

Removal efficiency / transformational products / heavy metal / nanoparticles

References

[1] Gautam PK,Banerjee S,Pandey JD. Heavy metals in the environment: fate, transport, toxicity and remediation technologies. Available from: https://www.researchgate.net/publication/314465070 [Last accessed on 27 Mar 2023]

[2] Liu J,Liu Y,Zhang AN.Quantitative contributions of the major sources of heavy metals in soils to ecosystem and human health risks: a case study of Yulin, China.Ecotoxicol Environ Saf2018;164:261-9

[3] Ali I,Melezhik AV,Burakova IV,Galunin EV,Kuznetsov DV.Removal of copper(II) and zinc(II) ions in water on a newly synthesized polyhydroquinone/graphene nanocomposite material: kinetics, thermodynamics and mechanism.ChemistrySelect2019;4:12708-18.

[4] Liang W,Zhou X.Application of zero-valent iron nanoparticles for the removal of aqueous zinc ions under various experimental conditions.PLoS One2014;9:e85686 PMCID:PMC3887099

[5] Madhu PM. Effect of heavy metals on growth and development of cultivated plants with reference to cadmium, chromium and lead–a review. Available from: https://cyberleninka.ru/article/n/effect-of-heavy-metals-on-growth-and-development-of-cultivated-plants-with-reference-to-cadmium-chromium-and-lead-a-review [Last accessed on 27 Mar 2023]

[6] Ali J,Khan A,Nasir MJ.Contamination of soil with potentially toxic metals and their bioaccumulation in wheat and associated health risk.Environ Monit Assess2020;192:138

[7] Sandeep G,Anitha T. Heavy metals and its impact in vegetable crops. Available from: https://www.researchgate.net/publication/341508109 [Last accessed on 27 Mar 2023]

[8] Panfili I,Ballerini E.Combination of aquatic species and safeners improves the remediation of copper polluted water.Sci Total Environ2017;601-602:1263-70

[9] Ho YS.Removal of copper ions from aqueous solution by tree fern.Water Res2003;37:2323-30

[10] Yan W,Koel BE.As(III) sequestration by iron nanoparticles: study of solid-phase redox transformations with X-ray photoelectron spectroscopy.J Phys Chem C2012;116:5303-11

[11] Aydin H,Yerlikaya C.Removal of copper (II) from aqueous solution by adsorption onto low-cost adsorbents.J Environ Manage2008;87:37-45

[12] Thanh DN,Vejpravova J,Lederer J.Removal of copper and nickel from water using nanocomposite of magnetic hydroxyapatite nanorods.J Magn Magn Mater2018;456:451-60.

[13] Hosseinzadeh H.Effective removal of copper from aqueous solutions by modified magnetic chitosan/graphene oxide nanocomposites.Int J Biol Macromol2018;113:859-68

[14] Wang L,Wang J.Green multi-functional monomer based ion imprinted polymers for selective removal of copper ions from aqueous solution.J Colloid Interface Sci2019;541:376-86

[15] Stefaniuk M,Ok YS.Review on nano zerovalent iron (nZVI): from synthesis to environmental applications.Chem Eng J2016;287:618-632

[16] Mukherjee R,Sinha A,Saha AK.A review on synthesis, characterization, and applications of nano zero valent iron (nZVI) for environmental remediation.Crit Rev Env Sci2015;46:443-66.

[17] Li S,Li J.Porous biochar-nanoscale zero-valent iron composites: Synthesis, characterization and application for lead ion removal.Sci Total Environ2020;746:141037

[18] Navaei Diva T, Zare K, Taleshi F, Yousefi M. Removal of Cd2⁺ from aqueous solution by nickel oxide/CNT nanocomposites. Available from:https://scholar.google.com.hk/scholar?q=Removal+of+Cd2%2B+from+Aqueous+Solution+by+Nickel+Oxide/CNT+Nanocomposites&hl=zh-CN&as_sdt=0&as_vis=1&oi=scholart [Last accessed on 27 Mar 2023]

[19] Lian JJ,Wang HL.Enhanced molybdenum(VI) removal using sulfide-modified nanoscale zerovalent iron: kinetics and influencing factors.Water Sci Technol2021;83:297-308

[20] Zhao Y,Song X.Effects of nZVI dosing on the improvement in the contaminant removal performance of constructed wetlands under the dye stress.Sci Total Environ2020;703:134789

[21] Liu J,Wang W,Zhang WX.Feasibility of nanoscale zero-valent iron (nZVI) for enhanced biological treatment of organic dyes.Chemosphere2019;237:124470

[22] Wei A,Chen J,Song J.Enhanced nitrate removal and high selectivity towards dinitrogen for groundwater remediation using biochar-supported nano zero-valent iron.Chem Eng J2018;353:595-605.

[23] Han L,Tao S.Graphene oxide-induced formation of a boron-doped iron oxide shell on the surface of nZVI for enhancing nitrate removal.Chemosphere2020;252:126496

[24] Cao Y,Zhong Q.Feasibility of nanoscale zero-valent iron to enhance the removal efficiencies of heavy metals from polluted soils by organic acids.Ecotoxicol Environ Saf2018;162:464-73

[25] Huang P,Xie W.Rapid magnetic removal of aqueous heavy metals and their relevant mechanisms using nanoscale zero valent iron (nZVI) particles.Water Res2013;47:4050-8

[26] Calderon B.Heavy metal release due to aging effect during zero valent iron nanoparticles remediation.Water Res2015;83:1-9

[27] Liang L,Guo Y,Su X.The removal of heavy metal cations by sulfidated nanoscale zero-valent iron (S-nZVI): The reaction mechanisms and the role of sulfur.J Hazard Mater2021;404:124057

[28] Lei C,Khan E.Removal of chlorinated organic solvents from hydraulic fracturing wastewater by bare and entrapped nanoscale zero-valent iron.Chemosphere2018;196:9-17

[29] Li Q,Wang H.Removal of organic compounds by nanoscale zero-valent iron and its composites.Sci Total Environ2021;792:148546

[30] Xu L.A heterogeneous fenton-like system with nanoparticulate zero-valent iron for removal of 4-chloro-3-methyl phenol.J Hazard Mater2011;186:256-64

[31] Abbas T,Khan A,Khan E.Virgin (Fe⁰) and microbially regenerated (Fe²⁺) iron turning waste for treating chlorinated pesticides in water.J Hazard Mater2020;398:122980

[32] Malakootian M,Hossaini H.Removal of phosphates from aqueous solution by sepiolite-nano zero valent iron composite optimization with response surface methodology.Int J Environ Sci Te2017;15:2129-40

[33] Pasinszki T.Synthesis and Application of Zero-Valent Iron Nanoparticles in Water Treatment, Environmental Remediation, Catalysis, and Their Biological Effects.Nanomaterials2020;10:917 PMCID:PMC7279245

[34] O’Carroll D,Krol M,Kocur C.Nanoscale zero valent iron and bimetallic particles for contaminated site remediation.Adv Water Resour2013;51:104-22.

[35] Filip J,Petala E,Šráček O.Nanoscale zerovalent iron particles for treatment of metalloids. In: Phenrat T, Lowry GV, editors. Nanoscale Zerovalent Iron Particles for Environmental Restoration. Cham: Springer International Publishing; 2019. pp. 157-99.

[36] Xu W,Lou Y.Effects of environmental factors on the removal of heavy metals by sulfide-modified nanoscale zerovalent iron.Environ Res2020;187:109662

[37] Dai C,Zhou X.Removal of Sb(III) and Sb(V) from aqueous solutions using nZVI.Water Air Soil Poll2013;225.

[38] Wen Z,Dai C.Removal of phosphate from aqueous solution using nanoscale zerovalent iron (nZVI).Colloid Surface A2014;457:433-40.

[39] Anang E,Fan X,Gong X.Compositional evolution of nanoscale zero valent iron and 2,4-dichlorophenol during dechlorination by attapulgite supported Fe/Ni nanoparticles.J Hazard Mater2021;412:125246

[40] Yang L,Marcus MA.Kinetics of Fe(II)-catalyzed transformation of 6-line ferrihydrite under anaerobic flow conditions.Environ Sci Technol2010;44:5469-75

[41] He F,Liu J.Stabilization of Fe− Pd nanoparticles with sodium carboxymethyl cellulose for enhanced transport and dechlorination of trichloroethylene in soil and groundwater.Ind Eng Chem Res2007;46:29-34

[42] Cheng S,Anang E,Fan X.Enhanced as(III) sequestration using nanoscale zero-valent iron modified by combination of loading and sulfidation: characterizations, performance, kinetics and mechanism.Water Sci Technol2021;83:2886-900

[43] Cornell R. M..The iron oxides: structure, properties, reactions, occurrences and uses.2003;

[44] Liu H,Zhu M,Sun Y.Fe(II)-induced transformation from ferrihydrite to lepidocrocite and goethite.J Solid State Chem2007;180:2121-8.

[45] Karabelli D,Shahwan T,Scott TB,Lieberwirth I.Batch removal of aqueous Cu2⁺ ions using nanoparticles of zero-valent iron: a study of the capacity and mechanism of uptake.Ind Eng Chem Res2008;47:4758-64

[46] Karabelli D,Shahwan T.Preparation and characterization of alumina-supported iron nanoparticles and its application for the removal of aqueous Cu2⁺ ions.Chem Eng J2011;168:979-84.

[47] Tarekegn MM,Dekebo AH.Correction: nano zero valent iron (nZVI) particles for the removal of heavy metals (Cd²⁺, Cu²⁺ and Pb²⁺) from aqueous solutions.RSC Adv2021;11:27084

[48] Zhou YT,Nie HL.Adsorption mechanism of Cu2⁺ from aqueous solution by chitosan-coated magnetic nanoparticles modified with alpha-ketoglutaric acid.Colloids Surf B Biointerfaces2009;74:244-52

[49] Aeppli M,Kretzschmar R,Hofstetter TB.Electrochemical analysis of changes in iron oxide reducibility during abiotic ferrihydrite transformation into goethite and magnetite.Environ Sci Technol2019;53:3568-78

[50] Chen C,Sparks DL.Influence of coprecipitated organic matter on Fe2⁺(aq)-catalyzed transformation of ferrihydrite: implications for carbon dynamics.Environ Sci Technol2015;49:10927-36

[51] Perez JP,Thomas AN,Dideriksen K,Benning LG.Adsorption and reduction of arsenate during the Fe2+-induced transformation of ferrihydrite.Acs Earth Space Chem2019;3:884-94.

[52] Bardos P,Daly P,Jones S,Merly C. A risk benefit appraisal for the application of nanoscale zero valent iron (nZVI) for the remediation of contaminated sites. Available from: https://www.researchgate.net/publication/264788812 [Last accessed on 27 Mar 2023]

[53] Elkhateeb SA,El-Shal AS.Ameliorative role of curcumin on copper oxide nanoparticles-mediated renal toxicity in rats: an investigation of molecular mechanisms.J Biochem Mol Toxicol2020;34:e22593