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Preparation and Application of Magnetic Materials for the Removal of As III from Aqueous Solutions Mini Namdeo and Ankita Mathur Centre of Excellence- Nanotechnology Indian Institute of Technology Roorkee Uttarakhand India Corresponding author: Mini Namdeo Centre of Excellence-Nanotechnology Indian Institute of Technology Roorkee Uttarakhand India Tel: +917060214491 Email: mini.namdeogmail.com Received date: October 5 2018 Accepted date: October 17 2018 Published date: October 24 2018 Copyright: © 2018 Namdeo M et al. This is an open-access article distributed under the terms of the Creative Commons Attribution License which permits unrestricted use distribution and reproduction in any medium provided the original author and source are credited. Abstract Higher environmental standards have made for the removal of arsenic from water an important problem for environmental engineering. Iron oxide is a particularly interesting sorbent to consider for this application. Its magnetic properties allow relatively routine dispersal and recovery of the adsorbent into and from groundwater or industrial processing facilities in addition iron oxide has strong and specific interactions with both As III and AsV. Finally this material can be produced with nanoscale dimensions which enhance both its capacity and removal. The present study focuses on iron-oxide based complexes that were found to adsorb arsenic from water. Their composition morphology magnetic behaviour and potential were studied by Fourier Transform Infra-Red FTIR Spectroscopy X-Ray Diffraction XRD Field Emission Scanning Electron Microscopy FESEM Transmission Electron Microscopy TEM Zeta potential and Vibrating Sampling Magnetometer VSM. Arsenic concentrations were recorded by Inductively Coupled Plasma-Mass Spectrometry ICP-MS. Finally the particles were also investigated for their antimicrobial properties that can be used against gram positive and gram-negative bacteria. The study suggests that among various iron oxide sorbents magnetite chitosan beads provides a low cost fast and effective method for removal of arsenic from potable water and thus making it suitable for drinking purpose. Keywords: Magnetite Chitosan Arsenic Adsorption Antibacterial activity Introduction Te removal of toxic and polluting heavy metal ions from industrial efuents water supplies and mine waters has received much attention in recent years. Arsenic As-contaminated drinking water is a major problem around the world. Countries such as Bangladesh India V ietnam Mexico Argentina Chile Hungary Romania and the United States face signifcant challenges in meeting the newly lowered standards for Arsenic in drinking water 1. Several methods of As removal are already available including precipitation adsorption ion exchange solvent extraction nanofltration foam fotation and biological sequestration 2. Adsorption is a low cost efcient and easy method to remove efuents from water 3. It is simple environmental- friendly requires less skill and can treat water of high quality 4. Various adsorbents have been used so far for removal of arsenic including zirconium oxide 5 manganese oxide 6 titanium oxide 7 orange juice 8 human hairs 9 etc. Nanoscale nickel/ nickel borides were also efective adsorbents for mitigating arsenic from drinking water 10. Various low-cost adsorbents have been synthesized like bagasse fy ash BFA by-product of sugarcane industry it can remove up to 95 arsenite and arsenate ions from water by column and batch modes 11. Similarly a biochar was prepared by pyrolysing hematite and pinewood biomass and was found efective in removing arsenic 12. Many papers have been published demonstrating that bulk iron oxides have a high afnity for the adsorption of arsenite and arsenate 1314. As III can form inner sphere monodentate or bidentate-binuclear complexes with iron oxides. Extended X-ray absorption fne structure spectroscopy has provided direct evidence for inner sphere adsorption of arsenite and arsenate on iron oxides 15-17. Chitosan as a natural polysaccharide derived from renewable sources is one of the most studied biopolymers with signifcant potential for diferent applications including medical pharmaceutical and biotechnological applications because of its good biocompatibility biodegradability and low toxicity 18. Te appropriate involving of magnetic material in chitosan-based materials would enlarge the areas of its possible application e.g. for fast and easy separation of microorganisms as magnetic drug-targeting carriers contrast enhancement agents in magnetic resonance imaging etc. Tat is why chitosan has recently attracted increasing interest as carrier in magneto-sensitive materials. one pot mag bead Usually the potable water is free from the pathogenic organisms however in the public potable water systems presence of viruses bacteria fungi and parasites is possible. Terefore using copper and chitosan may also help in fghting the pathogenic organisms in the potable water. 1920. In present work we demonstrate a comparative study of various Iron oxide nanoparticles on the adsorption behavior of Arsenic metal ion. In addition we evaluate and compare their antibacterial activities against gram positive and gram-negative bacteria. Experimental Work Materials Chitosan Molecular weight 200 kDa DA-80 was purchased from Hi-media. Other reagents such as Arsenic ferrous chloride ferric chloride potassium sodium tartrate ferric oxide red hematite copper sulphate pentahydrate sodium hydroxide pellets iron powder and formaldehyde were also purchased from Hi-Media and Merck are used as received. Te double distilled water was used throughout the investigations. Journal of Advanced Chemical Engineering ISSN: 2090-4568 Journal of Advanced Chemical Engineering Namdeo et al. J Adv Chem Eng 2018 8:2 DOI: 10.4172/2090-4568.1000189 Research Article Open Access J Adv Chem Eng an open access journal ISSN: 2090-4568 Volume 8 • Issue 2 • 1000189

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Synthesis of magnetic materials Magnetite nanoparticles: Magnetite nanoparticles Fe 3 O 4 were prepared by chemical co-precipitation of Fe 2+ and Fe 3+ ions in aqueous solution of sodium hydroxide followed by treatment under hydrothermal conditions 21. Iron II chloride and Iron III chloride were dissolved in 1:2 molar ratio in distilled water and chemically precipitated at 40C by adding 30 NaOH w/v dropwise with constant stirring at a controlled pH 10-10.4. Te suspension was heated at 90C for one hour under continuous stirring and separated by centrifuging several times in water and then in ethanol at 200 rpm. Tis purifcation step was used to remove impurities from Fe 3 O 4 nanoparticles. Te particles were fnally dried in vacuum at 70C. Magnetic chitosan beads: For preparation of chitosan beads with in situ prepared nanosized magnetite further denoted as CS-Fe 3 O 4 in situ solution containing 40 ml of 0.4 chitosan solution in 0.4 М HCl. 0.05 M FeCl 2 and 0.1 M FeCl 3 was prepared. Te obtained homogeneous solution was fltered and dropped through capillary diameter 0.5 mm into ammonium hydroxide precipitation bath 2.9 M NH 3 containing 0.026 М Na 2 SO 3 . Te prepared CS-Fe 3 O 4 in situ beads were kept in the precipitation bath for 24 h and then were repeatedly washed with deionized water to neutral reaction of the aqueous phase. Cu coating on nanoparticles: Copper coated nanoparticles were synthesised by electroless method 22 which involves following steps: - Activation of the particles surface: Magnetic chitosan beads were washed with acetone followed by absolute ethanol. Acetone and ethanol acts as degreasing agent and removes all the dust and other contaminants. Preparation of copper bath for coating of Magnetic Chitosan beads: Copper bath was prepared by adding 1:4 ratio of copper sulphate pentahydrate CuSO 4 .5H 2 O potassium sodium tartrate in preheated water at 70°C. Sodium hydroxide NaOH is used to adjust pH up to 10.8. Further above solution is followed to vigorous stirring. Add formaldehyde solution in 1:10 ratio soon aferwards activated particles of Magnetic chitosan beads were added into the copper bath. Filter the precipitate and dry it. Characterization Te crystal structure of the samples was studied using Bruker AXS D8 Advance powder X-Ray Difractometer using Cu Kα as target λ1.54 Å in the range 10-90 at a scan speed of 0.1per minute. Te morphology particle size and elemental composition analysis was performed by using transmission electron microscopy TEM Tecnai G2 20 feld emission scanning electron microscope FE-SEM Carl Zeiss Ultra Plus equipped with energy dispersive X-ray detector EDX operating at an accelerating voltage of 15-20 kV . Te chemical bonds were studied using Termo Nicolet Fourier Transform Infrared FTIR spectrometer in the range 4000-400cm -1 using KBr pellets. Te magnetic properties of the samples were studied by vibrating sample magnetometer VSM model number 155 Princeton Applied research. On the other hand stability of particles was evaluated by fnding out their potential at neutral pH using Malvern Zeta Sizer. For antibacterial activity tests 20 ml nutrient agar was poured in well- rinsed autoclaved petri plates and allowed to solidify. 100 µl of fresh bacterial culture of both the strains was homogeneously spread on the solidifed agar plates and 5 mg of iron oxide nanocomposites spread on plates. Te plates were incubated at 37°C for 24 h. Te zone size was determined by measuring the radius of the zone of inhibition by scale and divider. As III uptake studies Forty milliliters of As III solution of desired concentration was placed in diferent 125 ml Erlenmeyer fask containing 0.01 g of various iron oxide sorbents and was agitated in thermostatic water bath at 50 rpm for 3 h. At the end of experiment the sorbent was separated by fltration and supernatant was analyzed by ICP-MS Perkin Elmer SCIEX ELAN DRC-e. Result and Discussions FTIR analysis In Figure 1 a-c the bands at 3437 cm -1 1636 cm -1 1127 cm -1 and 617 cm -1 were involved in bonding. Band at 617 cm -1 represents the Fe-O-Fe vibrations. It is characteristic band of Fe 3 O 4 . Bands at 3437 cm -1 and 1636 cm -1 represent stretching and bending mode of O-H due to adsorption of water in sample 23. In Figure 1 c band at 2360 cm -1 represents acylamino bonds in chitosan. Figure 1: Showing FTIR Images of diferent Iron oxide composites: a Fe 3 O 4 b Fe 3 O 4 -Cu c Fe 3 O 4 - Chitosan d Fe 2 O 3 - Cu e Fe-Cu. Figure 1 d shows FTIR Image of Fe 2 O 3 coated with copper with bands at 3431 2360 1627 534 and 446 cm -1 . Bands at 534 and 446 cm -1 correspond to Fe-O-Fe vibrations and were characteristic peak of Fe 2 O 3 . Te rest bands are involved in bonding with copper. Similarly in Figure 1 e bands observed at 3430 1630 1380 1109 cm -1 are involved in bonding with copper and 747 and 517 cm -1 were characteristic peaks of Fe vibrations. XRD analysis Figure 2 projects the XRD images of all the samples. Figure 2 a shows the XRD pattern of Fe 2 O 3 coated with copper. Te peaks at 2θ32.75 35.58 40.47 and 56.59 correspond to hematite JCPDS Card No. 01-073-0603 phase in the material to the planes 004 110 113 and 211 respectively marked by in the image. Te peak at 2θ73.28 marked by in the image indicate existence of both Fe 2 O 3 and copper JCPDS Card No. 004-0836 phases. Tus the XRD pattern confrms the coating of copper over Fe 2 O 3 particles. Te peaks in Figure 2 b at 2θ43.60 50.72 and 74.37 correspond to copper atoms Citation: Namdeo M Mathur A 2018 Preparation and Application of Magnetic Materials for the Removal of As III from Aqueous Solutions. J Adv Chem Eng 8: 189. doi:10.4172/2090-4568.1000189 Page 2 of 6 J Adv Chem Eng an open access journal ISSN: 2090-4568 Volume 8 • Issue 2 • 1000189

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JCPDS Card No. 00-003-1015 marked by in the image and those at 2θ44.94 and 82.47 correspond to iron atoms JCPDS 00-001-1267 marked by in the image thus indicating the presence of both atoms. Figure 2: Represents XRD patterns of various Iron oxide composites: a Fe 2 O 3 - Cu b Fe-Cu c Fe 3 O 4 d Fe 3 O 4 - CS and e Fe 3 O 4 -Cu. In Figure 2 c shows the XRD pattern of magnetite particles. Te peaks at 2θ values 30.3 35.6 43.1 53.6 and 57.0 degree correspond to the plane 220 311 400 422 ad 511 respectively. It confrms the presence of Fe 3 O 4 and not γ-Fe 2 O 3 JCPDS Card no. 019-0629. In Figure 2 d was the XRD image of chitosan coated with Fe 3 O 4 with peak at 2θ31.64 corresponding to chitosan JCPDS Card No. 039-1894. Peaks at 2θ37.87 and 65.74 refers to Fe 3 O 4 JCPDS Card No. 019-0629. In Figure 2 e shows the XRD pattern of Fe 3 O 4 coated with copper. Te peaks at 2θ43.07 and 50.08 correspond copper JCPDS Card No. 04-0836 phase in the material to the planes 111 and 200 respectively marked by in the image. Te peak at 2θ73.89 marked by in the image indicate existence of both Fe 3 O 4 JCPDS Card No. 008-0087 and copper phases. Tus the XRD pattern confrms the coating of copper over Fe 3 O 4 particles. FE-SEM analysis Figure 3 represents FESEM images of all the samples along with EDX analysis. Figure 3 a shows the image of Fe 3 O 4 coated with copper with spherical shaped particles of size 55 µm mean diameter. Figure 3 b shows Fe 2 O 3 coated with copper nano rod like particles with average length 220nm. Figure 3 c is Fe 3 O 4 with non-uniform size of particles varying from around 15 µm to 85 µm. In Figure 3 d depicts uniform sized Fe particles coated with copper particles with average diameter of particles 150 µm. Figure 3 e is the image of Fe 3 O 4 - Chitosan beads were porous and spherical in shape the average diameter of each bead is 377 µm. Figure 3: Shows FESEM images following composites a Fe 3 O 4 - Cu b Fe 2 O 3 - Cu c Fe 3 O 4 d Fe-Cu e Fe 3 O 4 - Chitosan beads. TEM analysis Te morphological and structural features of Magnetite chitosan nanocomposites were also characterised by transmission electron microscopy TEM coupled to an energy dispersive EDX microprobe and selected area electron difraction SAED analysis. Te size distribution histogram presented fairly monodispersed nanoparticles with the average size of 10-20 nm in good agreement. EDX spectra showed the chemical analysis of nanocrystals with Fe and chitosan C N O as the major elements Figure 4. Figure 4: Represents TEM image of Fe 3 O 4 Chitosan bead a TEM image inset: SAED image b particle size distribution histogram of Fe 3 O 4 Chitosan beads and c EDX spectrum. Zeta potential analysis Figure 5 shows zeta potentials of samples taken in their stable colloidal suspension at neutral pH: a Fe 3 O 4 - Cu: -11.7 mV b Fe 2 O 3 - Cu: -16.1 mV c Fe 3 O 4 : 11.9 mV d Fe-Cu: -14.4 mV e Fe 3 O 4 - Chitosan: 19.1mV at acidic pH 5.5. Te positive zeta potential of Fe 3 O 4 chitosan is because of the presence of positively charged chitosan. Te negative potential of copper coated nanocomposites may be attributed to the presence of copper. Citation: Namdeo M Mathur A 2018 Preparation and Application of Magnetic Materials for the Removal of As III from Aqueous Solutions. J Adv Chem Eng 8: 189. doi:10.4172/2090-4568.1000189 Page 3 of 6 J Adv Chem Eng an open access journal ISSN: 2090-4568 Volume 8 • Issue 2 • 1000189

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Figure 5: Represents Zeta potential of diferent a Fe 3 O 4 - Cu b Fe 2 O 3 - Cu c Fe 3 O 4 d Fe-Cu and e Fe 3 O 4 - Chitosan. VSM analysis Figure 6 depicts VSM images of all the samples. Zero coercivity indicates superparamagnetic nature of the sample. Magnetic saturation is observed at 1.08 emu/g 0.8 emu/g 0.77 emu/g 0.64 emu/g and 0.54 emu/g respectively for Fe- Cu Fe 3 O 4 Fe 3 O 4 - Cu Fe 3 O 4 - Chitosan and Fe 2 O 3 - Cu. Tese values indicate that the samples have strong magnetic responsivity and can be easily separated from solution using magnetic feld. Figure 6: VSM image of a Fe-Cu b Fe 3 O 4 c Fe 3 O 4 - Cu d Fe 3 O 4 - chitosan and e Fe 2 O 3 -Cu. Sorption studies 0.1 g of Iron oxide nanocomposites was loaded with As III0.5 mg/l using 40 ml at pH 5.5 agitation period of 180 mins at RT and the agitation rate was 200 r/min. Adsorbed Iron oxide particles collected by magnetic device and was analysed by ICP-MS. Te removal percent of As III in wastewater was calculated from the following equation: Removal1-m2/m1 × 100 Where m1 is the initial amount mg of As III and m2 is the amount mg of As III unadsorbed. Te result of percent removal of As III by diferent Iron oxide composites were shown in Figure 7. Afer adsorption among diferent iron oxide materials chitosan magnetite bead was found to be higher in percentage removal of As III 93. Figure 7: Graph represents the percentage removal of As III by various iron oxide samples. Antibacterial activity We have investigated the biocidal action of diferent iron oxide nanocomposites. For this we considered E.coli and S.aureus as model bacteria and observed their growth in the presence of various iron oxide nanocomposites by spread plate method. For qualitative measurement spread plate method was used. Te nutrient agar was spread into the petri plate over the nanocomposites the culture of both the bacteria’s i.e gram positive and gram negative was spread on it. 5mg of each sample was taken and was incubated for 12 hours. Figure 8: Showing the antibacterial efect of: a Fe 2 O 3 - Cu and Fe 3 O 4 b Fe 3 O 4 - Cu and Fe-Cu c Fe 3 O 4 - Chitosan using E. coli DH5α. A marked diference was observed in the plates containing the Copper coated chitosan magnetite nanocomposite with a diameter of 1 cm as compared with the other iron oxide nanocomposites. Tis result is clearly evident in the Figure and which confrms from zone of inhibition area that Cu coated Chitosan magnetite nanocomposites have strong inhibitory action against E.coli and S.aureus 24-26. Citation: Namdeo M Mathur A 2018 Preparation and Application of Magnetic Materials for the Removal of As III from Aqueous Solutions. J Adv Chem Eng 8: 189. doi:10.4172/2090-4568.1000189 Page 4 of 6 J Adv Chem Eng an open access journal ISSN: 2090-4568 Volume 8 • Issue 2 • 1000189

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Figure 9: Showing the antibacterial efect of: a Fe- Cu and Fe 3 O 4 b Fe 3 O 4 - Cu and Fe 3 O 4 -Cu c Fe 3 O 4 - Chitosan using S. aureus. Conclusion Iron oxide nanocomposites were prepared for wastewater treatment. Adsorption occurs by exchange between OH 2 and -OH by As atoms in the coordination spheres of Fe atoms. Chitosan contains many hydroxyl and amino functional groups that act as adsorption sites for arsenic atoms. When dissolved in water these amino groups gets deprotonated and bind with metal ions through chelation mechanism. Te best adsorption conditions are pH 5.5 adsorption time 180 mins at RT. Te used level was 0.1 g iron oxide nanocomposites added in 40 ml solution contained 0.5 mg/l As III. Te removal percent of As III from aqueous solution by magnetic chitosan beads was found to be 93. It can be concluded that magnetic chitosan beads are an efective adsorbent for the removal of As III and microbes for the wastewater treatment. Acknowledgements Te project was supported by Water Technology Initiative WTI Department of Science and Technology DST New Delhi. Te authors would like to acknowledge their generous support. References 1. Bissen M Frimmel FH 2003 Arsenic-a Review. Part I: Occurrence Toxicity Speciation Mobility. Acta Hydrochim. Hydrobiol 31: 9. 2. Twidwell LG McCloskey J Miranda P Gale M Gaballah I et al. 1999 Proceedings of the Global Symposium on Recycling Waste Treatment and Clean Technology Warreandale Pennsylvania United States p: 1715. 3. Hua M Zhang S Pan B Zhang W Lv L et al. 2012 Heavy metal removal from water / wastewater by nanosized metal oxides: A review. J Hazard Mater 212: 317-331. 4. Ergül B Bektaş N Öncel MS 2014 Te Use of Manganese Oxide Minerals for the Removal Arsenic and Selenium Anions from Aqueous Solutions. Energy Environ 2: 103-112. 5. Suzuki TM Bomani JO Matsunaga H Y okoyama T 2000 Preparation of porous resin loaded with crystalline hydrous zirconium oxide and its application to the removal of arsenic. React Funct Polym 43: 165-172. 6. Ouvrard S Simonnot MO Sardin M 2002 Reactive behavior of natural manganese oxides toward the adsorption of phosphate and arsenate. Eng Chem 41: 2785-2791. 7. Pena ME Korfatis GP Patel M Lippincott L Meng X 2005 Adsorption of AsV and AsIII by nanocrystalline titanium dioxide. Water Res 11: 2327-2337. 8. Ghimire KN Inoue K Makino K Miyajima T 2002 Adsorptive Removal of Arsenic Using Orange Juice Residue. Sep Sci Technol 37: 2785-2799. 9. Wasiuddin NM Tango M Islam MR 2002 A Novel Method for Arsenic Removal at Low Concentrations. Energy Sour 24: 1031-1041. 10. Çifçi TD Henden E 2015 Nickel/nickel boride nanoparticles coated resin: A novel adsorbent for arsenic III and arsenicV removal. Powder Technol 269: 470-480. 11. Ali I Othman ZA Alwarthan A Asim M Khan TA 2014 Removal of arsenic species from water by batch and column operations on bagasse fy ash. Environ. Sci Pollut Res Int 21: 3218-3229. 12. Wang S Gao B Zimmerman AR Li Y Harris WG et al. 2015 Removal of arsenic by magnetic biochar prepared from pinewood and natural hematite. Bioresour Technol 175: 391-395. 13. Raven KP Jain A Loeppert RH 1998 Arsenite and Arsenate Adsorption on Ferrihydrite: Surface Charge Reduction and Net OH- Release Stoichiometry. Environ Sci Technol p: 344. 14. Pierce ML Moore CB 1981 Adsorption of Arsenite and Arsenate on Amorphous iron hydroxide from dilute aqueous solution. Water Res p: 1247. 15. Gross PR Eick M Calvin CA DL Sparks Sabine G 1997 Arsenate and Chromate Retention Mechanisms on Goethite. 2. Kinetic Evaluation Using a Pressure-Jump Relaxation Technique. Environ Sci Technol 31: 321-326. 16. Manceau A 1995 Te mechanism of anion adsorption on iron oxides: Evidence for the bonding of arsenate tetrahedra on free Fe O OH 6 edges. Geochimica et Cosmochimica Acta 59: 3647-3653. 17. GA Waychunas Rea BA Fuller CC Davis JA 1993 Surface chemistry of ferrihydrite: Part 1. EXAFS studies of the geometry of coprecipitated and adsorbed arsenate. Geochimica et Cosmochimica Acta 57: 2251-2269. 18. Arai K Kinumaki T Fujita T Tokai B 1968 Toxicity of Chitosan. Reg Fish Res Lab p: 89. 19. Konieczny J Rdzawski Z 2012 Antibacterial properties of copper and its alloys. Mater Sci Eng 56: 53-60. 20. Anitha A Divya VV Krishna R Sreeja V Selvamurugan N et al. 2009 Synthesis characterization cytotoxicity and antibacterial studies of chitosan O-carboxymethyl and NO-carboxymethyl chitosan nanoparticles. Carbohydr Polym 78: 672-677. 21. Huang SH Liao MH Chen DH 2003 Direct binding and characterization of lipase onto magnetic nanoparticles. Biotechnol Prog 19: 1095-1100. 22. Sharma R Agarwala RC Agarwala V 2006 Development of copper coatings on ceramic powder by electroless technique. Appl Surf Sci 252: 8487-8493. 23. Namdeo M Bajpai SK 2008 Chitosan magnetite nanocomposites CMNs as magnetic carrier particles for removal of FeIII from aqueous solutions. Colloids Surf A Physicochem Eng Asp 320: 161-168. 24. Ahamed M Siddiqui M Akhtar MJ Ahmad I Pant AB et al. 2010 Genotoxic potential of copper oxide nanoparticles in human lung epithelial cells. Biochem Biophys Res Commun 396: 578-583. 25. Singh P Bajpai J Bajpai AK and Shrivastava BR 2011 Removal of arsenic ions and bacteriological contamination from aqueous solutions using chitosan nanospheres. Indian J ChemTechn 18: 403-413. 26. Elson CM Davies DH Hayes ER 1980 Removal of arsenic from contaminated drinking water by a chitosan/ chitin mixture. Water Res 14: 1307-1311. Citation: Namdeo M Mathur A 2018 Preparation and Application of Magnetic Materials for the Removal of As III from Aqueous Solutions. J Adv Chem Eng 8: 189. doi:10.4172/2090-4568.1000189 Page 5 of 6 J Adv Chem Eng an open access journal ISSN: 2090-4568 Volume 8 • Issue 2 • 1000189

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Citation: Namdeo M Mathur A 2018 Preparation and Application of Magnetic Materials for the Removal of As III from Aqueous Solutions. J Adv Chem Eng 8: 189. doi:10.4172/2090-4568.1000189 Page 6 of 6 J Adv Chem Eng an open access journal ISSN: 2090-4568 Volume 8 • Issue 2 • 1000189

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