Skip to main content
SpringerLink
Log in

Optimized removal of phosphate and nitrate from aqueous media using zirconium functionalized nanochitosan-graphene oxide composite

  • Original Research
  • Published:
Cellulose Aims and scope Submit manuscript

Abstract

The decontamination of excess nutrients by polysaccharide-graphene oxide composites has gained much research attention. However, the usage of synthetic polymers and toxic crosslinking agents affects the environment. This investigation is, therefore, aimed at achieving a simple, effective and nontoxic technique of fabricating nanocomposites by ionotropic gelation of chitosan and tripolyphosphate crosslinking agent. The nanochitosan-graphene oxide composite (NCS@GO) was synthesized and investigated for its potential to remove phosphate (P) and nitrate (N) from aqueous solutions. High and low amounts of zirconium (Zr) were loaded in NCT@GO composite to make it selective for the adsorbate anions. The developed nanocomposites were comparatively explored by N2 isotherms, FTIR, XRD, TGA, DTA, FESEM, EDS with mapping analysis and water regain property. Experimental design was conducted by the five-factorial central composite design-as a branch of response surface methodology (RSM). According to the design of RSM, NCS@GO/H-Zr demonstrated an excellent P and N uptake of 172.41 mgP/g and 138.88 mgN/g, reasonable pH-compatibility from 3 to 11, suitable selectivity for both adsorbates among competitor anions, desired recyclability and desorption efficiency for P and N, and retained 76% and 85% for P and N adsorption ability after ten recycles. The removal capacity of P and N anions were also assessed in bi-component systems. Thermodynamic data were considered, in which it was found that the adsorptive removal of the both anions was endothermic and spontaneous in nature. The adsorption isotherm of P and N on the surface of the NCS@GO/H-Zr was suitable for the Freundlich isotherm model, suggesting the multilayer adsorption. On the basis of kinetic studies, specific rate constants involved in the processes were calculated and the obtained result indicates that the pseudo second order kinetics was found to be a better fit. Real samples analysis indicated that the NCS@GO/H-Zr works well for removal of P and N from contaminated waters.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Scheme 1
Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9
Fig. 10
Fig. 11

Similar content being viewed by others

References

  • Agarwal S, Rajoria P, Rani A (2018) Adsorption of tannic acid from aqueous solution onto chitosan/NaOH/fly ash composites: Equilibrium, kinetics, thermodynamics and modeling. J Environ Chem Eng 6:1486–1499

    CAS  Google Scholar 

  • Ali I (2014) Water treatment by adsorption columns: evaluation at ground level. Sep Purif Rev 43:175–205

    CAS  Google Scholar 

  • Ali I, Gupta V (2006) Advances in water treatment by adsorption technology. Nat Protoc 1:2661

    CAS  PubMed  Google Scholar 

  • Ali I, Asim M, Khan TA (2012) Low cost adsorbents for the removal of organic pollutants from wastewater. J Environ Manag 113:170–183

    CAS  Google Scholar 

  • Ali I, Alharbi OM, Tkachev A, Galunin E, Burakov A, Grachev VA (2018) Water treatment by new-generation graphene materials: hope for bright future. nviron. Sci Pollut Res 25:7315–7329

    CAS  Google Scholar 

  • Anbia M, Salehi S (2016) Synthesis of polyaniline/mesoporous carbon nanocomposites and their application for CO2 sorption. J Polym Res 23:124

    Google Scholar 

  • Antunes E, Jacob MV, Brodie G, Schneider P (2018) Isotherms, kinetics and mechanism analysis of phosphorus recovery from aqueous solution by calcium-rich biochar produced from biosolids via microwave pyrolysis. J Environ Chem Eng 6:395–403

    CAS  Google Scholar 

  • Bagheri M, Younesi H, Hajati S, Borghei SM (2015) Application of chitosan-citric acid nanoparticles for removal of chromium (VI). Int J Biol Macromol 80:431–444

    CAS  PubMed  Google Scholar 

  • Banu HT, Meenakshi S (2017) One pot synthesis of chitosan grafted quaternized resin for the removal of nitrate and phosphate from aqueous solution. Int J Biol Macromol 104:1517–1527

    CAS  PubMed  Google Scholar 

  • Banu HT, Karthikeyan P, Meenakshi S (2018) Lanthanum (III) encapsulated chitosan-montmorillonite composite for the adsorptive removal of phosphate ions from aqueous solution. Int J Biol Macromol 112:284–293

    Google Scholar 

  • Banu HT, Karthikeyan P, Meenakshi S (2019) Zr4+ ions embedded chitosan-soya bean husk activated bio-char composite beads for the recovery of nitrate and phosphate ions from aqueous solution. Int J Biol Macromol 130:573–583

    CAS  PubMed  Google Scholar 

  • Boeykens SP, Piol MN, Samudio Legal L, Saralegui AB, Vázquez C (2017) Eutrophication decrease: phosphate adsorption processes in presence of nitrates. J Environ Manag 203:888–895

    CAS  Google Scholar 

  • Chatterjee S, Woo SH (2009) The removal of nitrate from aqueous solutions by chitosan hydrogel beads. J Hazard Mater 164:1012–1018

    CAS  PubMed  Google Scholar 

  • Chatterjee S, Lee DS, Lee MW, Woo SH (2009) Nitrate removal from aqueous solutions by cross-linked chitosan beads conditioned with sodium bisulfate. J Hazard Mater 166:508–513

    CAS  PubMed  Google Scholar 

  • Cui X, Dai X, Khan KY, Li T, Yang X, He Z (2016) Removal of phosphate from aqueous solution using magnesium-alginate/chitosan modified biochar microspheres derived from Thalia dealbata. Bioresour Technol 218:1123–1132

    CAS  PubMed  Google Scholar 

  • Cui X, Li H, Yao Z, Shen Y, He Z, Yang X, Ng HY, Wang C-H (2019) Removal of nitrate and phosphate by chitosan composited beads derived from crude oil refinery waste: sorption and cost-benefit analysis. J Clean Prod 207:846–856

    CAS  Google Scholar 

  • Dewage NB, Liyanage AS, Pittman CU Jr, Mohan D, Mlsna T (2018) Fast nitrate and fluoride adsorption and magnetic separation from water on α-Fe2O3 and Fe3O4 dispersed on Douglas fir biochar. Bioresour Technol 263:258–265

    Google Scholar 

  • Dharupaneedi SP, Anjanapura RV, Han JM, Aminabhavi TM (2014) Functionalized graphene sheets embedded in chitosan nanocomposite membranes for ethanol and isopropanol dehydration via pervaporation. Ind Eng Chem Res 53:14474–14484

    CAS  Google Scholar 

  • Fan Y, Li Y, Wu D, Li C, Kong H (2017) Application of zeolite/hydrous zirconia composite as a novel sediment capping material to immobilize phosphorus. Water Res 123:1–11

    PubMed  Google Scholar 

  • Federation WE, Association APH (2005) Standard methods for the examination of water and wastewater. American Public Health Association (APHA), Washington

    Google Scholar 

  • Freundlich H (1907) Über die adsorption in lösungen. Z Phys Chem 57:385–470

    CAS  Google Scholar 

  • Hamoudi S, Belkacemi K (2013) Adsorption of nitrate and phosphate ions from aqueous solutions using organically-functionalized silica materials: kinetic modeling. Fuel 110:107–113

    CAS  Google Scholar 

  • Hu Q, Zhang Z (2019) Application of Dubinin-Radushkevich isotherm model at the solid/solution interface: a theoretical analysis. J Mol Liq 277:646–648

    CAS  Google Scholar 

  • Huang X, Liao X, Shi B (2009) Adsorption removal of phosphate in industrial wastewater by using metal-loaded skin split waste. J Hazard Mater 166:1261–1265

    CAS  PubMed  Google Scholar 

  • Huang W-Y, Li D, Liu Z-Q, Tao Q, Zhu Y, Yang J, Zhang Y-M (2014) Kinetics, isotherm, thermodynamic, and adsorption mechanism studies of La (OH) 3-modified exfoliated vermiculites as highly efficient phosphate adsorbents. Chem Eng J 236:191–201

    CAS  Google Scholar 

  • Islam M, Patel R (2010) Synthesis and physicochemical characterization of Zn/Al chloride layered double hydroxide and evaluation of its nitrate removal efficiency. Desalination 256:120–128

    CAS  Google Scholar 

  • Iyer K, Kunju A (1992) Extension of Harkins—Jura adsorption isotherm to solute adsorption. Colloids Surf 63:235–240

    CAS  Google Scholar 

  • Jiang H, Chen P, Luo S, Tu X, Cao Q, Shu M (2013) Synthesis of novel nanocomposite Fe3O4/ZrO2/chitosan and its application for removal of nitrate and phosphate. Appl Surf Sci 284:942–949

    CAS  Google Scholar 

  • Jovanovic D (1969) Physical adsorption of gases, I, Isotherms for monolayer and multilayer adsorption. Kolloid Z Z Polym 235:1203

    CAS  Google Scholar 

  • Jóźwiak T, Filipkowska U, Szymczyk P, Kuczajowska-Zadrożna M, Mielcarek A (2017) The use of cross-linked chitosan beads for nutrients (nitrate and orthophosphate) removal from a mixture of P-PO4, N-NO2 and N-NO3. Int J Biol Macromol 104:1280–1293

    PubMed  Google Scholar 

  • Jóźwiak T, Filipkowska U, Szymczyk P, Mielcarek A (2019) Sorption of nutrients (orthophosphate, nitrate III and V) in an equimolar mixture of P-PO4, N–NO2 and N–NO3 using chitosan. Arab J Chem 12:4104–4117

    Google Scholar 

  • Karthikeyan P, Banu HAT, Meenakshi S (2019) Synthesis and characterization of metal loaded chitosan-alginate biopolymeric hybrid beads for the efficient removal of phosphate and nitrate ions from aqueous solution. Int J Biol Macromol 130:407–418

    CAS  PubMed  Google Scholar 

  • Keshvardoostchokami M, Babaei S, Piri F, Zamani A (2017) Nitrate removal from aqueous solutions by ZnO nanoparticles and chitosan-polystyrene–Zn nanocomposite: kinetic, isotherm, batch and fixed-bed studies. Int J Biol Macromol 101:922–930

    CAS  PubMed  Google Scholar 

  • Kumar IA, Viswanathan N (2017) Fabrication of metal ions cross-linked alginate assisted biocomposite beads for selective phosphate removal. J Environ Chem Eng 5:1438–1446

    CAS  Google Scholar 

  • Kumar IA, Viswanathan N (2019) Micro-encapsulation and hydrothermal tuning of amine decorated magnetic alginate hybrid beads for nitrate and phosphate remediation. J Taiwan Inst Chem Eng 102:283–296

    CAS  Google Scholar 

  • Kumar IA, Jeyaprabha C, Meenakshi S, Viswanathan N (2019) Hydrothermal encapsulation of lanthanum oxide derived Aegle marmelos admixed chitosan bead system for nitrate and phosphate retention. Int J Biol Macromol 130:527–535

    CAS  PubMed  Google Scholar 

  • Langmuir I (1918) The adsorption of gases on plane surfaces of glass, mica and platinum. J Am Chem Soc 40:1361–1403

    CAS  Google Scholar 

  • Li R, Wang JJ, Zhou B, Awasthi MK, Ali A, Zhang Z, Gaston LA, Lahori AH, Mahar A (2016) Enhancing phosphate adsorption by Mg/Al layered double hydroxide functionalized biochar with different Mg/Al ratios. Sci Total Environ 559:121–129

    CAS  PubMed  Google Scholar 

  • Lin J, He S, Wang X, Zhang H, Zhan Y (2019) Removal of phosphate from aqueous solution by a novel Mg(OH)2/ZrO2 composite: adsorption behavior and mechanism. Colloids Surf A 561:301–314

    CAS  Google Scholar 

  • Luo W, Huang Q, Zhang X, Antwi P, Mu Y, Zhang M, Xing J, Chen H, Ren S (2020) Lanthanum/Gemini surfactant-modified montmorillonite for simultaneous removal of phosphate and nitrate from aqueous solution. J Water Process Eng 33:101036

    Google Scholar 

  • Mallakpour S, Hatami M (2019) Fabrication and characterization of pH-sensitive bio-nanocomposite beads havening folic acid intercalated LDH and chitosan: drug release and mechanism evaluation. Int J Biol Macromol 122:157–167

    CAS  PubMed  Google Scholar 

  • Mirhosseinian NS, Anbia M, Salehi S (2020) Preparation and characterization of superhydrophobic melamine and melamine-derived carbon sponges modified with reduced graphene oxide–TiO2 nanocomposite as oil absorbent materials. J Mater Sci 55:1536–1552

    CAS  Google Scholar 

  • Negm NA, Hefni HHH, Abd-Elaal AAA, Badr EA, Abou Kana MTH (2020) Advancement on modification of chitosan biopolymer and its potential applications. Int J Biol Macromol 152:681–702

    CAS  PubMed  Google Scholar 

  • Orlando U, Baes A, Nishijima W, Okada M (2002) Preparation of agricultural residue anion exchangers and its nitrate maximum adsorption capacity. Chemosphere 48:1041–1046

    CAS  PubMed  Google Scholar 

  • Pan J, Gao B, Song W, Xu X, Yue Q (2020) Modified biogas residues as an eco-friendly and easily-recoverable biosorbent for nitrate and phosphate removals from surface water. J Hazard Mater 382:121073

    CAS  PubMed  Google Scholar 

  • Pooja D, Kumar P, Singh P, Patil S (2020) Sensors in water pollutants monitoring: role of material. Springer, New York

    Google Scholar 

  • Qiang GYXJB, Yewei D (2013) Adsorption of sulfate onto Zr (IV) loaded cross-linked chitosan. Chin J Environ Eng 5:2019–2024

    Google Scholar 

  • Rahmi L, Nurfatimah R (2018) Preparation of polyethylene glycol diglycidyl ether (PEDGE) crosslinked chitosan/activated carbon composite film for Cd2+ removal. Carbohydr Polym 199:499–505

    CAS  PubMed  Google Scholar 

  • Rajeswari A, Amalraj A, Pius A (2015) Removal of phosphate using chitosan-polymer composites. J. Environ Chem Eng 3:2331–2341

    CAS  Google Scholar 

  • Rajeswari A, Amalraj A, Pius A (2016) Adsorption studies for the removal of nitrate using chitosan/PEG and chitosan/PVA polymer composites. J Water Process Eng 9:123–134

    Google Scholar 

  • Rathod M, Mody K, Basha S (2014) Efficient removal of phosphate from aqueous solutions by red seaweed, Kappaphycus alverezii. J Clean Prod 84:484–493

    CAS  Google Scholar 

  • Rodrigues LA, da Silva MLCP (2010) Thermodynamic and kinetic investigations of phosphate adsorption onto hydrous niobium oxide prepared by homogeneous solution method. Desalination 263:29–35

    CAS  Google Scholar 

  • Salehi S, Anbia M (2019) Performance comparison of chitosan–clinoptilolite nanocomposites as adsorbents for vanadium in aqueous media. Cellulose 26:5321–5345

    CAS  Google Scholar 

  • Salehi S, Hosseinifard M (2020) Highly efficient removal of phosphate by lanthanum modified nanochitosan-hierarchical ZSM-5 zeolite nanocomposite: characteristics and mechanism. Cellulose 5:6141–6152

    Google Scholar 

  • Salehi S, Anbia M, Hosseiny AH, Sepehrian M (2018) Enhancement of CO2 adsorption on polyethylenimine functionalized multiwalled carbon nanotubes/Cd-nanozeolite composites. J Mol Struct 1173:792–800

    CAS  Google Scholar 

  • Salehi S, Mandegarzad S, Anbia M (2020) Preparation and characterization of metal organic framework-derived nanoporous carbons for highly efficient removal of vanadium from aqueous solution. J Alloys Compd 812:152051

    CAS  Google Scholar 

  • Saxena S, Tyson TA, Shukla S, Negusse E, Chen H, Bai J (2011) Investigation of structural and electronic properties of graphene oxide. Appl Phys Lett 99:013104

    Google Scholar 

  • Shan W, Zhang D, Wang X, Wang D, Xing Z, Xiong Y, Fan Y, Yang Y (2019) One-pot synthesis of mesoporous chitosan-silica composite from sodium silicate for application in Rhenium(VII) adsorption. Microporous Mesoporous Mater 278:44–53

    CAS  Google Scholar 

  • Shen H, Wang Z, Zhou A, Chen J, Hu M, Dong X, Xia Q (2015) Adsorption of phosphate onto amine functionalized nano-sized magnetic polymer adsorbents: mechanism and magnetic effects. RSC Adv 5:22080–22090

    CAS  Google Scholar 

  • Shrock DL, Krasowski MD (2020) Chapter 23.5—Methemoglobinemia due to dietary nitrate. In: Ketha H, Garg U (eds) Toxicology cases for the clinical and forensic laboratory. Academic Press, Boca Raton, pp 469–472

    Google Scholar 

  • Sowmya A, Meenakshi S (2014) A novel quaternized chitosan–melamine–glutaraldehyde resin for the removal of nitrate and phosphate anions. Int J Biol Macromol 64:224–232

    CAS  PubMed  Google Scholar 

  • Swain S, Dey R, Islam M, Patel R, Jha U, Patnaik T, Airoldi C (2009) Removal of fluoride from aqueous solution using aluminum-impregnated chitosan biopolymer. Sep Sci Technol 44:2096–2116

    CAS  Google Scholar 

  • Tang T, Cao S, Xi C, Li X, Zhang L, Wang G, Chen Z (2020) Chitosan functionalized magnetic graphene oxide nanocomposite for the sensitive and effective determination of alkaloids in hotpot. Int J Biol Macromol 146:343–352

    CAS  PubMed  Google Scholar 

  • Teimouri A, Nasab SG, Vahdatpoor N, Habibollahi S, Salavati H, Chermahini AN (2016) Chitosan/Zeolite Y/Nano ZrO2 nanocomposite as an adsorbent for the removal of nitrate from the aqueous solution. Int J Biol Macromol 93:254–266

    CAS  PubMed  Google Scholar 

  • Temkin M (1940) Kinetics of ammonia synthesis on promoted iron catalysts. Acta Physiochim URSS 12:327–356

    CAS  Google Scholar 

  • Wang Z, Guo H, Shen F, Yang G, Zhang Y, Zeng Y, Wang L, Xiao H, Deng S (2015) Biochar produced from oak sawdust by Lanthanum (La)-involved pyrolysis for adsorption of ammonium (NH4 +), nitrate (NO3−), and phosphate (PO43−). Chemosphere 119:646–653

    CAS  PubMed  Google Scholar 

  • Wang S, Ma X, Zheng P (2019) Sulfo-functional 3D porous cellulose/graphene oxide composites for highly efficient removal of methylene blue and tetracycline from water. Int J Biol Macromol 140:119–128

    CAS  PubMed  Google Scholar 

  • Wu F-C, Tseng R-L, Juang R-S (2001) Kinetic modeling of liquid-phase adsorption of reactive dyes and metal ions on chitosan. Water Res 35:613–618

    CAS  PubMed  Google Scholar 

  • Wu B, Fang L, Fortner JD, Guan X, Lo IM (2017) Highly efficient and selective phosphate removal from wastewater by magnetically recoverable La(OH)3/Fe3O4 nanocomposites. Water Res 126:179–188

    CAS  PubMed  Google Scholar 

  • Xi Y, Mallavarapu M, Naidu R (2010) Preparation, characterization of surfactants modified clay minerals and nitrate adsorption. Appl Clay Sci 48:92–96

    CAS  Google Scholar 

  • Xiong W, Peng J (2008) Development and characterization of ferrihydrite-modified diatomite as a phosphorus adsorbent. Water Res 42:869–4877

    Google Scholar 

  • Yadav M, Ahmad S (2015) Montmorillonite/graphene oxide/chitosan composite: synthesis, characterization and properties. Int J Biol Macromol 79:923–933

    CAS  PubMed  Google Scholar 

  • Yan B, Zeng C, Yu L, Wang C, Zhang L (2018) Preparation of hollow zeolite NaA/chitosan composite microspheres via in situ hydrolysis-gelation-hydrothermal synthesis of TEOS. Microporous Mesoporous Mater 257:262–271

    CAS  Google Scholar 

  • Yang L, Yang M, Xu P, Zhao X, Bai H, Li H (2017) Characteristics of nitrate removal from aqueous solution by modified steel slag. Water 9:757

    Google Scholar 

  • Yazdi F, Anbia M, Salehi S (2019) Characterization of functionalized chitosan-clinoptilolite nanocomposites for nitrate removal from aqueous media. Int J Biol Macromol 130:545–555

    CAS  PubMed  Google Scholar 

  • Yin Q, Wang R, Zhao Z (2018) Application of Mg–Al-modified biochar for simultaneous removal of ammonium, nitrate, and phosphate from eutrophic water. J Clean Prod 176:230–240

    CAS  Google Scholar 

  • Zamparas M, Drosos M, Georgiou Y, Deligiannakis Y, Zacharias I (2013) A novel bentonite-humic acid composite material Bephos™ for removal of phosphate and ammonium from eutrophic waters. Chem Eng J 225:43–51

    CAS  Google Scholar 

  • Zhang L, Liu X, Xia W, Zhang W (2014) Preparation and characterization of chitosan-zirconium (IV) composite for adsorption of vanadium (V). Int J Biol Macromol 64:155–161

    CAS  PubMed  Google Scholar 

  • Zhang J, Chen N, Tang Z, Yu Y, Hu Q, Feng C (2015) A study of the mechanism of fluoride adsorption from aqueous solutions onto Fe-impregnated chitosan. Phys Chem Chem Phys 17:12041–12050

    CAS  PubMed  Google Scholar 

Download references

Acknowledgments

The authors would like to thank the Materials and Energy Research Center (Grant No. 9911940) for the financial support of this project.

Author information

Authors and Affiliations

  1. Environment Research Department, Energy and Environment Research Center, Niroo Research Institute, End of Dadman Blvd, Shahrak-e-Ghods, P.O. Box 14665-517, Tehran, Iran

    Samira Salehi

  2. Department of Semiconductors, Materials and Energy Research Center, P.O. Box 31787-316, Karaj, Iran

    Mojtaba Hosseinifard

Authors
  1. Samira Salehi
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Mojtaba Hosseinifard
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Mojtaba Hosseinifard.

Additional information

Publisher's Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary material 1 (DOCX 440 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Salehi, S., Hosseinifard, M. Optimized removal of phosphate and nitrate from aqueous media using zirconium functionalized nanochitosan-graphene oxide composite. Cellulose 27, 8859–8883 (2020). https://doi.org/10.1007/s10570-020-03382-5

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10570-020-03382-5

Keywords

Search

Navigation