Skip to main content
SpringerLink
Log in

Optimizing the removal of nitrate from aqueous solutions via reduced graphite oxide–supported nZVI: synthesis, characterization, kinetics, and reduction mechanism

  • Research Article
  • Published:
Environmental Science and Pollution Research Aims and scope Submit manuscript

Abstract

Graphene has been considered an ideal absorbent and excellent carrier for nanoparticles. Reduced graphite oxide (rGO)–supported nanoscale zero-valent iron (nZVI@rGO) is an effective material for removing nitrate from water. nZVI@rGO nanocomposites were prepared by a liquid-phase reduction method and then applied for nitrate-nitrogen (NO3−-N) removal in aqueous solution under anaerobic conditions. The experimental results showed that the stability and activity of the nZVI@rGO nanocomposites were enhanced compared with those of nZVI. The influence of the reaction conditions, including the initial concentration of NO3−-N, coexisting anions, initial pH of the solution, and water temperature, on NO3−-N removal was also investigated by batch experiments. In a neutral or slightly alkaline environment, 90% of NO3−-N at a concentration less than 50 mg/L could be removed within 1 h, and nitrogen production was approximately 15%. The process of NO3−-N removal by nZVI@rGO fits well with different reaction kinetics. In addition, magnetite was the main oxidation product. RGO-supported nZVI might become a promising filler in the permeable reactive barrier process for groundwater remediation.

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

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9

Similar content being viewed by others

References

  • Babaei AA, Azari A, Kalantary RR, Kakavandi B (2015) Enhanced removal of nitrate from water using nZVI@MWCNTs composite: synthesis, kinetics and mechanism of reduction. Water Sci Technol 72:1988–1999

    Article  CAS  Google Scholar 

  • Beigy MR, Rasekh B, Yazdian F, Aminzadeh B, Shekarriz M (2018) High nitrate removal by starch-stabilized Fe-0 nanoparticles in aqueous solution in a controlled system. Eng Life Sci 18:187–195

    Article  CAS  Google Scholar 

  • Bezbaruah AN, Krajangpan S, Chisholm BJ, Khan E, Bermudez JJ (2009) Entrapment of iron nanoparticles in calcium alginate beads for groundwater remediation applications. J Hazard Mater 166:1339–1343

    Article  CAS  Google Scholar 

  • Bhatnagar A, Sillanpää M (2011) A review of emerging adsorbents for nitrate removal from water. Chem Eng J 168:493–504

    Article  CAS  Google Scholar 

  • Chen H, Cao Y, Wei E, Gong T, Xian Q (2016) Facile synthesis of graphene nano zero-valent iron composites and their efficient removal of trichloronitromethane from drinking water. Chemosphere 146:32–39

    Article  CAS  Google Scholar 

  • Choe SH, Liljestrand HM, Khim J (2004) Nitrate reduction by zero-valent iron under different pH regimes. Appl Geochem 19:335–342

    Article  CAS  Google Scholar 

  • Dong L, Lin L, Li Q, Huang Z, Tang X, Wu M, Li C, Cao X, Scholz M (2018) Enhanced nitrate-nitrogen removal by modified attapulgite-supported nanoscale zero-valent iron treating simulated groundwater. J Environ Manag 213:151–158

    Article  CAS  Google Scholar 

  • Eljamal O, Sasaki K, Tsuruyama S, Hirajima T (2010) Kinetic model of arsenic sorption onto zero-valent iron (ZVI). Water Qual Expo Health 2:125–132

    Article  CAS  Google Scholar 

  • Fan M, Hu J, Cao R, Xiong K, Wei X (2017) Modeling and prediction of copper removal from aqueous solutions by nZVI/rGO magnetic nanocomposites using ANN-GA and ANN-PSO. Sci Rep 7:18040

    Article  CAS  Google Scholar 

  • Farooq U, Danish M, Lu S, Naqvi M, Gu X, Fu X, Zhang X, Nasir M (2016) Synthesis of nZVI@reduced graphene oxide: an efficient catalyst for degradation of 1,1,1-trichloroethane (TCA) in percarbonate system. Res Chem Intermed 43:3219–3236

    Article  CAS  Google Scholar 

  • Fasolino A, Los JH, Katsnelson MI (2007) Intrinsic ripples in graphene. Nat Mater 6:858–861

    Article  CAS  Google Scholar 

  • Fu F, Dionysiou DD, Liu H (2014) The use of zero-valent iron for groundwater remediation and wastewater treatment: a review. J Hazard Mater 267:194–205

    Article  CAS  Google Scholar 

  • Golestanifar H, Asadi A, Alinezhad A, Haybati B, Vosoughi M (2015) Isotherm and kinetic studies on the adsorption of nitrate onto nanoalumina and iron-modified pumice. Desalin Water Treat 57:5480–5487

    Article  CAS  Google Scholar 

  • Hu B, Chen G, Jin C, Hu J, Huang C, Sheng J, Sheng G, Ma J, Huang Y (2017) Macroscopic and spectroscopic studies of the enhanced scavenging of Cr(VI) and Se(VI) from water by titanate nanotube anchored nanoscale zero-valent iron. J Hazard Mater 336:214–221

    Article  CAS  Google Scholar 

  • Hui M, Shengyan P, Yaqi H, Rongxin Z, Anatoly Z, Wei C (2018) A highly efficient magnetic chitosan “fluid” adsorbent with a high capacity and fast adsorption kinetics for dyeing wastewater purification. Chem Eng J 345:556–565

    Article  CAS  Google Scholar 

  • Hwang YH, Kim DG, Ahn YT, Moon CM, Shin HS (2010) Fate of nitrogen species in nitrate reduction by nanoscale zero valent iron and characterization of the reaction kinetics. Water Sci Technol 61:705–712

    Article  CAS  Google Scholar 

  • Hwang Y, Lee Y-C, Mines PD, Huh YS, Andersen HR (2014) Nanoscale zero-valent iron (nZVI) synthesis in a Mg-aminoclay solution exhibits increased stability and reactivity for reductive decontamination. Appl Catal B Environ 147:748–755

    Article  CAS  Google Scholar 

  • Jabeen H, Kemp KC, Chandra V (2013) Synthesis of nano zerovalent iron nanoparticles--graphene composite for the treatment of lead contaminated water. J Environ Manag 130:429–435

    Article  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

    Article  CAS  Google Scholar 

  • Jiao W, Feng Z, Liu Y, Jiang H (2016) Degradation of nitrobenzene-containing wastewater by carbon nanotubes immobilized nanoscale zerovalent iron. J Nanopart Res 18:1–9

    Article  CAS  Google Scholar 

  • Li L, Hu J, Shi X, Fan M, Luo J, Wei X (2016a) Nanoscale zero-valent metals: a review of synthesis, characterization, and applications to environmental remediation. Environ Sci Pollut Res Int 23:17880–17900

    Article  CAS  Google Scholar 

  • Li X, Ai L, Jiang J (2016b) Nanoscale zerovalent iron decorated on graphene nanosheets for Cr(VI) removal from aqueous solution: surface corrosion retard induced the enhanced performance. Chem Eng J 288:789–797

    Article  CAS  Google Scholar 

  • Lin YT, Weng CH, Chen FY (2008) Effective removal of AB24 dye by nano/micro-size zero-valent iron. Sep Purif Technol 64:26–30

    Article  CAS  Google Scholar 

  • Liu F, Yang JH, Zuo J, Ma D, Gan L (2014) Graphene-supported nanoscale zerovalent iron: removal of phosphorus from aqueous solution and mechanistic study. J Environ Sci 26(8):1751–1762

    Article  CAS  Google Scholar 

  • Lv X, Xue X, Jiang G, Wu D, Sheng T, Zhou H, Xu X (2014) Nanoscale zero-valent iron (nZVI) assembled on magnetic Fe3O4/graphene for chromium (VI) removal from aqueous solution. J Colloid Interface Sci 417:51–59

    Article  CAS  Google Scholar 

  • Ma Y, Lv X, Yang QI, Wang Y, Chen X (2017) Reduction of carbon tetrachloride by nanoscale palladized zero-valent iron@ graphene composites: kinetics, activation energy, effects of reaction conditions and degradation mechanism. Appl Catal A Gen 542:252–261

    Article  CAS  Google Scholar 

  • Mines PD, Uthuppu B, Thirion D, Jakobsen MH, Yavuz CT, Andersen HR, Hwang Y (2018) Granular activated carbon with grafted nanoporous polymer enhances nanoscale zero-valent iron impregnation and water contaminant removal. Chem Eng J 339:22–31

    Article  CAS  Google Scholar 

  • Ogata F, Imai D, Kawasaki N (2015) Adsorption of nitrate and nitrite ions onto carbonaceous material produced from soybean in a binary solution system. J Environ Chem Eng 3:155–161

    Article  CAS  Google Scholar 

  • Penon O, Marin MJ, Amabilino DB, Russell DA, Perez-Garcia L (2016) Iron oxide nanoparticles functionalized with novel hydrophobic and hydrophilic porphyrins as potential agents for photodynamic therapy. J Colloid Interface Sci 462:154–165

    Article  CAS  Google Scholar 

  • Petala E, Dimos K, Douvalis A, Bakas T, Tucek J, Zboril R, Karakassides MA (2013) Nanoscale zero-valent iron supported on mesoporous silica: characterization and reactivity for Cr(VI) removal from aqueous solution. J Hazard Mater 261:295–306

    Article  CAS  Google Scholar 

  • Pu S, Ma H, Zinchenko A, Chu W (2017a) Novel highly porous magnetic hydrogel beads composed of chitosan and sodium citrate: an effective adsorbent for the removal of heavy metals from aqueous solutions. Environ Sci Pollut Res Int 24:16520–16530

    Article  CAS  Google Scholar 

  • Pu S, Zhu R, Ma H, Deng D, Pei X, Qi F, Chu W (2017b) Facile in-situ design strategy to disperse TiO 2 nanoparticles on graphene for the enhanced photocatalytic degradation of rhodamine 6G. Appl Catal B Environ 218:208–219

    Article  CAS  Google Scholar 

  • Pu S, Xue S, Yang Z, Hou Y, Zhu R, Chu W (2018) In situ co-precipitation preparation of a superparamagnetic graphene oxide/Fe3O4 nanocomposite as an adsorbent for wastewater purification: synthesis, characterization, kinetics, and isotherm studies, Environ Sci Pollut Res Int

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

    Article  Google Scholar 

  • Ribas D, Černík M, Benito JA, Filip J, Marti V (2017) Activation process of air stable nanoscale zero-valent iron particles. Chem Eng J 320:290–299

    Article  CAS  Google Scholar 

  • Ryu A, Jeong S-W, Jang A, Choi H (2011) Reduction of highly concentrated nitrate using nanoscale zero-valent iron: effects of aggregation and catalyst on reactivity. Appl Catal B Environ 105:128–135

    Article  CAS  Google Scholar 

  • Satayeva AR, Howell CA, Korobeinyk AV, Jandosov J, Inglezakis VJ, Mansurov ZA, Mikhalovsky SV (2018) Investigation of rice husk derived activated carbon for removal of nitrate contamination from water. Sci Total Environ 630:1237–1245

    Article  CAS  Google Scholar 

  • Sepehri S, Heidarpour M, Abedikoupai J (2014) Nitrate removal from aqueous solution using natural zeolite-supported zero-valent iron nanoparticles. Soil & Water Research 9(4):224–232

    Article  CAS  Google Scholar 

  • Shan C, Chen J, Yang Z, Jia H, Guan X, Zhang W, Pan B (2018) Enhanced removal of Se(VI) from water via pre-corrosion of zero-valent iron using H2O2/HCl: effect of solution chemistry and mechanism investigation. Water Res 133:173–181

    Article  CAS  Google Scholar 

  • Shekarriz M, Ramezani Z, Elhami F (2017) Preparation and characterization of ZSM5-supported nano-zero-valent iron and its potential application in nitrate remediation from aqueous solution. Int J Environ Sci Technol 14:1081–1090

    Article  CAS  Google Scholar 

  • Shi X, Ruan W, Hu J, Fan M, Cao R, Wei X (2017) Optimizing the removal of Rhodamine B in aqueous solutions by reduced graphene oxide-supported nanoscale zerovalent iron (nZVI/rGO) using an artificial neural network-genetic algorithm (ANN-GA), Nanomaterials (Basel) 7

  • Shubair T, Eljamal O, Khalil AME, Matsunaga N (2018a) Multilayer system of nanoscale zero valent iron and Nano-Fe/Cu particles for nitrate removal in porous media. Sep Purif Technol 193:242–254

    Article  CAS  Google Scholar 

  • Shubair T, Eljamal O, Khalil AME, Tahara A, Matsunaga N (2018b) Novel application of nanoscale zero valent iron and bimetallic nano-Fe/Cu particles for the treatment of cesium contaminated water. J Environ Chem Eng 6:4253–4264

    Article  CAS  Google Scholar 

  • Su Y, Adeleye AS, Huang Y, Sun X, Dai C, Zhou X, Zhang Y, Keller AA (2014) Simultaneous removal of cadmium and nitrate in aqueous media by nanoscale zerovalent iron (nZVI) and Au doped nZVI particles. Water Res 63:102–111

    Article  CAS  Google Scholar 

  • Sun Y, Ding C, Cheng W, Wang X (2014) Simultaneous adsorption and reduction of U(VI) on reduced graphene oxide-supported nanoscale zerovalent iron. J Hazard Mater 280:399–408

    Article  CAS  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

    Article  CAS  Google Scholar 

  • Teng W, Bai N, Liu Y, Liu Y, Fan J, Zhang WX (2018) Selective nitrate reduction to dinitrogen by electrocatalysis on nanoscale iron encapsulated in mesoporous carbon. Environ Sci Technol 52:230–236

    Article  CAS  Google Scholar 

  • Wada K, Hirata T, Hosokawa S, Iwamoto S, Inoue M (2012) Effect of supports on Pd–Cu bimetallic catalysts for nitrate and nitrite reduction in water. Catal Today 185:81–87

    Article  CAS  Google Scholar 

  • Wang J, Chen B (2015) Adsorption and coadsorption of organic pollutants and a heavy metal by graphene oxide and reduced graphene materials. Chem Eng J 281:379–388

    Article  CAS  Google Scholar 

  • Wang W, Cheng Y, Kong T, Cheng G (2015) Iron nanoparticles decoration onto three-dimensional graphene for rapid and efficient degradation of azo dye. J Hazard Mater 299:50–58

    Article  CAS  Google Scholar 

  • Wang J, Chen B, Xing B (2016) Wrinkles and folds of activated graphene nanosheets as fast and efficient adsorptive sites for hydrophobic organic contaminants. Environ Sci Technol 50:3798

    Article  CAS  Google Scholar 

  • Wang K, Ma H, Pu S, Yan C, Wang M, Yu J, Wang X, Chu W, Zinchenko A (2019) Hybrid porous magnetic bentonite-chitosan beads for selective removal of radioactive cesium in water. J Hazard Mater 362:160–169

    Article  CAS  Google Scholar 

  • Xu S, Hu Z (2015) Kinetics of nutrient removal by nano zero-valent iron under different biochemical environments. Water Environ Res 87:483–490

    Article  CAS  Google Scholar 

  • Yang Y, Chen T, Zhang X, Qing C, Wang J, Yue Z, Liu H, Yang Z (2018a) Simultaneous removal of nitrate and phosphate from wastewater by siderite based autotrophic denitrification. Chemosphere 199:130–137

    Article  CAS  Google Scholar 

  • Yang Z, Shan C, Mei Y, Jiang Z, Guan X, Pan B (2018b) Improving reductive performance of zero valent iron by H2O2/HCl pretreatment: a case study on nitrate reduction. Chem Eng J 334:2255–2263

    Article  CAS  Google Scholar 

  • Zhang Y, Li Y, Li J, Hu L, Zheng X (2011) Enhanced removal of nitrate by a novel composite: nanoscale zero valent iron supported on pillared clay. Chem Eng J 171:526–531

    Article  CAS  Google Scholar 

  • Zhang H, Liu X, He G, Zhang X, Bao S, Hu W (2015) Bioinspired synthesis of nitrogen/sulfur co-doped graphene as an efficient electrocatalyst for oxygen reduction reaction. J Power Sources 279:252–258

    Article  CAS  Google Scholar 

  • Zhang Y, Douglas GB, Pu L, Zhao Q, Tang Y, Xu W, Luo B, Hong W, Cui L, Ye Z (2017) Zero-valent iron-facilitated reduction of nitrate: chemical kinetics and reaction pathways. Sci Total Environ 598:1140–1150

    Article  CAS  Google Scholar 

  • Zhao X, Liu W, Cai ZQ, Han B, Qian TW, Zhao DY (2016) An overview of preparation and applications of stabilized zero-valent iron nanoparticles for soil and groundwater remediation. Water Res 100:245–266

    Article  CAS  Google Scholar 

  • Zhu F, He S, Liu T (2018a) Effect of pH, temperature and co-existing anions on the Removal of Cr(VI) in groundwater by green synthesized nZVI/Ni. Ecotoxicol Environ Saf 163:544–550

    Article  CAS  Google Scholar 

  • Zhu F, Ma S, Liu T, Deng X (2018b) Green synthesis of nano zero-valent iron/Cu by green tea to remove hexavalent chromium from groundwater. J Clean Prod 174:184–190

    Article  CAS  Google Scholar 

Download references

Funding

This work was supported by the National Natural Science Foundation of China (41772264, 51408074), the Applied Basic Research Programs of Science and Technology Foundation of Sichuan Province (18YYJC1745), and the Research Fund of State Key Laboratory of Geohazard Prevention and Geoenvironment Protection (SKLGP2019Z009). Prof. Chu is supported by the Shenzhen Basic Research Funding Scheme 2018 (JCYJ20170818105109311).

Author information

Authors and Affiliations

  1. State Key Laboratory of Geohazard Prevention and Geoenvironment Protection, Chengdu University of Technology, 1#, Dongsanlu, Erxianqiao, Chengdu, 610059, Sichuan, People’s Republic of China

    Shengyan Pu, Daili Deng, Kexin Wang, Miaoting Wang, Ying Zhang & Lixiang Shangguan

  2. Department of Civil and Environment Engineering, The Hong Kong Polytechnic University, Hong Kong, People’s Republic of China

    Shengyan Pu & Wei Chu

Authors
  1. Shengyan Pu
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Daili Deng
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Kexin Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Miaoting Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Ying Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Lixiang Shangguan
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Wei Chu
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Shengyan Pu.

Ethics declarations

Conflict of interest

The authors declare that they have no conflict of interest.

Additional information

Responsible editor: Ioannis A. Katsoyiannis

Electronic supplementary material

ESM 1

(DOCX 222 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Pu, S., Deng, D., Wang, K. et al. Optimizing the removal of nitrate from aqueous solutions via reduced graphite oxide–supported nZVI: synthesis, characterization, kinetics, and reduction mechanism. Environ Sci Pollut Res 26, 3932–3945 (2019). https://doi.org/10.1007/s11356-018-3813-1

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11356-018-3813-1

Keywords

Search

Navigation