Environmental Science and Pollution Research

, Volume 26, Issue 4, pp 3330–3339 | Cite as

Adsorptive removal of lead from acid mine drainage using cobalt-methylimidazolate framework as an adsorbent: kinetics, isotherm, and regeneration

  • Azile Nqombolo
  • Anele Mpupa
  • Aphiwe S. Gugushe
  • Richard M. Moutloali
  • Philiswa N. NomngongoEmail author
Research Article


In this work, cobalt-methylimidazolate framework has been used as an adsorbent in the removal of Pb(II) from acid mine drainage in adsorption batch system. X-ray diffraction, Fourier-transform infrared spectroscopy, Brunauer-Emmet-Teller and transmission electron microscope were used for structural, morphological, and surface characteristics of cobalt-methylimidazolate framework. The concentration of heavy metal ions in water samples was measured by inductively coupled plasma optical emission spectrometry. Different experimental factors/variables (such as contact time, dosage, and pH) affecting the adsorption of Pb(II) from acid mine drainage were optimized by response surface methodology based on central composite design. Under optimized experimental parameters, the maximum adsorption capacity of Pb(II) was found to be 105 mg g−1. The nature of the adsorption process was investigated using Langmuir and Freundlich isotherm models. The obtained data best fitted Langmuir isotherm model suggesting a homogeneous adsorption process. Furthermore, the adsorption mechanism was investigated using five kinetic models, that is, pseudo-first order, pseudo-second order, intraparticle diffusion and Elovich model. The adsorption data fitted better to pseudo-second-order followed by intra-particle diffusion kinetic models suggesting that the adsorption mechanism is dominated by both chemical and physical adsorption processes. The adsorbent could be regenerated up to 8 cycles and it was successfully used in the removal of lead in real acid mine drainage samples.


Heavy metals Zeolitic imidazolate framework Lead Wastewater Acid mine drainage Adsorption 


Funding information

The authors gratefully acknowledge the National Research Foundation (NRF) Innovation (Grant no. 113014) and DST/Mintek Nanotechnology Innovation Centre (NIC) for financial support. They are thankful to the Department of Applied Chemistry Faculty of Science University of Johannesburg.

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.

Supplementary material

11356_2018_3868_MOESM1_ESM.doc (196 kb)
ESM 1 (DOC 195 kb)


  1. Aldawsari A, Khan MA, Hameed BH, Alqadami AA, Siddiqui MR, Alothman ZA, Ahmed AYBH (2017) Mercerized mesoporous date pit activated carbon—a novel adsorbent to sequester potentially toxic divalent heavy metals from water. PLoS One 12(9):e0184493CrossRefGoogle Scholar
  2. Al-Qodah Z, Yahya MA, Al-Shannag M (2017) On the performance of bioadsorption processes for heavy metal ions removal by low-cost agricultural and natural by-products bioadsorbent: a review. Desalin Water Treat 85:339–357CrossRefGoogle Scholar
  3. Amini M, Younesi H, Bahramifar N, Lorestani AAZ, Ghorbani F, Daneshi A, Sharifzadeh M (2008) Application of response surface methodology for optimization of lead biosorption in an aqueous solution by Aspergillus niger. J Hazard Mater 154(1–3):694–702CrossRefGoogle Scholar
  4. An HJ, Bhadra BN, Khan NA, Jhung SH (2018) Adsorptive removal of wide range of pharmaceutical and personal care products from water by using metal azolate framework-6-derived porous carbon. Chem Eng J 343:447–454CrossRefGoogle Scholar
  5. Bo S, Ren W, Lei C, Xie Y, Cai Y, Wang S, Gao J, Ni Q, Yao J (2018) Flexible and porous cellulose aerogels/zeolitic imidazolate framework (ZIF-8) hybrids for adsorption removal of Cr (IV) from water. J Solid State Chem 262:135–141CrossRefGoogle Scholar
  6. Chen B (2016) Zeolitic imidazolate frameworks (ZIFs) and their derivatives: synthesis and energy related applicationsGoogle Scholar
  7. Dey T (2012) Nanotechnology for water purification. Universal-Publishers, IrvineGoogle Scholar
  8. Dimpe KM, Ngila JC, Nomngongo PN (2017) Application of waste tyre-based activated carbon for the removal of heavy metals in wastewater. Cogent Eng 4(1):1330912CrossRefGoogle Scholar
  9. Fernandez-Rojo L, Héry M, Le Pape P, Braungardt C, Desoeuvre A, Torres E, Tardy V, Resongles E, Laroche E, Delpoux S, Joulian C (2017) Biological attenuation of arsenic and iron in a continuous flow bioreactor treating acid mine drainage (AMD). Water Res 123:594–606CrossRefGoogle Scholar
  10. Freundlich H (1907) Über die adsorption in lösungen. Z. Phys. Chem. (N F) 57(1):385–470Google Scholar
  11. Ghaneian MT, Bhatnagar A, Ehrampoush MH, Amrollahi M, Jamshidi B, Dehvari M, Taghavi M (2017) Biosorption of hexavalent chromium from aqueous solution onto pomegranate seeds: kinetic modeling studies. Int J Environ Sci Technol 14(2):331–340CrossRefGoogle Scholar
  12. Gomar M, Yeganegi S (2018) Corrigendum to “Adsorption of 5-fluorouracil, hydroxyurea and mercaptopurine drugs on zeolitic imidazolate frameworks (ZIF-7, ZIF-8 and ZIF-9)”. Microporous Mesoporous Mater 258:277–280CrossRefGoogle Scholar
  13. Gross AF, Sherman E, Vajo JJ (2012) Aqueous room temperature synthesis of cobalt and zinc sodalite zeolitic imidizolate frameworks. Dalton Trans 41(18):5458–5460CrossRefGoogle Scholar
  14. Hameed BH, Tan IAW, Ahmad AL (2008) Adsorption isotherm, kinetic modeling and mechanism of 2, 4, 6-trichlorophenol on coconut husk-based activated carbon. Chem Eng J 144(2):235–244CrossRefGoogle Scholar
  15. Han TT, Bai HL, Liu YY, Ma JF (2018) Synthesis of nanoporous cobalt/carbon materials by a carbonized zeolitic imidazolate framework-9 and adsorption of dyes. New J Chem 42(1):717–724CrossRefGoogle Scholar
  16. Huang YB, Liang J, Wang XS, Cao R (2017) Multifunctional metal–organic framework catalysts: synergistic catalysis and tandem reactions. Chem Soc Rev 46(1):126–157CrossRefGoogle Scholar
  17. Huang L, He M, Chen B, Hu B (2018a) Magnetic Zr-MOFs nanocomposites for rapid removal of heavy metal ions and dyes from water. Chemosphere 199:435–444CrossRefGoogle Scholar
  18. Huang Y, Zeng X, Guo L, Lan J, Zhang L, Cao D (2018b) Heavy metal ion removal of wastewater by zeolite-imidazolate frameworks. Sep Purif Technol 194:462–469CrossRefGoogle Scholar
  19. Huo JB, Xu L, Yang JCE, Cui HJ, Yuan B, Fu ML (2018) Magnetic responsive Fe 3 O 4-ZIF-8 core-shell composites for efficient removal of As (III) from water. Colloids Surf A Physicochem Eng Asp 539:59–68CrossRefGoogle Scholar
  20. Jin WG, Chen W, Xu PH, Lin XW, Huang XC, Chen GH, Lu F, Chen XM (2017) An exceptionally water stable metal-organic framework with amide-functionalized cages: selective CO2/CH4 uptake, removal of antibiotics and dyes from water. Chemistry 23(53):13058–13066Google Scholar
  21. Jung BK, Jun JW, Hasan Z, Jhung SH (2015) Adsorptive removal of p-arsanilic acid from water using mesoporous zeolitic imidazolate framework-8. Chem Eng J 267:9–15CrossRefGoogle Scholar
  22. Kang Z, Wang S, Fan L, Xiao Z, Wang R, Sun D (2017) Surface wettability switching of metal-organic framework mesh for oil-water separation. Mater Lett 189:82–85CrossRefGoogle Scholar
  23. Kummu M, Guillaume JHA, De Moel H, Eisner S, Flörke M, Porkka M, Siebert S, Veldkamp TIE, Ward PJ (2016) The world’s road to water scarcity: shortage and stress in the 20th century and pathways towards sustainability. Sci Rep 6:38495CrossRefGoogle Scholar
  24. Langmuir I (1916) The constitution and fundamental properties of solids and liquids. Part I. Solids. J Am Chem Soc 38(11):2221–2295CrossRefGoogle Scholar
  25. Largitte L, Gervelas S, Tant T, Dumesnil PC, Hightower A, Yasami R, Bercion Y, Lodewyckx P (2014) Removal of lead from aqueous solutions by adsorption with surface precipitation. Adsorption 20(5–6):689–700CrossRefGoogle Scholar
  26. Le Pape P, Battaglia-Brunet F, Parmentier M, Joulian C, Gassaud C, Fernandez-Rojo L, Guigner JM, Ikogou M, Stetten L, Olivi L, Casiot C (2017) Complete removal of arsenic and zinc from a heavily contaminated acid mine drainage via an indigenous SRB consortium. J Hazard Mater 321:764–772CrossRefGoogle Scholar
  27. Lee H, Kim D, Kim J, Ji MK, Han YS, Park YT, Yun HS, Choi J (2015) As (III) and As (V) removal from the aqueous phase via adsorption onto acid mine drainage sludge (AMDS) alginate beads and goethite alginate beads. J Hazard Mater 292:146–154CrossRefGoogle Scholar
  28. Li X, Gao X, Ai L, Jiang J (2015) Mechanistic insight into the interaction and adsorption of Cr (VI) with zeolitic imidazolate framework-67 microcrystals from aqueous solution. Chem Eng J 274:238–246CrossRefGoogle Scholar
  29. Li Z, Huang X, Sun C, Chen X, Hu J, Stein A, Tang B (2017) Thin-film electrode based on zeolitic imidazolate frameworks (ZIF-8 and ZIF-67) with ultra-stable performance as a lithium-ion battery anode. J Mater Sci 52(7):3979–3991CrossRefGoogle Scholar
  30. Li Z, Wang L, Meng J, Liu X, Xu J, Wang F, Brookes P (2018) Zeolite-supported nanoscale zero-valent iron: new findings on simultaneous adsorption of Cd (II), Pb (II), and As (III) in aqueous solution and soil. J Hazard Mater 344:1–11CrossRefGoogle Scholar
  31. Lin KYA, Chang HA (2015a) Ultra-high adsorption capacity of zeolitic imidazole framework-67 (ZIF-67) for removal of malachite green from water. Chemosphere 139:624–631CrossRefGoogle Scholar
  32. Lin KYA, Chang HA (2015b) Zeolitic imidazole framework-67 (ZIF-67) as a heterogeneous catalyst to activate peroxymonosulfate for degradation of rhodamine B in water. J Taiwan Inst Chem Eng 53:40–45CrossRefGoogle Scholar
  33. Luo X, Ding L, Luo J (2015) Adsorptive removal of Pb (II) ions from aqueous samples with amino-functionalization of metal–organic frameworks MIL-101 (Cr). J Chem Eng Data 60(6):1732–1743CrossRefGoogle Scholar
  34. Luo X, Lei X, Xie X, Yu B, Cai N, Yu F (2016) Adsorptive removal of lead from water by the effective and reusable magnetic cellulose nanocomposite beads entrapping activated bentonite. Carbohydr Polym 151:640–648CrossRefGoogle Scholar
  35. Maarof HI, Daud WMAW, Aroua MK (2017) Recent trends in removal and recovery of heavy metals from wastewater by electrochemical technologies. Rev Chem Eng 33(4):359–386CrossRefGoogle Scholar
  36. Marzougui, Z., Damak, M., Elleuch, B., Elaissari, A., 2017. Occurrence and enhanced removal of heavy metals in industrial wastewater treatment plant using coagulation-flocculation process. In Euro-Mediterranean conference for environmental Integration 535–538Google Scholar
  37. Mashile PP, Mpupa A, Nomngongo PN (2018) Adsorptive removal of microcystin-LR from surface and wastewater using tyre-based powdered activated carbon: kinetics and isotherms. Toxicon 145:25–31CrossRefGoogle Scholar
  38. Mohajeri S, Aziz HA, Isa MH, Zahed MA, Adlan MN (2010) Statistical optimization of process parameters for landfill leachate treatment using electro-Fenton technique. J Hazard Mater 176(1–3):749–758CrossRefGoogle Scholar
  39. Nayak A, Bhushan B, Gupta V, Sharma P (2017) Chemically activated carbon from lignocellulosic wastes for heavy metal wastewater remediation: effect of activation conditions. J Colloid Interface Sci 493:228–240CrossRefGoogle Scholar
  40. Nomngongo PN, Ngila JC (2015) Multivariate optimization of dual-bed solid phase extraction for preconcentration of Ag, Al, As and Cr in gasoline prior to inductively coupled plasma optical emission spectrometric determination. Fuel 139:285–291CrossRefGoogle Scholar
  41. Panchariya DK, Rai RK, Anil Kumar E, Singh SK (2018) Core–shell zeolitic imidazolate frameworks for enhanced hydrogen storage. ACS Omega 3(1):167–175CrossRefGoogle Scholar
  42. Perrich JR (2018) Activated carbon adsorption for wastewater treatment. CRC Press, Boca RatonCrossRefGoogle Scholar
  43. Premkumar MP, Thiruvengadaravi KV, Kumar PS, Nandagopal J, Sivanesan S (2018) Eco-friendly treatment strategies for wastewater containing dyes and heavy metals. In: Gupta T, Agarwal A, Agarwal R, Labhsetwar N (eds) Environmental contaminants. Energy, environment, and sustainability. Springer, Singapore, pp 317–360Google Scholar
  44. Rajput S, Pittman CU Jr, Mohan D (2016) Magnetic magnetite (Fe3O4) nanoparticle synthesis and applications for lead (Pb2+) and chromium (Cr6+) removal from water. J Colloid Interface Sci 468:334–346CrossRefGoogle Scholar
  45. Sadegh H, Ali GA, Gupta VK, Makhlouf ASH, Shahryari-ghoshekandi R, Nadagouda MN, Sillanpää M, Megiel E (2017) The role of nanomaterials as effective adsorbents and their applications in wastewater treatment. J Nanostruct Chem 7(1):1–14CrossRefGoogle Scholar
  46. Saeed MO, Azizli K, Isa MH, Bashir MJ (2015) Application of CCD in RSM to obtain optimize treatment of POME using Fenton oxidation process. J Water Process Eng 8:7–16CrossRefGoogle Scholar
  47. Sahin O, Stewart RA, Porter MG (2015) Water security through scarcity pricing and reverse osmosis: a system dynamics approach. J Clean Prod 88:160–171CrossRefGoogle Scholar
  48. Salarian M, Ghanbarpour A, Behbahani M, Bagheri S, Bagheri A (2014) A metal-organic framework sustained by a nanosized Ag12 cuboctahedral node for solid-phase extraction of ultratraces of lead (II) ions. Microchim Acta 181(9–10):999–1007CrossRefGoogle Scholar
  49. Samal M, Panda J, Biswal BP, Sahu R (2018) Kitchen grinder: a tool for the synthesis of metal-organic framework towards size selective dye adsorption. Cryst Eng Comm 20(18):2486–2490Google Scholar
  50. Santhosh C, Daneshvar E, Kollu P, Peräniemi S, Grace AN, Bhatnagar A (2017) Magnetic SiO2@ CoFe2O4 nanoparticles decorated on graphene oxide as efficient adsorbents for the removal of anionic pollutants from water. Chem Eng J 322:472–487CrossRefGoogle Scholar
  51. Shahrak MN, Ghahramaninezhad M, Eydifarash M (2017) Zeolitic imidazolate framework-8 for efficient adsorption and removal of Cr (VI) ions from aqueous solution. Environ Sci Pollut Res Int 24(10):9624–9634CrossRefGoogle Scholar
  52. Siahkamari M, Jamali A, Sabzevari A, Shakeri A (2017) Removal of Lead (II) ions from aqueous solutions using biocompatible polymeric nano-adsorbents: a comparative study. Carbohydr Polym 157:1180–1189CrossRefGoogle Scholar
  53. Sun W, Zhai X, Zhao L (2016) Synthesis of ZIF-8 and ZIF-67 nanocrystals with well-controllable size distribution through reverse microemulsions. Chem Eng J 289:59–64CrossRefGoogle Scholar
  54. Ungureanu G, Santos S, Boaventura R, Botelho C (2015) Arsenic and antimony in water and wastewater: overview of removal techniques with special reference to latest advances in adsorption. J Environ Manag 151:326–342CrossRefGoogle Scholar
  55. Vergili I, Soltobaeva G, Kaya Y, Gonder ZB, Çavuş S, Gurdag S (2013) Study of the removal of Pb(II) using a weak acidic cation resin: kinetics, thermodynamics, equilibrium, and breakthrough curves. Ind Eng Chem Res 52:9227–9238CrossRefGoogle Scholar
  56. Wu X, Liu W, Wu H, Zong X, Yang L, Wu Y, Ren Y, Shi C, Wang S, Jiang Z (2018) Nanoporous ZIF-67 embedded polymers of intrinsic microporosity membranes with enhanced gas separation performance. J Membr Sci 548:309–318CrossRefGoogle Scholar
  57. Xu M, McKay G (2017) Removal of heavy metals, lead, cadmium, and zinc, using adsorption processes by cost-effective adsorbents. In Adsorption processes for water treatment and purification Cham: Springer. (pp. 109–138)Google Scholar
  58. Yadav DK, Srivastava S (2017) Carbon nanotubes as adsorbent to remove heavy metal ion (Mn+7) in wastewater treatment. Mater Today: Proc 4(2):4089–4094CrossRefGoogle Scholar
  59. Yan X, Hu X, Chen T, Zhang S, Zhou M (2017) Adsorptive removal of 1-naphthol from water with zeolitic imidazolate framework-67. J Phys Chem Solids 107:50–54CrossRefGoogle Scholar
  60. Yurekli Y (2016) Removal of heavy metals in wastewater by using zeolite nano-particles impregnated polysulfone membranes. J Hazard Mater 309:53–64CrossRefGoogle Scholar
  61. Zanin E, Scapinello J, de Oliveira M, Rambo CL, Franscescon F, Freitas L, de Mello JMM, Fiori MA, Oliveira JV, Dal Magro J (2017) Adsorption of heavy metals from wastewater graphic industry using clinoptilolite zeolite as adsorbent. Process Saf Environ Prot 105:194–200CrossRefGoogle Scholar
  62. Zhang W, Tan Y, Gao Y, Wu J, Hu J, Stein A, Tang B (2016) Nanocomposites of zeolitic imidazolate frameworks on graphene oxide for pseudocapacitor applications. J Appl Electrochem 46(4):441–450Google Scholar
  63. Zhang S, Yang Q, Yang X, Wang W, Li Z, Zhang L, Wang C, Wang Z (2017) A zeolitic imidazolate framework based nanoporous carbon as a novel fiber coating for solid-phase microextraction of pyrethroid pesticides. Talanta 166:46–53CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  • Azile Nqombolo
    • 1
    • 2
  • Anele Mpupa
    • 1
  • Aphiwe S. Gugushe
    • 1
  • Richard M. Moutloali
    • 1
    • 2
  • Philiswa N. Nomngongo
    • 1
    • 2
    Email author
  1. 1.Department of Applied ChemistryUniversity of JohannesburgJohannesburgSouth Africa
  2. 2.DST/Mintek Nanotechnology Innovation CentreJohannesburgSouth Africa

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