Aluminosilicate Inorganic Polymers (Geopolymers): Emerging Ion Exchangers for Removal of Metal Ions
Abstract
Geopolymers (GPs), also known as alkali-activated aluminosilicates or inorganic polymers, are synthesized from an aluminosilicate source (fly ash, metakaolin, or blast furnace slag) and very alkaline sodium hydroxide and/or silicate. Due to their high compressive strength, acid and fire resistance, GPs are used as construction and coating materials. However, since the structure of GP contains negatively charged Al(III) tetrahedra (balanced by alkali cations), they are feasible ion exchangers. The present chapter is aimed to encapsulate the developments in the field of using GPs for the removal of alkali metals (Li+, K+, Cs+), alkaline earth metals (Mg2+, Ca2+, Sr2+, and Ba2+), ammonium ion, and heavy metals (Pb2+, Cu2+, Cd2+, Zn2+, Ni2+, Cr3+) from water. GPs are the first cementing materials that have remarkable ion exchange capacity. GPs have higher ion exchange/adsorption capacity, but a lower rate of adsorption than their precursors (fly ash, metakaolin,…). Thus, geopolymerization increases the adsorption sites on one hand but imposes kinetics limitations that render GPs slow adsorption. GPs resemble zeolites in respect of cation exchange capacity, high surface area, and thermal stability. However, the synthesis of GPs is easier and inexpensive with lower energy and water demand than zeolite synthesis. The prepared GP could be directly formulated as high compressive strength granules at a low temperature. Since GPs are more acid resistant, they are accessible for regeneration than zeolites, but this issue requires further work.
Keywords
Aluminosilicate inorganic polymers Geopolymers Inorganic cation exchangers Cesium Ammonium Strontium Heavy metals AdsorptionAbbreviations
- BET
Brunauer–Emmett–Teller (BET) theory
- BFS
Blast furnace slag from iron manufacturing
- CEC
Cation exchange capacity (meq/mol)
- EDS
Energy-dispersive X-ray spectroscopy
- FA
Fly ash from electricity plant employing coal (low calcium, type F)
- GP
Geopolymer
- k2
Pseudo-second-order rate constant (g mg−1 min−1)
- KL
Langmuir affinity constant (L mg−1)
- MK
Metakaolin
- Qm
Adsorption capacity (mg g−1)
- SEM
Scanning electron micrographs
- XRD
X-ray diffraction
References
- 1.Davidovits J (1991) Geopolymers: inorganic polymeric new materials. J Therm Anal 37:1633–1656CrossRefGoogle Scholar
- 2.Provis JL, Fernández-Jiménez A, Kamseu E, Leonelli C, Palom A (2014) Binder chemistry—low-calcium alkali-activated materials. In: Provis JL, van Devente JSJ (eds) Alkali activated materials: state-of-the-art report, RILEM TC 224-AAM, Springer, pp 93–123Google Scholar
- 3.Ducman V, Korat L (2016) Characterization of geopolymer fly-ash based foams obtained with the. Mater Charact 113:207–213. https://doi.org/10.1016/j.matchar.2016.01.019CrossRefGoogle Scholar
- 4.Melar J, Renaudin G, Leroux F, Hardy-Dessources A, Nedelec J, Taviot-Gueho C, Petit E, Steins P, Poulesquen A, Frizon F (2015) The porous network and its interface inside geopolymers as a function of alkali cation and aging. J Phys Chem C 119(31):17619–17632. https://doi.org/10.1021/acs.jpcc.5b02340CrossRefGoogle Scholar
- 5.Zhang L, Zhang F, Liu M, Hu X (2017) Novel sustainable geopolymer based syntactic foams: an eco-friendly alternative to polymer based syntactic foams. Chem Eng J 313:74–82. https://doi.org/10.1016/j.cej.2016.12.046CrossRefGoogle Scholar
- 6.Zhang Z, Provis JL, Reid A, Wang H (2014) Geopolymer foam concrete: an emerging material for sustainable construction. Constr Build Mater 56:113–127. https://doi.org/10.1016/j.conbuildmat.2014.01.081CrossRefGoogle Scholar
- 7.Zhang F, Zhang L, Liu M, Mu C, Liang YN, Hu X (2017) Role of alkali cation in compressive strength of metakaolin based geopolymers. Ceram Int 43(4):3811–3817. https://doi.org/10.1016/j.ceramint.2016.12.034CrossRefGoogle Scholar
- 8.Duxson P, Fernandez-Jimenez A, Provis JL, Lukey GC, Palomo A, Van Deventer JSJ (2007) Geopolymer technology: the current state of the art. J Mater Sci 42:2917–2933CrossRefGoogle Scholar
- 9.Vance ER, Perera DS (2009) Geopolymers for nuclear waste immobilization. In: Provis JL, Van Deventer JSJ (eds) Geopolymers: structure, processing, properties and industrial applications. CRC Press and Woodhead Publishing Limited, Oxford, pp 401–420CrossRefGoogle Scholar
- 10.Wang Y, Han F, Mu J (2018) Solidification/stabilization mechanism of Pb(II), Cd(II), Mn(II) and Cr(III) in fly ash based geopolymers. Constr Build Mater 160:818–827. https://doi.org/10.1016/j.conbuildmat.2017.12.006CrossRefGoogle Scholar
- 11.Waijarean N, MacKenzie KJD, Asavapisit S, Piyaphanuwat R, Jameson GNL (2017) Synthesis and properties of geopolymers based on water treatment residue and their immobilization of some heavy metals. J. Mater. Sci. 52(12):7345–7359. https://doi.org/10.1007/s10853-017-0970-4CrossRefGoogle Scholar
- 12.El-Eswed BI, Aldagag OM, Khalili FI (2017) Efficiency and mechanism of stabilization/solidification of Pb(II), Cd(II), Cu(II), Th(IV) and U(VI) in metakaolin based geopolymers. Appl Clay Sci 140:148–156. https://doi.org/10.1016/j.clay.2017.02.003CrossRefGoogle Scholar
- 13.El-Eswed BI (2018) Solidification versus adsorption for immobilization of pollutants in geopolymeric materials: a review, solidification. Ares A (ed) InTech. https://doi.org/10.5772/intechopen.72299. Available from: https://www.intechopen.com/books/solidification/solidification-versus-adsorption-for-immobilization-of-pollutants-in-geopolymeric-materials-a-reviewGoogle Scholar
- 14.Al-Mashqbeh A, Abuali S, El-Eswed B, Khalili FI (2018) Immobilization of toxic inorganic anions (Cr2O72-, MnO4- and Fe(CN)63-) in metakaolin based geopolymers: A preliminary study. Ceram Int 44(5):5613–5620. https://doi.org/10.1016/j.ceramint.2017.12.208CrossRefGoogle Scholar
- 15.Davidovits J (2017) Geopolymers: ceramic-like inorganic polymers. J Ceram Sci Technol 08:335–350. https://doi.org/10.4416/JCST2017-00038CrossRefGoogle Scholar
- 16.Foo KY, Hameed BH (2010) Insights into the modeling of adsorption isotherm systems. Chem Eng J 156(1):2–10. https://doi.org/10.1016/j.cej.2009.09.013CrossRefGoogle Scholar
- 17.Tan KL, Hameed BH (2017) Insight into the adsorption kinetics models for the removal of contaminants from aqueous solutions. J Taiwan Inst Chem Eng 74:25–48. https://doi.org/10.1016/j.jtice.2017.01.024CrossRefGoogle Scholar
- 18.Bortnovsky O, Dědeček J, Tvarůžková Z, Sobalík Z, Šubrt J (2008) Metal ions as probes for characterization of geopolymer materials. J Am Ceram Soc 91:3052–3057. https://doi.org/10.1111/j.1551-2916.2008.02577.xCrossRefGoogle Scholar
- 19.Skorina T (2014) Ion exchange in amorphous alkali-activated aluminosilicates: potassium based geopolymers. Appl Clay Sci 87:205–211. https://doi.org/10.1016/j.clay.2013.11.003CrossRefGoogle Scholar
- 20.Luukkonen T, Věžníková K, Tolonen E, Runtti H, Yliniemi J, Hu T, Kemppainen K, Lassi U (2017) Removal of ammonium from municipal wastewater with powdered and granulated metakaolin geopolymer. Environ Technol:1–10. https://doi.org/10.1080/09593330.2017.1301572CrossRefGoogle Scholar
- 21.Yuan J, He P, Jia D, You J, Liu X, Zhang Y, Cai D, Yang Z, Duan X, Wang S, Zhou Y (2017) Effects of Na + substitution Cs + on the microstructure and thermal expansion behavior of ceramic derived from geopolymer. J Am Ceram Soc 100:4412–4424. https://doi.org/10.1111/jace.14968CrossRefGoogle Scholar
- 22.Arbel Haddad M, Ofer-Rozovsky E, Bar-Nes G, Borojovich EJC, Nikolski A, Mogiliansky D, Katz A (2017) Formation of zeolites in metakaolin-based geopolymers and their potential application for Cs immobilization. J Nucl Mater 493:168–179. https://doi.org/10.1016/j.jnucmat.2017.05.046CrossRefGoogle Scholar
- 23.López FJ, Sugita S, Tagaya M, Kobayashi T (2014) Metakaolin-based geopolymers for targeted adsorbents to heavy metal ion separation. J Mater Sci Chem Eng 2:16–27. https://doi.org/10.4236/msce.2014.27002CrossRefGoogle Scholar
- 24.Lee NK, Khalid HR, Lee HK (2017) Adsorption characteristics of cesium onto mesoporous geopolymers containing nano-crystalline zeolites. Microporous Mesoporous Mater 242:238–244. https://doi.org/10.1016/j.micromeso.2017.01.030CrossRefGoogle Scholar
- 25.O’Connor SJ, MacKenzie KJD, Smith ME, Hanna JV (2010) Ion exchange in the charge-balancing sites of aluminosilicate inorganic polymers. J Mater Chem 20:10234–10240. https://doi.org/10.1039/C0JM01254HCrossRefGoogle Scholar
- 26.Luukkonen T, Tolonen E, Runtti H, Kemppainen K, Perämäki P, Rämö J, Lassi U (2017) Optimization of the metakaolin geopolymer preparation for maximized ammonium adsorption capacity. J Mater Sci 16. https://doi.org/10.1007/s10853-017-1156-9CrossRefGoogle Scholar
- 27.Belchinskaya L, Novikova L, Khokhlov V, Tkhi JL (2013) Contribution of ion-exchange and non-ion-exchange reactions to sorption of ammonium ions by natural and activated aluminosilicate sorbent. J Appl Chem:1–9. http://dx.doi.org/10.1155/2013/789410CrossRefGoogle Scholar
- 28.Uehara M, Isogaya S, Yamazaki A (2008) Ion-exchange properties of hardened geopolymers paste from fly ash. Clay Sci 14(3):127–133. https://doi.org/10.11362/jcssjclayscience.14.3_127
- 29.Cheng TW, Lee ML, Ko MS, Ueng TH, Yang SF (2012) The heavy metal adsorption characteristics on metakaolin-based geopolymer. Appl Clay Sci 56:90–96. https://doi.org/10.1016/j.clay.2011.11.027CrossRefGoogle Scholar
- 30.Kara İ, Yilmazer D, Akar STI (2017) Metakaolin based geopolymer as an effective adsorbent for adsorption of zinc(II) and nickel(II) ions from aqueous solutions. Appl Clay Sci 139:54–63. https://doi.org/10.1016/j.clay.2017.01.008CrossRefGoogle Scholar
- 31.Tang Q, Ge Y, Wang K, He Y, Cui X (2015) Preparation and characterization of porous metakaolin-based inorganic polymer spheres as an adsorbent. Mater Des 88:1244–1249. https://doi.org/10.1016/j.matdes.2015.09.126CrossRefGoogle Scholar
- 32.Ge Y, Cui X, Kong Y, Li Z, He Y, Zhou Q (2015) Porous geopolymeric spheres for removal of Cu(II) from aqueous solution: synthesis and evaluation. J Hazard Mater 283:244–251. https://doi.org/10.1016/j.jhazmat.2014.09.038CrossRefGoogle Scholar
- 33.Luukkonen T, Runtti H, Niskanen M, Tolonen E, Sarkkinen M, Kemppainen K, Ramo J, Lassi U (2016) Simultaneous removal of Ni(II), As(III), and Sb(III) from spiked mine effluent with metakaolin and blast-furnace-slag geopolymers. J Environ Manage 166:579–588. https://doi.org/10.1016/j.jenvman.2015.11.007CrossRefGoogle Scholar
- 34.Medpelli D, Sandoval R, Sherrill L, Hristovski K, Seo D (2015) Iron oxide-modified nanoporous geopolymers for arsenic removal from ground water. Resour-Effi Technol 1(1):19–27. https://doi.org/10.1016/j.reffit.2015.06.007CrossRefGoogle Scholar
- 35.Wang S, Li L, Zhu ZH (2007) Solid-state conversion of fly ash to effective adsorbents for Cu removal from wastewater. J Hazard Mater 139(2):254–259. https://doi.org/10.1016/j.jhazmat.2006.06.018CrossRefGoogle Scholar
- 36.Al-Zboon K, Al-Harahsheh MS, Bani Hani F (2011) Fly ash-based geopolymer for Pb removal from aqueous solution. J Hazard Mater 188:414–421. https://doi.org/10.1016/j.jhazmat.2011.01.133CrossRefGoogle Scholar
- 37.Al-Harahsheh MS, Al Zboon K, Al-Makhadmeh L, Hararah M, Mahasneh M (2015) Fly ash based geopolymer for heavy metal removal: A case study on copper removal. J Environ Chem Eng 3(3):1669–1677. https://doi.org/10.1016/j.jece.2015.06.005CrossRefGoogle Scholar
- 38.Mužek MN, Svilović S, Zelić J (2013) Fly ash-based geopolymeric adsorbent for copper ion. Desalin Water Treat 52:2519–2526. https://doi.org/10.1080/19443994.2013.792015CrossRefGoogle Scholar
- 39.Mužek MN, Svilović S, Zelić J (2016) Kinetic studies of cobalt ion removal from aqueous solutions using fly ash-based geopolymer and zeolite NaX as sorbents. Sep Sci Technol 51(18):2868–2875. https://doi.org/10.1080/01496395.2016.1228675CrossRefGoogle Scholar
- 40.Muzek MN, Svilovic S, Ugrina M, Zelic J (2016) Removal of copper and cobalt ions by fly ash-based geopolymer from. Desalin Water Treat 57:10689–10699. https://doi.org/10.1080/19443994.2015.1040077CrossRefGoogle Scholar
- 41.Liu Y, Yan C, Zhang Z, Wang H, Zhou S, Zhou W (2016) A comparative study on fly ash, geopolymer and faujasite block for Pb removal from aqueous solution. Fuel 185:181–189. https://doi.org/10.1016/j.fuel.2016.07.116CrossRefGoogle Scholar
- 42.Duan P, Yan C, Zhou W, Ren D (2016) Development of fly ash and iron ore tailing based porous geopolymer for removal of Cu(II) from wastewater. Ceram Int 42(12):13507–13518. https://doi.org/10.1016/j.ceramint.2016.05.143CrossRefGoogle Scholar
- 43.Yousef RI, El-Eswed B, Alshaaer M, Khalili F, Khoury H (2009) The influence of using Jordanian natural zeolite on the adsorption, physical, and mechanical properties of geopolymers products. J Hazard Mater 165:379–387. https://doi.org/10.1016/j.jhazmat.2008.10.004CrossRefGoogle Scholar
- 44.El-Eswed B, Yousef RI, Alshaaer M, Khalili F, Khoury H (2009) Alkali solid-state conversion of kaolin and zeolite to effective adsorbents for removal of lead from aqueous solution. Desalin Water Treat 8:124–130. https://doi.org/10.5004/dwt.2009.672CrossRefGoogle Scholar
- 45.El-Eswed B, Alshaaer M, Yousef RI, Hamadneh I, Khalili F (2012) Adsorption of Cu(II), Ni(II), Zn(II), Cd(II) and Pb(II) onto Kaolin/Zeolite based- geopolymers. Adv Mater Phys Chem 2:119–125. https://doi.org/10.4236/ampc.2012.24B032CrossRefGoogle Scholar
- 46.Alzboon K, Al Smadi B, Al-Khawaldh S (2016) Natural volcanic tuff-based geopolymer for Zn removal: adsorption isotherm, kinetic, and thermodynamic study. Water Air Soil Pollut:227–248. https://doi.org/10.1007/s11270-016-2937-5
- 47.Papa E, Medri V, Amari S, Manaud J, Benito P, Vaccari A, Landi E (2018) Zeolite-geopolymer composite materials: production and characterization. J Clean Prod 171:76–84. https://doi.org/10.1016/j.jclepro.2017.09.270CrossRefGoogle Scholar
- 48.Alshaaer M, Zaharaki D, Komnitsas K (2014) Microstructural characteristics and adsorption potential of a zeolitic tuff–metakaolin geopolymer. Desalin Water Treat 56(2):338–345. https://doi.org/10.1080/19443994.2014.938306CrossRefGoogle Scholar
- 49.Andrejkovičov S, Sudagar A, Rocha J, Patinha C, Hajjaji W, Ferreira da Silva E, Velosa A, Rocha F (2016) The effect of natural zeolite on microstructure, mechanical and heavy metals adsorption properties of metakaolin based geopolymers. Appl Clay Sci 126:141–152. https://doi.org/10.1016/j.clay.2016.03.009CrossRefGoogle Scholar
- 50.Li L, Wang S, Zhu Z (2006) Geopolymeric adsorbents from fly ash for dye removal from aqueous solution. J Colloid Interface Sci 30(1):52–59. https://doi.org/10.1016/j.jcis.2006.03.062CrossRefGoogle Scholar
- 51.Mills A, Hazafy D, Parkinson J, Tuttle T, Hutchings MG (2011) Effect of alkali on methylene blue (C.I. Basic Blue 9) and other thiazine dyes. Dyes Pigm 88(2):149–155. https://doi.org/10.1016/j.dyepig.2010.05.015CrossRefGoogle Scholar
- 52.Barbosa TR, Foletto EL, Dotto GL, Jahn SL (2018) Preparation of mesoporous geopolymer using metakaolin and rice husk ash as synthesis precursors and its use as potential adsorbent to remove organic dye from aqueous solutions. Ceram Int 44:416–423. https://doi.org/10.1016/j.ceramint.2017.09.193CrossRefGoogle Scholar
- 53.Provis JL, Lukey GC, van Deventer JSJ (2005) Do geopolymers actually contain nanocrystalline zeolites? A reexamination of existing results. Chem Mater 17:3075–3085. https://doi.org/10.1021/cm050230iCrossRefGoogle Scholar
- 54.Schmidt W (2012) Synthetic inorganic ion exchange materials. In: Inamuddin, Luqman M (eds) Ion exchange technology I. Theory and materials. Springer, pp 277–298Google Scholar
- 55.Bajpai PK (1986) Synthesis of mordenite type zeolite. Zeolites 6:2–8CrossRefGoogle Scholar
- 56.Querol Carceller X, Moreno N, Alastuey A, Juan Mainar R, Andres Gimeno JM, Lopez-Soler Á, Ayora C, Medinaceli A, Valero A (2007) Synthesis of high ion exchange zeolites from coal fly ash. Geologica Acta 5(1):49–57. http://dx.doi.org/10.1344/105.000000309
- 57.Franus W, Wdowin M, Franus M (2014) Synthesis and characterization of zeolites prepared from industrial fly ash. Environ Monit Assess 186:5721–5729. https://doi.org/10.1007/s10661-014-3815-5CrossRefGoogle Scholar
- 58.Jha B (2016) Basics of zeolites. In: Jha B, Singh DN (eds) Fly ash zeolites: innovations, applications, and directions, advanced structured materials. Springer. https://doi.org/10.1007/978-981-10-1404-8_2Google Scholar
- 59.Van Jaarsveld JGS, Van Deventer JSJ, Schwartzman A (1999) The potential use of geopolymeric materials to immobilise toxic metals: part II. Material and leaching characteristics. Mineral Eng 12(1):75–91. https://doi.org/10.1016/S0892-6875(98)00121-6CrossRefGoogle Scholar
- 60.Van Jaarsveld JGS, Van Deventer JSJ (1999) The effect of metal contaminants on the formation and properties of waste-based geopolymers. Cem Concr Res 29:1189–1200. https://doi.org/10.1016/S0008-8846(99)00032-0CrossRefGoogle Scholar
- 61.Novais RM, Buruberri LH, Seabra MP, Labrincha JA (2016) Novel porous fly-ash containing geopolymer monoliths for lead adsorption from wastewaters. J Hazard Mater 318:631–640. https://doi.org/10.1016/j.jhazmat.2016.07.059CrossRefGoogle Scholar
- 62.Buic Z, Zelić B (2009) Application of clay for petrochemical wastewater pretreatment. Water Qual Res J Can 44:399–406CrossRefGoogle Scholar
- 63.Nasef MM, Ujang Z (2012) Introduction to ion exchange processes. In: Inamuddin, Luqman M (eds) Ion exchange technology I. Theory and materials. Springer, pp 1–40Google Scholar
- 64.Margeta K, Logar NZ, Šiljeg M, Farkas A (2013) Natural zeolites in water treatment—how effective is their use, water treatment. In: Dr. Elshorbagy W (ed) InTech. https://doi.org/10.5772/50738. Available from: https://www.intechopen.com/books/water-treatment/natural-zeolites-in-water-treatment-how-effective-is-their-useGoogle Scholar
- 65.Katsou E, Malamis S, Tzanoudaki M, Haralambous KJ, Loizidou M (2011) Regeneration of natural zeolite polluted by lead and zinc in wastewater treatment systems. J Hazard Mater 189(3):773–786. https://doi.org/10.1016/j.jhazmat.2010.12.061CrossRefGoogle Scholar
- 66.Cincotti A, Mameli A, Locci AM, Orrù R, Cao G (2006) Heavy metals uptake by Sardinian natural zeolites: experiment and modeling. Ind Eng Chem Res 45(3):1074–1084. https://doi.org/10.1021/ie050375zCrossRefGoogle Scholar
- 67.Sprynskyy M, Buszewski B, Terzyk AP, Namieśnik J (2006) Study of the selection mechanism of heavy metal (Pb2 + , Cu2 + , Ni2 + , and Cd2 +) adsorption on clinoptilolite. J Colloid Interface Sci 304(1):21–28. https://doi.org/10.1016/j.jcis.2006.07.068CrossRefGoogle Scholar
- 68.Zhou CF, Zhu JH (2005) Adsorption of nitrosamines in acidic solution by zeolites. Chemosphere 58(1):109–114. https://doi.org/10.1016/j.chemosphere.2004.08.056CrossRefGoogle Scholar
- 69.Abora K, Beleña I, Bernal SA, Dunster A, Nixon PA, Provis JL, Tagnit-Hamou A, Winnefeld F (2014) Durability and testing—chemical matrix degradation processes. In: Provis JL, van Devente JSJ (eds) Alkali activated materials: state-of-the-art report, RILEM TC 224-AAM. Springer, pp 177–221Google Scholar
- 70.Li Q, Sun Z, Tao D, Xu Y, Li P, Cui H, Zhai J (2013) Immobilization of simulated radionuclide 133Cs + by fly ash-based geopolymer. J Hazard Mater 262:325–331. https://doi.org/10.1016/j.jhazmat.2013.08.049CrossRefGoogle Scholar
- 71.Bernal SA, Krivenko PV, Provis JL, Puertas F, Rickard WDA, Shi C, Van Riessen A (2014) Other potential applications for alkali-activated materials. In: Provis JL, van Devente JSJ (eds) Alkali Activated materials: state-of-the-art report, RILEM TC 224-AAM. Springer, pp 339–379Google Scholar
- 72.Hizal J, Tutem E, Guclu K, Hugul M, Ayhan S, Apak R, Kilinckale F (2013) Heavy metal removal from water by red mud and coal fly ash: an integrated adsorption–solidification/stabilization process. Desalin Water Treat 51:7181–7193. https://doi.org/10.1080/19443994.2013.771289CrossRefGoogle Scholar
- 73.Ipatti A (1992) Solidification of ion-exchange resins with alkali-activated blast-furnace slag. Cem Concr Res 22:281–286. https://doi.org/10.1016/0008-8846(92)90066-5CrossRefGoogle Scholar
- 74.Kuenzel C, Cisneros JF, Neville TP, Vandeperre LJ, Simons SJR, Bensted J, Cheeseman CR (2015) Encapsulation of Cs/Sr contaminated clinoptilolite in geopolymers produced from metakaolin. J Nucl Mater 466:94–99. https://doi.org/10.1016/j.jnucmat.2015.07.034CrossRefGoogle Scholar
- 75.Ferone C, Roviello G, Colangelo F, Cioffi R, Tarallo O (2013) Novel hybrid organic-geopolymer materials. Appl Clay Sci 73:42–50. https://doi.org/10.1016/j.clay.2012.11.001CrossRefGoogle Scholar