Abstract
The selectivity of clinoptilolite toward Pb2+ has stimulated many studies aimed to evaluate the metal uptake. Conversely, the management of a Pb-bearing clinoptilolite has not received the same attention, although it can release a harmful metal. This work aims to evaluate the possibility to control, through thermal treatments, the release of lead from a Pb-clinoptilolite, prepared to simulate the condition of highest dangerousness of an exhausted exchanger. A zeolite-rich rock from Sardinia (Italy) has been processed, obtaining a powder with almost 90 % (wt.) of clinoptilolite. This material has been initially Na- and then Pb-exchanged, reaching a Pb2+ content of 2.28 meq/g. The lead release has been tested before and after 2-h heating at eight different temperatures from 200 to 900 °C. The unheated material releases 64 % of the lead. Heating weakly affects lead release up to 400 °C (54 %), but higher temperatures determine an abrupt reduction from 44 % at 500 °C to 1 % at 700 °C, when the zeolite breakdown occurs. At 800 °C the nucleation of Pb-feldspar and silica polymorphs begins. Basically, the material heated at 900 °C does not release lead (0.03 %), because the metal is trapped in the lead feldspar, whose content attains 42 % (wt.). This solid-state transformation does not involve the emission of lead vapors, another significant environmental aspect.
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References
Armbruster T (2001) Clinoptilolite-heulandite: applications and basic research. Stud Surf Sci Catal 135:13–27. doi:10.1016/S0167-2991(01)81183-6
Bektaş N, Kara S (2004) Removal of lead from aqueous solutions by natural clinoptilolite: equilibrium and kinetic studies. Sep Purif Technol 39(3):189–200. doi:10.1016/j.seppur.2003.12.001
Bish DL, Carey JW (2001) Thermal behavior of natural zeolites. In: Bish DL, Ming D (eds) Natural zeolites: occurrence, properties, applications. Reviews in mineralogy and geochemistry, vol 45. The Mineralogical Society of America, Washington (DC), pp 403–452
Blanchard G, Maunaye M, Martin G (1984) Removal of heavy-metals from waters by means of natural zeolites. Water Res 18:1501–1507. doi:10.1016/0043-1354(84)90124-6
Brundu A, Cerri G (2015) Thermal transformation of Cs-clinoptilolite to CsAlSi5O12. Microporous Mesoporous Mater 208:44–49. doi:10.1016/j.micromeso.2015.01.029
Cerri G, Cappelletti P, Langella A, de’ Gennaro M (2001) Zeolitization of Oligo-Miocene volcaniclastic rocks from Logudoro (northern Sardinia, Italy). Contrib Mineral Petrol 140:404–421. doi:10.1007/s004100000196
Cerri G, de’ Gennaro M, Bonferoni MC, Caramella C (2004) Zeolites in biomedical application: Zn-exchanged clinoptilolite-rich rock as active carrier for antibiotics in anti-acne topical therapy. Appl Clay Sci 27(3–4):141–150. doi:10.1016/j.clay.2004.04.004
Cerri G, Farina M, Brundu A, Daković A, Giunchedi P, Gavini E, Rassu G (2016) Natural zeolites for pharmaceutical formulations: preparation and evaluation of a clinoptilolite-based material. Microporous Mesoporous Mater 223:58–67. doi:10.1016/j.micromeso.2015.10.034
Chen S, Zhao B, Hayes PC, Jak E (2001) Experimental study of phase equilibria in the PbO–Al2O3–SiO2 system. Metall Mater Trans B 32(6):997–1005. doi:10.1007/s11663-001-0088-5
Cruciani G (2006) Zeolites upon heating: factors governing their thermal stability and structural changes. J Phys Chem Solids 67:1973–1994. doi:10.1016/j.jpcs.2006.05.057
Dascălu D, Pitulice L, Ionel R, Bizerea-Spiridon O (2015) The usage of a zeolitic composite for quality improvement of copper contaminated mining wastewaters. Int J Environ Sci Technol 12:2285–2298. doi:10.1007/s13762-014-0629-5
Enamorado-Horrutiner Y, Villanueva-Tagle ME, Behar M, Rodríguez-Fuentes G, Ferraz Dias J, Pomares-Alfonso MS (2016) Cuban zeolite for lead sorption: application for water decontamination and metal quantification in water using nondestructive techniques. Int J Environ Sci Technol 13(5):1245–1256. doi:10.1007/s13762-016-0956-9
Garcia-Basabe Y, Rodriguez-Iznaga I, de Menorval LC, Llewellyn P, Maurin G, Lewis DW, Binions R, Autie M, Ruiz-Salvador AR (2010) Step-wise dealumination of natural clinoptilolite: structural and physicochemical characterization. Microporous Mesoporous Mater 135:187–196. doi:10.1016/j.micromeso.2010.07.008
Gatta GD, Brundu A, Cappelletti P, Cerri G, de’ Gennaro B, Farina M, Fumagalli P, Guaschino L, Lotti P, Mercurio M (2016) New insights on pressure, temperature, and chemical stability of CsAlSi5O12, a potential host for nuclear waste. Phys Chem Minerals 43:639–647. doi:10.1007/s00269-016-0823-8
Guzel P, Aydin YA, Deveci Aksoy N (2016) Removal of chromate from wastewater using amine-based-surfactant-modified clinoptilolite. Int J Environ Sci Technol 13(5):1277–1288. doi:10.1007/s13762-016-0954-y
Hamidpour M, Afyuni M, Kalbasi M, Khoshgoftarmanes AH, Inglezakis VJ (2010a) Mobility and plant-availability of Cd(II) and Pb(II) adsorbed on zeolite and bentonite. Appl Clay Sci 48:342–348. doi:10.1016/j.clay.2010.01.004
Hamidpour M, Kalbasi M, Afyuni M, Shariatmadari H, Holm PE, Hansen HC (2010b) Sorption hysteresis of Cd(II) and Pb(II) on natural zeolite and bentonite. J Hazard Mater 181:686–691. doi:10.1016/j.jhazmat.2010.05.067
Inglezakis VJ, Stylianou MA, Gkantzou D, Loizidou MD (2007) Removal of Pb(II) from aqueous solutions by using clinoptilolite and bentonite as adsorbents. Desalination 210(1–3):248–256. doi:10.1016/j.desal.2006.05.049
Kalló D (2001) Applications of natural zeolites in water and wastewater treatment. In: Bish DL, Ming D (eds) Natural zeolites: occurrence, properties, applications. Reviews in mineralogy and geochemistry, vol 45. The Mineralogical Society of America, Washington (DC), pp 519–550
Kesraoul-Oukl S, Cheeseman C, Perry R (1993) Effects of conditioning and treatment of chabazite and clinoptilolite prior to lead and cadmium removal. Environ Sci Technol 27:1108–1116. doi:10.1021/es00043a009
Langella A, Pansini M, Cappelletti P, De Gennaro B, de’ Gennaro M, Colella C (2000) NH4+, Cu2+, Zn2+, Cd2+ and Pb2+ exchange for Na+ in a sedimentary clinoptilolite, North Sardinia, Italy. Microporous Mesoporous Mater 37:337–343. doi:10.1016/S1387-1811(99)00276-0
Lata S, Singh PK, Samadder SR (2015) Regeneration of adsorbents and recovery of heavy metals: a review. Int J Environ Sci Technol 12:1461–1478. doi:10.1007/s13762-014-0714-9
Loizidou MD, Townsend RP (1987) Ion exchange properties of natural clinoptilolite, ferrierite and mordenite: part 2. Lead–sodium and lead–ammonium equilibria. Zeolites 7:153–159. doi:10.1016/0144-2449(87)90078-9
Lu X, Shih K, Cheng H (2013) Lead glass-ceramics produced from the beneficial use of waterworks sludge. Water Res 47(3):1353–1360. doi:10.1016/j.watres.2012.11.045
Matoušek J, Janů T (2001) Evaporation of PbO–SiO2 and K2O–PbO–SiO2 melts. Ceram-Silikáty 45(4):137–141. http://www.ceramics-silikaty.cz/2001/pdf/2001_04_137.pdf
Moattar F, Hayeripour S (2004) Application of chitin and zeolite adsorbents for treatment of low level radioactive liquid wastes. Int J Environ Sci Technol 1(1):45–50. doi:10.1007/BF03325815
Moroni M, Brigida C, Poli S, Valle M (2004) Fixing chromium and lead in ceramic materials: a petrological approach to inertization and recycling of toxic industrial waste. Period Mineral 73(3):99–111. http://tetide.geo.uniroma1.it/riviste/permin/testi/V73/38.pdf
Motsa MM, Mamba BB, Thwala JM, Msagati TAM (2011) Preparation, characterization, and application of polypropylene–clinoptilolite composites for the selective adsorption of lead from aqueous media. J Colloid Interface Sci 359(1):210–219. doi:10.1016/j.jcis.2011.02.067
Nuić I, Trgo M, Perić J, Vukojević Medvidović N (2013) Analysis of breakthrough curves of Pb and Zn sorption from binary solutions on natural clinoptilolite. Microporous Mesoporous Mater 167:55–61. doi:10.1016/j.micromeso.2012.04.037
Pabalan RT, Bertetti FP (2001) Cation-exchange properties of natural zeolites. In: Bish DL, Ming D (eds) Natural zeolites: occurrence, properties, applications. Reviews in mineralogy and geochemistry, vol 45. The Mineralogical Society of America, Washington (DC), pp 453–518
Radosavljevic-Mihajlovic AS, Kremenovic AS, Dosen AM, Andrejic JZ, Dondur VT (2015) Thermally induced phase transformation of Pb-exchanged LTA and FAU-framework zeolite to feldspar phases. Microporous Mesoporous Mater 201:210–218. doi:10.1016/j.micromeso.2014.08.059
Rahmani AR, Mahvi AH, Mesdaghinia AR, Nasseri S (2004) Investigation of ammonia removal from polluted waters by Clinoptilolite zeolite. Int J Environ Sci Technol 1(2):125–133. doi:10.1007/BF03325825
Ranjbar F, Jalali M (2016) Empirical and mechanistic evaluation of sodium exchange isotherms on natural mineral and organic adsorbents and organically functionalized nanoparticles. Int J Environ Sci Technol. doi:10.1007/s13762-016-0983-6
Semmens MJ, Seyfarth M (1978) The selectivity of clinoptilolite for certain heavy metals. In: Sand LB, Mumpton FA (eds) Natural zeolites: occurrence, properties, use. Pergamon Press, Elmsford, pp 517–526
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 304:21–28. doi:10.1016/j.jcis.2006.07.068
Um W, Papelis C (2004) Metal ion sorption and desorption on zeolitized tuffs from the nevada test site. Environ Sci Technol 38(2):496–502. doi:10.1021/es0343050
Vukojević Medvidović N, Perić J, Trgo M, Mužek MN (2007) Removal of lead ions by fixed bed of clinoptilolite—the effect of flow rate. Microporous Mesoporous Mater 105(3):298–304. doi:10.1016/j.micromeso.2007.04.015
Wingenfelder U, Hansen C, Furrer G, Schulin R (2005) Removal of heavy metals from mine waters by natural zeolites. Environ Sci Technol 39(12):4606–4613. doi:10.1021/es048482s
Acknowledgments
The authors thank Marco Biagioli (Sassari University) for AAS analyses. Antonio Brundu acknowledges the financial support of “Regione Autonoma della Sardegna”—P.O. Sardegna FSE 2007-2013, L.R. 7/2007.
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Brundu, A., Cerri, G. Release of lead from Pb-clinoptilolite: managing the fate of an exhausted exchanger. Int. J. Environ. Sci. Technol. 14, 223–232 (2017). https://doi.org/10.1007/s13762-016-1149-2
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DOI: https://doi.org/10.1007/s13762-016-1149-2