Iron(II) modified natural zeolites for hexavalent chromium removal from contaminated water

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Three different types of Fe(II)-modified natural zeolites were tested as supports in continuous-flow columns for the treatment of Cr(VI) contaminated water. The natural zeolites chosen as support were commercially available Zeosand (80% clinoptilolite), ATZ (79% phillipsite/chabazite), and ZS-55RW (90% Chabazite). All the examined modified zeolites turned out active for hexavalent chromium abatement, lowering its concentration below the European regulation level, even at relatively high flow rates (40 mL/h, linear velocity 15 cm/h). Zeosand, having a broader pH range of stability, was found to be the best one in terms of both Fe(II) uptake (0.54 wt%) and Cr removal (90 mg Cr/Kg zeolite).

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  • Barrer R.M. (1978). Zeolites and Clay Minerals as Sorbents and Molecular Sieves London: Academic Press London 1978.

  • Bowman R.S. & Helferich R. (2001). Production and article of iron/surfactant-modified zeolite pellets to retain and destroy water pollutants U.S. Patent No. 6261986 B1 17 July 2001. Washington D.C.: U.S. Patent and Trademark Office.

  • Byrne R.H. Luo Y.-R. & Young R.W. (2000). Iron hydrolysis and solubility revisited: observations and comments on iron hydrolysis characterizations Marine Chemistry 70 pp. 23–35.

  • Byrne R.H. Yao W. Luo Y.-R. & Wang B. (2005). The dependence of Fe(III) hydrolysis on ionic strength in NaCl solutions Marine Chemistry 97 pp. 34–48.

  • Campos V. Morais L.C. & Buchler P.M. (2007). Removal of chromate from aqueous solution using treated natural zeolite Environmental Geology 52 pp. 1521–1525.

  • Dimirkou A. & Doula M.K. (2008). Use of clinoptilolite and an Fe-overexchanged clinoptilolite in Zn2+ and Mn2+ removal from drinking water Desalination 224 pp. 280–292.

  • Doula M.K. (2007). Synthesis of a clinoptilolite–Fe system with high Cu sorption capacity Chemosphere 67 pp. 731–740.

  • Eary L.E. & Rai D. (1987). Kinetics of chromium(III) oxidation to chromium(VI) by reaction with manganese dioxide Environmental Science & Technology 27 pp. 1187–1193.

  • Eary L.E. & Rai D. (1988). Chromate removal from aqueous wastes by reduction with ferrous ion Environmental Science & Technology 22 pp. 972–977.

  • Erdogan B.C. & Ulku S. (2012). Cr(VI) sorption by using clinoptilolite and bacteria loaded clinoptilolite rich mineral Microporous Mesoporous Mater 152 pp. 253–261.

  • Faghihian H. & Bowman R.S. (2005). Adsorption of chromate by clinoptilolite exchanged with various metal cations Water Research 39 pp. 1099–1104.

  • Fruchter J. (2002). In situ treatment of chromium-contaminated groundwater Environmental Science & Technology 36 pp. 464A–472A.

  • Gode F. & Pehlivan E. (2005). Removal of Cr(VI) from aqueous solution by two Lewatit-anion exchange resins Journal of Hazardous Materials 119 pp. 175–182.

  • Hu S.J. Buerge I.J. & Weidler P.G. (1997). Transformations of chromium in the environment Analysis 25 pp. 12–15.

  • Hwang I. Batchelor B. Schlautman M.A. & Wang R. (2002). Effects of ferrous iron and molecular oxygen on chromium(VI) redox kinetics in the presence of aquifer solids Journal of Hazardous Materials 92 pp. 143–159.

  • Inglezakis V. J. Loizidou M. D. & Grigoropoulou H. P. (2003). Ion exchange of Pb2+ Cu2+ Fe3+ and Cr3+ on natural clinoptilolite: selectivity determination and influence of acidity on metal uptake Journal of Colloid and Interface Science 261 pp. 49–54.

  • Kiser J.R. & Manning B.A. (2010). Reduction and immobilization of chromium(VI) by iron(II)-treated faujasite Journal of Hazardous Materials 174 pp. 167–174.

  • Kotaś J. & Stasicka Z. (2000). Chromium occurrence in the environment and methods of its speciation Environmental Pollution 107 pp. 263−283.

  • Leyva-Ramos R. Jacobo-Azuara A. Diaz-Flores P.E. Guerrero-Coronado R.M. Mendoza-Barron J. & Berber-Mendoza M.S. (2008). Adsorption of chromium(VI) from an aqueous solution on a surfactant-modified zeolite Colloids and Surfaces A: Physicochemical and Engineering Aspects 330 pp. 35–41.

  • Li Z. Jones H.K. Bowman R.S. & Helferich R. (1999). Enhanced reduction of chromate and PCE by pelletized surfactant-modified zeolite/zerovalent iron Environmental Science & Technology 33 pp. 4326–4330.

  • Li Z. (2006). Chromate transport through surfactant-modified zeolite columns Groundwater Monitoring & Remediation 26 pp. 117–124.

  • Li Z. Jones H.K. Zhang P. & Bowman R.S. (2007). Chromate transport through columns packed with surfactant-modified zeolite/zero valent iron pellets Chemosphere 68 pp. 1861–1866.

  • Liguori B. Cassese A. & Colell A. (2006). Safe immobilization of Cr(III) in heat-treated zeolite tuff compacts Journal of Hazardous Materials 137 pp. 1206–1210.

  • Litz J.E. (2006). Hexa-valent chromium removal from aqueous media using ferrous-form zeolite materials U.S. Patent No. 7105087 B2 12 September 2006. Washington D.C.: U.S. Patent and Trademark Office.

  • Loyaux-Lawniczak S. Lecomte P. & Ehrhardt J.-J. (2001). Behavior of hexavalent chromium in a polluted groundwater: redox processes and immobilization in soils Environmental Science & Technology 35 pp. 1350–1357.

  • Lu G. Li Z. Jiang W.-T. Ackley C. Fenske N. & Demarco N. (2013). Removal of Cr(VI) from water using Fe(II) modified natural zeolites Chemical Engineering Research and Design CHERD-1335 922 pp. 384–390

  • Ludwig R.D. Su C. Lee T.R. Wilkin R.T. Acree S. D. Ross R.R. & Keeley A. (2007). In situ chemical reduction of Cr(VI) in groundwater using a combination of ferrous sulfate and sodium dithionite: a field investigation Environmental Science & Technology 41 pp. 5299–5305.

  • Mackay D.M. & Cherry J.A. (1989). Groundwater contamination: pump-and-treat remediation Environmental Science & Technology 23 pp. 630–636.

  • Martin T.A. & Kempton J.H. (2000). In situ stabilization of metal-contaminated groundwater by hydrous ferric oxide: an experimental and modeling investigation Environmental Science & Technology 34 pp. 3229–3234.

  • Meir M.V. Callejas R.L. Gehr R. Cisneros B.E.J. & Alvarez P.J.J. (2001). Heavy metal removal with Mexican clinoptilolite: Multi-component ionic exchange Water Research 35 pp. 373–378.

  • Misaelides P. Zamboulis D. Sarridis P. Warchoł J. & Godelitsas A. (2008). Chromium (VI) uptake by polyhexamethylene-guanidine-modified natural zeolitic materials Microporous and Mesoporous Materials 108 pp. 162–167.

  • Ouki S.K. & Kavannagh M. (1999). Treatment of metals-contaminated wastewaters by use of natural zeolites Water Science and Technology 39 pp. 115–122.

  • Palmer C.D. & Wittbrodt P.R. (1991). Processes affecting the remediation of chromium-contaminated sites Environmental Health Perspectives 92 pp. 25–40.

  • Park J.-B. Lee S.-H. Lee J.-W. & Lee C.-Y. (2002). Lab scale experiments for permeable reactive barriers against contaminated groundwater with ammonium and heavy metals using clinoptilolite (01-29B) Journal of Hazardous Materials 95 pp. 65–79.

  • Patterson R.R. Fendorf S. & Fendorf M. (1997). Reduction of hexavalent chromium by amorphous iron sulphide Environmental Science & Technology 31 pp. 2039–2044.

  • Qin G. Mcguire M.J. Blute N.K. Seidel C. & Fong L. (2005). Hexavalent chromium removal by reduction with ferrous sulfate coagulation and filtration: a pilot-scale study Environmental Science & Technology 39 pp. 6321–6327.

  • Rai D. Sass B.M. & Moore D.A. (1987). Chromium(VI) hydrolysis constants and solubility of chromium hydroxide Inorganic Chemistry 26 pp. 345–349.

  • Rama Krishna K. & Philip L. (2005). Bioremediation of Cr(VI) in contaminated soils Journal of Hazardous Materials 121 pp. 109–117.

  • Rengaraj S. Joo C.K. Kim Y. & Yi J. (2003). Kinetics of removal of chromium from water and electronic process wastewater by ion exchange resins: 1200H 1500H and IRN97H Journal of Hazardous Materials 102 pp. 257–275.

  • Rhodes C.J. (2007). Zeolites: physical aspects and environmental applications Annual Reports of the Progress of Chemistry C 103 pp. 287–325.

  • Robson H. (2001). Verified Syntheses of Zeolitic Materials Elsevier Science B.V. Amsterdam 2001.

  • Sass B.M. & Rai D. (1987). Solubility of amorphous chromium(III)-iron(III) hydroxide solid solutions Inorganic Chemistry 26 pp. 2228–2232.

  • Schlautman M.A. & Han I. (2001). Effects of pH and dissolved oxygen on the reduction of hexavalent chromium by dissolved ferrous iron in poorly buffered aqueous systems Water Research 35 pp. 1534–1546.

  • Sheta A.S. Falatah A.M. Al-Sewailem M.S. Khaled E.M. Sallam A.S.H. (2003). Sorption characteristics of zinc and iron by natural zeolite and bentonite Microporous and Mesoporous Materials 61 pp. 127–136.

  • Stefánsson A. (2007). Iron(III) hydrolysis and solubility at 25°C Environmental Science & Technology 41 pp. 6117–6123.

  • Sung W. & Morgan J.J. (1980). Kinetics and products of ferrous iron oxygenation in aqueous systems Environmental Science & Technology 14 pp. 561–568.

  • Tokunaga T.K. Wan J. Firestone M.K. Hazen T.C. Olson K.R. Herman D.J. Sutton S.R. & Lanzirotti A. (2003). In situ reduction of chromium(VI) in heavily contaminated soils through organic carbon amendment Journal of Environmental Quality 32 pp. 1641–1649.

  • Vignola R. Sisto R. Grillo G. Cova U. & Cesti P. (2007). Process for the treatment of contaminated water by means of a bifunctional system consisting of iron and zeolites International Patent WO 2007/054358 A1 18 May 2007.

  • Vignola R. Cova U. Della Penna G. & Sisto R. (2008). Process for the treatment of contaminated water based on the use of apolar zeolites having different characteristics U.S. Patent No. 7341665 B2 11 March 2008. Washington D.C.: U.S. Patent and Trademark Office.

  • Wingenfelder U. Hansen C. Furrer G. & Schulin R. (2005). Removal of heavy metals from mine waters by natural zeolites Environmental Science & Technology 39 pp. 4606–4613.

  • Wu D. Sui Y. He S. Wang X. Li C. & Kong H. (2008). Removal of trivalent chromium from aqueous solution by zeolite synthesized from coal fly ash Journal of Hazardous Materials 155 pp. 415–423.

  • Yang J.E. Kim J.S. Ok Y.S. & Yoo K.R. (2007). Mechanistic evidence and efficiency of the Cr(VI) reduction in water by different sources of zerovalent irons Water Science and Technology 55 pp. 197–202.

  • Zayed A.M. & Terry N. (2003). Chromium in the environment: factors affecting biological remediation Plant and Soil 249 pp. 139–156.

  • Zeng Y. Woo H. Lee G. & Park J. (2010). Adsorption of Cr(VI) on hexadecylpyridinium bromide (HDPB) modified natural zeolites Microporous Mesoporous Mater 130 pp. 83–91.

  • Zhao D. SenGupta A.K. & Stewart L. (1998). Selective removal of Cr(VI) oxyanions with a new anion exchanger Industrial & Engineering Chemistry Research 37 pp. 4383–4387.

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