Abstract
The presence of nitrate and other redox-active anionic contaminants in terrestrial ecosystems poses a significant risk to humans and other forms of life on Earth. The purpose of the present study was to test a potential in situ system, using poly-(D) glucosamine (chitosan) adsorbed to mineral surfaces under redox-active conditions in order to degrade nitrate to lower oxidation states. Chitosan is a linear polysaccharide derived from the chitin found in the shells of shrimp and other shellfish. Five different loadings of chitosan (0, 0.075, 0.25, 0.50, and 1.0 g/L; labeled C0, C1, C2, C3, and C4, respectively) were adsorbed to ferruginous smectite (SWa-1) to form chitosan-SWa-1 composites (CSC) in the pH range 5.8–4. The CSC was then reduced by Na2S2O4 in a citrate-bicarbonate buffered dispersion and washed free of excess salts under inert-atmosphere conditions. Upon addition of the nitrate, the solution pH remained slightly acidic, ranging from 5.5 to 4.7. Samples were analyzed for Fe(II) content, reacted with a NaNO3 solution, and then re-analyzed for structural Fe(II) content. Supernatant solutions were analyzed for nitrate, nitrite, and ammonium. In samples C1 to C4, extensive concentrations of nitrite were observed in the supernatants with a corresponding increase in the reoxidation of structural Fe(II), proving that a coupled redox reaction had occurred between the nitrate and the structural Fe in the clay mineral. The most efficient loading, defined as the largest percentage of adsorbed nitrate reduced to nitrite, occurred in sample C1. The total amount of nitrate reduced and Fe(II) reoxidized followed the trend 0 = C0 < C2 < C3 < C4 ≈ C1. Chitosan showed the potential to reverse the surface charge of constituent clay minerals, thereby enabling the CSC to remove nitrate anions from aqueous mineral systems via redox reactions with structural Fe(II) in clay minerals.
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References
Abugoch, L.E., Tapia, C., Villamán, M.C., Pedram, M.Y., and Dosque, M.D. (2011) Characterization of quinoa protein chitosan blend edible films. Food Hydrocolloids, 25, 879–886.
Ahn, S.C., Oh, S.-Y., and Cha, D.K. (2008) Enhanced reduction of nitrate by zero-valent iron at elevated temperatures. Journal of Hazardous Materials, 156, 17–22.
Auta, M. and Hameed, B.H. (2014) Chitosan-clay composite as highly effective and low-cost adsorbent for batch and fixedbed adsorption of methylene blue. Chemical Engineering Journal, 237, 352–361.
Bhatnagar, A. and Sillanpää, M. (2009) Applications of chitinand chitosan-derivatives for the detoxification of water and wastewater — a short review. Advances in Colloid and Interface Science, 152, 26–38.
Bhatnagar, A. and Sillanpää, M. (2011) A review of emerging adsorbents for nitrate removal from water. Chemical Engineering Journal, 168, 493–504.
Bhatnagar, A., Kumar, E., and Sillanpää, M. (2010) Nitrate removal from water by nano-alumina: Characterization and sorption studies. Chemical Engineering Journal, 163, 317–323.
Bishop, J., Madejová, J., Komadel, P., and Fröschl, H. (2002) The influence of structural Fe, Al and Mg on the infrared OH bands in spectra of dioctahedral smectites. Clay Minerals, 37, 607–616.
Bleiman, N. and Mishael, Y.G. (2010) Selenium removal from drinking water by adsorption to chitosan-clay composites and oxides: Batch and columns tests. Journal of Hazardous Materials, 183, 590–595.
Bowen, J.L., Kroeger, K.D., Tomasky, G., Pabich, W.J., Cole, M.L., Carmichael, R.H., and Valiela, I. (2007) A review of land-sea coupling by groundwater discharge of nitrogen to New England estuaries: Mechanisms and effects. Applied Geochemistry, 22, 175–191.
Breen, C. (1999) The characterization and use of polycation-exchanged bentonites. Applied Clay Science, 15, 187–219.
Brtáňová, A., Melichová, Z., and Komadel, P. (2012) Sorption of Cu2+ from aqueous solutions by Slovak bentonites. Ceramics — Silikáty, 56, 55–60.
Brtáňová, A., Madejová, J., Bizovská, V., and Komadel, P. (2014) Utilization of near infrared spectroscopy for studying solvation properties of Cu-montmorillonites. Spectrochimica Acta — Par t A: Molecular and Biomolecular Spectroscopy, 123, 385–391.
Brugnerotto, J., Lizardi, J., Goycoolea, F.M., Argüelles-Monal, W., Desbrières, J., and Rinaudo, M. (2001) An infrared investigation in relation with chitin and chitosan characterization. Polymer, 42, 3569–3580.
Burow, K.R., Nolan, B.T., Rupert, M.G., and Dubrovsky, N.M. (2010) Nitrate in groundwater of the United States, 1991–2003. Environmental Science & Technology, 44, 4988–4997.
Camargo, J.A. and Alonso, A. (2006) Review Article. Ecological and toxicological effects of inorganic nitrogen pollution in aquatic ecosystems: A global assessment. Environment International, 32, 831–849.
Chabani, M., Amrane, A., and Bensmaili, A. (2006) Kinetic modelling of the adsorption of nitrates by ion exchange resin. Chemical Engineering Journal, 125, 111–117.
Cheng, I.F., Muftikian, R., Fernando, Q., and Korte, N. (1997) Reduction of nitrate to ammonia by zero valent iron. Chemosphere, 35, 2689–2695.
Churchman, G.J. (2002) Formation of complexes between bentonite and different cationic polyelectrolytes and their use as sorbents for non-ionic and anionic pollutants. Applied Clay Science, 21, 177–189.
Crini, G. and Badot, P.M. (2008) Application of chitosan, a natural aminopolysaccharide, for dye removal from aqueous solution by adsorption process using batch studies: A review of recent literature. Progress in Polymer Science, 33, 399–447.
Czímerová, A., Janković, L., and Bujdák, J. (2004) Effect of the exchangeable cations on the spectral properties of methylene blue in clay dispersions. Journal of Colloid and Interface Science, 1, 126–132.
Darder, M., Colilla, M., and Ruiz-Hitzky, E. (2005) Chitosan-clay nanocomposites: application as electrochemical sensors. Applied Clay Science, 28, 199–208.
Dinu, M.V. and Dragan, E.S. (2010) Evaluation of Cu2+, Co2+, and Ni2+ ions removal from aqueous solution using a novel chitosan/clinoptilolite composite: Kinetics and isotherms. Chemical Engineering Journal, 160, 157–163.
Dutta, P.K., Duta, J., and Tripathi, V.S. (2004) Chitin and Chitosan: Chemistry, properties and applications. Journal of Scientific and Industrial Research, 63, 20–31.
Ernstsen, V. (1996) Reduction of nitrate by Fe2+ in clay minerals. Clays and Clay Minerals, 44, 599–608.
Ernstsen, V., Gates, W.P., and Stucki, J.W. (1998) Microbial reduction of structural iron in clays - A renewable source of reduction capacity. Journal of Environmental Quality, 27, 761–766.
Farmer, V.C. (1974) The Infrared Spectra of Minerals. Monograph 4, Mineralogical Society, London, 539 pp.
Freeze, R.A. and Cherry, J.A. (1979) Groundwater. Prentice Hall, Englewood Cliffs, New Jersey, USA, 604 pp.
Frost, R.L., Kloprogge, J.T., and Ding, Z. (2002) The Garfield and Uley nontronites - An infrared spectroscopic comparison. Spectrochimica Acta — Part A Molecular and Biomolecular Spectroscopy, 58, 1881–1894.
Fu, F. and Wang, Q. (2011) Removal of heavy metal ions from wastewaters: A review. Journal of Environmental Management, 92, 407–418.
Fu, X. and Qutubuddin, S. (2001) Polymer-clay nanocomposites: Exfoliation of organophilic montmorillonite nanolayers in polystyrene. Polymer, 42, 807–813.
Hell, F., Lahnsteiner, J., Frischherz, H., and Baumgartner, G. (1998) Experience with full-scale electrodialysis for nitrate and hardness removal. Desalination, 117, 173–180.
Howarth, R.W. (2008) Coastal nitrogen pollution: A review of sources and trends globally and regionally. Harmful Algae, 8, 14–20.
Huang, C.P., Wang, H.W., and Chiu, P.C. (1998) Nitrate reduction by metallic iron. Water Research, 32, 2257–2264.
Hwang, Y.H., Kim, D.G., and Shin, H.S. (2011) Mechanism study of nitrate reduction by nano zero-valent iron. Journal of Hazardous Materials, 185, 1513–1521.
Jeon, C. and Park, K.H. (2005) Adsorption and desorption characteristics of mercury (II) ions using aminated chitosan beads. Water Research, 36, 3938–3944.
Khan, S.A., Mulvaney, R.L., and Mulvaney, C.S. (1997) Accelerated diffusion methods for inorganic-nitrogen analysis of soil extracts and water. Soil Science Society of America Journal, 61, 936–942.
Komadel, P. and Stucki, J.W. (1988) Quantitative assay of minerals for Fe2+ and Fe3+ using 1,10-phenanthroline: III. A rapid photochemical method. Clays and Clay Minerals, 36, 379–381.
Korom, S.F. (1992) Natural denitrification in the saturated zone: A review. Water Resources Research, 28, 1657–1668.
Kumar, M. and Chakraborty, S. (2006) Chemical denitrification of water by zero-valent magnesium powder. Journal of Hazardous Materials, 135, 112–121.
Kumirska, J., Czerwicka, M., Kaczyński, Z., Bychowska, A., Brzozowski, K., Thöming, J., and Stepnowski, P. (2010) Application of spectroscopic methods for structural analysis of Chitin and Chitosan. Marine Drugs, 8, 1567–1636.
Liu, H., Guo, M., and Zhang, Y. (2014) Nitrate removal by Fe0/Pd/Cu nano-composite in groundwater. Environmental Technology, 35, 917–924.
Manceau, A., Lanson, B., Drits, V.A., Chateigner, D., Gates, W.P., Wu, J., Huo, D., and Stucki, J.W. (2000) Oxidation-reduction mechanism of iron in dioctahedral smectites: I. Crystal chemistry of oxidized reference nontronites. American Mineralogist, 85, 133–152.
Madejová, J. (2003) FTIR techniques in clay mineral studies. Vibrational Spectroscopy, 31, 1–10.
Madejová, J. and Komadel, P. (2001) Baseline studies of the Clay Mineral Society Source Clays: Infrared methods. Clays and Clay Minerals, 49, 410–432.
Madejová, J., Pentrák, M., Pálková, H., and Komadel, P. (2009a) Near-infrared spectroscopy: A powerful tool in studies of acid treated clay minerals. Vibrational Spectroscopy, 49, 211–218.
Madejová, J., Pálková, H., Pentrák, M., and Komadel, P. (2009b) Near-infrared spectroscopic analysis of acid-treated organo-clays. Clays and Clay Minerals, 57, 392–403.
Madejová, J., Jankovič, L., Pentrák, M., and Komadel, P. (2011) Benefits of near-infrared spectroscopy for characterization of selected organo-montmorillonites. Vibrational Spectroscopy, 57, 8–14.
Miretzky, P. and Cirelli, A.F. (2009) Hg(II) removal from water by chitosan and chitosan derivatives: A review. Journal of Hazardous Materials, 167, 10–23.
Monier, M., Ayad, D.M., Weia, Y., and Sarhanb, A.A. (2010) Immobilization of horseradish peroxidase on modified chitosan beads. International Journal of Biological Macromolecules, 46, 324–330.
Mucha, M. and Pawlak, A. (2002) Complex study of chitosan degradability. Polimery, 47, 509–516.
Mulvaney, R.L., Khan, S.A., Stevens, W.B., and Mulvaney, C.S. (1997) Improved diffusion methods for determination of inorganic nitrogen in soil extracts and water. Biology and Fertility of Soils, 24, 413–420.
Ngah, W.W.S., Teong, L.C., and Hanafiah, M.A.K.M. (2011) Adsorption of dyes and heavy metal ions by chitosan composites: A review. Carbohydrate Polymers, 83, 1446–1456.
Osman, Z. and Arof, A.K. (2003) FTIR studies of chitosan acetate based polymer electrolytes. Electrochimica Acta, 48, 993–999.
Öztürk, N. and Bektaş, T.E. (2004) Nitrate removal from aqueous solution by adsorption onto various materials. Journal of Hazardous Materials, 112, 155–162.
Pálková, H., Madejová, J., and Komadel, P. (2009) The effect of layer charge and exchangeable cations on sorption of biphenyl on montmorillonites. Central European Journal of Chemistry, 7, 494–504.
Pálková, H., Jankovič, L., Zimowska, M., and Madejová, J. (2011) Alterations of the surface and morphology of tetraalkyl-ammonium modified montmorillonites upon acid treatment. Journal of Colloid and Interface Science, 363, 213–222.
Paulino, A.T., Simionato, J.I., Garcia, J.C., and Nozaki, J. (2006) Characterization of chitosan and chitin produced from silkworm chrysalides. Carbohydrate Polymers, 64, 98–103.
Pawlak, A. and Mucha, M. (2003) Thermogravimetric and FTIR studies of chitosan blends. Thermochimica Acta, 396, 153–166.
Pentrák, M., Bizovská, V., and Madejová, J. (2012) Near-IR study of water adsorption on acid-treated montmorillonite. Vibrational Spectroscopy, 63, 360–366.
Pentrák, M., Pentráková, L., and Stucki, J.W. (2013) Iron and manganese reduction-oxidation. Pp. 701–722 in: Methods in Biogeochemistry of Wetlands (R.D. DeLaune, K.R. Reddy, C.J. Richardson, and J.P. Megonigal, editors). SSSA Book Series, 10, Soil Science Society of America, Madison, Wisconsin, USA.
Pintar, A., Batista, J., and Levec, J. (2001) Catalytic denitrification: direct and indirect removal of nitrates from potable water. Catalysis Today, 66, 503–510.
Prakash, N., Latha, S., Sudha, P.N., and Renganathan, N.G. (2013) Influence of clay on the adsorption of heavy metals like copper and cadmium on chitosan. Environmental Science & Pollution Research, 20, 925–938.
Rabalais, N.N. (2002) Nitrogen in aquatic ecosystems. Ambio, 31, 102–112.
Radian, A. and Mishael, Y.G. (2008) Characterizing and designing polycation-clay nanocomposites as a basis for imazapyr controlled release formulations. Environmental Science & Technology, 42, 1511–1516.
Rinaudo, M. (2006) Chitin and chitosan: Properties and applications. Progress in Polymer Science, 31, 603–632.
Samatya, S., Kabay, N., Yüksel, U., Arda, M., and Yüksel M. (2006) Removal of nitrate from aqueous solution by nitrate selective ion exchange resins. Reactive and Functional Polymers, 66, 1206–1214.
Schoeman, J.J. and Steyn, A. (2003) Nitrate removal with reverse osmosis in a rural area in South Africa. Desalination, 155, 15–26.
Seitzinger, S.P. (1988) Denitrification in freshwater and coastal marine ecosystems: Ecological and geochemical significance. Limnology and Oceanography, 33, 702–724.
Soares, M.I.M. (2000) Biological denitrification of groundwater. Water Air and Soil Pollution, 123, 183–193.
Sohn, K., Kang, S.W., Ahn, S., Woo, M., and Yang, S.K. (2006) Fe(0) nanoparticles for nitrate reduction: Stability, reactivity and transformation. Environmental Science & Technology, 40, 5514–5519.
Stucki, J.W. (2013) Properties and behavior of iron in clay minerals. Pp. 559–611 in: Handbook of Clay Science (F. Bergaya and G. Lagaly, editors). Developments in Clay Science, 5A, Elsevier, Amsterdam.
Stucki, J.W. and Kostka, J.E. (2006) Microbial reduction of iron in smectite. Comptes Rendus Geoscience, 338, 468–475.
Stucki, J.W., Komadel, P., and Wilkinson, H.T. (1987) Microbial reduction of structural iron(III) in smectites: Soil Science Society of America Journal, 51, 1663–1665.
Stucki, J.W., Goodman, B.A., and Schwertmann, U. (1988) Iron in Soils and Clay Minerals. D. Reidel, Dordrecht, The Netherlands, 980 pp.
Stucki, J.W., Gan, H., and Wilkinson, H.T (1992) Effects of microorganisms on phyllosilicate properties and behavior. Pp. 227–254 in: Advances in Soil Science (R.J. Wagenet, P. Baveye, and B.A. Stewart, editors). Lewis Publishers, Boca Raton, Florida, USA.
Stucki, J.W., Lee, K., Goodman, B.A., and Kostka, J.E. (2007) Effects of in situ biostimulation on iron mineral speciation in a sub-surface soil. Geochimica et Cosmochimica Acta, 71, 835–843.
Stucki, J.W., Su, K., Pentráková, L., and Pentrák, M. (2014) Methods for handling redox-sensitive smectite dispersions. Clay Minerals, 49, 359–377.
Su, K., Radian, A., Mishael, Y., Yang, L., and Stucki, J.W. (2012) Nitrate reduction by redox-activated, polydiallyldimethylammonium-exchanged ferruginous smectite. Clays and Clay Minerals, 60, 464–472.
Thomson, T.S. (2001) Nitrate concentration in private rural drinking water supplies in Saskatchewan, Canada. Bulletin of Environmental Contamination and Toxicology, 66, 64–70.
Usuki, A., Kawasumi, M., Kojima, Y., Okada, A., Kurauchi, T., and Kamigaito, O. (1993) Swelling behavior of montmorillonite cation exchanged for o-amino acids by e-caprolactam. Journal of Materials Research, 8, 1174–1178.
Ward, M.H., de Kok, T.M., Levallois, P., Brender, J., Gulis, G., Nolan, B.T., and Van Derslice, J. (2005) Workgroup report: drinking-water nitrate and recent health findings and research needs. Environmental Health Perspectives, 113, 1607–1614.
Westerhoff, P. (2003) Reduction of nitrate, bromate and chlorate by zero valent iron (Fe-0). Journal of Environmental Engineering — ASCE, 129, 10–16.
Xue, H., He, H., Zhu, J., and Yuan, P. (2007) FTIR investigation of CTAB-Al-montmorillonite complexes. Spectrochimica Acta A, 67, 1030–1036.
Yan, L.B. and Stucki, J.W. (2000) Structural perturbations in the solid-water interface of the redox transformed nontronite. Journal of Colloid and Interface Science, 225, 429–439.
Yan, L., Roth, C.B., and Low, P.F. (1996) Changes in the Si-O vibrations of smectite layers accompanying the sorption of interlayer water. Langmuir, 12, 4421–4429.
Zadaka, D., Radian, A., and Mishael, Y.G. (2010) Applying zeta potential measurements to characterize the adsorption on montmorillonite of organic cations as monomers, micelles, or polymers. Journal of Colloid and Interface Science, 352, 171–177.
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Pentrák, M., PentráKová, L., Radian, A. et al. Nitrate Reduction by Redox-Modified Smectites Exchanged with Chitosan. Clays Clay Miner. 62, 403–414 (2014). https://doi.org/10.1346/CCMN.2014.0620504
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DOI: https://doi.org/10.1346/CCMN.2014.0620504