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Adsorption of Nitrilotriacetate (NTA), Co and CoNTA By Gibbsite

Published online by Cambridge University Press:  28 February 2024

D. C. Girvin ,
P. L. Gassman  and
H. Bolton Jr
D. C. Girvin
Affiliation:
Interfacial Geochemistry Group, Pacific Northwest National Laboratory, PO Box 999, MSIN: K3-61, Richland, Washington 99352
P. L. Gassman
Affiliation:
Interfacial Geochemistry Group, Pacific Northwest National Laboratory, PO Box 999, MSIN: K3-61, Richland, Washington 99352
H. Bolton Jr
Affiliation:
Environmental Microbiology Group, Pacific Northwest National Laboratory, Richland, Washington 99352
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Abstract

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Adsorption of Co2+ nitrilotriacetic acid (NTA) and equal-molar Co2+ and NTA by a low surface area (LSA) commercial gibbsite (3.5 m2 g−1) was investigated in batch as a function of pH (4.5 to 10.5), adsorbate (0.5 to 10 µM) and adsorbent (0.5 to 75 g L−1) concentrations and ionic strength (0.01 to 1 M NaClO4). The adsorption of Co2+ (Co-only) and the acid form of NTA (NTA-only) by gibbsite in 0.01 M NaClO4 exhibit cation-like and anion-like adsorption edges, respectively. For the equal-molar CoNTA chelate, Co and NTA adsorption edges were similar but not identical to the Co-only and NTA-only edges. Differences suggest the existence of a ternary CoNTA surface complex with the Co in the intact chelate coordinated to surface hydroxyls. NTA-only adsorption was insensitive to ionic strength variation, indicating weak electrostatic contributions to surface coordination reactions. This is consistent with the formation of inner-sphere surface NTA complexes and ligand exchange reactions in which monodentate, bidentate and binuclear NTA surface complexes form. Cobalt adsorption increases (edge shifts to lower pH by 1 pH unit) on LSA gibbsite as ionic strength increases from 0.01 to 1 M NaClO4. For the same ionic strength change, a similar shift in the Co-only edge was observed for another commercial gibbsite (16.8 m2 g−1); however, no change was observed for δ-Al2O3. Ionic strength shifts in Co2+ adsorption by gibbsite were described as an outer-sphere CoOH+ surface complex using the triple-layer model. Results suggest that, at waste disposal sites where 60Co and NTA have been co-disposed, NTA will not promote ligand-like adsorption of Co for acid conditions, but will reduce cation-like adsorption for basic conditions. Thus, where gibbsite is the dominant mineral sorbent, NTA will not alter 60Co mobility in acidic pore waters and groundwaters; however, NTA could enhance 60Co mobility where alkaline conditions prevail, unless microbial degradation of the NTA occurs.

Keywords

δ-Al2O3AdsorptionChelateCobaltDesorptionGibbsite (α-Al(OH)3)Nitrilotriacetic Acid (NTA)
Type
Research Article
Information
Clays and Clay Minerals , Volume 44 , Issue 6 , December 1996 , pp. 757 - 768
Copyright
Copyright © 1996, The Clay Minerals Society

References

Ayers, J.A.. 1970. Decontamination of nuclear reactors and equipment. New York: Ronald Pr. 164 p.CrossRefGoogle Scholar
Ball, J.W., Nordstrom, D.K. and Jenne, E.A.. 1980. Additional and revised thermodynamic data and computer code for WATEQ2—A computerized chemical model for trace and major element speciation and mineral equilibria of natural waters. Water Resources Investigations 78-116. Menlo Park, CA: US Geological Survey. 81 p.Google Scholar
Bar-Tal, A., Sparks, D.L., Pesek, J.D. and Feigenbaum, S.. 1990. Analyses of adsorption kinetics using a stirred-flow chamber: I. Theory and critical tests. Soil Sci Soc Am J 54: 1273–1278.CrossRefGoogle Scholar
Bolton, H. Jr. and Girvin, D.C.. 1996. Effect of adsorption and aqueous speciation on the biodegradation of nitrilotriacetate by chelatobacter heintzii. Environ Sci Tech 30(3): 931–938.CrossRefGoogle Scholar
Bourg, C.M. and Schindler, P.W.. 1979. Effect of ethylenediamine-tetraacetic acid on the adsorption of copper(II) at amorphous silica. Inorg Nucl Chem Lett 15: 225–229.CrossRefGoogle Scholar
Bowers, A.R.. 1982. Adsorption characteristics of various metals at the oxide-solution interface: effect of complex formation [dissertation]. Newark, DE: Univ of Delaware. 202 p.Google Scholar
Bowers, A.R. and Huang, C.P.. 1986. Adsorption characteristics of metal-EDTA complexes onto hydrous oxides. J Colloid Interface Sci 110: 575–590.CrossRefGoogle Scholar
Bragg, W.L. and Claringbull, G.F.. 1965. The crystalline state, vol 4. London: Bell and Sons. 118 p.Google Scholar
Brown, G.E.. 1990. Spectroscopic studies of chemisorption reaction mechanisms at oxide-water interfaces. In: Hochella, M.F. Jr., White, A.F., editors. Reviews in mineralogy, vol 23, Mineral-water interface geochemistry. Washington, DC: Mineralogical Society of America. p 309–363.CrossRefGoogle Scholar
Chang, H., Healy, T.W. and Matijevic, E.. 1983. Interactions of metal hydrous oxides with chelating agents, III. Adsorption on spherical colloidal hematite particles. J Colloid Interface Sci 92: 469–478.CrossRefGoogle Scholar
Chemical Rubber Company (CRC) Handbook of chemistry and physics. 1977. 58th ed. Boca Raton, FL: CRC Pr. 2179 p.Google Scholar
Chisholm-Brause, C.J., Brown, G.E. Jr. and Parks, G.A.. 1991. In-situ EXAFS study of changes in Co(II) sorption complexes on γ-Al2O3 with increasing sorption densities. In: Hasnain, S.S., editor. XAFS VI, Sixth international conference on X-ray adsorption fine structure. Chichester, UK: Ellis Horwood. p 263–265.Google Scholar
Chisholm-Brause, C.J., O'Day, P.A., Brown, G.E. Jr. and Parks, G.A.. 1990. Evidence for multinuclear metal-ion complexes at solid/water interfaces from X-ray adsorption spectroscopy. Nature 348: 528–530.CrossRefGoogle Scholar
Davis, J.A. and Hem, J.D.. 1989. The surface chemistry of aluminum oxides and hydroxides. In: Sposito, G., editor. The environmental chemistry of aluminum. Boca Raton, FL: CRC Pr. p 185–219.Google Scholar
Davis, J.A., James, R.O. and Leckie, J.O.. 1978. Surface ionization and complexation at the oxide/water interface II. Surface properties of amorphous iron oxyhydroxide and adsorption of metal ions. J Colloid Interface Sci 67: 90–107.CrossRefGoogle Scholar
Davis, J.A. and Leckie, J.O.. 1978. Surface ionization and complexation at the oxide/water interface I. Computation of electrical double layer properties in simple electrolytes. J Colloid Interface Sci 63: 480–499.CrossRefGoogle Scholar
Elliott, H.A.. 1979. The adsorption of copper(II) at the solid-solution interface: effect of complex formation [dissertation]. Newark, DE: Univ of Delaware. 235 p.Google Scholar
Elliott, H.A. and Huang, C.P.. 1979. The adsorption characteristics of Cu(II) in the presence of chelating agents. J Colloid Interface Sci 70: 29–45.CrossRefGoogle Scholar
Felmy, A.R.. 1990. GMIN: a computerized chemical equilibrium model using a constrained minimization of the Gibbs free energy. Report PNL-7281. Richland, WA: Pacific Northwest National Laboratory. 52 p.CrossRefGoogle Scholar
Felmy, A.R., Girvin, D.C. and Jenne, E.A.. 1984. MINTEQ—A computer program for calculating aqueous geochemical equilibria. EPA 600-3-84-032. Springfield, VA: National Technical Information Service. 187 p.Google Scholar
Gastuche, M.C. and Herbillon, A.. 1962. Alumina gels: crystallization in a de-ionized medium. Bull Soc Chem Fr 5: 1402–1412.Google Scholar
Girvin, D.C., Gassman, P.L. and Bolton, H. Jr. 1993. Adsorption of aqueous cobalt ethylenediaminetetraacetate by δ-Al2O3. Soil Sci Soc Am J 57(1): 47–57.CrossRefGoogle Scholar
Hayes, K.F.. 1987. Equilibrium spectroscopic and kinetic studies of ion adsorption at the oxide/aqueous interface [dissertation]. Palo Alto, CA: Stanford Univ. 260 p.Google Scholar
Hayes, K.F. and Leckie, J.O.. 1987. Modeling ionic strength effects on cation adsorption at hydrous oxide/solution interfaces. J Colloid Interface Sci 115: 564–572.CrossRefGoogle Scholar
Hayes, K.F., Papelis, C. and Leckie, J.O.. 1987. Modeling ionic strength effects on anion adsorption at hydrous oxide/solution interfaces. J Colloid Interface Sci 125: 717–726.CrossRefGoogle Scholar
Hiemstra, T., van Riemsdijk, W.H. and Bruggenwert, M.G.M.. 1987. Proton adsorption mechanism at the gibbsite and aluminum oxide solid/solution interface. Netherlands J of Agric Sci 35: 281–293.CrossRefGoogle Scholar
Hingston, F.J., Posner, A.M. and Quirk, J.P.. 1972. Anion adsorption by goethite and gibbsite. I. The role of the proton in determining adsorption envelopes. J Soil Sci 23: 177–192.CrossRefGoogle Scholar
Hingston, F.J., Posner, A.M. and Quirk, J.P.. 1974. Anion adsorption by goethite and gibbsite. II. Desorption of anions from hydrous oxide surfaces. J Soil Sci 25: 16–26.CrossRefGoogle Scholar
Hsu, P.H.. 1989. Aluminum hydroxides and oxyhydroxides. In: Dickson, J.B., Weed, F.B., editors. Minerals in soil environments. 2nd ed. Madison, WI: Soil Science Society of America. p 331–378.Google Scholar
Kavanagh, B.V., Posner, A.M. and Quirk, J.P.. 1975. Effect of polymer adsorption on properties of the electrical double layer. Faraday Discuss Chem Soc 59: 242–249.CrossRefGoogle Scholar
Kummert, R. and Stumm, W.. 1980. The surface complexation of organic acids on hydrous δ-Al2O3. J Colloid Interface Sci 75: 373–385.CrossRefGoogle Scholar
Kyle, J.H., Posner, A.M. and Quirk, J.P.. 1975. Kinetics of isotopic exchange of phosphate adsorbed on gibbsite. J Soil Sci 26: 32–43.CrossRefGoogle Scholar
Martell, A.E. and Smith, R.M.. 1974. Critical stability constants, vol 1: Amino acids. New York: Plenum Pr. 469 p.Google Scholar
McBride, M.B.. 1985. Influence of glycine on Cu2+ adsorption by microcrystalline gibbsite and boehmite. Clays Clay Miner 33: 397–402.CrossRefGoogle Scholar
McKinley, J.P., Zachara, J.M., Smith, S.C. and Turner, G.D.. 1995. The influence of uranyl hydrolysis and multiple site-binding reactions on adsorption of U(VI) to montmorillonite. Clays Clay Miner 43: 586–598.CrossRefGoogle Scholar
Means, J.L. and Alexander, C.A.. 1981. The environmental biogeochemistry of chelating agents and recommendations for the disposal of chelated radioactive wastes. Nucl Chem Waste Manage 2: 183–196.CrossRefGoogle Scholar
Means, J.L., Crerar, D.A. and Duguid, J.O.. 1978. Migration of radionuclide wastes: Radionuclide mobilization by complexing agents. Science 200: 1477–1486.CrossRefGoogle ScholarPubMed
Naumov, G.B., Ryzhenko, B.N. and Khodakovsky, I.L.. 1974. Handbook of thermodynamic data. PB 226 722. Springfield, VA: National Technical Information Service. 286 p.Google Scholar
Olsen, C.R., Lowry, P.D., Lee, S.Y., Larsen, I.L. and Cutshall, N.H.. 1986. Geochemical and environmental processes affecting radionuclide migration from a formerly used seepage trench. Geochim Cosmochim Acta 50: 593–607.CrossRefGoogle Scholar
Osaki, S., Yasuhiro, K., Sugihara, S. and Takashima, Y.. 1990. Effects of metal ions and organic ligands on the adsorption of Co(II) onto silicagel. Sci Total Environ 99: 93–103.CrossRefGoogle Scholar
Parfitt, R.L., Fraser, A.R., Russell, J.D. and Farmer, V.C.. 1977. Adsorption on hydrous oxides. II Oxalate, benzoate and phosphate on gibbsite. J Soil Sci 28: 40–47.CrossRefGoogle Scholar
Piciulo, P.L., Adams, J.W., Davis, M.S., Milian, L.W. and Anderson, C.I.. 1986. Release of organic chelating agents from solidified decontamination wastes. NUREG/Cr-4790, BNL-NEWREG-52014. Washington, DC: US Nuclear Regulatory Commission. 121 p.Google Scholar
Rabenstein, D.L. and Kula, R.J.. 1969. Ligand-exchange kinetics and solution equilibria of cadmium, zinc, and lead nitrilotriacetate complexes. J Am Chem Soc 91: 2492–2503.CrossRefGoogle Scholar
Riley, R.G., Zachara, J.M. and Wobber, F.J.. 1992. Chemical contaminants on DOE lands and selection of contaminant mixtures of subsurface science research. DOE/ER-0547T. Washington, DC: US Department of Energy. 77 p.Google Scholar
Saalfeld, N.. 1960. Strukturen des Hydrargillitis und der Zwischenstufen biem Entwassern. Neues Jb Miner Abh 95: 1–87.Google Scholar
Schindler, P.W.. 1990. Co-adsorption ions and organic ligands: formation of ternary surface complexes. In: Hochella, M.F. Jr., White, A.F., editors. Reviews in mineralogy, vol 23: Mineral-water interface geochemistry. Washington, DC: Mineralogical Society of America. p 281–307.Google Scholar
Seyfried, M.S., Sparks, D.L., Bar-Tal, A. and Feigenbaum, S.. 1989. Kinetics of calcium-magnesium exchange on soil using a stirred-flow reaction chamber. Soil Sci Soc Am J 53: 406–410.CrossRefGoogle Scholar
Sposito, G.. 1984. The surface chemistry of soils. New York: Oxford Univ Pr. 234 p.Google Scholar
Szecsody, J.E., Zachara, J.M. and Bruckhart, P.L.. 1994. Adsorption-dissolution reactions affecting the distribution and stability of Co(II)EDTA in Fe-oxide coated sand. Environ Sci Technol 28: 1706–1716.CrossRefGoogle Scholar
Toste, A.P., Lucke, R.B., Lechner-Fish, T.J., Hendren, D.J. and Myers, R.B.. 1987. Organic analysis of mixed nuclear wastes. In: Post, R.G., editor. Waste management '87: proceedings of a symposium on waste management; March 1987; vol 3, Low-level waste. Tucson, AZ: Univ of Arizona. p 323–329.Google Scholar
Toste, A.P., Pahl, T.R., Lucke, R.B. and Myers, R.B.. 1987. Analysis of complex organic mixtures in nuclear wastes. In: Gray RH, Chess EK, Mellinger PJ, Riley RG, Springer DL, editors. Health and environmental research on complex organic mixtures. Proceedings of 24th Hanford Life Sciences Symposium: 1985 Oct 20-24; Conference-851027. Springfield, VA: National Technical Information Service. p 133–150.Google Scholar
Vuceta, J.. 1976. Adsorption of Pb(II) and Cu(II) on α-quartz from aqueous solutions: influence of pH, ionic strength, and complexing ligands [dissertation]. Pasadena, CA: California Inst of Technology. 204 p.Google Scholar
Westall, J.. 1982a. FITEQL: a computer program for determination of equilibrium constants from experimental data. Version 1.2. Report 82-01. Corvallis, OR: Department of Chemistry, Oregon State Univ. 98 p.Google Scholar
Westall, J.. 1982b. FITEQL: a computer program for determination of equilibrium constants from experimental data. Version 2.0. Report 82-02. Corvallis, OR: Department of Chemistry, Oregon State Univ. 61 p.Google Scholar
Zachara, J.M., Smith, S.C. and Kuzel, L.S.. 1994. Adsorption and dissolution of Co-EDTA complex Fe-oxide containing subsurface sands. Geochim Cosmochim Acta 59: 4825–4844.CrossRefGoogle Scholar