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Clays and Clay Minerals

, Volume 44, Issue 6, pp 757–768 | Cite as

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

  • D. C. Girvin
  • P. L. Gassman
  • H. BoltonJr
Article

Abstract

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.

Key Words

δ-Al2O3 Adsorption Chelate Cobalt Desorption Gibbsite (α-Al(OH)3Nitrilotriacetic Acid (NTA) 

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References

  1. Ayers JA. 1970. Decontamination of nuclear reactors and equipment.New York: Ronald Pr. 164 p.CrossRefGoogle Scholar
  2. Ball JW, Nordstrom DK, Jenne EA. 1980. Additional and revised thermodynamic data and computer code for WAT-EQ2—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
  3. Bar-Tal A, Sparks DL, Pesek JD, 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
  4. Bolton H, Jr, Girvin DC. 1996. Effect of adsorption and aqueous speciation on the biodegradation of nitrilotriacetate by chelatobacter heintzii. Environ Sci Tech 30(3):931–938.CrossRefGoogle Scholar
  5. Bourg CM, Schindler PW. 1979. Effect of ethylenediaminetetraacetic acid on the adsorption of copper(II) at amorphous silica. Inorg Nucl Chem Lett 15:225–229.CrossRefGoogle Scholar
  6. Bowers AR. 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
  7. Bowers AR, Huang CP. 1986. Adsorption characteristics of metal-EDTA complexes onto hydrous oxides. J Colloid Interface Sci 110:575–590.CrossRefGoogle Scholar
  8. Bragg, WL, Claringbull GE 1965. The crystalline state, vol 4. London: Bell and Sons. 118 p.Google Scholar
  9. Brown GE. 1990. Spectroscopic studies of chemisorption reaction mechanisms at oxide-water interfaces. In: Hochella MF, Jr., White AF, editors. Reviews in mineralogy, vol 23, Mineral-water interface geochemistry. Washington, DC: Mineralogical Society of America, p 309–363.CrossRefGoogle Scholar
  10. Chang H, Healy TW, 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
  11. Chemical Rubber Company (CRC) Handbook of chemistry and physics. 1977. 58th ed. Boca Raton, FL: CRC Pr. 2179 p.Google Scholar
  12. Chisholm-Brause CJ, Brown GE, Jr, Parks GA. 1991. In-situ EXAFS study of changes in Co(II) sorption complexes on γ-Al2O3 with increasing sorption densities. In: Hasnain SS, editor. XAFS VI, Sixth international conference on X-ray adsorption fine structure. Chichester, UK: Ellis Horwood. p 263–265.Google Scholar
  13. Chisholm-Brause CJ, O’Day PA, Brown GE, Jr, Parks GA. 1990. Evidence for multinuclear metal-ion complexes at solid/water interfaces from X-ray adsorption spectroscopy. Nature 348:528–530.CrossRefGoogle Scholar
  14. Davis JA, Hem JD. 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
  15. Davis JA, James RO, Leckie JO. 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
  16. Davis JA, Leckie JO. 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
  17. Elliott HA. 1979. The adsorption of copper(II) at the solidsolution interface: effect of complex formation [dissertation]. Newark, DE: Univ of Delaware. 235 p.Google Scholar
  18. Elliott HA, Huang CR 1979. The adsorption characteristics of Cu(II) in the presence of chelating agents. J Colloid Interface Sci 70:29–45.CrossRefGoogle Scholar
  19. Felmy AR. 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
  20. Felmy AR, Girvin DC, Jenne EA. 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
  21. Gastuche MC, Herbillon A. 1962. Alumina gels: crystallization in a de-ionized medium. Bull Soc Chem Fr 5:1402–1412.Google Scholar
  22. Girvin DC, Gassman PL, Bolton H, Jr. 1993. Adsorption of aqueous cobalt ethylenediaminetetraacetate by δ-Al2O3. Soil Sci Soc Am J 57(1):47–57.CrossRefGoogle Scholar
  23. Hayes KE 1987. Equilibrium spectroscopic and kinetic studies of ion adsorption at the oxide/aqueous interface [dissertation]. Palo Alto, CA: Stanford Univ. 260 p.Google Scholar
  24. Hayes KF, Leckie JO. 1987. Modeling ionic strength effects on cation adsorption at hydrous oxide/solution interfaces. J Colloid Interface Sci 115:564–572.CrossRefGoogle Scholar
  25. Hayes KP, Papelis C, Leckie JO. 1987. Modeling ionic strength effects on anion adsorption at hydrous oxide/so-lution interfaces. J Colloid Interface Sci 125:717–726.CrossRefGoogle Scholar
  26. Hiemstra T, van Riemsdijk WH, Bruggenwert MGM. 1987. Proton adsorption mechanism at the gibbsite and aluminum oxide solid/solution interface. Netherlands J of Agric Sci 35:281–293.Google Scholar
  27. Hingston FJ, Posner AM, Quirk JP. 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
  28. Hingston FJ, Posner AM, Quirk JP. 1974. Anion adsorption by goethite and gibbsite. II. Desorption of anions from hydrous oxide surfaces. J Soil Sci 25:16–26.CrossRefGoogle Scholar
  29. Hsu PH. 1989. Aluminum hydroxides and oxyhydroxides. In: Dickson JB, Weed FB, editors. Minerals in soil environments. 2nd ed. Madison, WI: Soil Science Society of America, p 331–378.Google Scholar
  30. Kavanagh BV, Posner AM, Quirk JP. 1975. Effect of polymer adsorption on properties of the electrical double layer. Faraday Discuss Chem Soc 59:242–249.CrossRefGoogle Scholar
  31. Kümmert R, Stumm W. 1980. The surface complexation of organic acids on hydrous δ-Al2O3. J Colloid Interface Sci 75:373–385.CrossRefGoogle Scholar
  32. Kyle JH, Posner AM, Quirk JP. 1975. Kinetics of isotopic exchange of phosphate adsorbed on gibbsite. J Soil Sci 26: 32–43.CrossRefGoogle Scholar
  33. Martell AE, Smith RM. 1974. Critical stability constants, vol 1: Amino acids. New York: Plenum Pr. 469 p.Google Scholar
  34. McBride MB. 1985. Influence of glycine on Cu2+ adsorption by microcrystalline gibbsite and boehmite. Clays Clay Miner 33:397–402.CrossRefGoogle Scholar
  35. McKinley JP, Zachara JM, Smith SC, Turner GD. 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
  36. Means JL, Alexander CA. 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
  37. Means JL, Crerar DA, Duguid JO. 1978. Migration of ra dionuclide wastes: Radionuclide mobilization by complexing agents. Science 200:1477–1486.CrossRefGoogle Scholar
  38. Naumov GB, Ryzhenko BN, Khodakovsky IL. 1974. Handbook of thermodynamic data. PB 226 722. Springfield, VA: National Technical Information Service. 286 p.Google Scholar
  39. Olsen CR, Lowry PD, Lee SY, Larsen IL, Cutshall NH. 1986. Geochemical and environmental processes affecting radio-nuclide migration from a formerly used seepage trench. Geochim Cosmochim Acta 50:593–607.CrossRefGoogle Scholar
  40. Osaki S, Yasuhiro K, Sugihara S, 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
  41. Parfitt RL, Fraser AR, Russell JD, Farmer VC. 1977. Adsorption on hydrous oxides. II Oxalate, benzoate and phosphate on gibbsite. J Soil Sci 28:40–47.CrossRefGoogle Scholar
  42. Piciulo PL, Adams JW, Davis MS, Milian LW, Anderson CI. 1986. Release of organic chelating agents from solidified decontamination wastes. NUREG/Cr-4790, BNL-NE-WREG-52014. Washington, DC: US Nuclear Regulatory Commission. 121 p.Google Scholar
  43. Rabenstein DL, Kula RJ. 1969. Ligand-exchange kinetics and solution equilibria of cadmium, zinc, and lead nitrilotriacetate complexes. J Am Chem Soc 91:2492–2503.CrossRefGoogle Scholar
  44. Riley RG, Zachara JM, Wobber FJ. 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
  45. Saalfeld N. 1960. Strukturen des Hydrargillitis und der Zwischenstufen biem Entwassern. Neues Jb Miner Abh 95:1–87.Google Scholar
  46. Schindler PW. 1990. Co-adsorption ions and organic ligands: formation of ternary surface complexes. In: Hochella MF, Jr, White AF, editors. Reviews in mineralogy, vol 23: Mineral-water interface geochemistry. Washington, DC: 1Mineralogical Society of America, p 281–307.CrossRefGoogle Scholar
  47. Seyfried MS, Sparks DL, Bar-Tal A, 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
  48. Sposito G. 1984. The surface chemistry of soils.New York: Oxford Univ Pr. 234 p.Google Scholar
  49. Szecsody JE, Zachara JM, Bruckhart PL. 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
  50. Toste AP, Lucke RB, Lechner-Fish TJ, Hendren DJ, Myers RB. 1987. Organic analysis of mixed nuclear wastes. In: Post RG, 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
  51. Toste AP, Pahl TR, Lücke RB, Myers RB. 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
  52. 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
  53. 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
  54. 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
  55. Zachara JM, Smith SC, Kuzel LS. 1994. Adsorption and dissolution of Co-EDTA complex Fe-oxide containing subsurface sands. Geochim Cosmochim Acta 59:4825–4844.CrossRefGoogle Scholar

Copyright information

© The Clay Minerals Society 1996

Authors and Affiliations

  • D. C. Girvin
    • 1
  • P. L. Gassman
    • 1
  • H. BoltonJr
    • 2
  1. 1.Interfacial Geochemistry GroupPacific Northwest National LaboratoryRichlandUSA
  2. 2.Environmental Microbiology GroupPacific Northwest National LaboratoryRichlandUSA

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