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

D. C. Girvin1, P. L. Gassman1 and H. Bolton Jr2
1 Interfacial Geochemistry Group, Pacific Northwest National Laboratory, PO Box 999, MSIN: K3-61, Richland, Washington 99352
2 Environmental Microbiology Group, Pacific Northwest National Laboratory, Richland, Washington 99352

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)3) • Nitrilotriacetic Acid (NTA)

Clays and Clay Minerals; December 1996 v. 44; no. 6; p. 757-768; DOI: 10.1346/CCMN.1996.0440606
© 1996, The Clay Minerals Society
Clay Minerals Society (www.clays.org)