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Rare earth element complexation by PO sub 4 sup 3 minus ions in aqueous solution

Journal Article · · Geochimica et Cosmochimica Acta; (United States)
; ;  [1]
  1. Univ. of South Florida, Petersburg (United States)
Complexation of trivalent rare earths by PO{sub 4}{sup 3{minus}} ions has been assessed at t = 25C by examining the influence of aqueous phosphate concentrations on the distributions of {sup 144}Ce and {sup 153}Gd between 0.68 molar NaClO{sub 4} and tributyl phosphate (TBP). The authors estimates of these formation constants at zero ionic strength are approximately seven to eight orders of magnitude lower than previously reported estimates for lanthanide and actinide PO{sub 4}{sup 3{minus}} complexation. Linear free energy relationships relating the complexation of Ca{sup 2+} and lanthanides (Ln{sup 3+}) by a variety of organic ligands, in conjunction with previous direct observations of CaPO{sub 4}{sup {minus}} formation, are consistent with the experimentally derived CePO{sub 4}{sup 0} and GdPO{sub 4}{sup 0} formation constants reported in this work. Gadolinium speciation calculations indicate that the PO{sub 4}{sup 3{minus}} ion can effectively compete with the CO{sub 3}{sup 2{minus}} ion for free Gd{sup 3+} in model groundwater at pH 7-9. Rare earth element phosphate complexation is a significant process in natural freshwater systems which are neutral to mildly basic when the concentration ratio (HPO{sub 4}{sup 2{minus}})/(HCO{sub 3}{sup {minus}}) is greater than approximately 1 {times} 10{sup 3{minus}}.
OSTI ID:
7114351
Journal Information:
Geochimica et Cosmochimica Acta; (United States), Journal Name: Geochimica et Cosmochimica Acta; (United States) Vol. 55:10; ISSN GCACA; ISSN 0016-7037
Country of Publication:
United States
Language:
English