A Study of the Kinetic Interactions of Complex Metal Ion - Humic and Magnetite Ternary Systems

  • Nigel Li

Student thesis: Phd


The sorption of humic acid (HA) and HA size fractions onto magnetite has been studied. There is considerable irreversibility in the interaction of the humic with the magnetite surface, but the presence of Eu3+ ions has no effect on the sorption of humic onto magnetite. The magnitude of the sorption to magnetite increases with HA fraction size for all ionic strengths between 0.01 and 3 mol dm-3. Increasing ionic strength also increases sorption. Asymmetric Flow Field Flow Fractionation analysis of HA sorption to magnetite after 1 day revealed preferential sorption of lower molecular weight material. Eu3+ sorption onto magnetite was studied as a function of Eu concentration, which showed an increase in relative sorption as Eu concentration decreased. The behaviour of Eu3+ in ternary (HA/Eu3+/magnetite) systems is heavily influenced by HA, and from the data there is direct evidence for ternary complex formation. Larger HA size fractions retain more Eu3+ in solution than the smaller fractions. The binding strengths of HA size fractions were determined through ion exchange resin experiments: generally the larger fractions (> 10 kDa) showed stronger binding than the smaller components, but the unfractionated sample showed the strongest binding.First order dissociation rate constants have been determined for the whole HA and HA size fractions. The dissociation rate constants are independent of HA fraction size, but the larger species bind more Eu non-exchangeably. Time series ultrafiltration of Eu3+/whole humic mixtures has shown a shift in the distribution of metal ions to larger size fractions after a few days.Two ternary system kinetic speciation models have been developed to predict the behaviour of HA and Eu3+ in ternary systems. The two differ in their description of the multi-component behaviour of the binary HA-mineral interaction. The first assumes a single HA species and two surface binding sites and was found to perform better overall than the second, which has a single surface sorption site and two HA species in solution. The exchangeable binding strengths for the different HA samples calculated from both models showed similarities to those measured experimentally.
Date of Award1 Aug 2012
Original languageEnglish
Awarding Institution
  • The University of Manchester
SupervisorNicholas Bryan (Supervisor)


  • Modelling
  • Ternary Systems
  • Flow Field Flow Fractionation
  • Ultrafiltration
  • Kinetics
  • Binary Systems
  • Magnetite
  • Humic Substances
  • Adsorption
  • Europium
  • Humic Fractions

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