Porous titania beads for remediation of arsenic contamination from acid mine drainage.

Hierarchically porous titania beads with and without amine functionalisation have been developed and tested as adsorbents for removal of highly toxic As(V) from environments affected by acid mine drainage (AMD). The unique acid stability of the titania framework enables these adsorbents to function in highly acidified environments and their granular form facilitates practical deployment under continuous flow conditions. Herein, both non-functionalised and amine-functionalised titania beads have been demonstrated to selectively remove As(V) from simulated and real AMD solutions at pH 2.6. Novel selectivity for As(V) over Na(I), Mg(II), Al(III), Si(VI), Ca(II), Co(II), Cu(II), Zn(II), Nd(III) and Ho(III) was achieved, with competing element concentrations similar to or up to an order of magnitude greater than that of As(V). Although Fe(III) and some Fe(II) were also adsorbed by the titania beads, Fe adsorption did not inhibit As(V) adsorption, indicating different adsorption mechanisms for these two elements. The As(V) adsorption capacity of the titania beads decreased from ∼20 mg/g from pure As(V) solution to ∼10 mg/g from real AMD solution, demonstrating the importance of adsorbent testing under applied conditions. Amine functionalisation increased the kinetics of adsorption, but the non-functionalised titania beads showed greater selectivity for As(V) over Fe(II) and Fe(III) and hence were considered preferable for As remediation applications. Nevertheless, the functionalisation ability of the porous titania beads makes them a promising, flexible technology for remediation of a wide range of AMD affected environments.

Phosphate functionalised titania for heavy metal removal from acidic sulfate solutions.

Adsorbent materials based on titania and phosphate are ideal for treatment of solutions contaminated with heavy metals under acidic conditions, due to their inherent chemical stability and low pKa. Herein, phosphate functionalised titania has been investigated for the first time for removal of heavy metals (Cr, Fe, Cu, Eu, U) under conditions relevant to acid mine drainage (pH 2-5 sulfuric acid). Successful functionalisation was found to depend on the phase of titania used, with anatase preferred according to computational results from density functional theory. The effect of phosphate ligand structure was explored, revealing that the phosphate ethyl ester maximised heavy metal removal. The presence and concentration of counterions (sulfate, nitrate, ammonium) also impacted the speciation and binding of heavy metal cations, demonstrating the importance of adsorbent testing under realistic conditions. Increasing the porosity of the titania framework enhanced heavy metal removal, while maintaining selectivity for the toxic heavy metals over non-toxic cations Na and K. As such, phosphate functionalised titania shows great promise for heavy metal remediation in acidic sulfate environments.

New insights into the radiolytic stability of metal(iv) phosphonate hybrid adsorbent materials.

Stable metal(iv) phosphonate hybrids are a promising class of materials for the critical issue of nuclear waste cleanup. However, to be of practical use, adsorbent materials must demonstrate radiolytic stability and this property remains poorly understood. Therefore, the radiolytic stabilities of post-functionalised mesoporous zirconium titanate and zirconium phosphonate coordination polymers were compared. For the first time, solid-state 31P MAS-NMR was used to probe the radiolytic degradation of metal(iv) phosphonates and provide mechanistic insight. Polyphosphonate-functionalized hybrids were more stable than monophosphonate hybrids, as the monophosphonate readily detached from the oxide surface. The zirconium phosphonate coordination polymer (Zr-ATMP) demonstrated the greatest radiolytic stability, attributed to its high ligand loading and intimately mixed structure. Zr-ATMP maintained highly efficient sorption from strongly acidic solutions even after receiving doses of gamma radiation up to 2.9 MGy.

Zirconium bistriazolylpyridine phosphonate materials for efficient, selective An(iii)/Ln(iii) separations.

Direct synthesis of ZrCl4 and bistriazolylpyridine phosphonate has produced novel sorbent materials that, for the first time, demonstrate selective extraction of Am(iii) in the presence of excess Eu(iii). Further, the high ligand content of these materials affords them high extraction efficiencies.

Separation of actinides from spent nuclear fuel: A review.

This review summarises the methods currently available to extract radioactive actinide elements from solutions of spent nuclear fuel. This separation of actinides reduces the hazards associated with spent nuclear fuel, such as its radiotoxicity, volume and the amount of time required for its' radioactivity to return to naturally occurring levels. Separation of actinides from environmental water systems is also briefly discussed. The actinide elements typically found in spent nuclear fuel include uranium, plutonium and the minor actinides (americium, neptunium and curium). Separation methods for uranium and plutonium are reasonably well established. On the other hand separation of the minor actinides from lanthanide fission products also present in spent nuclear fuel is an ongoing challenge and an area of active research. Several separation methods for selective removal of these actinides from spent nuclear fuel will be described. These separation methods include solvent extraction, which is the most commonly used method for radiochemical separations, as well as the less developed but promising use of adsorption and ion-exchange materials.

Selective sorption of actinides by titania nanoparticles covalently functionalized with simple organic ligands.

Although current and proposed reprocessing of used nuclear fuel is performed predominantly by solvent extraction processes, solid phase sorbent materials have many advantages including the ability to avoid production of large volumes of organic waste. Therefore, three titania nanoparticle based sorbent materials have been developed, functionalized with organic ligands designed to impart selectivity for elements relevant to important separations at the back end of the nuclear fuel cycle. A novel, simplified method of covalent functionalization to the titania surface has been utilized, and the resulting materials have been shown to be hydrolytically stable at pH 2. The sorption behavior of these organofunctionalized titania materials was investigated over a wide pH range with a selection of elements including fission products and actinides. Titania nanoparticles functionalized with an amine or phosphate moiety were able to demonstrate exclusive extraction of uranium under optimized conditions. Titania nanoparticles functionalized with a picolinamide moiety exhibited superior minor actinide sorption properties, in terms of both efficiency and selectivity, to solvent extraction processes using similar organic moieties. As such, organo-functionalized titania materials as solid phase sorbents show promise as a future alternative to solvent extraction processes for nuclear separations.