In all geodisposal scenarios it is key to understand the interaction of radionuclides with mineral particles during their formation/recrystallisation. Studying processes at the molecular scale provides insight into long-term radionuclide behaviour. Uranium is a significant radionuclide in higher activity wastes destined for geological disposal, and iron (oxyhydr) oxides (e.g. goethite, 􀟙-FeOOH). are ubiquitous in and around these systems, formed via processes including metal corrosion and microbially induced reactions. There are numerous reports of uranium-incorporation into iron (oxyhydr) oxides, therefore it has been suggested that they may be a barrier to uranium migration in geodisposal systems. However, long-term stability of these phases during environmental perturbations are unexplored. Specifically, U-incorporated iron (oxyhydr) oxide phases may interact with Fe(II) and sulphide from biological or geological origin. Firstly, electron transfer occurs between adsorbed Fe(II) and iron oxyhydroxides, with potential for changes in the speciation of incorporated uranium e.g. oxidation state changes and/or release. Secondly, on exposure to aqueous sulfide, iron (oxyhydr) oxides undergo reductive dissolution and recrystallisation to iron sulphides. Understanding the fate of incorporated uranium during these process in key to understanding its long term behaviour in subsurface systems. A series of experimental studies were undertaken where U(VI)-goethite was synthesized then reacted with either aqueous Fe(II) or S(-II), and the system monitored over time using geochemical analysis and X-ray absorption spectroscopy (XAS) techniques e.g. U LIII-edge and MIV-edge HERFD-XANES. Reaction with aqueous Fe(II) resulted in electron transfer between Fe(II) and U(VI)-goethite, with > 50% U(VI) reduced to U(V). XAS analysis revealed that U remained within the goethite structure, and electron transfer only occurred within the outermost atomic layers of goethite. which led to U reduction. Rapid reductive dissolution of U(VI)-goethite occurred on reaction with sulfide at pH7. A transient release of aqueous U was observed during the first day, likely due to uranyl(VI)-persulfide species. However, U was retained in the solid phase in the longer term. In contrast, the sulfidation of U adsorbed to ferrihydrite at pH 12.2 led to the immediate release of U (< 10% Utotal) associated with a colloidal erdite (NaFeS2·2H2O) phase. Moreover, in the bulk phase the surface of ferrihydrite was passivated by sulfide, and U was found to have been trapped within surface associated erdite-like fibres. Overall, these studies further understanding of the long-term behaviour of U-incorporated iron (oxyhydr)oxides supporting the overarching concept of iron (oxyhydr) oxides acting as a barrier to U migration.

Controversy has surrounded the potential impacts of phytoplankton on the tropical climate, since climate models produce diverse behaviors in terms of the equatorial mean state and El Niño-Southern Oscillation (ENSO) amplitude. We explored biophysical impacts on the tropical ocean temperature using an ocean general circulation model coupled to a biogeochemistry model in which chlorophyll can modify solar attenuation and in turn feed back to ocean physics. Compared with a control model run excluding biophysical processes, our model with biogeochemistry showed that subsurface chlorophyll concentrations led to an increase in sea surface temperature (particularly in the western Pacific) via horizontal accumulation of heat contents. In the central Pacific, however, a mild cold anomaly appeared, accompanying the strengthened westward currents. The magnitude and skewness of ENSO were also modulated by biophysical feedbacks resulting from the chlorophyll affecting El Niño and La Niña in an asymmetric way. That is, El Niño conditions were intensified by the higher contribution of the second baroclinic mode to sea surface temperature anomalies, whereas La Niña conditions were slightly weakened by the absorption of shortwave radiation by phytoplankton. In our model experiments, the intensification of El Niño was more dominant than the dampening of La Niña, resulting in the amplification of ENSO and higher skewness.