Understanding advances in the simulation of the Madden-Julian Oscillation in a numerical weather prediction model.

The Madden-Julian Oscillation (MJO) is the dominant mode of intraseasonal variability in the Trop- ics. It can be characterised as a planetary-scale coupling between the atmospheric circulation and organised deep convection that propagates east through the equatorial Indo-Pacific region. The MJO interacts with weather and climate systems on a near-global scale and is a crucial source of predictability for weather forecasts on medium to seasonal timescales. Despite its global signifi- cance, accurately representing the MJO in numerical weather prediction (NWP) and climate models remains a challenge. This thesis focuses on the representation of the MJO in the Integrated Forecasting System (IFS) at the European Centre for Medium-Range Weather Forecasting (ECMWF), a state-of-the-art NWP model. Recent modifications to the model physics in Cycle 32r3 (Cy32r3) of the IFS led to ad- vances in the simulation of the MJO; for the first time the observed amplitude of the MJO was maintained throughout the integration period. A set of hindcast experiments, which differ only in their formulation of convection, have been performed between May 2008 and April 2009 to asses the sensitivity of MJO simulation in the IFS to the Cy32r3 convective parameterization. Unique to this thesis is the attribution of the advances in MJO simulation in Cy32r3 to the mod- ified convective parameterization, specifically, the relative-humidity-dependent formulation for or- ganised deep entrainment. Increasing the sensitivity of the deep convection scheme to environmen- tal moisture is shown to modify the relationship between precipitation and moisture in the model. Through dry-air entrainment, convective plumes ascending in low-humidity environments terminate lower in the atmosphere. As a result, there is an increase in the occurrence of cumulus congestus, which acts to moisten the mid-troposphere. Due to the modified precipitation-moisture relationship more moisture is able to build up which effectively preconditions the tropical atmosphere for the transition to deep convection. Results from this thesis suggest that a tropospheric moisture control on convection is key to simulating the interaction between the physics and large-scale circulation associated with the MJO.

Internal nanoparticle structure of temperature-responsive self-assembled PNIPAM-b-PEG-b-PNIPAM triblock copolymers in aqueous solutions: NMR, SANS and light scattering studies

In this study we report detailed information on the internal structure of PNIPAM-b-PEG-b-PNIPAM nanoparticles formed from self-assembly in aqueous solutions upon increase in temperature. NMR spectroscopy, light scattering and small-angle neutron scattering (SANS) were used to monitor different stages of nanoparticle formation as a function of temperature, providing insight into the fundamental processes involved. The presence of PEG in a copolymer structure significantly affects the formation of nanoparticles, making their transition to occur over a broader temperature range. The crucial parameter that controls the transition is the ratio of PEG/PNIPAM. For pure PNIPAM, the transition is sharp; the higher the PEG/PNIPAM ratio results in a broader transition. This behavior is explained by different mechanisms of PNIPAM block incorporation during nanoparticle formation at different PEG/PNIPAM ratios. Contrast variation experiments using SANS show that the structure of nanoparticles above cloud point temperatures for PNIPAM-b-PEG-b-PNIPAM copolymers is drastically different from the structure of PNIPAM mesoglobules. In contrast with pure PNIPAM mesoglobules, where solid-like particles and chain network with a mesh size of 1-3 nm are present; nanoparticles formed from PNIPAM-b-PEG-b-PNIPAM copolymers have non-uniform structure with “frozen” areas interconnected by single chains in Gaussian conformation. SANS data with deuterated “invisible” PEG blocks imply that PEG is uniformly distributed inside of a nanoparticle. It is kinetically flexible PEG blocks which affect the nanoparticle formation by prevention of PNIPAM microphase separation.