HESS Opinions ``Ensembles, uncertainty and flood prediction''

Ensemble predictions are being used more frequently to model the propagation of uncertainty through complex, coupled meteorological, hydrological and coastal models, with the goal of better characterising flood risk. In this paper, we consider the issues that we judge to be important when designing and evaluating ensemble predictions, and make recommendations for the guidance of future research.

Global hydrology modelling and uncertainty: running multiple ensembles with a campus grid.

Uncertainties associated with the representation of various physical processes in global climate models (GCMs) mean that, when projections from GCMs are used in climate change impact studies, the uncertainty propagates through to the impact estimates. A complete treatment of this ‘climate model structural uncertainty’ is necessary so that decision-makers are presented with an uncertainty range around the impact estimates. This uncertainty is often underexplored owing to the human and computer processing time required to perform the numerous simulations. Here, we present a 189-member ensemble of global river runoff and water resource stress simulations that adequately address this uncertainty. Following several adaptations and modifications, the ensemble creation time has been reduced from 750 h on a typical single-processor personal computer to 9 h of high-throughput computing on the University of Reading Campus Grid. Here, we outline the changes that had to be made to the hydrological impacts model and to the Campus Grid, and present the main results. We show that, although there is considerable uncertainty in both the magnitude and the sign of regional runoff changes across different GCMs with climate change, there is much less uncertainty in runoff changes for regions that experience large runoff increases (e.g. the high northern latitudes and Central Asia) and large runoff decreases (e.g. the Mediterranean). Furthermore, there is consensus that the percentage of the global population at risk to water resource stress will increase with climate change.

Probabilistic simulations of crop yield over western India using the DEMETER seasonal hindcast ensembles

Process-based integrated modelling of weather and crop yield over large areas is becoming an important research topic. The production of the DEMETER ensemble hindcasts of weather allows this work to be carried out in a probabilistic framework. In this study, ensembles of crop yield (groundnut, Arachis hypogaea L.) were produced for 10 2.5 degrees x 2.5 degrees grid cells in western India using the DEMETER ensembles and the general large-area model (GLAM) for annual crops. Four key issues are addressed by this study. First, crop model calibration methods for use with weather ensemble data are assessed. Calibration using yield ensembles was more successful than calibration using reanalysis data (the European Centre for Medium-Range Weather Forecasts 40-yr reanalysis, ERA40). Secondly, the potential for probabilistic forecasting of crop failure is examined. The hindcasts show skill in the prediction of crop failure, with more severe failures being more predictable. Thirdly, the use of yield ensemble means to predict interannual variability in crop yield is examined and their skill assessed relative to baseline simulations using ERA40. The accuracy of multi-model yield ensemble means is equal to or greater than the accuracy using ERA40. Fourthly, the impact of two key uncertainties, sowing window and spatial scale, is briefly examined. The impact of uncertainty in the sowing window is greater with ERA40 than with the multi-model yield ensemble mean. Subgrid heterogeneity affects model accuracy: where correlations are low on the grid scale, they may be significantly positive on the subgrid scale. The implications of the results of this study for yield forecasting on seasonal time-scales are as follows. (i) There is the potential for probabilistic forecasting of crop failure (defined by a threshold yield value); forecasting of yield terciles shows less potential. (ii) Any improvement in the skill of climate models has the potential to translate into improved deterministic yield prediction. (iii) Whilst model input uncertainties are important, uncertainty in the sowing window may not require specific modelling. The implications of the results of this study for yield forecasting on multidecadal (climate change) time-scales are as follows. (i) The skill in the ensemble mean suggests that the perturbation, within uncertainty bounds, of crop and climate parameters, could potentially average out some of the errors associated with mean yield prediction. (ii) For a given technology trend, decadal fluctuations in the yield-gap parameter used by GLAM may be relatively small, implying some predictability on those time-scales.

Synthesis, crystal structure and hydrolysis of a dinuclear copper(II) complex constructed by N2O donor Schiff base and 4,4 '-bipyridine: discrete supra-molecular ensembles vs. oligomers

The tridentate Schiff base ligand, 7-amino-4-methyl-5-aza-3-hepten-2-one (HAMAH), prepared by the mono-condensation of 1,2diaminoethane and acetylacetone, reacts with Cu(BF4)(2) center dot 6H(2)O to produce initially a dinuclear Cu(II) complex, [{Cu(AMAH)}(2) (mu-4,4'-bipyJ](BF4)(2) (1) which undergoes hydrolysis in the reaction mixture and finally produces a linear polymeric chain compound, [Cu(acac)(2)(mu-4,4'-bipy)](n) (2). The geometry around the copper atom in compound 1 is distorted square planar while that in compound 2 is essentially an elongated octahedron. On the other hand, the ligand HAMAH reacts with Cu(ClO4)(2) center dot 6H(2)O to yield a polymeric zigzag chain, [{Cu(acac)(CH3OH)(mu-4,4'-bipy)}(ClO4)](n) (3). The geometry of the copper atom in 3 is square pyramidal with the two bipyridine molecules in the cis equatorial positions. All three complexes have been characterized by elemental analysis, IR and UV-Vis spectroscopy and single crystal X-ray diffraction studies. A probable explanation for the different size and shape of the reported polynuclear complexes formed by copper(II) and 4,4'-bipyridine has been put forward by taking into account the denticity and crystal field strength of the blocking ligand as well as the Jahn-Teller effect in copper(II). (c) 2007 Elsevier Ltd. All rights reserved.

Comparative characterisation by atomic force microscopy and ellipsometry of soft and solid thin films

Ellipsometry and atomic force microscopy (AFM) were used to study the film thickness and the surface roughness of both 'soft' and solid thin films. 'Soft' polymer thin films of polystyrene and poly(styrene-ethylene/butylene-styrene) block copolymer were prepared by spin-coating onto planar silicon wafers. Ellipsometric parameters were fitted by the Cauchy approach using a two-layer model with planar boundaries between the layers. The smooth surfaces of the prepared polymer films were confirmed by AFM. There is good agreement between AFM and ellipsometry in the 80-130 nm thickness range. Semiconductor surfaces (Si) obtained by anisotropic chemical etching were investigated as an example of a randomly rough surface. To define roughness parameters by ellipsometry, the top rough layers were treated as thin films according to the Bruggeman effective medium approximation (BEMA). Surface roughness values measured by AFM and ellipsometry show the same tendency of increasing roughness with increased etching time, although AFM results depend on the used window size. The combined use of both methods appears to offer the most comprehensive route to quantitative surface roughness characterisation of solid films. Copyright (c) 2007 John Wiley & Sons, Ltd.

Cu-II acetate complexes involving N,N,O donor Schiff base ligands: Mono-atomic oxygen bridged dimers and alternating chains of the dimers and Cu-2(OAc)(4)

Two tridentate N,N,O donor Schiff bases, HL1 (4-(2-ethylamino-ethylimino)-pentan-2-one) and HL2 (3-(2-amino-propylimino)-1-phenyl-butan-1-one) on reaction with Cu-II acetate in presence of triethyl amine yielded two basal-apical, mono-atomic acetate oxygen-bridging dimeric copper(II) complexes, [Cu2L21(OAc)(2)] (1), [Cu2L22(OAc)(2)] (2). Whereas two other similar tridentate ligands HL3 (4-(2-amino-propylimino)-pentane-2-one) and HL3 (3-(2-amino-ethylimino)-1-phenyl-butan-1-one) under the same conditions produced a mixture of the corresponding dinners and a one-dimensional alternating chain of the dimer and copper acetate moiety, [Cu4L23(OAc)(6)](n) (3) and [Cu4L24(OAc)(6)](n) (4), formed by a very rare mu(3) bridging mode of the acetate ion. All four complexes (1-4) have been characterized by X-ray crystallography. The isotropic Hamiltonian, H = -JS(1)S(2) has been used to interpret the magnetic data. Magnetic measurements of 1 and 2 in the temperature range 2-300 K reveal a very weak antiferromagnetic coupling for both complexes U = -0.56 and -1.19 cm(-1) for 1 and 2, respectively). (C) 2008 Elsevier Ltd. All rights reserved.

Crystal structure of the complementary quadruplex formed by d(GCATGCT) at atomic resolution

Here we report the crystal structure of the DNA heptanucleotide sequence d(GCATGCT) determined to a resolution of 1.1 Angstrom. The sequence folds into a complementary loop structure generating several unusual base pairings and is stabilised through cobalt hexammine and highly defined water sites. The single stranded loop is bound together through the G(N2)-C(O2) intra-strand H-bonds for the available G/C residues, which form further Watson-Crick pairings to a complementary sequence, through 2-fold symmetry, generating a pair of non-planar quadruplexes at the heart of the structure. Further, four adenine residues stack in pairs at one end, H-bonding through their N7-N6 positions, and are additionally stabilised through two highly conserved water positions at the structural terminus. This conformation is achieved through the rotation of the central thymine base at the pinnacle of the loop structure, where it stacks with an adjacent thymine residue within the lattice. The crystal packing yields two halved biological units, each related across a 2-fold symmetry axis spanning a cobalt hexammine residue between them, which stabilises the quadruplex structure through H-bonds to the phosphate oxygens and localised hydration.

Surface structure of thin asymmetric PS-b-PMMA diblock copolymers investigated by atomic force microscopy

Asymmetric poly(styrene-b-methyl methacrylate) (PS-b-PMMA) diblock copolymers of molecular weight M-n = 29,700g mol(-1) (M-PS = 9300 g mol(-1) M-PMMA = 20,100 g mol(-1), PD = 1.15, chi(PS) = 0.323, chi(PMMA) = 0.677) and M-n = 63,900 g mol(-1) (M-PS = 50,500 g mol(-1), M-PMMA = 13,400 g mol(-1), PD = 1.18, chi(PS) = 0.790, chi(PMMA) = 0.210) were prepared via reversible addition-fragmentation chain transfer (RAFT) polymerization. Atomic force microscopy (AFM) was used to investigate the surface structure of thin films, prepared by spin-coating the diblock copolymers on a silicon substrate. We show that the nanostructure of the diblock copolymer depends on the molecular weight and volume fraction of the diblock copolymers. We observed a perpendicular lamellar structure for the high molar mass sample and a hexagonal-packed cylindrical patterning for the lower molar mass one. Small-angle X-ray scattering investigation of these samples without annealing did not reveal any ordered structure. Annealing of PS-b-PMMA samples at 160 degrees C for 24 h led to a change in surface structure.

Direct visualisation of lipid bilayer cubic phases using Atomic Force Microscopy

Inverse bicontinuous cubic (Q(II)) phases are nanostructured materials formed by lipid self-assembly. We have successfully imaged thin films of hydrated Q(II) phases from two different systems using AFM. The images show periodic arrays of water channels with spacing and symmetry consistent with published SAXS data on the bulk materials.