Data assimilation: From photon counts to Earth System forecasts

Data assimilation – the set of techniques whereby information from observing systems and models is combined optimally – is rapidly becoming prominent in endeavours to exploit Earth Observation for Earth sciences, including climate prediction. This paper explains the broad principles of data assimilation, outlining different approaches (optimal interpolation, three-dimensional and four-dimensional variational methods, the Kalman Filter), together with the approximations that are often necessary to make them practicable. After pointing out a variety of benefits of data assimilation, the paper then outlines some practical applications of the exploitation of Earth Observation by data assimilation in the areas of operational oceanography, chemical weather forecasting and carbon cycle modelling. Finally, some challenges for the future are noted.

The effect of temperature, photosynthetic photon flux density, and photoperiod on the vegetative growth and flowering of 'Autumn Bliss' raspberry

The effects of temperature, photosynthetic photon flux density (PPFD) and photoperiod on vegetative growth and flowering of the raspberry (Rubus idaeus L.) 'Autumn Bliss' were investigated. Increased temperature resulted in an increased rate of vegetative growth and a greater rate of progress to flowering. Optimum temperatures lay in the low to mid 20degreesC range. Above this the rate of plant development declined. Increased PPFD also advanced flowering. While photoperiod did not significantly affect the rate of vegetative growth, flowering occurred earliest at intermediate photoperiods and was delayed by extreme photoperiods. These responses suggest that there is potential for adjusting cropping times of raspberry grown under protection by manipulating the environment, especially temperature.

Alkene-arene meta photocycloadditions with a four-carbon-atom tether: efficient approach toward the polycyclic ring systems of aphidicolin and stemodinone

At the end of its tether! The fusion of a six-membered ring onto the four-carbon-atom tether of substrate 1 provides an efficient approach toward the polycyclic ring systems of the natural products aphidicolin and stemodinone. The reaction represents a unique example of a preference for product formation from an endo exciplex in an intramolecular system (exo:endo 2:3=1.0:1.2).

A fluxional (CuN2O2)-N-I core: binding of a keto oxygen atom to Cu-I and Ag-I

[Cu(2-acetylpyridine)(2)]ClO4 (1), characterised here, has a novel Cu'N202 core in the solid state. Variable-temperature H-1 NMR studies show that the two chelate rings open up in solution at room temperature and the keto oxygen atoms dangle freely. As the temperature is lowered, the 0 atoms tend to bind to the metal atom. The corresponding silver(I) complex, [Ag(2-acetylpyridine)2]ClO4 (4), characterised by single-crystal X-ray crystallography, has an (AgN2)-N-I core in the solid state as well as in solution. Thus, while 1 is fluxional, 4 is not. In cyclic voltammetry, complex 1 displays a quasireversible Cu-II/I couple with a half-wave potential of 0.40 V vs. SCE. Complex I is easily oxidised by air and H2O2 in methanol to give rise to a dinuclear copper(II) complex where the ligand framework is not simple acetylpyridine. ((c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005).

Experimental and theoretical study of the infrared spectra of BrHI- and BrDI-

Gas phase vibrational spectra of BrHI- and BrDI- have been measured from 6 to 17 mum (590-1666 cm-1) using tunable infrared radiation from the free electron laser for infrared experiments in order to characterize the strong hydrogen bond in these species. BrHI-.Ar and BrDI-.Ar complexes were produced and mass selected, and the depletion of their signal due to vibrational predissociation was monitored as a function of photon energy. Additionally, BrHI- and BrDI- were dissociated into HBr (DBr) and I- via resonant infrared multiphoton dissociation. The spectra show numerous transitions, which had not been observed by previous matrix studies. New ab initio calculations of the potential-energy surface and the dipole moment are presented and are used in variational ro-vibrational calculations to assign the spectral features. These calculations highlight the importance of basis set in the simulation of heavy atoms such as iodine. Further, they demonstrate extensive mode mixing between the bend and the H-atom stretch modes in BrHI- and BrDI- due to Fermi resonances. These interactions result in major deviations from simple harmonic estimates of the vibrational energies. As a result of this new analysis, previous matrix-isolation spectra assignments are reevaluated. (C) 2004 American Institute of Physics.

Structure of adsorbed organometallic rhodium: model single atom catalysts

We have determined the structure of a complex rhodium carbonyl chloride [Rh(CO)(2)Cl] molecule adsorbed on the TiO2 (110) surface by the normal incidence x-ray standing wave technique. The data show that the technique is applicable to reducible oxide systems and that the dominant adsorbed species is undissociated with Rh binding atop bridging oxygen and to the Cl found close to the fivefold coordinated Ti ions in the surface. A minority geminal dicarboryl species, where Rh-Cl bond scission has occurred, is found bridging the bridging oxygen ions forming a high-symmetry site.

Critical Mass: Sermon for the Church of the Atom (part of A Theatre to Address at Arnolfini, Bristol and Late at Tate Britain)

A Theatre to Address explores the work of contemporary artists who use text as both a visual and sonic form. In this programme, text appears not primarily as a means of communication, but as something which has shape and structure of its own. The Reading Room will also be displaying work that looks at text as concrete or visual poetry, and the script in artists' practice. Clare Gasson presents a new work The traveller - walking walking walking through ... that explores the connection between the text, the rhythm and the action. Maryam Jafri presents a performance-lecture Death With Friends, a body of visual and textual material that forms the basis for her new film of the same name. Pil and Galia Kollectiv present a radical worship for the apocalypse, featuring a sermon for the Church of the Atom with live music by Gelbart.

Where the interaction is: collisions of the situated and mediated in living room interactions

This article presents three ethnographic tales of interactions with living room media to help recreate the experience of significant moments in time, of affective encounters at the interface in which there is a collision or confusion of situated and virtual worlds. It draws on a year-long video ethnography of the practice and performance of everyday interactions with living room media. By studying situated activity and the lived practice of (new) media, rather than taking an exclusive focus on the virtual as a detached space, this ethnographic work demonstrates how the situated and mediated clash, or are crafted into complex emotional encounters during everyday living room life.

Two-photon excitation with pico-second fluorescence lifetime imaging to detect nuclear association of flavanols

Two-photon excitation enabled for the first time the observation and measurement of excited state fluorescence lifetimes from three flavanols in solution, which were ∼1.0 ns for catechin and epicatechin, but <45 ps for epigallocatechin gallate (EGCG). The shorter lifetime for EGCG is in line with a lower fluorescence quantum yield of 0.003 compared to catechin (0.015) and epicatechin (0.018). In vivo experiments with onion cells demonstrated that tryptophan and quercetin, which tend to be major contributors of background fluorescence in plant cells, have sufficiently low cross sections for two-photon excitation at 630 nm and therefore do not interfere with detection of externally added or endogenous flavanols in Allium cepa or Taxus baccata cells. Applying two-photon excitation to flavanols enabled 3-D fluorescence lifetime imaging microscopy and showed that added EGCG penetrated the whole nucleus of onion cells. Interestingly, EGCG and catechin showed different lifetime behaviour when bound to the nucleus: EGCG lifetime increased from <45 to 200 ps, whilst catechin lifetime decreased from 1.0 ns to 500 ps. Semi-quantitative measurements revealed that the relative ratios of EGCG concentrations in nucleoli associated vesicles: nucleus: cytoplasm were ca. 100:10:1. Solution experiments with catechin, epicatechin and histone proteins provided preliminary evidence, via the appearance of a second lifetime (τ2 = 1.9–3.1 ns), that both flavanols may be interacting with histone proteins. We conclude that there is significant nuclear absorption of flavanols. This advanced imaging using two-photon excitation and biophysical techniques described here will prove valuable for probing the intracellular trafficking and functions of flavanols, such as EGCG, which is the major flavanol of green tea.

Preventing carbon contamination of optical devices for X-rays: the effect of oxygen on photon-induced dissociation of CO on platinum

Platinum is one of the most common coatings used to optimize mirror reflectivity in soft X-ray beamlines. Normal operation results in optics contamination by carbon-based molecules present in the residual vacuum of the beamlines. The reflectivity reduction induced by a carbon layer at the mirror surface is a major problem in synchrotron radiation sources. A time-dependent photoelectron spectroscopy study of the chemical reactions which take place at the Pt(111) surface under operating conditions is presented. It is shown that the carbon contamination layer growth can be stopped and reversed by low partial pressures of oxygen for optics operated in intense photon beams at liquidnitrogen temperature. For mirrors operated at room temperature the carbon contamination observed for equivalent partial pressures of CO is reduced and the effects of oxygen are observed on a long time scale.

The tensor-kinetic field in nuclear collisions

The role of the tensor terms in the Skyrme interaction is studied for their effect in dynamic calculations where non-zero contributions to the mean-field may arise, even when the starting nucleus, or nuclei are even-even and have no active time-odd potentials in the ground state. We study collisions in the test-bed 16O-16O system, and give a qualitative analysis of the behaviour of the time-odd tensor-kinetic density, which only appears in the mean field Hamiltonian in the presence of the tensor force. We find an axial excitation of this density is induced by a collision.