Extraction of tidal channel networks from airborne scanning laser altimetry and aerial photography

The study of the morphodynamics of tidal channel networks is important because of their role in tidal propagation and the evolution of salt-marshes and tidal flats. Channel dimensions range from tens of metres wide and metres deep near the low water mark to only 20-30cm wide and 20cm deep for the smallest channels on the marshes. The conventional method of measuring the networks is cumbersome, involving manual digitising of aerial photographs. This paper describes a semi-automatic knowledge-based network extraction method that is being implemented to work using airborne scanning laser altimetry (and later aerial photography). The channels exhibit a width variation of several orders of magnitude, making an approach based on multi-scale line detection difficult. The processing therefore uses multi-scale edge detection to detect channel edges, then associates adjacent anti-parallel edges together to form channels using a distance-with-destination transform. Breaks in the networks are repaired by extending channel ends in the direction of their ends to join with nearby channels, using domain knowledge that flow paths should proceed downhill and that any network fragment should be joined to a nearby fragment so as to connect eventually to the open sea.

Uses of airborne scanning laser altimetry for river flood modelling and coastal geomorphology

Two ongoing projects at ESSC that involve the development of new techniques for extracting information from airborne LiDAR data and combining this information with environmental models will be discussed. The first project in conjunction with Bristol University is aiming to improve 2-D river flood flow models by using remote sensing to provide distributed data for model calibration and validation. Airborne LiDAR can provide such models with a dense and accurate floodplain topography together with vegetation heights for parameterisation of model friction. The vegetation height data can be used to specify a friction factor at each node of a model’s finite element mesh. A LiDAR range image segmenter has been developed which converts a LiDAR image into separate raster maps of surface topography and vegetation height for use in the model. Satellite and airborne SAR data have been used to measure flood extent remotely in order to validate the modelled flood extent. Methods have also been developed for improving the models by decomposing the model’s finite element mesh to reflect floodplain features such as hedges and trees having different frictional properties to their surroundings. Originally developed for rural floodplains, the segmenter is currently being extended to provide DEMs and friction parameter maps for urban floods, by fusing the LiDAR data with digital map data. The second project is concerned with the extraction of tidal channel networks from LiDAR. These networks are important features of the inter-tidal zone, and play a key role in tidal propagation and in the evolution of salt-marshes and tidal flats. The study of their morphology is currently an active area of research, and a number of theories related to networks have been developed which require validation using dense and extensive observations of network forms and cross-sections. The conventional method of measuring networks is cumbersome and subjective, involving manual digitisation of aerial photographs in conjunction with field measurement of channel depths and widths for selected parts of the network. A semi-automatic technique has been developed to extract networks from LiDAR data of the inter-tidal zone. A multi-level knowledge-based approach has been implemented, whereby low level algorithms first extract channel fragments based mainly on image properties then a high level processing stage improves the network using domain knowledge. The approach adopted at low level uses multi-scale edge detection to detect channel edges, then associates adjacent anti-parallel edges together to form channels. The higher level processing includes a channel repair mechanism.

C–H local modes in cyclobutene. II. Laser photoacoustic studies 10 000–17 000 cm−1. Vibrational structure and C–H local mode dynamics

In part I of this study [Baggott, Clase, and Mills, Spectrochim. Acta Part A 42, 319 (1986)] we presented FTIR spectra of gas phase cyclobutene and modeled the v=1–3 stretching states of both olefinic and methylenic C–H bonds in terms of a local mode model. In this paper we present some improvements to our original model and make use of recently derived ‘‘x,K relations’’ to find the equivalent normal mode descriptions. The use of both the local mode and normal mode approaches to modeling the vibrational structure is described in some detail. We present evidence for Fermi resonance interactions between the methylenic C–H stretch overtones and ring C–C stretch vibrations, revealed in laser photoacoustic spectra in the v=4–6 region. An approximate model vibrational Hamiltonian is proposed to explain the observed structure and is used to calculate the dynamics of the C–H stretch local mode decay resulting from interaction with lower frequency ring modes. The implications of our experimental and theoretical studies for mode‐selective photochemistry are discussed briefly.

High resolution photoacoustic overtone spectroscopy of monofluoroacetylene, HCCF, with a titanium:sapphire ring laser

Intracavity photoacoustic overtone spectrum of monofluoroacetylene, HCCF, has been recorded in the wave number region 10 750–14 500 cm−1 with a titanium:sapphire ring laser. The spectrum contains many dense vibration–rotation band systems which can be resolved with Doppler limited resolution. Altogether 58 individual overtone bands have been analyzed rotationally. Many of the observed bands show perturbations of which some have been attributed to anharmonic resonance interactions. A Fermi resonance model based on conventional rectilinear normal coordinate theory has been used to assign vibrationally bands from this work and from earlier studies. Many of the observed vibrational term values and rotational constants can be reproduced well with this model. The results show the importance of the Fermi resonance interactions at the high overtone excitations.

Threshold effects in price transmission: The case of Brazilian wheat, maize, and soya prices

Recent studies into price transmission have recognized the important role played by transport and transaction costs. Threshold models are one approach to accommodate such costs. We develop a generalized Threshold Error Correction Model to test for the presence and form of threshold behavior in price transmission that is symmetric around equilibrium. We use monthly wheat, maize, and soya prices from the United States, Argentina, and Brazil to demonstrate this model. Classical estimation of these generalized models can present challenges but Bayesian techniques avoid many of these problems. Evidence for thresholds is found in three of the five commodity price pairs investigated.

Landscape gene flow, coexistence and threshold effect: The case of genetically modified herbicide tolerant oilseed rape (Brassica napus)

Globally there have been a number of concerns about the development of genetically modified crops many of which relate to the implications of gene flow at various levels. In Europe these concerns have led the European Union (EU) to promote the concept of 'coexistence' to allow the freedom to plant conventional and genetically modified (GM) varieties but to minimise the presence of transgenic material within conventional crops. Should a premium for non-GM varieties emerge on the market, the presence of transgenes would generate a 'negative externality' to conventional growers. The establishment of maximum tolerance level for the adventitious presence of GM material in conventional crops produces a threshold effect in the external costs. The existing literature suggests that apart from the biological characteristics of the plant under consideration (e.g. self-pollination rates, entomophilous species, anemophilous species, etc.), gene flow at the landscape level is affected by the relative size of the source and sink populations and the spatial arrangement of the fields in the landscape. In this paper, we take genetically modified herbicide tolerant oilseed rape (GM HT OSR) as a model crop. Starting from an individual pollen dispersal function, we develop a spatially explicit numerical model in order to assess the effect of the size of the source/sink populations and the degree of spatial aggregation on the extent of gene flow into conventional OSR varieties under two alternative settings. We find that when the transgene presence in conventional produce is detected at the field level, the external cost will increase with the size of the source area and with the level of spatial disaggregation. on the other hand when the transgene presence is averaged among all conventional fields in the landscape (e.g. because of grain mixing before detection), the external cost will only depend on the relative size of the source area. The model could readily be incorporated into an economic evaluation of policies to regulate adoption of GM HT OSR. (c) 2007 Elsevier B.V. All rights reserved.

High-throughput proteomics using matrix-assisted laser desorption/ ionization mass spectrometry

It has become evident that the mystery of life will not be deciphered just by decoding its blueprint, the genetic code. In the life and biomedical sciences, research efforts are now shifting from pure gene analysis to the analysis of all biomolecules involved in the machinery of life. One area of these postgenomic research fields is proteomics. Although proteomics, which basically encompasses the analysis of proteins, is not a new concept, it is far from being a research field that can rely on routine and large-scale analyses. At the time the term proteomics was coined, a gold-rush mentality was created, promising vast and quick riches (i.e., solutions to the immensely complex questions of life and disease). Predictably, the reality has been quite different. The complexity of proteomes and the wide variations in the abundances and chemical properties of their constituents has rendered the use of systematic analytical approaches only partially successful, and biologically meaningful results have been slow to arrive. However, to learn more about how cells and, hence, life works, it is essential to understand the proteins and their complex interactions in their native environment. This is why proteomics will be an important part of the biomedical sciences for the foreseeable future. Therefore, any advances in providing the tools that make protein analysis a more routine and large-scale business, ideally using automated and rapid analytical procedures, are highly sought after. This review will provide some basics, thoughts and ideas on the exploitation of matrix-assisted laser desorption/ ionization in biological mass spectrometry - one of the most commonly used analytical tools in proteomics - for high-throughput analyses.

Liquid ultraviolet matrix-assisted laser desorption/ionization - mass spectrometry for automated proteomic analysis

We have combined several key sample preparation steps for the use of a liquid matrix system to provide high analytical sensitivity in automated ultraviolet -- matrix-assisted laser desorption/ionisation -- mass spectrometry (UV-MALDI-MS). This new sample preparation protocol employs a matrix-mixture which is based on the glycerol matrix-mixture described by Sze et al. The low-femtomole sensitivity that is achievable with this new preparation protocol enables proteomic analysis of protein digests comparable to solid-state matrix systems. For automated data acquisition and analysis, the MALDI performance of this liquid matrix surpasses the conventional solid-state MALDI matrices. Besides the inherent general advantages of liquid samples for automated sample preparation and data acquisition the use of the presented liquid matrix significantly reduces the extent of unspecific ion signals in peptide mass fingerprints compared to typically used solid matrices, such as 2,5-dihydroxybenzoic acid (DHB) or alpha-cyano-hydroxycinnamic acid (CHCA). In particular, matrix and low-mass ion signals and ion signals resulting from cation adduct formation are dramatically reduced. Consequently, the confidence level of protein identification by peptide mass mapping of in-solution and in-gel digests is generally higher.

Direct detection of dimethylstannylene and tetramethyldistannene in solution and the gas phase by laser flash photolysis of 1,1-dimethylstannacyclopent-3-enes

The photochemistry of 1,1-dimethyl- and 1,1,3,4-tetramethylstannacyclopent-3-ene (4a and 4b,respectively) has been studied in the gas phase and in hexane solution by steady-state and 193-nm laser flash photolysis methods. Photolysis of the two compounds results in the formation of 1,3-butadiene (from 4a) and 2,3-dimethyl-1,3-butadiene (from 4b) as the major products, suggesting that cycloreversion to yield dimethylstannylene (SnMe2) is the main photodecomposition pathway of these molecules. Indeed, the stannylene has been trapped as the Sn-H insertion product upon photolysis of 4a in hexane containing trimethylstannane. Flash photolysis of 4a in the gas phase affords a transient absorbing in the 450-520nm range that is assigned to SnMe2 by comparison of its spectrum and reactivity to those previously reported from other precursors. Flash photolysis of 4b in hexane solution affords results consistent with the initial formation of SnMe2 (lambda(max) approximate to 500 nm), which decays over similar to 10 mu s to form tetramethyldistannene (5b; lambda(max) approximate to 470 nm). The distannene decays over the next ca. 50 mu s to form at least two other longer-lived species, which are assigned to higher SnMe2 oligomers. Time-dependent DFT calculations support the spectral assignments for SnMe2 and Sn2Me4, and calculations examining the variation in bond dissociation energy with substituent (H, Me, and Ph) in disilenes, digermenes, and distannenes rule out the possibility that dimerization of SnMe2 proceeds reversibly. Addition of methanol leads to reversible reaction with SnMe2 to form a transient absorbing at lambda(max) approximate to 360 nm, which is assigned to the Lewis acid-base complex between SnMe2 and the alcohol.

Experimental and theoretical evidence for homogeneous catalysis in the gas-phase reaction of SiH2 with H2O (and D2O): a combined kinetic and quantum chemical study

Time-resolved kinetic studies of the reaction of silylene, SiH2, with H2O and with D2O have been carried out in the gas phase at 297 K and at 345 K, using laser flash photolysis to generate and monitor SiH2. The reaction was studied independently as a function of H2O (or D2O) and SF6 (bath gas) pressures. At a fixed pressure of SF6 (5 Torr), [SiH2] decay constants, k(obs), showed a quadratic dependence on [H2O] or [D2O]. At a fixed pressure of H2O or D2O, k(obs) Values were strongly dependent on [SF6]. The combined rate expression is consistent with a mechanism involving the reversible formation of a vibrationally excited zwitterionic donor-acceptor complex, H2Si...OH2 (or H2Si...OD2). This complex can then either be stabilized by SF6 or it reacts with a further molecule of H2O (or D2O) in the rate-determining step. Isotope effects are in the range 1.0-1.5 and are broadly consistent with this mechanism. The mechanism is further supported by RRKM theory, which shows the association reaction to be close to its third-order region of pressure (SF6) dependence. Ab initio quantum calculations, carried out at the G3 level, support the existence of a hydrated zwitterion H2Si...(OH2)(2), which can rearrange to hydrated silanol, with an energy barrier below the reaction energy threshold. This is the first example of a gas-phase-catalyzed silylene reaction.