Wave-driven wind jets in the marine atmospheric boundary layer

The interaction between ocean surface waves and the overlying wind leads to a transfer of momentum across the air–sea interface. Atmospheric and oceanic models typically allow for momentum transfer to be directed only downward, from the atmosphere to the ocean. Recent observations have suggested that momentum can also be transferred upward when long wavelength waves, characteristic of remotely generated swell, propagate faster than the wind speed. The effect of upward momentum transfer on the marine atmospheric boundary layer is investigated here using idealized models that solve the momentum budget above the ocean surface. A variant of the classical Ekman model that accounts for the wave-induced stress demonstrates that, although the momentum flux due to the waves penetrates only a small fraction of the depth of the boundary layer, the wind profile is profoundly changed through its whole depth. When the upward momentum transfer from surface waves sufficiently exceeds the downward turbulent momentum flux, then the near-surface wind accelerates, resulting in a low-level wave-driven wind jet. This increases the Coriolis force in the boundary layer, and so the wind turns in the opposite direction to the classical Ekman layer. Calculations of the wave-induced stress due to a wave spectrum representative of fast-moving swell demonstrate upward momentum transfer that is dominated by contributions from waves in the vicinity of the peak in the swell spectrum. This is in contrast to wind-driven waves whose wave-induced stress is dominated by very short wavelength waves. Hence the role of swell can be characterized by the inverse wave age based on the wave phase speed corresponding to the peak in the spectrum. For a spectrum of waves, the total momentum flux is found to reverse sign and become upward, from waves to wind, when the inverse wave age drops below the range 0.15–0.2, which agrees reasonably well with previously published oceanic observations.

Synoptic controls on boundary-layer characteristics

We report the characteristics of the three-dimensional, time evolving, atmospheric boundary layer that develops beneath an idealised, dry, baroclinic weather system. The boundary-layer structure is forced by thermal advection associated with the weather system. Large positive heat fluxes behind the cold front drive a vigorous convective boundary layer, whereas moderate negative heat fluxes in the warm sector between the cold and warm fronts generate shallow, stably stratified or neutral boundary layers. The forcing of the boundary-layer structure is quantified by forming an Eulerian mass budget integrated over the depth of the boundary layer. The mass budget indicates that tropospheric air is entrained into the boundary layer both in the vicinity of the high-pressure centre, and behind the cold front. It is then transported horizontally within the boundary layer and converges towards the cyclone's warm sector, whence it is ventilated out into the troposphere. This cycling of air is likely to be important for the ventilation of pollution out of the boundary layer, and for the transformation of the properties of large-scale air masses.

Controls on boundary layer ventilation: Boundary layer processes and large-scale dynamics

Midlatitude cyclones are important contributors to boundary layer ventilation. However, it is uncertain how efficient such systems are at transporting pollutants out of the boundary layer, and variations between cyclones are unexplained. In this study 15 idealized baroclinic life cycles, with a passive tracer included, are simulated to identify the relative importance of two transport processes: horizontal divergence and convergence within the boundary layer and large-scale advection by the warm conveyor belt. Results show that the amount of ventilation is insensitive to surface drag over a realistic range of values. This indicates that although boundary layer processes are necessary for ventilation they do not control the magnitude of ventilation. A diagnostic for the mass flux out of the boundary layer has been developed to identify the synoptic-scale variables controlling the strength of ascent in the warm conveyor belt. A very high level of correlation (R-2 values exceeding 0.98) is found between the diagnostic and the actual mass flux computed from the simulations. This demonstrates that the large-scale dynamics control the amount of ventilation, and the efficiency of midlatitude cyclones to ventilate the boundary layer can be estimated using the new mass flux diagnostic. We conclude that meteorological analyses, such as ERA-40, are sufficient to quantify boundary layer ventilation by the large-scale dynamics.

Black carbon measurements in the boundary layer over western and northern Europe

Europe is a densely populated region that is a significant global source of black carbon (BC) aerosol, but there is a lack of information regarding the physical properties and spatial/vertical distribution of rBC in the region. We present the first aircraft observations of sub-micron refractory BC (rBC) aerosol concentrations and physical properties measured by a single particle soot photometer (SP2) in the lower troposphere over Europe. The observations spanned a region roughly bounded by 50° to 60° N and from 15° W to 30° E. The measurements, made between April and September 2008, showed that average rBC mass concentrations ranged from about 300 ng m−3 near urban areas to approximately 50 ng m−3 in remote continental regions, lower than previous surface-based measurements. rBC represented between 0.5 and 3% of the sub-micron aerosol mass. Black carbon mass size distributions were log-normally distributed and peaked at approximately 180 nm, but shifted to smaller diameters (~160 nm) near source regions. rBC was correlated with carbon monoxide (CO) but had different ratios to CO depending on location and air mass. Light absorption coefficients were measured by particle soot absorption photometers on two separate aircraft and showed similar geographic patterns to rBC mass measured by the SP2. We summarize the rBC and light absorption measurements as a function of longitude and air mass age and also provide profiles of rBC mass concentrations and size distribution statistics. Our results will help evaluate model-predicted regional rBC concentrations and properties and determine regional and global climate impacts from rBC due to atmospheric heating and surface dimming.

Research note: amendments to the model for predicting age at sexual maturity for growing pullets of layer strains following changes in photoperiod

A model was published by Lewis et al. (2002) to predict the mean age at first egg (AFE) for pullets of laying strains reared under non-limiting environmental conditions and exposed to a single change in photoperiod during the rearing stage. Subsequently, Lewis et al. (2003) reported the effects of two opposing changes in photoperiod, which showed that the first change appears to alter the pullet's physiological age so that it responds to the second change as though it had been given at an earlier age (if photoperiod was decreased), or later age (if photoperiod was increased) than the true chronological age. During the construction of a computer model based on these two publications, it became apparent that some of the components of the models needed adjustment. The amendments relate to (1) the standard deviation (S.D.) used for calculating the proportion of a young flock that has attained photosensitivity, (2) the equation for calculating the slope of the line relating AFE to age at transfer from one photoperiod to another, (3) the equation used for estimating the distribution of AFE as a function of the mean value, (4) the point of no return when pullets which have started spontaneous maturation in response to the current photoperiod can no longer respond to a late change in photoperiod and (5) the equations used for calculating the distribution of AFE when the trait is bimodal.

Effect of two opposing changes in photoperiod upon age at first egg in layer-hybrid pullets

An experiment was designed to test the response of growing pullets to two changes in photoperiod (an increase from 8 to 14 h followed 5 weeks later by the reverse change, or a decrease from 14 to 8 h followed by an increase). The first change was made either at 35 days or at 56 days of age, to test the influence of age on the responses observed. Control groups were kept oil constant 8-h and constant 14-h photoperiods and the responses to appropriate single changes were also tested. Mean age at first egg varied from 111 days for birds given a single increment at 56 days to 166 days for pullets given an increase in photoperiod at 35 days followed by a reduction at 70 days. Responses to the single changes confirmed earlier reports that sensitivity to change in photoperiod varies with age ill a manner that is quantitatively predictable. Responses to the double changes could be explained by Postulating that the initial change altered the 'physiological age' of the bird to all extent that was also quantitatively predictable. An early increase in photoperiod advances sexual development and makes the bird more sensitive to a subsequent decrease than would be expected by reference to its chronological age. An early decrease in photoperiod delays sexual development, which can have the effect of making the bird more or less sensitive to a subsequent increase since, ill layer-strain pullets, sensitivity to an increment in photoperiod normally increases Lip to about 9 weeks of age but decreases thereafter. Mean age at first egg predicted using these concepts was very highly correlated with observed age at first egg. The results provide a rational basis for constructing a model to predict age at first egg for any combination of increases and decreases in photoperiod applied to growing pullets.

Cellulose microfibril angle in the cell wall of wood fibres

The term microfibril angle (MFA) in wood science refers to the angle between the direction of the helical windings of cellulose microfibrils in the secondary cell wall of fibres and tracheids and the long axis of cell. Technologically, it is usually applied to the orientation of cellulose microfibrils in the S2 layer that makes up the greatest proportion of the wall thickness, since it is this which most affects the physical properties of wood. This review describes the organisation of the cellulose component of the secondary wall of fibres and tracheids and the various methods that have been used for the measurement of MFA. It considers the variation of MFA within the tree and the biological reason for the large differences found between juvenile (or core) wood and mature (or outer) wood. The ability of the tree to vary MFA in response to environmental stress, particularly in reaction wood, is also described. Differences in MFA have a profound effect on the properties of wood, in particular its stiffness. The large MFA in juvenile wood confers low stiffness and gives the sapling the flexibility it needs to survive high winds without breaking. It also means, however, that timber containing a high proportion of juvenile wood is unsuitable for use as high-grade structural timber. This fact has taken on increasing importance in view of the trend in forestry towards short rotation cropping of fast grown species. These trees at harvest may contain 50% or more of timber with low stiffness and therefore, low economic value. Although they are presently grown mainly for pulp, pressure for increased timber production means that ways will be sought to improve the quality of their timber by reducing juvenile wood MFA. The mechanism by which the orientation of microfibril deposition is controlled is still a matter of debate. However, the application of molecular techniques is likely to enable modification of this process. The extent to which these techniques should be used to improve timber quality by reducing MFA in juvenile wood is, however, uncertain, since care must be taken to avoid compromising the safety of the tree.

Chemoselective catalytic hydrogenation of acrolein on Ag(111): effect of molecular orientation on reaction selectivity

The adsorption and hydrogenation of acrolein on the Ag(111) surface has been investigated by high resolution synchrotron XPS, NEXAFS, and temperature programmed reaction. The molecule adsorbs intact at all coverages and its adsorption geometry is critically important in determining chemoselectivity toward the formation of allyl alcohol, the desired but thermodynamically disfavored product. In the absence of hydrogen adatoms (H(a)), acrolein lies almost parallel to the metal surface; high coverages force the C=C bond to tilt markedly, likely rendering it less vulnerable toward reaction with hydrogen adatoms. Reaction with coadsorbed H(a) yields allyl alcohol, propionaldehyde, and propanol, consistent with the behavior of practical dispersed Ag catalysts operated at atmospheric pressure: formation of all three hydrogenation products is surface reaction rate limited. Overall chemoselectivity is strongly influenced by secondary reactions of allyl alcohol. At low H(a) coverages, the C=C bond in the newly formed allyl alcohol molecule is strongly tilted with respect to the surface, rendering it immune to attack by H(a) and leading to desorption of the unsaturated alcohol. In contrast with this, at high H(a) coverages, the C=C bond in allyl alcohol lies almost parallel to the surface, undergoes hydrogenation by H(a), and the saturated alcohol (propanol) desorbs.

Ordering in thin films of block copolymers: fundamentals to potential applications

The ordering of block copolymers in thin films is reviewed, starting, from the fundamental principles and extending to recent promising developments as templates for nanolithography which may find important applications in the semiconductor industry. Ordering in supported thin films of symmetric and asymmetric AB diblock and ABA triblock copolymers is discussed, along with that of more complex materials such as ABC triblocks and liquid crystalline block copolymers Techniques to prepare thin films, and to characterise ordering within them, are summarized. Several methods to align Hock copolymer nanostructures, important in several applications are outlined A number of potential applications in nanolithography, production of porous materials, templating. and patterning of organic and inorganic materials are then presented. The influence of crystallization on the morphology of a block copolymer film is briefly discussed, as are structures in grafted block copolymer films. (C) 2009 Elsevier Ltd All rights reserved.

Ordering on multiple lengthscales in a series of side group liquid crystal block copolymers containing a cholesteryl-based mesogen

Hierarchical ordering in a side group liquid crystal block copolymer is investigated by differential scanning calorimetry, polarized optical microscopy, small-angle X-ray and neutron scattering (SAXS and SANS) and transmission electron microscopy (TEM). A series of block copolymers with a range of compositions was prepared by atom transfer radical polymerization, comprising a polystyrene block and a poly(methyl methacrylate) block bearing chiral cholesteryl mesogens. Smectic ordering is observed as well as microphase separation of the block copolymer. Lamellar structures were observed for far larger volume fractions than for coil-coil copolymers (up to a volume fraction of liquid crystal block, f(LC) = 0.8). A sample with f(LC) = 0.86 exhibited a hexagonal-packed cylinder morphology, as confirmed by SAXS and TEM. The matrix comprised the liquid crystal block, with the mesogens forming smectic layers. For the liquid crystal homopolymer and samples with high f(LC), a smectic-smectic phase transition was observed below the clearing point. At low temperature, the smectic phase comprises coexisting domains with monolayer S-A,S-1 coexisting with interdigitated S-A,S-d domains. At high temperature a SA,1 phase is observed. This is the only structure observed for samples with lower f(LC). These unprecedented results point to the influence of block copolymer microphase separation on the smectic ordering.

Orientational ordering in the nematic phase of a polyethylene glycol-peptide conjugate in aqueous solution

The orientational ordering of the nematic phase of a polyethylene glycol (PEG)-peptide block copolymer in aqueous solution is probed by small-angle neutron scattering (SANS), with the sample subjected to steady shear in a Couette cell. The PEG-peptide conjugate forms fibrils that behave as semiflexible rodlike chains. The orientational order parameters (P) over bar (2) and (P) over bar (4) are obtained by modeling the data using a series expansion approach to the form factor of uniform cylinders. The method used is independent of assumptions on the form of the singlet orientational distribution function. Good agreement with the anisotropic two-dimensional SANS patterns is obtained. The results show shear alignment starting at very low shear rates, and the orientational order parameters reach a plateau at higher shear rates with a pseudologarithmic dependence on shear rate. The most probable distribution functions correspond to fibrils parallel to the flow direction under shear, but a sample at rest shows a bimodal distribution with some of the rodlike peptide fibrils oriented perpendicular to the flow direction.

Structural analysis of PEO-PBO copolymer monolayers at the air-water interface

X-ray reflectivity (XR) and grazing incidence X-ray diffraction (GIXD) have been used to examine an oxyethylene-b-oxybutylene (E23B8) copolymer film at the air-water interface. The XR data were fitted using both a one- and a two-layer model that outputted the film thickness, roughness, and electron density. The best fit to the experimental data was obtained using a two-layer model (representing the oxyethylene and oxybutylene blocks, respectively), which showed a rapid thickening of the copolymer film at pressures above 7 mN/m. The large roughness values found indicate a significant degree of intermixing between the blocks and back up the GIXD data, which showed no long range lateral ordering within the layer. It was found from the electron density model results that there is a large film densification at 7 mN/m, possibly suggesting conformational changes within the film, even though no such change occurs on the pressure-area isotherm at the same surface pressure.

Function of the hydration layer around an antifreeze protein revealed by atomistic molecular dynamics simulations

Atomistic molecular dynamics simulations are used to investigate the mechanism by which the antifreeze protein from the spruce budworm, Choristoneura fumiferana, binds to ice. Comparison of structural and dynamic properties of the water around the three faces of the triangular prism-shaped protein in aqueous solution reveals that at low temperature the water structure is ordered and the dynamics slowed down around the ice-binding face of the protein, with a disordering effect observed around the other two faces. These results suggest a dual role for the solvation water around the protein. The preconfigured solvation shell around the ice-binding face is involved in the initial recognition and binding of the antifreeze protein to ice by lowering the barrier for binding and consolidation of the protein:ice interaction surface. Thus, the antifreeze protein can bind to the molecularly rough ice surface by becoming actively involved in the formation of its own binding site. Also, the disruption of water structure around the rest of the protein helps prevent the adsorbed protein becoming covered by further ice growth.

Directing the structures of silver-antimony sulphides: a new topological variant of the [Ag5Sb3S8](2-) double layer

A new silver-antimony sulphide, [C6H20N4][Ag5Sb3S8], has been synthesised solvothermally in the presence of triethylenetetramine and characterised by single-crystal X-ray diffraction, thermogravimetry and elemental analysis. The compound crystallises in the space group P2(1)/m (a = 6.2778(7), b = 15.8175(16) and c = 12.4617(15) angstrom and beta = 104.561(5)degrees) and adopts a structure in which honeycomb-like sheets of fused six-membered silver-antimony-sulphide rings are linked through Ag-S bonds to form double layers. The idealised structure can be considered to be derived from that of antifluorite and represents a second structure type for the [Ag5Sb3S8](2-) double layer. (c) 2005 Elsevier Inc. All rights reserved.

A stable pure hydroxyl layer on Pt{110}-(1x2)

The adsorption of water and coadsorption with oxygen on the missing-row reconstructed Pt{110}-(1x2) surface was studied by using temperature-programmed desorption (TPD) and X-ray photoelectron spectroscopy. Coadsorbed oxygen below saturation (<0.65 +/- 0.05 ML) leads to the formation of 014, which occupies sites near the ridge Pt atoms, In contrast to the more closely packed Pt{111} Surface, OH appears not to form hydrogen bonds with coadsorbed water molecules and is stable after the desorption of water tip to about 205 K (as determined by TPD). Because OH and atomic oxygen compete for adsorption sites, water dissociation is only observed for oxygen coverages below saturation. In the absence of coadsorbed oxygen, water stays intact at all temperatures and forms a strongly bound layer of 2 ML coverage oil the clean Pt{110}-(1x2) surface at temperatures between 140 and 175 K.