The vibrational spectrum and ultimate modulus of polyethylene

We have performed the first completely ab initio lattice dynamics calculation of the full orthorhombic cell of polyethylene using periodic density functional theory in the local density approximation (LDA) and the generalized gradient approximation (GGA). Contrary to current perceptions, we show that LDA accurately describes the structure whereas GGA fails. We emphasize that there is no parametrization of the results. We then rigorously tested our calculation by computing the phonon dispersion curves across the entire Brillouin zone and comparing them to the vibrational spectra, in particular the inelastic neutron scattering (INS) spectra, of polyethylene (both polycrystalline and aligned) and perdeuteriopolyethylene. The F-point frequencies (where the infrared and Raman active modes occur) are in good agreement with the latest low temperature data. The near-perfect reproduction of the INS spectra, gives confidence in the results and allows Lis to deduce a number of physical properties including the elastic moduli, parallel and perpendicular to the chain. We find that the Young's modulus for an infinitely long, perfectly crystalline polyethylene is 360.2 GPa at 0 K. The highest experimental value is 324 GPa, indicating that current high modulus fibers are similar to 90% of their maximum possible strength.

The significance of volcanic eruption strength and frequency for climate

A simple physical model of the atmospheric effects of large explosive volcanic eruptions is developed. Using only one input parameter - the initial amount of sulphur dioxide injected into the stratosphere - the global-average stratospheric optical-depth perturbation and surface temperature response are modelled. The simplicity of this model avoids issues of incomplete data (applicable to more comprehensive models), making it a powerful and useful tool for atmospheric diagnostics of this climate forcing mechanism. It may also provide a computationally inexpensive and accurate way of introducing volcanic activity into larger climate models. The modelled surface temperature response for an initial sulphur-dioxide injection, coupled with emission-history statistics, is used to demonstrate that the most climatically significant volcanic eruptions are those of sufficient explosivity to just reach into the stratosphere (and achieve longevity). This study also highlights the fact that this measure of significance is highly sensitive to the representation of the climatic response and the frequency data used, and that we are far from producing a definitive history of explosive volcanism for at least the past 1000 years. Given this high degree of uncertainty, these results suggest that eruptions that release around and above 0.1 Mt SO2 into the stratosphere have the maximum climatic impact.

Hydrogelation and self-assembly of Fmoc-tripeptides: unexpected influence of sequence on self-assembled fibril structure, and hydrogel modulus and anisotropy

The self-assembly and hydrogelation properties of two Fmoc-tripeptides [Fmoc = N-(fluorenyl-9-methoxycarbonyl)] are investigated, in borate buffer and other basic solutions. A remarkable difference in self-assembly properties is observed comparing Fmoc-VLK(Boc) with Fmoc-K(Boc)LV, both containing K protected by N(epsilon)-tert-butyloxycarbonate (Boc). In borate buffer, the former peptide forms highly anisotropic fibrils which show local alignment, and the hydrogels show flow-aligning properties. In contrast, Fmoc-K(Boc)LV forms highly branched fibrils that produce isotropic hydrogels with a much higher modulus (G' > 10(4) Pa), and lower concentration for hydrogel formation. The distinct self-assembled structures are ascribed to conformational differences, as revealed by secondary structure probes (CD, FTIR, Raman spectroscopy) and X-ray diffraction. Fmoc-VLK(Boc) forms well-defined beta-sheets with a cross-beta X-ray diffraction pattern, whereas Fmoc-KLV(Boc) forms unoriented assemblies with multiple stacked sheets. Interchange of the K and V residues when inverting the tripeptide sequence thus leads to substantial differences in self-assembled structures, suggesting a promising approach to control hydrogel properties.

The effects of explicit versus parameterized convection on the MJO in a large-domain high-resolution tropical case study. Part I: Characterization of large-scale organization and propagation

High-resolution simulations over a large tropical domain (∼20◦S–20◦N and 42◦E–180◦E) using both explicit and parameterized convection are analyzed and compared to observations during a 10-day case study of an active Madden-Julian Oscillation (MJO) event. The parameterized convection model simulations at both 40 km and 12 km grid spacing have a very weak MJO signal and little eastward propagation. A 4 km explicit convection simulation using Smagorinsky subgrid mixing in the vertical and horizontal dimensions exhibits the best MJO strength and propagation speed. 12 km explicit convection simulations also perform much better than the 12 km parameterized convection run, suggesting that the convection scheme, rather than horizontal resolution, is key for these MJO simulations. Interestingly, a 4 km explicit convection simulation using the conventional boundary layer scheme for vertical subgrid mixing (but still using Smagorinsky horizontal mixing) completely loses the large-scale MJO organization, showing that relatively high resolution with explicit convection does not guarantee a good MJO simulation. Models with a good MJO representation have a more realistic relationship between lower-free-tropospheric moisture and precipitation, supporting the idea that moisture-convection feedback is a key process for MJO propagation. There is also increased generation of available potential energy and conversion of that energy into kinetic energy in models with a more realistic MJO, which is related to larger zonal variance in convective heating and vertical velocity, larger zonal temperature variance around 200 hPa, and larger correlations between temperature and ascent (and between temperature and diabatic heating) between 500–400 hPa.

The effects of explicit versus parameterized convection on the MJO in a large-domain high-resolution tropical case study. Part II: Processes leading to differences in MJO development

High-resolution simulations over a large tropical domain (∼20◦S–20◦N and 42◦E–180◦E) using both explicit and parameterized convection are analyzed and compared during a 10-day case study of an active Madden-Julian Oscillation (MJO) event. In Part II, the moisture budgets and moist entropy budgets are analyzed. Vertical subgrid diabatic heating profiles and vertical velocity profiles are also compared; these are related to the horizontal and vertical advective components of the moist entropy budget which contribute to gross moist stability, GMS, and normalized GMS (NGMS). The 4-km model with explicit convection and good MJO performance has a vertical heating structure that increases with height in the lower troposphere in regions of strong convection (like observations), whereas the 12-km model with parameterized convection and a poor MJO does not show this relationship. The 4-km explicit convection model also has a more top-heavy heating profile for the troposphere as a whole near and to the west of the active MJO-related convection, unlike the 12-km parameterized convection model. The dependence of entropy advection components on moisture convergence is fairly weak in all models, and differences between models are not always related to MJO performance, making comparisons to previous work somewhat inconclusive. However, models with relatively good MJO strength and propagation have a slightly larger increase of the vertical advective component with increasing moisture convergence, and their NGMS vertical terms have more variability in time and longitude, with total NGMS that is comparatively larger to the west and smaller to the east.

Modelling European winter wind storm losses in current and future climate

Severe wind storms are one of the major natural hazards in the extratropics and inflict substantial economic damages and even casualties. Insured storm-related losses depend on (i) the frequency, nature and dynamics of storms, (ii) the vulnerability of the values at risk, (iii) the geographical distribution of these values, and (iv) the particular conditions of the risk transfer. It is thus of great importance to assess the impact of climate change on future storm losses. To this end, the current study employs—to our knowledge for the first time—a coupled approach, using output from high-resolution regional climate model scenarios for the European sector to drive an operational insurance loss model. An ensemble of coupled climate-damage scenarios is used to provide an estimate of the inherent uncertainties. Output of two state-of-the-art global climate models (HadAM3, ECHAM5) is used for present (1961–1990) and future climates (2071–2100, SRES A2 scenario). These serve as boundary data for two nested regional climate models with a sophisticated gust parametrizations (CLM, CHRM). For validation and calibration purposes, an additional simulation is undertaken with the CHRM driven by the ERA40 reanalysis. The operational insurance model (Swiss Re) uses a European-wide damage function, an average vulnerability curve for all risk types, and contains the actual value distribution of a complete European market portfolio. The coupling between climate and damage models is based on daily maxima of 10 m gust winds, and the strategy adopted consists of three main steps: (i) development and application of a pragmatic selection criterion to retrieve significant storm events, (ii) generation of a probabilistic event set using a Monte-Carlo approach in the hazard module of the insurance model, and (iii) calibration of the simulated annual expected losses with a historic loss data base. The climate models considered agree regarding an increase in the intensity of extreme storms in a band across central Europe (stretching from southern UK and northern France to Denmark, northern Germany into eastern Europe). This effect increases with event strength, and rare storms show the largest climate change sensitivity, but are also beset with the largest uncertainties. Wind gusts decrease over northern Scandinavia and Southern Europe. Highest intra-ensemble variability is simulated for Ireland, the UK, the Mediterranean, and parts of Eastern Europe. The resulting changes on European-wide losses over the 110-year period are positive for all layers and all model runs considered and amount to 44% (annual expected loss), 23% (10 years loss), 50% (30 years loss), and 104% (100 years loss). There is a disproportionate increase in losses for rare high-impact events. The changes result from increases in both severity and frequency of wind gusts. Considerable geographical variability of the expected losses exists, with Denmark and Germany experiencing the largest loss increases (116% and 114%, respectively). All countries considered except for Ireland (−22%) experience some loss increases. Some ramifications of these results for the socio-economic sector are discussed, and future avenues for research are highlighted. The technique introduced in this study and its application to realistic market portfolios offer exciting prospects for future research on the impact of climate change that is relevant for policy makers, scientists and economists.

Trends in aerosol optical depth in the Russian Arctic and their links with synoptic climatology

Temporal and spatial variability of aerosol optical depth (AOD) are examined using observations of direct solar radiation in the Eurasian Arctic for 1940-1990. AOD is estimated using empirical methods for 14 stations located between 66.2 degrees N and 80.6 degrees N, from the Kara Sea to the Chukchi Sea. While AOD exhibits a well-known springtime maximum and summertime minimum at all stations, atmospheric turbidity is higher in spring in the western (Kara-Laptev) part of the Eurasian Arctic. Between June and August, the eastern (East Siberian-Chukchi) sector experiences higher transparency than the western part. A statistically significant positive trend in AOD was observed in the Kara-Laptev sector between the late 1950s and the early 1930s predominantly in spring when pollution-derived aerosol dominates the Arctic atmosphere but not in the eastern sector. Although all stations are remote, those with positive trends are located closer to the anthropogenic sources of air pollution. By contrast, a widespread decline in AOD was observed between 1982 and 1990 in the eastern Arctic in spring but was limited to two sites in the western Arctic. These results suggest that the post-1982 decline in anthropogenic emissions in Europe and the former Soviet Union has had a limited effect on aerosol load in the Arctic. The post-1982 negative trends in AOD in summer, when marine aerosol is present in the atmosphere, were more common in the west. The relationships between AOD and atmospheric circulation are examined using a synoptic climatology approach. In spring, AOD depends primarily on the strength and direction of air flow. Thus strong westerly and northerly flows result in low AOD values in the East Siberian-Chukchi sector. By contrast, strong southerly flow associated with the passage of depressions results in high A OD in the Kara-Laptev sector and trajectory analysis points to the contribution of industrial regions of the sub-Arctic. In summer, low pressure gradient or anticyclonic conditions result in high atmospheric turbidity. The frequency of this weather type has declined significantly since the early 1980s in the Kara-Laptev sector, which partly explains the decline in summer AOD values. (c) 2004 Elsevier B.V. All rights reserved.

PRISM and ENES: a European approach to Earth system modelling

Europe's widely distributed climate modelling expertise, now organized in the European Network for Earth System Modelling (ENES), is both a strength and a challenge. Recognizing this, the European Union's Program for Integrated Earth System Modelling (PRISM) infrastructure project aims at designing a flexible and friendly user environment to assemble, run and post-process Earth System models. PRISM was started in December 2001 with a duration of three years. This paper presents the major stages of PRISM, including: (1) the definition and promotion of scientific and technical standards to increase component modularity; (2) the development of an end-to-end software environment (graphical user interface, coupling and I/O system, diagnostics, visualization) to launch, monitor and analyse complex Earth system models built around state-of-art community component models (atmosphere, ocean, atmospheric chemistry, ocean bio-chemistry, sea-ice, land-surface); and (3) testing and quality standards to ensure high-performance computing performance on a variety of platforms. PRISM is emerging as a core strategic software infrastructure for building the European research area in Earth system sciences. Copyright (c) 2005 John Wiley & Sons, Ltd.

Effect of ethanol on the micellization and gelation of Pluronic P123

In certain applications copolymer P123 (E21P67E21) is dissolved in water-ethanol mixtures, initially to form micellar solutions and eventually to gel. For P123 in 10, 20, and 30 wt % aqueous ethanol we used dynamic light scattering from dilute solutions to confirm micellization, oscillatory rheometry, and visual observation of mobility (tube inversion) to determine gel formation in concentrated solutions and small-angle X-ray scattering (SAXS) to determine gel structure. Except for solutions in 30 wt % aqueous ethanol, a clear-turbid transition was encountered on heating dilute and concentrated micellar solutions alike, and as for solutions in water alone (Chaibundit et al. Langmuir 2007, 23, 9229) this could be ascribed to formation of wormlike micelles. Dense clouding, typical of phase separation, was observed at higher temperatures. Regions of isotropic and birefringent gel were defined for concentrated solutions and shown (by SAXS) to have Cubic (fcc and hcp) and hexagonal structures, consistent with packed spherical and elongated micelles, respectively. The cubic gels (0, 10, and 20 wt % ethanol) were clear, while the hex gels were either turbid (0 and 10 wt % ethanol), turbid enclosing a clear region (20 wt % ethanol), or entirely clear (30 wt % ethanol). The SAXS profile was unchanged between turbid and clear regions of the 20 wt % ethanol gel. Temperature scans of dynamic moduli showed (as expected) a clear distinction between high-modulus cubic gels (G'(max) approximate to 20-30 kPa) and lower modulus hex gels (G'(max) < 10 kPa).

Structure, rheology and shear alignment of Pluronic block copolymer mixtures

The structure and flow behaviour of binary mixtures of Pluronic block copolymers P85 and P123 is investigated by small-angle scattering, rheometry and mobility tests. Micelle dimensions are probed by dynamic light scattering. The micelle hydrodynamic radius for the 50/50 mixture is larger than that for either P85 or P123 alone, Clue to the formation of mixed micelles with a higher association number. The phase diagram for 50/50 mixtures contains regions Of Cubic and hexagonal phases similar to those for the parent homopolymers, however the region of stability of the cubic phase is enhanced at low temperature and concentrations above 40 wt%. This is ascribed to favourable packing of the mixed micelles containing core blocks with two different chain lengths, but similar corona chain lengths. The shear flow alignment of face-centred cubic and hexagonal phases is probed by in situ small-angle X-ray or neutron scattering with simultaneous rheology. The hexagonal phase can be aligned using steady shear in a Couette geometry, however the high modulus Cubic phase cannot be aligned well in this way. This requires the application of oscillatory shear or compression. (C) 2008 Elsevier Inc. All rights reserved.

Comparison of white metal and resin socket terminations for wire ropes

Previously the authors have presented both theoretical and experimental work discussing the operating mechanism of a wire rope held in a tapered socket by means of a cast resin cone. The work reported here extends the investigation to address the question of whether the same socket fabricated with white metal operates in the same manner. To date, previous investigations have compared the operational efficiency of resin and white metal in terms of both strength and/or fatigue endurance. Some other work has analysed the operation of resin sockets or specific cast metal terminations. This paper seeks to draw the results from this work together, and, in addition to a theoretical analysis, presents experimental data obtained from a direct comparison of the operation mechanism for the same sockets filled with resin or white metal. Results show that white metal terminations have a very different distribution of stresses along the length of the socket basket from resin terminations, and a smaller but still significant amount of socket draw. For both types of termination the socket draw develops high frictional gripping forces which can transfer the load from the rope to the socket. The different stress distributions mean that the consequences of termination fabrication defects may not be the same for resin and white metal terminations.

Recovery of lactoferrin and lactoperoxidase from sweet whey using colloidal gas aphrons (CGAs) generated from an anionic surfactant, AOT

The recovery of lactoferrin and lactoperoxidase from sweet whey was studied using colloidal gas aphrons (CGAs), which are surfactant-stabilized microbubbles (10-100 mum). CGAs are generated by intense stirring (8000 rpm for 10 min) of the anionic surfactant AOT (sodium bis-2-ethylhexyl sulfosuccinate). A volume of CGAs (10-30 mL) is mixed with a given volume of whey (1 - 10 mL), and the mixture is allowed to separate into two phases: the aphron (top) phase and the liquid (bottom) phase. Each of the phases is analyzed by SDS-PAGE and surfactant colorimetric assay. A statistical experimental design has been developed to assess the effect of different process parameters including pH, ionic strength, the concentration of surfactant in the CGAs generating solution, the volume of CGAs and the volume of whey on separation efficiency. As expected pH, ionic strength and the volume of whey (i.e. the amount of total protein in the starting material) are the main factors influencing the partitioning of the Lf(.)Lp fraction into the aphron phase. Moreover, it has been demonstrated that best separation performance was achieved at pH = 4 and ionic strength = 0.1 mol/L i.e., with conditions favoring electrostatic interactions between target proteins and CGAs (recovery was 90% and the concentration of lactoferrin and lactoperoxidase in the aphron phase was 25 times higher than that in the liquid phase), whereas conditions favoring hydrophobic interactions (pH close to pI and high ionic strength) led to lower performance. However, under these conditions, as confirmed by zeta potential measurements, the adsorption of both target proteins and contaminant proteins is favored. Thus, low selectivity is achieved at all of the studied conditions. These results confirm the initial hypothesis that CGAs act as ion exchangers and that the selectivity of the process can be manipulated by changing main operating parameters such as type of surfactant, pH and ionic strength.

Quantitative genetic divergence and standing genetic (co)variance in thermal reaction norms along latitude

Although the potential to adapt to warmer climate is constrained by genetic trade-offs, our understanding of how selection and mutation shape genetic (co)variances in thermal reaction norms is poor. Using 71 isofemale lines of the fly Sepsis punctum, originating from northern, central, and southern European climates, we tested for divergence in juvenile development rate across latitude at five experimental temperatures. To investigate effects of evolutionary history in different climates on standing genetic variation in reaction norms, we further compared genetic (co)variances between regions. Flies were reared on either high or low food resources to explore the role of energy acquisition in determining genetic trade-offs between different temperatures. Although the latter had only weak effects on the strength and sign of genetic correlations, genetic architecture differed significantly between climatic regions, implying that evolution of reaction norms proceeds via different trajectories at high latitude versus low latitude in this system. Accordingly, regional genetic architecture was correlated to region-specific differentiation. Moreover, hot development temperatures were associated with low genetic variance and stronger genetic correlations compared to cooler temperatures. We discuss the evolutionary potential of thermal reaction norms in light of their underlying genetic architectures, evolutionary histories, and the materialization of trade-offs in natural environments.

The AeroCom evaluation and intercomparison of organic aerosol in global models

This paper evaluates the current status of global modeling of the organic aerosol (OA) in the troposphere and analyzes the differences between models as well as between models and observations. Thirty-one global chemistry transport models (CTMs) and general circulation models (GCMs) have participated in this intercomparison, in the framework of AeroCom phase II. The simulation of OA varies greatly between models in terms of the magnitude of primary emissions, secondary OA (SOA) formation, the number of OA species used (2 to 62), the complexity of OA parameterizations (gas-particle partitioning, chemical aging, multiphase chemistry, aerosol microphysics), and the OA physical, chemical and optical properties. The diversity of the global OA simulation results has increased since earlier AeroCom experiments, mainly due to the increasing complexity of the SOA parameterization in models, and the implementation of new, highly uncertain, OA sources. Diversity of over one order of magnitude exists in the modeled vertical distribution of OA concentrations that deserves a dedicated future study. Furthermore, although the OA / OC ratio depends on OA sources and atmospheric processing, and is important for model evaluation against OA and OC observations, it is resolved only by a few global models. The median global primary OA (POA) source strength is 56 Tg a−1 (range 34–144 Tg a−1) and the median SOA source strength (natural and anthropogenic) is 19 Tg a−1 (range 13–121 Tg a−1). Among the models that take into account the semi-volatile SOA nature, the median source is calculated to be 51 Tg a−1 (range 16–121 Tg a−1), much larger than the median value of the models that calculate SOA in a more simplistic way (19 Tg a−1; range 13–20 Tg a−1, with one model at 37 Tg a−1). The median atmospheric burden of OA is 1.4 Tg (24 models in the range of 0.6–2.0 Tg and 4 between 2.0 and 3.8 Tg), with a median OA lifetime of 5.4 days (range 3.8–9.6 days). In models that reported both OA and sulfate burdens, the median value of the OA/sulfate burden ratio is calculated to be 0.77; 13 models calculate a ratio lower than 1, and 9 models higher than 1. For 26 models that reported OA deposition fluxes, the median wet removal is 70 Tg a−1 (range 28–209 Tg a−1), which is on average 85% of the total OA deposition. Fine aerosol organic carbon (OC) and OA observations from continuous monitoring networks and individual field campaigns have been used for model evaluation. At urban locations, the model–observation comparison indicates missing knowledge on anthropogenic OA sources, both strength and seasonality. The combined model–measurements analysis suggests the existence of increased OA levels during summer due to biogenic SOA formation over large areas of the USA that can be of the same order of magnitude as the POA, even at urban locations, and contribute to the measured urban seasonal pattern. Global models are able to simulate the high secondary character of OA observed in the atmosphere as a result of SOA formation and POA aging, although the amount of OA present in the atmosphere remains largely underestimated, with a mean normalized bias (MNB) equal to −0.62 (−0.51) based on the comparison against OC (OA) urban data of all models at the surface, −0.15 (+0.51) when compared with remote measurements, and −0.30 for marine locations with OC data. The mean temporal correlations across all stations are low when compared with OC (OA) measurements: 0.47 (0.52) for urban stations, 0.39 (0.37) for remote stations, and 0.25 for marine stations with OC data. The combination of high (negative) MNB and higher correlation at urban stations when compared with the low MNB and lower correlation at remote sites suggests that knowledge about the processes that govern aerosol processing, transport and removal, on top of their sources, is important at the remote stations. There is no clear change in model skill with increasing model complexity with regard to OC or OA mass concentration. However, the complexity is needed in models in order to distinguish between anthropogenic and natural OA as needed for climate mitigation, and to calculate the impact of OA on climate accurately.