765 resultados para Liquid-equilibria
Resumo:
This study examines criteria for the existence of two stable states of the Atlantic Meridional Overturning Circulation (AMOC) using a combination of theory and simulations from a numerical coupled atmosphere–ocean climate model. By formulating a simple collection of state parameters and their relationships, the authors reconstruct the North Atlantic Deep Water (NADW) OFF state behavior under a varying external salt-flux forcing. This part (Part I) of the paper examines the steady-state solution, which gives insight into the mechanisms that sustain the NADW OFF state in this coupled model; Part II deals with the transient behavior predicted by the evolution equation. The nonlinear behavior of the Antarctic Intermediate Water (AAIW) reverse cell is critical to the OFF state. Higher Atlantic salinity leads both to a reduced AAIW reverse cell and to a greater vertical salinity gradient in the South Atlantic. The former tends to reduce Atlantic salt export to the Southern Ocean, while the latter tends to increases it. These competing effects produce a nonlinear response of Atlantic salinity and salt export to salt forcing, and the existence of maxima in these quantities. Thus the authors obtain a natural and accurate analytical saddle-node condition for the maximal surface salt flux for which a NADW OFF state exists. By contrast, the bistability indicator proposed by De Vries and Weber does not generally work in this model. It is applicable only when the effect of the AAIW reverse cell on the Atlantic salt budget is weak.
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The homologous series of side chain liquid crystal polymers, the poly[x-(4-methoxyazobenzene- 40-oxy)alkyl methacrylate]s, has been prepared in which the length of the flexible alkyl spacer has been varied from 3 to 11 methylene units. All the polymers exhibit liquid crystalline behaviour. The propyl and butyl members show exclusively nematic behaviour. The pentyl, hexyl, octyl and decyl members show a nematic and a smectic A phase while the heptyl, nonyl and undecyl homologues exhibit only a smectic A phase. The smectic A phase has been studied using X-ray diffraction and assigned as a smectic A1 phase in which the side chains are fully overlapped and the backbones are confined to lie between the smectic layers. For the nonyl member an incommensurate smectic phase is observed. The dependence of the transition temperatures on the length of the flexible spacer is understood in terms of the average shapes of the side chains.
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This paper shows the robust non-existence of competitive equilibria even in a simple three period representative agent economy with dynamically inconsistent preferences. We distinguish between a sophisticated and naive representative agent. Even when underlying preferences are monotone and convex, at given prices, we show by example that the induced preference of the sophisticated representative agent over choices in first-period markets is both non-convex and satiated. Even allowing for negative prices, the market-clearing allocation is not contained in the convex hull of demand. Finally, with a naive representative agent, we show that perfect foresight is incompatible with market clearing and individual optimization at given prices.
Resumo:
Liquid clouds play a profound role in the global radiation budget but it is difficult to remotely retrieve their vertical profile. Ordinary narrow field-of-view (FOV) lidars receive a strong return from such clouds but the information is limited to the first few optical depths. Wideangle multiple-FOV lidars can isolate radiation scattered multiple times before returning to the instrument, often penetrating much deeper into the cloud than the singly-scattered signal. These returns potentially contain information on the vertical profile of extinction coefficient, but are challenging to interpret due to the lack of a fast radiative transfer model for simulating them. This paper describes a variational algorithm that incorporates a fast forward model based on the time-dependent two-stream approximation, and its adjoint. Application of the algorithm to simulated data from a hypothetical airborne three-FOV lidar with a maximum footprint width of 600m suggests that this approach should be able to retrieve the extinction structure down to an optical depth of around 6, and total opticaldepth up to at least 35, depending on the maximum lidar FOV. The convergence behavior of Gauss-Newton and quasi-Newton optimization schemes are compared. We then present results from an application of the algorithm to observations of stratocumulus by the 8-FOV airborne “THOR” lidar. It is demonstrated how the averaging kernel can be used to diagnose the effective vertical resolution of the retrieved profile, and therefore the depth to which information on the vertical structure can be recovered. This work enables exploitation of returns from spaceborne lidar and radar subject to multiple scattering more rigorously than previously possible.
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We present a new approach to determine palaeotemperatures (mean annual surface temperatures) based on measurements of the liquid–vapour homogenisation temperature of fluid inclusions in stalagmites. The aim of this study is to explore the potential and the limitations of this new palaeothermometer and to develop a reliable methodology for routine applications in palaeoclimate research. Therefore, we have investigated recent fluid inclusions from the top part of actively growing stalagmites that have formed at temperatures close to the present-day cave air temperature. A precondition for measuring homogenisation temperatures of originally monophase inclusions is the nucleation of a vapour bubble by means of single ultra-short laser pulses. Based on the observed homogenisation temperatures (Th(obs)) and measurements of the vapour bubble diameter at a known temperature, we calculated stalagmite formation temperatures (Tf) by applying a thermodynamic model that takes into account the effect of surface tension on liquid–vapour homogenisation. Results from recent stalagmite samples demonstrate that calculated stalagmite formation temperatures match the present-day cave air temperature within ± 0.2 °C. To avoid artificially induced changes of the fluid density we defined specific demands on the selection, handling and preparation of the stalagmite samples. Application of the method is restricted to stalagmites that formed at cave temperatures greater than ~ 9–11 °C.
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Denaturing high-performance liquid chromatography (DHPLC) was evaluated as a rapid screening and identification method for DNA sequence variation detection in the quinolone resistance-determining region of gyrA from Salmonella serovars. A total of 203 isolates of Salmonella were screened using this method. DHPLC analysis of 14 isolates representing each type of novel or multiple mutations and the wild type were compared with LightCycler-based PCR-gyrA hybridization mutation assay (GAMA) and single-strand conformational polymorphism (SSCP) analyses. The 14 isolates gave seven different SSCP patterns, and LightCycler detected four different mutations. DHPLC detected 11 DNA sequence variants at eight different codons, including those detected by LightCycler or SSCP. One of these mutations was silent. Five isolates contained multiple mutations, and four of these could be distinguished from the composite sequence variants by their DHPLC profile. Seven novel mutations were identified at five different loci not previously described in quinolone-resistant salmonella. DHPLC analysis proved advantageous for the detection of novel and multiple mutations. DHPLC also provides a rapid, high-throughput alternative to LightCycler and SSCP for screening frequently occurring mutations.
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Aims: Quinolone antibiotics are the agents of choice for treating systemic Salmonella infections. Resistance to quinolones is usually mediated by mutations in the DNA gyrase gene gyrA. Here we report the evaluation of standard HPLC equipment for the detection of mutations (single nucleotide polymorphisms; SNPs) in gyrA, gyrB, parC and parE by denaturing high performance liquid chromatography (DHPLC). Methods: A panel of Salmonella strains was assembled which comprised those with known different mutations in gyrA (n = 8) and fluoroquinolone-susceptible and -resistant strains (n = 50) that had not been tested for mutations in gyrA. Additionally, antibiotic-susceptible strains of serotypes other than Salmonella enterica serovar Typhimurium strains were examined for serotype-specific mutations in gyrB (n = 4), parC (n = 6) and parE (n = 1). Wild-type (WT) control DNA was prepared from Salmonella Typhimurium NCTC 74. The DNA of respective strains was amplified by PCR using Optimase (R) proofreading DNA polymerase. Duplex DNA samples were analysed using an Agilent A1100 HPLC system with a Varian Helix (TM) DNA column. Sequencing was used to validate mutations detected by DHPLC in the strains with unknown mutations. Results: Using this HPLC system, mutations in gyrA, gyrB, parC and parE were readily detected by comparison with control chromatograms. Sequencing confirmed the gyrA predicted mutations as detected by DHPLC in the unknown strains and also confirmed serotype-associated sequence changes in non-Typhimurium serotypes. Conclusions: The results demonstrated that a non-specialist standard HPLC machine fitted with a generally available column can be used to detect SNPs in gyrA, gyrB, parC and parE genes by DHPLC. Wider applications should be possible.
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The ground-based Atmospheric Radiation Measurement Program (ARM) and NASA Aerosol Robotic Net- work (AERONET) routinely monitor clouds using zenith ra- diances at visible and near-infrared wavelengths. Using the transmittance calculated from such measurements, we have developed a new retrieval method for cloud effective droplet size and conducted extensive tests for non-precipitating liquid water clouds. The underlying principle is to combine a liquid-water-absorbing wavelength (i.e., 1640 nm) with a non-water-absorbing wavelength for acquiring information on cloud droplet size and optical depth. For simulated stratocumulus clouds with liquid water path less than 300 g m−2 and horizontal resolution of 201 m, the retrieval method underestimates the mean effective radius by 0.8μm, with a root-mean-squared error of 1.7 μm and a relative deviation of 13%. For actual observations with a liquid water path less than 450 g m−2 at the ARM Oklahoma site during 2007– 2008, our 1.5-min-averaged retrievals are generally larger by around 1 μm than those from combined ground-based cloud radar and microwave radiometer at a 5-min temporal resolution. We also compared our retrievals to those from combined shortwave flux and microwave observations for relatively homogeneous clouds, showing that the bias between these two retrieval sets is negligible, but the error of 2.6 μm and the relative deviation of 22 % are larger than those found in our simulation case. Finally, the transmittance-based cloud effective droplet radii agree to better than 11 % with satellite observations and have a negative bias of 1 μm. Overall, the retrieval method provides reasonable cloud effective radius estimates, which can enhance the cloud products of both ARM and AERONET.
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In biological mass spectrometry (MS), two ionization techniques are predominantly employed for the analysis of larger biomolecules, such as polypeptides. These are nano-electrospray ionization [1, 2] (nanoESI) and matrix-assisted laser desorption/ionization [3, 4] (MALDI). Both techniques are considered to be “soft”, allowing the desorption and ionization of intact molecular analyte species and thus their successful mass-spectrometric analysis. One of the main differences between these two ionization techniques lies in their ability to produce multiply charged ions. MALDI typically generates singly charged peptide ions whereas nanoESI easily provides multiply charged ions, even for peptides as low as 1000 Da in mass. The production of highly charged ions is desirable as this allows the use of mass analyzers, such as ion traps (including orbitraps) and hybrid quadrupole instruments, which typically offer only a limited m/z range (< 2000–4000). It also enables more informative fragmentation spectra using techniques such as collisioninduced dissociation (CID) and electron capture/transfer dissociation (ECD/ETD) in combination with tandem MS (MS/MS). [5, 6] Thus, there is a clear advantage of using ESI in research areas where peptide sequencing, or in general, the structural elucidation of biomolecules by MS/MS is required. Nonetheless, MALDI with its higher tolerance to contaminants and additives, ease-of-operation, potential for highspeed and automated sample preparation and analysis as well as its MS imaging capabilities makes it an ionization technique that can cover bioanalytical areas for which ESI is less suitable. [7, 8] If these strengths could be combined with the analytical power of multiply charged ions, new instrumental configurations and large-scale proteomic analyses based on MALDI MS(/MS) would become feasible.
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X-ray Rheology is an experimental technique which uses time-ressolved x-ray scattering as probe of the molecular level structural reorganisation which accompanies flow. It provides quantitative information on the direction alignment and on the level of global orientation. This information is very helpful in interpreting the classic rheological data on liquid crystal polymers. In this research we use data obtained from a cellulose derivate which exhibits a thermotropic liquid crystal phase. We show how increased shear rates lead to a rapid rise in the global orientation and we related this to therories of flow in liquid crystal polymers from the literature. We show that the relaxation time is independent of the prior shear rate.
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Multiple equilibria in a coupled ocean–atmosphere–sea ice general circulation model (GCM) of an aquaplanet with many degrees of freedom are studied. Three different stable states are found for exactly the same set of parameters and external forcings: a cold state in which a polar sea ice cap extends into the midlatitudes; a warm state, which is ice free; and a completely sea ice–covered “snowball” state. Although low-order energy balance models of the climate are known to exhibit intransitivity (i.e., more than one climate state for a given set of governing equations), the results reported here are the first to demonstrate that this is a property of a complex coupled climate model with a consistent set of equations representing the 3D dynamics of the ocean and atmosphere. The coupled model notably includes atmospheric synoptic systems, large-scale circulation of the ocean, a fully active hydrological cycle, sea ice, and a seasonal cycle. There are no flux adjustments, with the system being solely forced by incoming solar radiation at the top of the atmosphere. It is demonstrated that the multiple equilibria owe their existence to the presence of meridional structure in ocean heat transport: namely, a large heat transport out of the tropics and a relatively weak high-latitude transport. The associated large midlatitude convergence of ocean heat transport leads to a preferred latitude at which the sea ice edge can rest. The mechanism operates in two very different ocean circulation regimes, suggesting that the stabilization of the large ice cap could be a robust feature of the climate system. Finally, the role of ocean heat convergence in permitting multiple equilibria is further explored in simpler models: an atmospheric GCM coupled to a slab mixed layer ocean and an energy balance model
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We study the degree to which Kraichnan–Leith–Batchelor (KLB) phenomenology describes two-dimensional energy cascades in α turbulence, governed by ∂θ/∂t+J(ψ,θ)=ν∇2θ+f, where θ=(−Δ)α/2ψ is generalized vorticity, and ψ^(k)=k−αθ^(k) in Fourier space. These models differ in spectral non-locality, and include surface quasigeostrophic flow (α=1), regular two-dimensional flow (α=2) and rotating shallow flow (α=3), which is the isotropic limit of a mantle convection model. We re-examine arguments for dual inverse energy and direct enstrophy cascades, including Fjørtoft analysis, which we extend to general α, and point out their limitations. Using an α-dependent eddy-damped quasinormal Markovian (EDQNM) closure, we seek self-similar inertial range solutions and study their characteristics. Our present focus is not on coherent structures, which the EDQNM filters out, but on any self-similar and approximately Gaussian turbulent component that may exist in the flow and be described by KLB phenomenology. For this, the EDQNM is an appropriate tool. Non-local triads contribute increasingly to the energy flux as α increases. More importantly, the energy cascade is downscale in the self-similar inertial range for 2.5<α<10. At α=2.5 and α=10, the KLB spectra correspond, respectively, to enstrophy and energy equipartition, and the triad energy transfers and flux vanish identically. Eddy turnover time and strain rate arguments suggest the inverse energy cascade should obey KLB phenomenology and be self-similar for α<4. However, downscale energy flux in the EDQNM self-similar inertial range for α>2.5 leads us to predict that any inverse cascade for α≥2.5 will not exhibit KLB phenomenology, and specifically the KLB energy spectrum. Numerical simulations confirm this: the inverse cascade energy spectrum for α≥2.5 is significantly steeper than the KLB prediction, while for α<2.5 we obtain the KLB spectrum.
Resumo:
Electrospinning was used to generate polymer nanofibres from blends of poly-vinyl cinnamate (PVCN) and a cholesteric silicone polymer. Only blends that contained at least 40 % of PVCN produced fibres. Both differential scanning calorimetry and electron dispersion spectroscopy data indicate that the samples are miscible over a wide temperature interval. The variation of fibre diameter with concentration is nonlinear with a well-defined minimum corresponding to an 80 % PVCN blend. The fibres are birefringent with Kerr constants similar to that of cholesteric liquid crystals. Although not significant, the Kerr constant increases with increasing silicone polymer concentration.
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This paper is to present a model of spatial equilibrium using a nonlinear generalization of Markov-chain type model, and to show the dynamic stability of a unique equilibrium. Even at an equilibrium, people continue to migrate among regions as well as among agent-types, and yet their overall distribution remain unchanged. The model is also adapted to suggest a theory of traffic distribution in a city.