A simple analysis of thermodynamic properties for classical plasmas: I. theory

By eliminating the short range negative divergence of the Debye–Hückel pair distribution function, but retaining the exponential charge screening known to operate at large interparticle separation, the thermodynamic properties of one-component plasmas of point ions or charged hard spheres can be well represented even in the strong coupling regime. Predicted electrostatic free energies agree within 5% of simulation data for typical Coulomb interactions up to a factor of 10 times the average kinetic energy. Here, this idea is extended to the general case of a uniform ionic mixture, comprising an arbitrary number of components, embedded in a rigid neutralizing background. The new theory is implemented in two ways: (i) by an unambiguous iterative algorithm that requires numerical methods and breaks the symmetry of cross correlation functions; and (ii) by invoking generalized matrix inverses that maintain symmetry and yield completely analytic solutions, but which are not uniquely determined. The extreme computational simplicity of the theory is attractive when considering applications to complex inhomogeneous fluids of charged particles.

New results on the thermodynamical properties of the climate system

In this paper the authors exploit two equivalent formulations of the average rate of material entropy production in the climate system to propose an approximate splitting between contributions due to vertical and eminently horizontal processes. This approach is based only on 2D radiative fields at the surface and at the top of atmosphere. Using 2D fields at the top of atmosphere alone, lower bounds to the rate of material entropy production and to the intensity of the Lorenz energy cycle are derived. By introducing a measure of the efficiency of the planetary system with respect to horizontal thermodynamic processes, it is possible to gain insight into a previous intuition on the possibility of defining a baroclinic heat engine extracting work from the meridional heat flux. The approximate formula of the material entropy production is verified and used for studying the global thermodynamic properties of climate models (CMs) included in the Program for Climate Model Diagnosis and Intercomparison (PCMDI)/phase 3 of the Coupled Model Intercomparison Project (CMIP3) dataset in preindustrial climate conditions. It is found that about 90% of the material entropy production is due to vertical processes such as convection, whereas the large-scale meridional heat transport contributes to only about 10% of the total. This suggests that the traditional two-box models used for providing a minimal representation of entropy production in planetary systems are not appropriate, whereas a basic—but conceptually correct—description can be framed in terms of a four-box model. The total material entropy production is typically 55 mW m−2 K−1, with discrepancies on the order of 5%, and CMs’ baroclinic efficiencies are clustered around 0.055. The lower bounds on the intensity of the Lorenz energy cycle featured by CMs are found to be around 1.0–1.5 W m−2, which implies that the derived inequality is rather stringent. When looking at the variability and covariability of the considered thermodynamic quantities, the agreement among CMs is worse, suggesting that the description of feedbacks is more uncertain. The contributions to material entropy production from vertical and horizontal processes are positively correlated, so that no compensation mechanism seems in place. Quite consistently among CMs, the variability of the efficiency of the system is a better proxy for variability of the entropy production due to horizontal processes than that of the large-scale heat flux. The possibility of providing constraints on the 3D dynamics of the fluid envelope based only on 2D observations of radiative fluxes seems promising for the observational study of planets and for testing numerical models.

Statistical properties of cloud lifecycles in cloud-resolving models

A new technique is described for the analysis of cloud-resolving model simulations, which allows one to investigate the statistics of the lifecycles of cumulus clouds. Clouds are tracked from timestep-to-timestep within the model run. This allows for a very simple method of tracking, but one which is both comprehensive and robust. An approach for handling cloud splits and mergers is described which allows clouds with simple and complicated time histories to be compared within a single framework. This is found to be important for the analysis of an idealized simulation of radiative-convective equilibrium, in which the moist, buoyant, updrafts (i.e., the convective cores) were tracked. Around half of all such cores were subject to splits and mergers during their lifecycles. For cores without any such events, the average lifetime is 30min, but events can lengthen the typical lifetime considerably.

Micellar and surface properties of a poly(methyl methacrylate)-block-poly(N-isopropylacrylamide) copolymer in aqueous solution

Critical micelle concentrations (cmc) of aqueous solutions of poly(methyl methacrylate)-block-poly(N-isopropylacrylamide) were determined at several temperatures by surface tensiometry. Below the lower critical solution temperature (LCST), the low Delta(mic) H-0 determined can be assigned to the PMMA block being tightly coiled in the dispersed molecular state, so that the unfavorable interactions of hydrophobic entities with water are minimized. Above the LCST the cmc value was found to increase; an anomalous behavior that can be directly related to the micelle-globule transition of the hydrophilic block. Interestingly, above the LCST the surface tension of relatively concentrated solutions was found to depend weakly on temperature not following the usual strong decrease with temperature expected for aqueous solutions. (C) 2007 Elsevier Inc. All rights reserved.

Use of the statistical properties of the wavelet-transform coefficients for optimization of integration time in Fourier transform spectrometry

We show that an analysis of the mean and variance of discrete wavelet coefficients of coaveraged time-domain interferograms can be used as a specification for determining when to stop coaveraging. We also show that, if a prediction model built in the wavelet domain is used to determine the composition of unknown samples, a stopping criterion for the coaveraging process can be developed with respect to the uncertainty tolerated in the prediction.

The statistical properties of tropical ice clouds generated by the West-African and Australian monsoons from ground-based radar-lidar observations

In the present paper we characterize the statistical properties of non-precipitating tropical ice clouds (deep ice anvils resulting from deep convection and cirrus clouds) over Niamey, Niger, West Africa, and Darwin, northern Australia, using ground-based radar–lidar observations from the Atmospheric Radiation Measurement (ARM) programme. The ice cloud properties analysed in this paper are the frequency of ice cloud occurrence, cloud fraction, the morphological properties (cloud-top height, base height, and thickness), the microphysical and radiative properties (ice water content, visible extinction, effective radius, terminal fall speed, and concentration), and the internal cloud dynamics (in-cloud vertical air velocity). The main highlight of the paper is that it characterizes for the first time the probability density functions of the tropical ice cloud properties, their vertical variability and their diurnal variability at the same time. This is particularly important over West Africa, since the ARM deployment in Niamey provides the first vertically resolved observations of non-precipitating ice clouds in this crucial area in terms of redistribution of water and energy in the troposphere. The comparison between the two sites also provides an additional observational basis for the evaluation of the parametrization of clouds in large-scale models, which should be able to reproduce both the statistical properties at each site and the differences between the two sites. The frequency of ice cloud occurrence is found to be much larger over Darwin when compared to Niamey, and with a much larger diurnal variability, which is well correlated with the diurnal cycle of deep convective activity. The diurnal cycle of the ice cloud occurrence over Niamey is also much less correlated with that of deep convective activity than over Darwin, probably owing to the fact that Niamey is further away from the deep convective sources of the region. The frequency distributions of cloud fraction are strongly bimodal and broadly similar over the two sites, with a predominance of clouds characterized either by a very small cloud fraction (less than 0.3) or a very large cloud fraction (larger than 0.9). The ice clouds over Darwin are also much thicker (by 1 km or more statistically) and are characterized by a much larger diurnal variability than ice clouds over Niamey. Ice clouds over Niamey are also characterized by smaller particle sizes and fall speeds but in much larger concentrations, thereby carrying more ice water and producing more visible extinction than the ice clouds over Darwin. It is also found that there is a much larger occurrence of downward in-cloud air motions less than 1 m s−1 over Darwin, which together with the larger fall speeds retrieved over Darwin indicates that the life cycle of ice clouds is probably shorter over Darwin than over Niamey.

Thermodynamic and kinetic properties of interpolymer complexes assessed by isothermal titration calorimetry and surface plasmon resonance

Interpolymer complexes (IPCs) formed between complimentary polymers in solution have shown a wide range of applications from drug delivery to biosensors. This work describes the combined use of isothermal titration calorimetry and surface plasmon resonance to investigate the thermodynamic and kinetic processes during hydrogen-bonded interpolymer complexation. Varied polymers that are commonly used in layer-by-layer coatings and pharmaceutical preparations were selected to span a range of chemical functionalities including some known IPCs previously characterized by other techniques, and other polymer combinations with unknown outcomes. This work is the first to comprehensively detail the thermodynamic and kinetic data of hydrogen bonded IPCs, aiding understanding and detailed characterization of the complexes. The applicability of the two techniques in determining thermodynamic, gravimetric and kinetic properties of IPCs is considered.

Correlations between microphysical properties of large-scale semi-transparent cirrus and the state of the atmosphere

By making use of TOVS Path-B satellite retrievals and ECMWF reanalyses, correlations between bulk microphysical properties of large-scale semi-transparent cirrus (visible optical thickness between 0.7 and 3.8) and thermodynamic and dynamic properties of the surrounding atmosphere have been studied on a global scale. These clouds constitute about half of all high clouds. The global averages (from 60°N to 60°S) of mean ice crystal diameter, De, and ice water path (IWP) of these clouds are 55 μm and 30 g m−2, respectively. IWP of these cirrus is slightly increasing with cloud-top temperature, whereas De of cold cirrus does not depend on this parameter. Correlations between De and IWp of large-scale cirrus seem to be different in the midlatitudes and in the tropics. However, we observe in general stronger correlations between De and IWP and atmospheric humidity and winds deduced from the ECMWF reanalyses: De and IWP increase both with increasing atmospheric water vapour. There is also a good distinction between different dynamical situations: In humid situations, IWP is on average about 10 gm−2 larger in regions with strong large-scale vertical updraft only that in regions with strong large-scale horizontal winds only, whereas the mean De of cold large-scale cirrus decreases by about 10 μm if both strong large-scale updraft and horizontal winds are present.

Growth rate and physical properties of Erythrina variegata with regard to dry matter production

Erythrina variegata grown from seeds showed a great deal of variation with respect to height, diameter, density of wood and dry matter production. Statistical analysis showed that the density of wood produced by any plant was not related to its growth rate, but dry matter production was associated with plant growth rate (height and diameter) that could lead to overall increased dry matter or biomass production.

Synthesis and properties of new trinuclear Mo(II) complexes containing imidazole and benzimidazole ferrocene units

The reaction of FcCOC1 (Fc = (C5H5) Fe(C5H4)) with benzimidazole or imidazole in 1: 1 ratio gives the ferrocenyl derivatives FcCO(benzim) (L1) or FcCO(im) (L2), respectively. Two molecules of L1 or L2 can replace two nitrile ligands in [Mo(eta(3)-C3H5)( CO)(2)(CH3CN)(2)Br] or [Mo(eta(3)-C5H5O)(CO)(2)(CH3CN)(2)Br] leading to the new trinuclear complexes [Mo(eta(3)-C3H5)(CO)(2)(L)(2)Br] (C1 for L = L1; C3 for L = L2) and [Mo(eta(3)-C5H5O)(CO)(2)(L)(2)Br] (C-2 for L = L1; C4 for L = L2) with L1 and L2 acting as N-monodentade ligands. L1, L2 and C2 were characterized by X-ray diffraction studies. [Mo(eta(3)-C5H5O)(CO) 2(L1)(2)Br] was shown to be a trinuclear species, with the two L1 molecules occupying one equatorial and one axial position in the coordination sphere of Mo(II). Cyclic voltammetric studies were performed for the two ligands L1 and L2, as well as for their molybdenum complexes, and kinetic and thermodynamic data for the corresponding redox processes obtained. In agreement with the nature of the frontier orbitals obtained from DFT calculations, L1 and L2 exhibit one oxidation process at the Fe(II) center, while C1, C3, and C4 display another oxidation wave at lower potentials, associated with the oxidation of Mo(II). (C) 2007 Elsevier B. V. All rights reserved.

Thermodynamic analysis of snowball Earth hysteresis experiment: Efficiency, entropy production and irreversibility

We present an extensive thermodynamic analysis of a hysteresis experiment performed on a simplified yet Earth-like climate model. We slowly vary the solar constant by 20% around the present value and detect that for a large range of values of the solar constant the realization of snowball or of regular climate conditions depends on the history of the system. Using recent results on the global climate thermodynamics, we show that the two regimes feature radically different properties. The efficiency of the climate machine monotonically increases with decreasing solar constant in present climate conditions, whereas the opposite takes place in snowball conditions. Instead, entropy production is monotonically increasing with the solar constant in both branches of climate conditions, and its value is about four times larger in the warm branch than in the corresponding cold state. Finally, the degree of irreversibility of the system, measured as the fraction of excess entropy production due to irreversible heat transport processes, is much higher in the warm climate conditions, with an explosive growth in the upper range of the considered values of solar constants. Whereas in the cold climate regime a dominating role is played by changes in the meridional albedo contrast, in the warm climate regime changes in the intensity of latent heat fluxes are crucial for determining the observed properties. This substantiates the importance of addressing correctly the variations of the hydrological cycle in a changing climate. An interpretation of the climate transitions at the tipping points based upon macro-scale thermodynamic properties is also proposed. Our results support the adoption of a new generation of diagnostic tools based on the second law of thermodynamics for auditing climate models and outline a set of parametrizations to be used in conceptual and intermediate-complexity models or for the reconstruction of the past climate conditions. Copyright © 2010 Royal Meteorological Society

The R1441C mutation alters the folding properties of the ROC domain of LRRK2

LRRK2 is a 250 kDa multidomain protein, mutations in which cause familial Parkinson's disease. Previously, we have demonstrated that the R1441C mutation in the ROC domain decreases GTPase activity. Here we show that the R1441C alters the folding properties of the ROC domain, lowering its thermodynamic stability. Similar to small GTPases, binding of different guanosine nucleotides alters the stability of the ROC domain, suggesting that there is an alteration in conformation dependent on GDP or GTP occupying the active site. GTP/GDP bound state also alters the self-interaction of the ROC domain, accentuating the impact of the R1441C mutation on this property. These data suggest a mechanism whereby the R1441C mutation can reduce the GTPase activity of LRRK2, and highlights the possibility of targeting the stability of the ROC domain as a therapeutic avenue in LRRK2 disease.

An historical perspective on the development of the thermodynamic equation of seawater - 2010

Oceanography is concerned with understanding the mechanisms controlling the movement of seawater and its contents. A fundamental tool in this process is the characterization of the thermophysical properties of seawater as functions of measured temperature and electrical conductivity, the latter used as a proxy for the concentration of dissolved matter in seawater. For many years a collection of algorithms denoted the Equation of State 1980 (EOS-80) has been the internationally accepted standard for calculating such properties. However, modern measurement technology now allows routine observations of temperature and electrical conductivity to be made to at least one order of magnitude more accurately than the uncertainty in this standard. Recently, a new standard has been developed, the Thermodynamical Equation of Seawater 2010 (TEOS-10). This new standard is thermodynamically consistent, valid over a wider range of temperature and salinity, and includes a mechanism to account for composition variations in seawater. Here we review the scientific development of this standard, and describe the literature involved in its development, which includes many of the articles in this special issue.