The role of surface roughness, albedo, and Bowen ratio on ecosystem energy balance in the Eastern United States

Land cover and land use influence surface climate through differences in biophysical surface properties, including partitioning of sensible and latent heat (e.g., Bowen ratio), surface roughness, and albedo. Clusters of closely spaced eddy covariance towers (e.g., \u3c10 \u3ekm) over a variety of land cover and land use types provide a unique opportunity to study the local effects of land cover and land use on surface temperature. We assess contributions albedo, energy redistribution due to differences in surface roughness and energy redistribution due to differences in the Bowen ratio using two eddy covariance tower clusters and the coupled (land-atmosphere) Variable-Resolution Community Earth System Model. Results suggest that surface roughness is the dominant biophysical factor contributing to differences in surface temperature between forested and deforested lands. Surface temperature of open land is cooler (−4.8 °C to −0.05 °C) than forest at night and warmer (+0.16 °C to +8.2 °C) during the day at northern and southern tower clusters throughout the year, consistent with modeled calculations. At annual timescales, the biophysical contributions of albedo and Bowen ratio have a negligible impact on surface temperature, however the higher albedo of snow-covered open land compared to forest leads to cooler winter surface temperatures over open lands (−0.4 °C to −0.8 °C). In both the models and observation, the difference in mid-day surface temperature calculated from the sum of the individual biophysical factors is greater than the difference in surface temperature calculated from radiative temperature and potential temperature. Differences in measured and modeled air temperature at the blending height, assumptions about independence of biophysical factors, and model biases in surface energy fluxes may contribute to daytime biases

Spontaneous Water Oxidation at Hematite (α-Fe_2O_3) Crystal Faces

Hematite (α-Fe_2O_3) persists as a promising candidate for photoelectrochemical water splitting, but a slow oxygen evolution reaction (OER) at its surfaces remains a limitation. Here we extend a series of studies that examine pH-dependent surface potentials and electron-transfer properties of effectively perfect low-index crystal faces of hematite in contact with simple electrolyte. Zero-resistance amperometry (ZRA) was performed in a two electrode configuration to quantify spontaneous dark current between hematite crystal face pairs (001)/(012), (001)/(113), and (012)/(113) at pH 3. Exponentially decaying currents initially of up to 200 nA were reported between faces over 4 min experiments. Fourth-order ZRA kinetics indicated rate limitation by the OER for current that flows between (001)/(012) and (001)/(113) face pairs, with the (012) and (113) faces serving as the anodes when paired with (001). The cathodic partner reaction is reductive dissolution of the (001) face, converting surface Fe^(3+) to solubilized aqueous Fe^(2+), at a rate maintained by the OER at the anode. In contrast, OER rate limitation does not manifest for the (012)/(113) pair. The uniqueness of the (001) face is established in terms of a faster intrinsic ability to accept the protons required for the reductive dissolution reaction. OER rate limitation inversely may thus arise from sluggish kinetics of hematite surfaces to dispense with the protons that accompany the four-electron OER. The results are explained in terms of semiquantitative energy band diagrams. The finding may be useful as a consideration for tailoring the design of polycrystalline hematite photoanodes that present multiple terminations to the interface with electrolyte

Thermodynamic parameters of bonds in glassy materials from viscosity-temperature relationships

Doremus's model of viscosity assumes that viscous flow in amorphous materials is mediated by broken bonds (configurons). The resulting equation contains four coefficients, which are directly related to the entropies and enthalpies of formation and motion of the configurons. Thus by fitting this viscosity equation to experimental viscosity data these enthalpy and entropy terms can be obtained. The non-linear nature of the equation obtained means that the fitting process is non-trivial. A genetic algorithm based approach has been developed to fit the equation to experimental viscosity data for a number of glassy materials, including SiO2, GeO2, B2O3, anorthite, diopside, xNa2O–(1-x)SiO2, xPbO–(1-x)SiO2, soda-lime-silica glasses, salol, and α-phenyl-o-cresol. Excellent fits of the equation to the viscosity data were obtained over the entire temperature range. The fitting parameters were used to quantitatively determine the enthalpies and entropies of formation and motion of configurons in the analysed systems and the activation energies for flow at high and low temperatures as well as fragility ratios using the Doremus criterion for fragility. A direct anti-correlation between fragility ratio and configuron percolation threshold, which determines the glass transition temperature in the analysed materials, was found

Measuring equilibrium properties in aging systems

We corroborate the idea of a close connection between replica symmetry breaking and aging in the linear response function for a large class of finite-dimensional systems with short-range interactions. In these system, characterized by a continuity condition with respect to weak random perturbations of the Hamiltonian, the ``fluctuation dissipation ratio'' in off-equilibrium dynamics should be equal to the static cumulative distribution function of the overlaps. This allows for an experimental measurement of the equilibrium order parameter function.Comment: 5 pages, LaTeX. The paper has been completely rewritten and shortene

The ecological diversity of vegetation within Urban Parks in the Dabrowski Basin (southern Poland)

The aim of this work is to present the diversity of flora in terms of ecological requirements. The research was conducted in the area of two urban parks in the area of two cities in southern Poland: Bedzin and Czeladz. These parks were established in different historical periods, and were planned (and are managed) differently. The results of the investigation have shown that the occurrence of 192 vascular species has been observed in the Gora Zamkowa (Castle Hill) Park, while in the Grabek park, 334 such species are known to exist. Such disparity is the result of the occurrence of micro-habitats and of the differences between the ways the two parks are managed. It is also due to these parks’ different functions. In the first case, the park area is protected by law. In the latter case, human activity has created a new ecological niche for organisms with a high degree of ecological tolerance. Based on the ecological values, the following groups of plants were distinguished: saxifrages grasslands, xerothermic grasslands, beech forests, alder forests and artificial planted trees. Analysis has shown that urban parks are potential places for growth various type of vegetation and also for increasing biodiversity, and can constitute particularly important hotspots for biodiversity in the cityscape, even if their primary role is recreational. As the study shows, the environment of a highly urbanized and industrialized region can also have a positive influence on ecological and floristic diversity

Topologically disordered systems at the glass transition

The thermodynamic approach to the viscosity and fragility of amorphous oxides was used to determine the topological characteristics of the disordered network-forming systems. Instead of the disordered system of atoms we considered the congruent disordered system of interconnecting bonds. The Gibbs free energy of network-breaking defects (configurons) was found based on available viscosity data. Amorphous silica and germania were used as reference disordered systems for which we found an excellent agreement of calculated and measured glass transition temperatures. We reveal that the Hausdorff dimension of the system of bonds changes from Euclidian three-dimensional below to fractal 2.55 ± 0.05-dimensional geometry above the glass transition temperature

Frequency dependent specific heat of viscous silica

We apply the Mori-Zwanzig projection operator formalism to obtain an expression for the frequency dependent specific heat c(z) of a liquid. By using an exact transformation formula due to Lebowitz et al., we derive a relation between c(z) and K(t), the autocorrelation function of temperature fluctuations in the microcanonical ensemble. This connection thus allows to determine c(z) from computer simulations in equilibrium, i.e. without an external perturbation. By considering the generalization of K(t) to finite wave-vectors, we derive an expression to determine the thermal conductivity \lambda from such simulations. We present the results of extensive computer simulations in which we use the derived relations to determine c(z) over eight decades in frequency, as well as \lambda. The system investigated is a simple but realistic model for amorphous silica. We find that at high frequencies the real part of c(z) has the value of an ideal gas. c'(\omega) increases quickly at those frequencies which correspond to the vibrational excitations of the system. At low temperatures c'(\omega) shows a second step. The frequency at which this step is observed is comparable to the one at which the \alpha-relaxation peak is observed in the intermediate scattering function. Also the temperature dependence of the location of this second step is the same as the one of the $\alpha-$peak, thus showing that these quantities are intimately connected to each other. From c'(\omega) we estimate the temperature dependence of the vibrational and configurational part of the specific heat. We find that the static value of c(z) as well as \lambda are in good agreement with experimental data.Comment: 27 pages of Latex, 8 figure

Computer Simulations of Supercooled Liquids and Glasses

After a brief introduction to the dynamics of supercooled liquids, we discuss some of the advantages and drawbacks of computer simulations of such systems. Subsequently we present the results of computer simulations in which the dynamics of a fragile glass former, a binary Lennard-Jones system, is compared to the one of a strong glass former, SiO_2. This comparison gives evidence that the reason for the different temperature dependence of these two types of glass formers lies in the transport mechanism for the particles in the vicinity of T_c, the critical temperature of mode-coupling theory. Whereas the one of the fragile glass former is described very well by the ideal version of mode-coupling theory, the one for the strong glass former is dominated by activated processes. In the last part of the article we review some simulations of glass formers in which the dynamics below the glass transition temperature was investigated. We show that such simulations might help to establish a connection between systems with self generated disorder (e.g. structural glasses) and quenched disorder (e.g. spin glasses).Comment: 37 pages of Latex, 11 figures, to appear as a Topical Review article in J. Phys.: Condens. Matte