Convective scaling of the average dissipation rate of temperature variance in the atmospheric surface layer

The flux of sensible heat from the land surface is related to the average rate of dissipation of temperature fluctuations in the atmospheric surface layer through the temperature variance budget equation. In many cases it is desirable to estimate the heat flux from measurement or inference of the dissipation rate. Here we study how the dissipation rate scales with atmospheric stability, using three inertial range methods to calculate the dissipation rate: power spectra, second order structure functions, and third order structure functions. Experimental data are analyzed from a pair of field experiments, during which turbulent fluctuations of velocity and temperature were measured over a broad range of neutral and unstable atmospheric flows. It is shown that the temperature dissipation rate scales with a single convective power law continuously from near-neutral to strongly unstable stratification. The dissipation scaling is found to nearly match production in the near-neutral region, but to be consistently lower than production in the more convective regimes. The convective scaling is shown to offer a simplified means of computing sensible heat flux from the dissipation rate of temperature variance.Also at Johns Hopkins University, Baltimore, MarylandAlso at Los Alamos National Laboratory, Los Alamos, New Mexico.     

Macroscopic representation of structural geometry for simulating water and solute movement in dual-porosity media

The structure of macroporous or aggregated soils and fractured rocks is generally so complex that it is impractical to measure the geometry at the microscale (i.e., the size and the shape of soil aggregates or rock matrix blocks, and the myriad of fissures or fractures), and use such data in geometry-dependent macroscale flow and transport models. This paper analyzes a first-order type dual-porosity model which contains a geometry-dependent coefficient, β, in the mass transfer term to macroscopically represent the size and shape of soil or rock matrix blocks. As a reference, one- and two-dimensional geometry-based diffusion models were used to simulate mass transport into and out of porous blocks of defined shapes. Estimates for β were obtained analytically for four different matrix block geometries. Values for β were also calculated by directly matching analytical solutions of the diffusion models for a number of selected matrix block geometries to results obtained with the first-order model assuming standard boundary conditions. Direct matching improved previous results for cylindrical macropore geometries, especially when relatively small ratios between the outer soil mantle and the radius of the inner cylinder were used. Results of our analysis show that β is closely related to the ratio of the effective surface area available for mass transfer, and the soil matrix volume normalized by the effective characteristic length of the matrix system. Using values of β obtained by direct matching, an empirical function is derived to estimate macroscopic geometry coefficients from medium properties which in principle are measurable. The method permits independent estimates of β, thus allowing the dual-porosity approach eventually to be applied to media with complex and mixed types of structural geometry.     

Approach to chemical equilibrium in diagenetic chlorites

Electron microprobe analyses were made on diagenetic chlorites in sandstones and mudstones from two deep wells according to the petrographic character of the chlorite occurrence: as pseudomorphic phases, rims on quartz or glauconite or as distinct phases in the clay matrix. Chlorite compositions do not depend upon crystallization site (reacting phases) making it apparent that new chlorites can form in an approach to chemical equilibrium at or near the surface (40° C, 1 km depth). Comparison of this data with that for late diagenetic and early metamorphic chlorites indicates that the compositional range for different grains in the same thin section is similar for the samples throughout the 40°–270° C temperature span. Compositional range decreases upon further metamorphism.Al content appears to be a more reliable indicator of temperature variations than other substitutions in the chlorite structure. The clay mineral assemblage which indicates sedimentary facies affects the trends in composition (Al increase or decrease) as a function of temperature. The octahedral site occupancy show a general increase in going from diagenesis to metamorphic conditions in pelitic rocks. The range of Fe-Mg ratios seems to depend more on the chemistry of each sample than the temperature of formation of the minerals.     

Oxygen-containing functional groups in land-derived humic acids—I. Evaluation by derivatization methods

Determinations of reactive oxygen-containing functional groups were performed by usual chemical derivatization methods of four humic acids isolated from soils and deltaic sediments. Statistical tests and calculations based on elemental analysis demonstrated the validity and limits of these techniques and allowed us to identify from 60 to 71% of the total humic oxygen. Oxygen budgets of humic acids are discussed.     

Oxygen-containing functional groups in land-derived humic acids—II. Changes in the oxygen distribution of humic acids during early diagenesis as revealed by derivatization methods

Extensive functional group analyses were performed on humic acids representative of eight increasing depth levels from a core drilled in the Mahakam delta (East Kalimantan, Indonesia). Oxygen amounts decrease observed during early diagenesis was related chiefly to loss of hydroxyl (lignol?) groups. Comparison between upper and deeper levels shows the following variations: hydroxyl group abundances go from 19 to 6% of humic oxygen. Identified functional groups amounts represent 47 to 32% of weight of moisture- and ash-free humic acids. No evidence of decarboxylation of humic material was detected.