Assessment of alternative adsorption models and global sensitivity analysis to characterize hexavalent chromium loss from soil to surface runoff

We investigate our ability to assess transfer of hexavalent chromium, Cr(VI), from the soil to surface runoff by considering the effect of coupling diverse adsorption models with a two‐layer solute transfer model. Our analyses are grounded on a set of two experiments associated with soils characterized by diverse particle size distributions. Our study is motivated by the observation that Cr(VI) is receiving much attention for the assessment of environmental risks due to its high solubility, mobility, and toxicological significance. Adsorption of Cr(VI) is considered to be at equilibrium in the mixing layer under our experimental conditions. Four adsorption models, that is, the Langmuir, Freundlich, Temkin, and linear models, constitute our set of alternative (competing) mathematical formulations. Experimental results reveal that the soil samples characterized by the finest grain sizes are associated with the highest release of Cr(VI) to runoff. We compare the relative abilities of the four models to interpret experimental results through maximum likelihood model calibration and four model identification criteria (i.e., the Akaike information criteria [AIC and AIC_C] and the Bayesian and Kashyap information criteria). Our study results enable us to rank the tested models on the basis of a set of posterior weights assigned to each of them. A classical variance‐based global sensitivity analysis is then performed to assess the relative importance of the uncertain parameters associated with each of the models considered, within subregions of the parameter space. In this context, the modelling strategy resulting from coupling the Langmuir isotherm with a two‐layer solute transfer model is then evaluated as the most skilful for the overall interpretation of both sets of experiments. Our results document that (a) the depth of the mixing layer is the most influential factor for all models tested, with the exception of the Freundlich isotherm, and (b) the total sensitivity of the adsorption parameters varies in time, with a trend to increase as time progresses for all of the models. These results suggest that adsorption has a significant effect on the uncertainty associated with the release of Cr(VI) from the soil to the surface runoff component.     

The mass ratio of Charon to Pluto from Hubble Space Telescope astrometry with the fine guidance sensors

The mass ratio of Charon to Pluto is a basic parameter describing the binary system and is necessary for determining the individual masses and densities of these two bodies. Previous measurements of the mass ratio have been made, but the solutions differ significantly (Null et al., 1993; Young et al., 1994; Null and Owen, 1996; Foust et al., 1997; Tholen and Buie, 1997). We present the first observations of Pluto and Charon with a well-calibrated astrometric instrument—the fine guidance sensors on the Hubble Space Telescope. We observed the motion of Pluto and Charon about the system barycenter over 4.4 days (69% of an orbital period) and determined the mass ratio to be 0.122±0.008 which implies a density of 1.8 to 2.1 g cm⁻³ for Pluto and 1.6 to 1.8 g cm⁻³ for Charon. The resulting rock-mass fractions for Pluto and Charon are higher than expected for bodies formed in the outer solar nebula, possibly indicating significant postaccretion loss of volatiles.     

An approximate method for evaluating the shear band thickness in saturated soils

A formula for the thickness of a shear band formed in saturated soils under a simple shear or a combined stress state has been proposed. It is shown that the shear band thickness is dependent on the pore pressure properties of the material and the dilatancy rate, but is independent of the details of the combined stress state. This is in accordance with some separate experimental observations. Copyright © 2004 John Wiley & Sons, Ltd.     

P‐wave transmission across fractures with nonlinear deformational behaviour

Stress wave attenuation across fractured rock masses is a great concern of underground structure safety. When the wave amplitude is large, fractures experience nonlinear deformation during the wave propagation. This paper presents a study on normal transmission of P‐wave across parallel fractures with nonlinear deformational behaviour (static Barton–Bandis model). The results show that the magnitude of transmission coefficient is a function of incident wave amplitude, nondimensional fracture spacing and number of fractures. Two important indices of nondimensional fracture spacing are identified, and they divide the area of nondimensional fracture spacing into three parts (individual fracture area, transition area and small spacing area). In the different areas, the magnitude of transmission coefficient has different trends with nondimensional fracture spacing and number of fractures. In addition, the study reveals that under some circumstances, the magnitude of transmission coefficient increases with increasing number of fractures, and is larger than 1. Copyright © 2006 John Wiley & Sons, Ltd.     

The range-averaged intensity model: a tool for underwater acousticfield analysis

The range-averaged intensity model (RAIM) long known as a powerful method for transmission loss estimation in waveguides, is extended to other aspects of the acoustic field: impulse response and angular pattern estimations at a receiver, general time spreading in a waveguide, signal fluctuations, reverberation levels, and ambient noise structure. An example of its application to a SOFAR propagation and detection case is presented. This method appears to be a very efficient and reliable analysis tool for many underwater acoustics configurations: particularly long-range horizontal telemetry and shallow-water sonar     

Biological and granulometric controls on sedimentary organic matter of an intertidal mudflat

A variety of measures of organic matter concentration and quality were made on samples collected from the top few mm of intertidal mudflat sediment over the course of a year, in order to assess the relative importance of biological and sedimentological influences on sedimentary organic matter. Winter and summer were times of relatively fine-grained sediment accumulation, caused by biological deposition or stabilization processes and resulting in higher organic matter concentrations. Stable carbon isotope and Br:C ratios indicated a planktonic source of bulk organic matter. Ratios of organic carbon to specific surface area of the sediments were consistent with an organic monolayer coverage of sediment grains. Correction for changing grain size during the year showed no change in the organic concentration per unit surface area, in spite of organic matter inputs by in situ primary production, buildup of heterotroph biomass and mucus coatings, and biodeposition of organic-rich seston. There were also no indications of changes in bulk organic quality, measured as hydrolyzable carbohydrates and amino acids, in response to these biological processes. It is concluded that biological processes on a seasonal time scale affect the bulk organic matter of these sediments via a modulation of grain size rather than creation or decay of organic matter.     

Scanning electron microscopy,cathodoluminescence, and Raman spectroscopy of experimentally shock‐metamorphosed quartzite

Abstract— We studied unshocked and experimentally (at 12, 25, and 28 GPa, with 25, 100, 450, and 750°C pre‐shock temperatures) shock‐metamorphosed Hospital Hill quartzite from South Africa using cathodoluminescence (CL) images and spectroscopy and Raman spectroscopy to document systematic pressure or temperature‐related effects that could be used in shock barometry. In general, CL images of all samples show CL‐bright luminescent patchy areas and bands in otherwise nonluminescent quartz, as well as CL‐dark irregular fractures. Fluid inclusions appear dominant in CL images of the 25 GPa sample shocked at 750°C and of the 28 GPa sample shocked at 450°C. Only the optical image of our 28 GPa sample shocked at 25°C exhibits distinct planar deformation features (PDFs). Cathodoluminescence spectra of unshocked and experimentally shocked samples show broad bands in the near‐ultraviolet range and the visible light range at all shock stages, indicating the presence of defect centers on, e.g., SiO₄ groups. No systematic change in the appearance of the CL images was obvious, but the CL spectra do show changes between the shock stages. The Raman spectra are characteristic for quartz in the unshocked and 12 GPa samples. In the 25 and 28 GPa samples, broad bands indicate the presence of glassy SiO₂, while high‐pressure polymorphs are not detected. Apparently, some of the CL and Raman spectral properties can be used in shock barometry.