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.     

Determination of subcatchment and watershed boundaries in a complex and highly urbanized landscape

Urban development significantly alters the landscape by introducing widespread impervious surfaces, which quickly convey surface run‐off to streams via stormwater sewer networks, resulting in “flashy” hydrological responses. Here, we present the inadequacies of using raster‐based digital elevation models and flow‐direction algorithms to delineate large and highly urbanized watersheds and propose an alternative approach that accounts for the influence of anthropogenically modified land cover. We use a semi‐automated approach that incorporates conventional drainage networks into overland flow paths and define the maximal run‐off contributing area. In this approach, stormwater pipes are clustered according to their slope attributes, which define flow direction. Land areas drained by each cluster and contributing (or exporting) flow to a topographically delineated catchment were determined. These land masses were subsequently added or removed from the catchment, modifying both the shape and the size. Our results in a highly urbanized Toronto, Canada, area watershed indicate a moderate net increase in the directly connected watershed area by 3% relative to a topographically forced method; however, differences across three smaller scale subcatchments are greater. Compared to topographic delineation, the directly connected watershed areas of both the upper and middle subcatchments decrease by 5% and 8%, respectively, whereas the lower subcatchment area increases by 15%. This is directly related to subsurface storm sewer pipes that cross topographic boundaries. When directly connected subcatchment area is plotted against total streamflow and flashiness indices using this method, the coefficients of variation are greater (0.93 to 0.97) compared to the use of digital elevation model‐derived subcatchment areas (0.78 to 0.85). The accurate identification of watershed and subcatchment boundaries should incorporate ancillary data such as stormwater sewer networks and retention basin drainage areas to reduce water budget errors in urban systems.     

Analytical study of ground motion caused by seismic wave propagation across faulted rock masses

Studying seismic wave propagation across rock masses and the induced ground motion is an important topic, which receives considerable attention in design and construction of underground cavern/tunnel constructions and mining activities. The current study investigates wave propagation across a rock mass with one fault and the induced ground motion using a recursive approach. The rocks beside the fault are assumed as viscoelastic media with seismic quality factors, Q_p and Q_s. Two kinds of interactions between stress waves and a discontinuity and between stress waves and a free surface are analyzed, respectively. As the result of the wave superposition, the mathematical expressions for induced ground vibration are deduced. The proposed approach is then compared with the existing analysis for special cases. Finally, parametric studies are carried out, which includes the influences of fault stiffness, incident angle, and frequency of incident waves on the peak particle velocities of the ground motions.     

Dynamic modelling of retrogressive landslides with emphasis on the role of clay sensitivity

This paper presents a detailed numerical study of the retrogressive failure of landslides in sensitive clays. The dynamic modelling of the landslides is carried out using a novel continuum approach, the particle finite element method, complemented with an elastoviscoplastic constitutive model. The multiwedge failure mode in the collapse is captured successfully, and the multiple retrogressive failures that have been widely observed in landslides in sensitive clays are reproduced with the failure mechanism, the kinematics, and the deposition being discussed in detail. Special attention has been paid to the role of the clay sensitivity on each retrogressive failure as well as on the final retrogression distance and the final run‐out distance via parametric studies. Moreover, the effects of the viscosity of sensitive clays on the failure are also investigated for different clay sensitivities.     

Petrochronology of oxidized granulites from southern Peru

Sapphirine–quartz granulites from the Cocachacra region of the Arequipa Massif in southern Peru record early Neoproterozoic ultrahigh‐temperature metamorphism. Phase equilibrium modelling and zircon petrochronology are used to quantify timing and pressure–temperature (P–T) conditions of metamorphism. Modelling of three magnetite‐bearing sapphirine–quartz samples indicates peak temperatures of >950°C at ~0.7 GPa and a clockwise P–T evolution. Elevated concentrations of Al in orthopyroxene are also consistent with ultrahigh‐temperature conditions. Neoblastic zircon records ages of c. 1.0–0.9 Ga that are interpreted to record protracted ultrahigh‐temperature metamorphism. Th/U ratios of zircon of up to 100 reflect U‐depleted whole‐rock compositions. Concentrations of heavy rare earth elements in zircon do not show systematic trends with U–Pb age but do correlate with variable whole‐rock compositions. Very large positive Ce anomalies in zircon from two samples probably relate to strongly oxidizing conditions during neoblastic zircon crystallization. Low concentrations of Ti‐in‐zircon (<10 ppm) are interpreted to result from reduced titania activities due to the strongly oxidized nature of the granulites and the sequestration of titanium‐rich minerals away from the reaction volume. Whole‐rock compositions and oxidation state have a strong influence on the trace element composition of metamorphic zircon, which has implications for interpreting the geological significance of ages retrieved from zircon in oxidized metamorphic rocks.     

Solution for a plane strain rough‐walled hydraulic fracture driven by turbulent fluid through impermeable rock

The impact of turbulent flow on plane strain fluid‐driven crack propagation is an important but still poorly understood consideration in hydraulic fracture modeling. The changes that hydraulic fracturing has experienced over the past decade, especially in the area of fracturing fluids, have played a major role in the transition of the typical fluid regime from laminar to turbulent flow. Motivated by the increasing preponderance of high‐rate, water‐driven hydraulic fractures with high Reynolds number, we present a semianalytical solution for the propagation of a plane strain hydraulic fracture driven by a turbulent fluid in an impermeable formation. The formulation uses a power law relationship between the Darcy‐Weisbach friction factor and the scale of the fracture roughness, where one specific manifestation of this generalized friction factor is the classical Gauckler‐Manning‐Strickler approximation for turbulent flow in a rough‐walled channel. Conservation of mass, elasticity, and crack propagation are also solved simultaneously. We obtain a semianalytical solution using an orthogonal polynomial series. An approximate closed‐form solution is enabled by a choice of orthogonal polynomials embedding the near‐tip asymptotic behavior and thus giving very rapid convergence; a precise solution is obtained with 2 terms of the series. By comparison with numerical simulations, we show that the transition region between the laminar and turbulent regimes can be relatively small so that full solutions can often be well approximated by either a fully laminar or fully turbulent solution.     

Micromechanical approach to effective viscoelastic properties of micro‐fractured geomaterials

The aim of this paper is to formulate a micromechanics‐based approach to non‐aging viscoelastic behavior of materials with randomly distributed micro‐fractures. Unlike cracks, fractures are discontinuities that are able to transfer stresses and can therefore be regarded from a mechanical viewpoint as interfaces endowed with a specific behavior under normal and shear loading. Making use of the elastic‐viscoelastic correspondence principle together with a Mori‐Tanka homogenization scheme, the effective viscoelastic behavior is assessed from properties of the material constituents and damage parameters related to density and size of fractures. It is notably shown that the homogenized behavior thus formulated can be described in most cases by means of a generalized Maxwell rheological model. For practical implementation in structural analyses, an approximate model for the isotropic homogenized fractured medium is formulated within the class of Burger models. Although the approximation is basically developed for short‐term and long‐term behaviors, numerical applications indicate that the approximate Burger model accurately reproduce the homogenized viscoelastic behavior also in the transient conditions.     

Active capture and anomalous adsorption: New mechanisms for the incorporation of heavy noble gases

Abstract— Active capture is a new process for the incorporation of large quantities of heavy noble gases into growing surfaces. Adsorption in the conventional sense involves surface bonding by polarization (Van der Waals forces). What is referred to as “anomalous adsorption” of heavy noble gases involves chemical bonds and can occur when other (more chemically active) species are not available to preempt sites with unfilled bonds. Anomalous adsorption has been observed under conditions of fracture, vacuum deposition and ionizing radiation. Active capture depends upon anomalous adsorption to retain noble gases on a surface long enough to be captured in a growing surface film as it is deposited. The fundamental principle may be the impingement onto the growing film with sufficient energy to liberate surface electrons (work function energy of a few electronvolts) so that they are retained by anomalous adsorption long enough to be entrapped in the growing surface. Trapping efficiencies of ?1% have been observed for Kr and Xe in laboratory experiments, implying a fundamentally new mechanism for the incorporation of heavy noble gases onto surfaces. It may play a role in explaining the large concentrations of planetary noble gases contained in phase‐Q.