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.     

Strain localization in sand: an overview of the experimental results obtained in Grenoble using stereophotogrammetry

Experimental results are presented from the extensive program of drained plane strain compression tests on sand carried out in Grenoble over the last two decades. Systematic analysis of photographs of the deforming specimen allowed for measuring deformations and determining strain fields throughout the test, that is: prior to, at, and after the onset of strain localization. The principles, details and accuracy of the procedure are described, as well as its suitability to properly depict the patterns of deformation. Findings concerning the occurrence and progression of strain localization are discussed. The issues of shear band orientation and thickness are addressed, as well as temporary and persistent complex localization patterns, and the volumetric behaviour inside a band after its formation. The influence of such variables as initial state of the sand (effective stress and relative density), specimen size and slenderness, as well as grain size, is discussed. Copyright © 2004 John Wiley & Sons, Ltd     

Bond rolling resistance and its effect on yielding of bonded granulates by DEM analyses

A discrete element modelling of bonded granulates and investigation on the bond effect on their behaviour are very important to geomechanics. This paper presents a two‐dimensional (2‐D) discrete element theory for bonded granulates with bond rolling resistance and provides a numerical investigation into the effect of bond rolling resistance on the yielding of bonded granulates. The model consists of mechanical contact models and equations governing the motion of bonded particles. The key point of the theory is that the assumption in the original bond contact model previously proposed by the authors (55th CSCE‐ASCE Conference, Hamilton, Ont., Canada, 2002; 313–320; J. Eng. Mech. (ASCE) 2005; 131 (11):1209–1213) that bonded particles are in contact at discrete points, is here replaced by a more reliable assumption that bonded particles are in contact over a width. By making the idealization that the bond contact width is continuously distributed with the normal/tangential basic elements (BE) (each BE is composed of spring, dashpot, bond, slider or divider), we establish a bond rolling contact model together with bond normal/tangential contact models, and also relate the governing equations to local equilibrium. Only one physical parameter β needs to be introduced in the theory in comparison to the original bond discrete element model. The model has been implemented into a 2‐D distinct element method code, NS2D. Using the NS2D, a total of 86 1‐D, constant stress ratio, and biaxial compressions tests have been carried out on the bonded granular samples of different densities, bonding strengths and rolling resistances. The numerical results show that: (i) the new theory predicts a larger internal friction angle, a larger yielding stress, more brittle behaviour and larger final broken contact ratio than the original bond model; (ii) the yielding stress increases nonlinearly with the increasing value of β, and (iii) the first‐yield curve (initiation of bond breakage), which define a zone of none bond breakage and which shape and size are affected by the material density, is amplified by the bond rolling resistance in analogous to that predicted by the original bond model. Copyright © 2006 John Wiley & Sons, Ltd.     

Sensitivity analysis of a deterministic water temperature model to forest canopy and soil temperature in Catamaran Brook (New Brunswick,Canada)

A coupled deterministic hydrological and water temperature model, CEQUEAU, was modified to include soil temperature and crown closure in its calculation of local advective terms in the heat budget. The modified model was than tested to verify its sensitivity to these modifications. An analysis of the heat budget of a small forested catchment in eastern Canada revealed that the advective term related to interflow plays a significant role in the daily water heat budget, providing on average 28% of the local advective budget (which also includes advective heat terms from surface runoff and groundwater) and nearly 14% of the total heat budget (which includes all radiative terms at the water surface, convection and evaporation, as well as the local advective terms). Relative sensitivity indices (RSIs) were used to verify the impact of the newly introduced parameters and variables. Among them, parameters related to the forest cover (crown closure and leaf area index) have a maximum RSI of ?0·6; i.e. a 100% increase in value produces a 60% decrease in the local advective term. Parameters with the greatest influence are the volume of water contributing to interflow and the amplitude of the net radiative flux at the soil surface, which, if doubled, would double the contribution of the local interflow advective term to the heat budget. Copyright © 2003 John Wiley & Sons, Ltd.     

Studying Hydrodynamic Instability Using Shock-Tube Experiments

The hydrodynamic instability, which develops on the contact surface between two fluids, has great importance in astrophysical phenomena such as the inhomogeneous density distribution following a supernova event. In this event acceleration waves pass across a material interface and initiate and enhance unstable conditions in which small perturbations grow dramatically. In the present study, an experimental technique aimed at investigating the above-mentioned hydrodynamic instability is presented. The experimental investigation is based on a shock-tube apparatus by which a shock wave is generated and initiates the instability that develops on the contact surface between two gases. The flexibility of the system enables one to vary the initial shape of the contact surface, the shock-wave Mach number, and the density ratio across the contact surface. Three selected sets of shock-tube experiments are presented in order to demonstrate the system capabilities: (1) large-initial amplitudes with low-Mach-number incident shock waves; (2) small-initial amplitudes with moderate-Mach-number incident shock waves; and (3) shock bubble interaction. In the large-amplitude experiments a reduction of the initial velocity with respect to the linear growth prediction was measured. The results were compared to those predicted by a vorticity-deposition model and to previous experiments with moderate- and high-Mach number incident shock waves that were conducted by others. In this case, a reduction of the initial velocity was noted. However, at late times the growth rate had a 1/t behavior as in the small-amplitude low-Mach number case. In the small-amplitude moderate-Mach number shock experiments a reduction from the impulsive theory was noted at the late stages. The passage of a shock wave through a spherical bubble results in the formation of a vortex ring. Simple dimensional analysis shows that the circulation depends linearly on the speed of sound of the surrounding material and on the initial bubble radius.     

Experimental solidification of anhydrous latitic and trachytic melts at different cooling rates: The role of nucleation kinetics

Two sets of cooling experiments were run at atmospheric conditions for two anhydrous starting latitic and trachytic melts: 1) five cooling rates (25, 12.5, 3, 0.5, and 0.125 °C/min) between 1300° and 800 °C, and 2) a 0.5 °C/min cooling rate from 1300 °C with quench temperatures at 1200°, 1100°, 1000° and 900 °C. Trachytic run-products are invariably glassy. Nucleation is also suppressed in the latitic run-products at the three highest cooling rates. Conversely, in the 0.5 and 0.125 °C/min runs, latites have a crystal content of  90 vol.%. The phases are: plagioclase, clinopyroxene, glass and iron-bearing oxide (in order of abundance). The variable quench temperatures, investigated by coupling experiments with Pt wire and Pt capsule sample containers in set 2, again did not produce crystallization of trachyte, whereas latitic samples are characterized by  10 vol.% of oxides, pyroxenes and plagioclase (in order of appearance), at temperature < 1000 °C. Effects of (preferential) heterogeneous nucleation on sample holders, of superheating degree, and chemical species loss during cooling are absent for both melt compositions. The difference of solidification paths between these two silicate melts can be ascribed only to their small chemical differences. In comparison with calculated equilibrium conditions all the experimental latitic and trachytic run-products revealed strong kinetic effects, interpretable in the light of the nucleation theory. The glass-forming ability (GFA) of trachyte is higher, whereas their critical cooling rate (Rc) is lower (< 0.125 °C/min), in comparison to latitic melts (Rc > 0.5 °C/min). The experimental results carried out in this study can be applied to lava flows and domes; trachytic lavas are able to flow for longer period with respect to latitic ones in a metastable condition. Glass-rich terrestrial lavas, i.e. obsidians, can be the result of sluggish nucleation kinetics due to the relative high polymerisation of evolved silicate melts.     

The Ca-Eskola component in eclogitic clinopyroxene as a function of pressure, temperature and bulk composition: an experimental study to 15 GPa with possible implications for the formation of oriented SiO2-inclusions in omphacite

Experiments have been conducted in the P-T range 2.5–15 GPa and 850–1,500°C using bulk compositions in the systems SiO₂–TiO₂–Al₂O₃–Fe₂O₃–FeO–MnO–MgO–CaO–Na₂O–K₂O–P₂O₅ and SiO₂–TiO₂–Al₂O₃–MgO–CaO–Na₂O to investigate the Ca-Eskola (CaEs Ca_0.5□_0.5AlSi₂O₆) content of clinopyroxene in eclogitic assemblages containing garnet + clinopyroxene + SiO₂ ± TiO₂ ± kyanite as a function of P, T, and bulk composition. The results show that CaEs_ss in clinopyroxene increases with increasing T and is strongly bulk composition dependent whereby high CaEs-contents are favoured by bulk compositions with high normative anorthite and low diopside contents. In this study, a maximum of 18 mol% CaEs_ss was found at 6 GPa and 1,350°C in a kyanite-eclogite assemblage garnet + clinopyroxene + kyanite + rutile + coesite. By comparison, no significant increase in CaEs_ss with increasing P could be observed. If the formation of oriented SiO₂-rods frequently observed in eclogititc clinopyroxenes is due to the retrogressive breakdown of a CaEs-component then these textures are a cooling rather than a decompression phenomenon and are most likely to be found in kyanite-bearing eclogites cooled from temperatures ≥750°C. The presence of clinopyroxene with approx. 4 mol% CaEs_ss in an experiment conducted at 2.5 GPa/850°C confirms earlier suggestions based on field data that vacancy-rich clinopyroxenes are not necessarily restricted to ultrahigh pressure metamorphic conditions. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

北方泥炭沼泽中酚类物质释放的热敏感性研究:以英国威尔士地区雨养和矿养泥炭沼泽为例

利用高精度多梯度热培养系统,对英国威尔士地区两类典型的北方泥炭沼泽中酚类物质和溶解有机碳释放的热敏感性进行了为期1年的调查研究.研究结果表明,雨养泥炭沼泽(Bog)酚类物质释放的热敏感性Q10(总酚)月变化为0.92～1.57,而矿养泥炭沼泽(Fen)的月变化范围为0.93～1.30.酚类释放的热敏感性与土壤温度大致呈正相关关系.此外,土壤温度与溶解有机碳释放的热敏感性Q10(DOC)也呈正相关关系.总体上,雨养泥炭沼泽的热敏感性比矿养泥炭沼泽略高.除温度外,水文条件和植被等多种环境因子对酚类物质和溶解有机碳释放的热敏感性也有较大影响.研究结果还表明酚碳热敏感性比值Q10o(总酚)/Q10(DOC)相对稳定,土壤温度的变化对其影响有限.     

不同粘土矿物水敏性特征

通过改变砂样中的粘土矿物的种类和含量,结合咸淡水之间的单一和驱替实验,研究不同粘土矿物的水敏性特征。在单一的咸水和淡水情况下,当砂柱中的粘粒含量≤1.5%(重量比)时,其渗透系数基本不发生改变,即使粘粒含量从1.5%增加10%,其渗透系数也仅下降约一个数量级。各种粘土矿物中,蒙脱石导致含水介质渗透系数的下降最为明显,高岭土和伊利石约是其影响值的一半。咸淡水驱替实验中,加入蒙脱石颗粒的砂柱的渗透系数急剧下降,当蒙脱石含量达3~4%时,渗透系数已经下降的极低,可以看作不透水层,而加入高岭土和伊利石的砂柱的渗透系数没有急剧变化。对于这种现象的解释是:不同类型的粘土颗粒吸附不同数量的水分子,形成数量和大小不同的胶体团,使得介质渗透系数的变化量不同。     

大黄鱼皮肤溃烂病病原的研究

从福建省厦门西海域某渔排养殖大黄鱼(Pseudosciaena cyogga)患皮肤溃烂病的肝脏、肌肉分离到2株优势菌。人工感染试验证实其中1株为致病菌。该菌的主要生理生化特性为革兰氏阴性，短杆状，极生单鞭毛，发酵葡萄糖，氧化酶阳性，赖氨酸脱羧酶、鸟氨酸脱羧酶阳性，精氨酸脱羧酶、水杨素、枸橼酸盐阴性，不产生H2S，利用葡萄糖、甘露醇产酸，对O／129(10μg)不敏感。在含0％，10％NaCl的普通培养基上不生长；在含2％，4％，6％，8％NaCl的普通培养基中生长；在温度30，35，40℃下生长良好，但4℃不生长。初步鉴定该病原菌为副溶血弧菌(Vibrio parahaemolyticus)。药敏试验表明，该菌对卡那霉素、复方新诺明、链霉素等10种药物敏感，对青霉素G、氨苄青霉素、利福平等6种药物不敏感。