Precise/ Small Sample Size Determinations of Lithium Isotopic Compositions of Geological Reference Materials and Modern Seawater by MC-ICP-MS

The Li isotope ratios of four international rock reference materials, USGS BHVO-2, GSJ JB-2, JG-2, JA-1 and modern seawater (Mediterranean, Pacific and North Atlantic) were determined using multi-collector inductively coupled plasma-mass spectrometry (MC-ICP-MS). These reference materials of natural samples were chosen to span a considerable range in Li isotope ratios and cover several different matrices in order to provide a useful benchmark for future studies. Our new analytical technique achieves significantly higher precision and reproducibility (< ± O.3%o 2s) than previous methods, with the additional advantage of requiring very low sample masses of ca . 2 ng of Li.     

Preliminary Characterisation of New Glass Reference Materials (GSA-1G, GSC-1G, GSD-1G and GSE-1G) by Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry Using 193 nm, 213 nm and 266 nm Wavelengths

New glass reference materials GSA-1G, GSC-1G, GSD-1G and GSE-1G have been characterised using a prototype solid state laser ablation system capable of producing wavelengths of 193 nm, 213 nm and 266 nm. This system allowed comparison of the effects of different laser wavelengths under nearly identical ablation and ICP operating conditions. The wavelengths 213 nm and 266 nm were also used at higher energy densities to evaluate the influence of energy density on quantitative analysis. In addition, the glass reference materials were analysed using commercially available 266 nm Nd:YAG and 193 nm ArF excimer lasers. Laser ablation analysis was carried out using both single spot and scanning mode ablation. Using laser ablation ICP-MS, concentrations of fifty-eight elements were determined with external calibration to the NIST SRM 610 glass reference material. Instead of applying the more common internal standardisation procedure, the total concentration of all element oxide concentrations was normalised to 100%. Major element concentrations were compared with those determined by electron microprobe. In addition to NIST SRM 610 for external calibration, USGS BCR-2G was used as a more closely matrix-matched reference material in order to compare the effect of matrix-matched and non matrix-matched calibration on quantitative analysis. The results show that the various laser wavelengths and energy densities applied produced similar results, with the exception of scanning mode ablation at 266 nm without matrix-matched calibration where deviations up to 60% from the average were found. However, results acquired using a scanning mode with a matrix-matched calibration agreed with results obtained by spot analysis. The increased abundance of large particles produced when using a scanning ablation mode with NIST SRM 610, is responsible for elemental fractionation effects caused by incomplete vaporisation of large particles in the ICP.     

青海省新型功能材料研究和产业的分析(续完)

介绍了部分新型功能材料的前沿领域发展情况;通过对青海省在能源、矿产资源方面的优势及青海省可持续发展能力的分析,对我省目前及未来可以发展的新型功能材料产业提出了意见和建议。     

Discrete element model for crack propagation in brittle materials

We propose a discrete element model for brittle rupture. The material consists of a bidimensional set of closed‐packed particles in contact. We explore the isotropic elastic behavior of this regular structure to derive a rupture criterion compatible to continuum mechanics. We introduce a classical criterion of mixed mode crack propagation based on the value of the stress intensity factors, obtained by the analysis of two adjacent contacts near a crack tip. Hence, the toughness becomes a direct parameter of the model, without any calibration procedure. We verify the consistency of the formulation as well as its convergence by comparison with theoretical solutions of tensile cracks, a pre‐cracked beam, and an inclined crack under biaxial stress. Copyright © 2015 John Wiley & Sons, Ltd.     

Elastic behavior of weakly cemented contact

We investigate the elastic behavior of weakly cemented contact. We show that the radial distribution of stresses and the stiffnesses of a cemented contact are governed by the ratio a/RΛ, where R, a, and Λ are, respectively, the grain radius, the contact size, and the ratio of the elastic moduli of cement and grains. Moreover, we show that a cemented contact is always less stiff than a Hertzian contact having a similar size. Finally, we propose accurate approximate expressions of the contact stiffnesses. Copyright © 2014 John Wiley & Sons, Ltd.     

Chemo‐mechanics of cemented granular solids subjected to precipitation and dissolution of mineral species

This paper studies the chemo‐mechanics of cemented granular solids in the context of continuum thermodynamics for fluid‐saturated porous media. For this purpose, an existing constitutive model formulated in the frame of the Breakage Mechanics theory is augmented to cope with reactive processes. Chemical state variables accounting for the reactions between the solid constituents and the solutes in the pore fluid are introduced to enrich the interactions among the microstructural units simulated by the model (i.e., grains and cement bonds). Two different reactive processes are studied (i.e., grain dissolution and cement precipitation), using the chemical variables to describe the progression of the reactions and track changes in the size of grains and bonds. Finally, a homogenization strategy is used to derive the energy potentials of the solid mixture, adopting probability density functions that depend on both mechanical and chemical indices. It is shown that the connection between the statistics of the micro‐scale attributes and the continuum properties of the solid enables the mathematical capture of numerous mechanical effects of lithification and chemical deterioration, such as changes in stiffness, expansion/contraction of the elastic domain, and development of inelastic strains during reaction. In particular, the model offers an interpretation of the plastic strains generated by aggressive environments, which are here interpreted as an outcome of chemically driven debonding and comminution. As a result, the model explains widely observed macroscopic signatures of geomaterial degradation by reconciling the energetics of the deformation/reaction processes with the evolving geometry of the microstructural attributes. Copyright © 2015 John Wiley & Sons, Ltd.     

Generalized plasticity state parameter‐based model for saturated and unsaturated soils. Part II: Unsaturated soil modeling

The aim of this paper is to extend the generalized plasticity state parameter‐based model presented in part 1 to reproduce the hydro‐mechanical behavior of unsaturated soils. The proposed model is based on two pairs of stress–strain variables and a suitable hardening law taking into account the bonding—debonding effect of suction and degree of saturation. A generalized state parameter for unsaturated state is proposed to reproduce soil behavior using a single set of material parameters. Generalized plasticity gives a suitable framework to reproduce not only monotonic stress path but also cyclic behavior. The hydraulic hysteresis during a drying—wetting cycle and the void ratio effect on the hydraulic behavior is introduced. Comparison between model simulations and a series of experimental data available, both cohesive and granular, are given to illustrate the accuracy of the enhanced generalized plasticity equation. Copyright © 2010 John Wiley & Sons, Ltd.     

A long‐term study of stable isotopes as tracers of processes governing water flow and quality in a lowland river basin: the upper Thames,UK

A long‐term study of O, H and C stable isotopes has been undertaken on river waters across the 7000‐km² upper Thames lowland river basin in the southern UK. During the period, flow conditions ranged from drought to flood. A 10‐year monthly record (2003–2012) of the main River Thames showed a maximum variation of 3‰ (δ¹⁸O) and 20‰ (δ²H), although interannual average values varied little around a mean of –6.5‰ (δ¹⁸O) and –44‰ (δ²H). A δ²H/δ¹⁸O slope of 5.3 suggested a degree of evaporative enrichment, consistent with derivation from local rainfall with a weighted mean of –7.2‰ (δ¹⁸O) and –48‰ (δ²H) for the period. A tendency towards isotopic depletion of the river with increasing flow rate was noted, but at very high flows (>100 m³/s), a reversion to the mean was interpreted as the displacement of bank storage by rising groundwater levels (corroborated by measurements of specific electrical conductivity). A shorter quarterly study (October 2011–April 2013) of isotope variations in 15 tributaries with varying geology revealed different responses to evaporation, with a well‐correlated inverse relationship between Δ¹⁸O and baseflow index for most of the rivers. A comparison with aquifer waters in the basin showed that even at low flow, rivers rarely consist solely of isotopically unmodified groundwater. Long‐term monitoring (2003–2007) of carbon stable isotopes in dissolved inorganic carbon (DIC) in the Thames revealed a complex interplay between respiration, photosynthesis and evasion, but with a mean interannual δ¹³C‐DIC value of –14.8 ± 0.5‰, exchange with atmospheric carbon could be ruled out. Quarterly monitoring of the tributaries (October 2011–April 2013) indicated that in addition to the aforementioned factors, river flow variations and catchment characteristics were likely to affect δ¹³C‐DIC. Comparison with basin groundwaters of different alkalinity and δ¹³C‐DIC values showed that the origin of river baseflow is usually obscured. The findings show that long‐term monitoring of environmental tracers can help to improve the understanding of how lowland river catchments function. Copyright © NERC 2015. Hydrological Processes © 2015 John Wiley & Sons, Ltd.     

A probabilistic approach for computing water retention of particulate systems from statistics of grain size and tessellated pore network

The paper offers an analytical determination of the hydraulic properties of an unsaturated soil with reference to its retention curve, which describes the relationship between the volumetric water content and capillarity through matric suction. The analysis combines a particulate approach focused on the physics at the pore scale, including microstructural aspects, with a probabilistic approach where the void space and grain size are considered as random variables. In the end, the soil water characteristic curve of an unsaturated granular medium along a drying path can be derived analytically based on the sole information of particle size distribution. The analysis hinges on the tessellation of a wet granular system into an assemblage of tetrahedral unit cells revealing a pore network upon which capillary physics are computed with respect to pore throat invasion by a non-wetting fluid with evolving pendular capillary bridges. The crux of the paper is to pass from particle size probability distribution to a matching void space distribution to eventually reveal key information such as void cell and solid volume statistics. Making reasonable statistically based assumptions to render calculations tractable, the water retention curve can be readily constructed. Model predictions compare quite favourably with experimental data available for actual soils, especially in the high saturation range. Having a sound scientific basis, the model can be made amenable to address a variety of soils with a wider range of particle sizes.     

Dissolved inorganic carbon evolution in neutral discharge from mine tailings piles

We measured the concentrations of dissolved inorganic carbon (DIC) and major ions and the stable carbon isotope ratios of DIC (δ¹³C_DIC) in two creeks discharging from carbonate‐rich sulphide‐containing mine tailings piles. Our aim was to assess downstream carbon evolution of the tailings discharge as it interacted with the atmosphere. The discharge had pH of 6.5–8.1 and was saturated with respect to carbonates. Over the reach of one creek, the DIC concentrations decreased by 1.1 mmol C/l and δ¹³C_DIC increased by ~4.0‰ 200 m from the seep source. The decrease in the DIC concentrations was concomitant with decreases in the partial pressure of CO_2(aq) because of the loss of excess CO_2(aq) from the discharge. The corresponding enrichment in the δ¹³C_DIC is because of kinetic isotope fractionation accompanying the loss of CO_2(g). Over the reach of the other creek, there was no significant decrease in the DIC concentrations or notable changes in the δ¹³C_DIC. The insignificant change in the DIC concentrations and the δ¹³C_DIC is because the first water sample was collected 160 m away from the discharge seep, not accessible during this research. In this case, most of the excess CO_2(aq) was lost before our first sampling station. Our results indicate that neutral discharges from tailings piles quickly lose excess CO_2(aq) to the atmosphere and the DIC becomes enrich in ¹³C. We suggest that a significant amount of carbon cycling in neutral discharges from tailings piles occur close to the locations where the discharge seeps to the surface. Copyright © 2015 John Wiley & Sons, Ltd.