浓硫酸钠水溶液中的离子对

不同浓度的Na2SO4水溶液的拉曼光谱显示了SO42-的四个拉曼活性带:980 cm-1处的SO42-的对称伸缩振动模式v1带,1 106 cm-1处的反对称伸缩振动模式v3带,448 cm-1处的变形振动模式v2带和617 cm-1处的变形振动模式v4带。482 cm-1处的肩膀峰是由于NaSO4-离子对的形成对448 cm-1的v2带的影响而形成的SO42-的一个新的振动峰。浓Na2SO4水溶液中,水共享离子对[Na+.H2O.SO42-]-是主要的离子对物种。随着Na2SO4水溶液浓度的增加,Na+和SO42-的相互作用增强,NaSO4-离子对所占的摩尔分数增加。     

The influence of coupled physical swelling and chemical reactions on deformable geomaterials

Coupled thermo‐hydro‐mechanical‐chemical modelling has attracted attention in past decades due to many contemporary geotechnical engineering applications (e.g., waste disposal, carbon capture and storage). However, molecular‐scale interactions within geomaterials (e.g., swelling and dissolution/precipitation) have a significant influence on the mechanical behaviour, yet are rarely incorporated into existing Thermal‐Hydro‐Mechanical‐Chemical (THMC) frameworks. This paper presents a new coupled hydro‐mechanical‐chemical constitutive model to bridge molecular‐scale interactions with macro‐physical deformation by combining the swelling and dissolution/precipitation through an extension of the new mixture‐coupling theory. Entropy analysis of the geomaterial system provides dissipation energy, and Helmholtz free energy gives the relationship between solids and fluids. Numerical simulation is used to compare with the selected recognized models, which demonstrates that the swelling and dissolution/precipitation processes may have a significant influence on the mechanical deformation of the geomaterials.     

Quantifying the impact of landscape changes on hydrological variables in the alpine and cold region using hydrological model and remote sensing data

Quantifying the impact of landscape on hydrological variables is essential for the sustainable development of water resources. Understanding how landscape changes influence hydrological variables will greatly enhance the understanding of hydrological processes. Important vegetation parameters are considered in this study by using remote sensing data and VIC-CAS model to analyse the impact of landscape changes on hydrology in upper reaches of the Shule River Basin (URSLB). The results show there are differences in the runoff generation of landscape both in space and time. With increasing altitude, the runoff yields increased, with approximately 79.9% of the total runoff generated in the high mountains (4200–5900 m), and mainly consumed in the mid-low mountain region. Glacier landscape produced the largest runoff yields (24.9% of the total runoff), followed by low-coverage grassland (LG; 22.5%), alpine cold desert (AL; 19.6%), mid-coverage grassland (MG; 15.6%), bare land (12.5%), high-coverage grassland (HG; 4.5%) and shrubbery (0.4%). The relative capacity of runoff generation by landscapes, from high to low, was the glaciers, AL, LG, HG, MG, shrubbery and bare land. Furthermore, changes in landscapes cause hydrological variables changes, including evapotranspiration, runoff and baseflow. The study revealed that HG, MG, and bare land have a positive impact on evapotranspiration and a negative impact on runoff and baseflow, whereas AL and LG have a positive impact on runoff and baseflow and a negative impact on evapotranspiration. In contrast, glaciers have a positive impact on runoff. After the simulation in four vegetation scenarios, we concluded that the runoff regulation ability of grassland is greater than that of bare land. The grassland landscape is essential since it reduced the flood peak and conserved the soil and water.     

Diatom‐based reconstruction of summer sea‐surface salinity in the South China Sea over the last 15 000 years

We present a new reconstruction of summer sea‐surface salinity (SSS) over the past 15 000 years based on a diatom record from piston core 17940, located on the northern slope of the South China Sea (SCS). The reconstructed diatom‐based summer SSS values for the modern period are in accord with instrumental observations of summer SSS in the area. Here, the modern summer SSS is primarily controlled by river runoff, in particular from the Pearl River. The reconstruction presented in this study shows that the summer SSS varied between 33.3 and 34.2 psu over the past 15 000 years. The long‐term summer SSS trend closely followed the trend of the orbitally controlled solar insolation at 20°N, suggesting that orbital forcing was the dominant driver of changes in summer SSS in this area. Comparisons to speleothem δ¹⁸O data and studies of surface hydrography in the region suggest that changes in solar insolation affected the summer SSS through changes in the East Asian Monsoon and sea‐level changes associated with the last deglaciation. Univariate spectral analyses indicate that centennial‐scale oscillatory variations in summer SSS were superimposed on the long‐term trend. During the deglacial period (c. 12 000–9000 cal. a BP), the dominant periodicity was centred around 230–250 years, whereas a ～350‐year oscillation dominated in the period 2200–4500 cal. a BP. The balance of evidence suggests that these centennial‐scale changes in summer SSS may have been driven by solar‐induced changes in the East Asian Monsoon, but further evidence is needed to firmly establish this relationship.     

A two‐dimensional coupled hydromechanical discontinuum model for simulating rock hydraulic fracturing

Within the framework of our discontinuous deformation analysis for rock failure algorithm, this paper presents a two‐dimensional coupled hydromechanical discontinuum model for simulating the rock hydraulic fracturing process. In the proposed approach, based on the generated joint network, the calculation of fluid mechanics is performed first to obtain the seepage pressure near the tips of existing cracks, and then the fluid pressure is treated as linearly distributed loads on corresponding block boundaries. The contribution of the hydraulic pressure to the initiation/propagation of the cracks is considered by adding the components of these blocks into the force matrix of the global equilibrium equation. Finally, failure criteria are applied at the crack tips to determine the occurrence of cracking events. Several verification examples are simulated, and the results show that this newly proposed numerical model can simulate the hydraulic fracturing process correctly and effectively. Although the numerical and experimental verifications focus on one unique preexisting crack, because of the capability of discontinuous deformation analysis in simulating block‐like structures, the proposed approach is capable of modeling rock hydraulic fracturing processes. Copyright © 2014 John Wiley & Sons, Ltd.     

Influence of heterogeneity on unsaturated hydraulic properties: (1) local heterogeneity and scale effect

Spatial heterogeneity is ubiquitous in nature, which may significantly affect the soil hydraulic property curves. The models of a closed‐form functional relationship of soil hydraulic property curves (e.g. VG model or exponential model) are valid at point or local scale based on a point‐scale hydrological process, but how do scale effects of heterogeneity have an influence on the parameters of these models when the models are used in a larger scale process? This paper uses a two‐dimensional variably saturated flow and solute transport finite element model (VSAFT2) to simulate variations of pressure and moisture content in the soil flume under a constant head boundary condition. By changing different numerical simulation block sizes, a quantitative evaluation of parameter variations in the VG model, resulting from the scale effects, is presented. Results show that the parameters of soil hydraulic properties are independent of scale in homogeneous media. Parameters of α and n in homogeneous media, which are estimated by using the unsaturated hydraulic conductivity curve (UHC) or the soil water retention curve (WRC), are identical. Variations of local heterogeneities strongly affect the soil hydraulic properties, and the scale affects the results of the parameter estimations when numerical experiments are conducted. Furthermore, the discrepancy of each curve becomes considerable when moisture content becomes closer to a dry situation. Parameters estimated by UHC are totally different from the ones estimated by WRC. Copyright © 2012 John Wiley & Sons, Ltd.     

固体聚合膜电解浓集法测量天然水中低含量氚的化学淬灭效应研究

固体聚合膜电解浓集法是浓缩氚含量较低(1 Bq/m~3)的天然水样的常用方法,但因水样自身含有杂质离子或电解装置聚合膜带入杂质进入浓集液,使浓集液偏酸性,在测量过程中易产生化学淬灭效应,导致氚的测量值偏低。本文研究了水样自身存在的杂质离子和聚合膜上残留的杂质离子、样品溶液的pH值及其电导率所产生的化学淬灭效应的影响,实验表明,为减少化学淬灭效应,提高测量低含量氚的准确性,需保证水样溶液呈中性,电导率≤1μS/cm,同时避免杂质沉积在聚合膜上。如果水样溶液的pH值偏酸性、电导率大于1μS/cm,可采用酸碱混合型离子交换树脂去除水样中自身的杂质;对于聚合膜引入的杂质,可在电解后的水样中加入微量氨水将其pH值调节至中性。