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。     

An alternative Boussinesq equation considering the effect of hysteresis on coastal groundwater waves

This paper presents an alternative Boussinesq equation considering hysteresis effect via a third‐order derivative term. By introducing an improved moisture–pressure retention function, this equation describes, with reasonable precision, groundwater propagation in coastal aquifers subject to Dirichlet boundary condition of different oscillation frequencies. Test results confirmed that it is necessary to consider horizontal and vertical flows in unsaturated zone, because of their variable influences on hysteresis. Hysteresis in unsaturated zone can affect the water table wave number of groundwater wave motion, such as wave damping rate and phase lag. Oscillations with different periods exert different hysteresis effect on wave propagation. Truncation/shrinkage of unsaturated zones also affects the strength of hysteresis. These impacts can be reflected in the alternative Boussinesq equation by adjusting the parameter representing the variation rate of moisture associated with pressure change, as opposed to traditional computationally expensive hysteresis algorithms. The present Boussinesq equation is simple to use and can provide feasible basis for future coupling of groundwater and surface water models. Copyright © 2016 John Wiley & Sons, Ltd.     

Validating the ability of the discontinuous deformation analysis method to model normal P‐wave propagation across rock fractures

The effects of fractures on wave propagation problems are increasingly abstracting the attention of scholars and engineers in rock engineering field. This study aims to fully validate the ability of discontinuous deformation analysis (DDA) to model normal P‐wave propagation across rock fractures. The effects of a single fracture and multiple parallel fractures are all tested. The results indicate that DDA can accurately reflect the fracture effects, including the fractures stiffness, the fracture spacing and the fracture number, and the effects of incident wave frequency on one‐dimensional P‐wave propagation problems. Thus, DDA is able to deal well with normal incident P‐wave propagation problems. Copyright © 2017 John Wiley & Sons, Ltd.     

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.     

Trend and extreme occurrence of precipitation in a mid‐latitude Eurasian steppe watershed at various time scales

The confounding effects of step change invalidate the stationarity assumption of commonly used trend analysis methods such as the Mann–Kendall test technique, so previous studies have failed to explain inconsistencies between detected trends and observed large precipitation anomalies. The objectives of this study were to (1) formulate a trend analysis approach that considers nonstationarity due to step changes, (2) use this approach to detect trends and extreme occurrences of precipitation in a mid‐latitude Eurasian steppe watershed in North China, and (3) examine how runoff responds to precipitation trends in the study watershed. Our results indicate that annual precipitation underwent a marginal step jump around 1995. The significant annual downward trend after 1994 was primarily due to a decrease in summer rainfall; other seasons exhibited no significant precipitation trends. At a monthly scale, July rainfall after 1994 exhibited a significant downward trend, whereas precipitation in other months had no trend. The percentage of wet days also underwent a step jump around 1994 following a significant decreasing trend, although the precipitation intensity exhibited neither a step change nor any significant trend. However, both low‐frequency and high‐frequency precipitation events in the study watershed occurred more often after than before 1994; probably as either a result or an indicator of climate change. In response to these precipitation changes, the study watershed had distinctly different precipitation‐runoff relationships for observed annual precipitations of less than 300 mm, between 300 and 400 mm, and greater than 400 mm. Copyright © 2013 John Wiley & Sons, Ltd.     

The effect of expansion ratio on the critical Reynolds number in single fracture flow with sudden expansion

Flow in a single fracture (SF) is an important research subject in groundwater hydrology, hydraulic engineering, radioactive nuclear waste repository and geotechnical engineering. An abruptly changing aperture is a unique type of SF. This study discusses the relation between the values of the critical Reynolds number (Re_c) for the onset of symmetry breaking of flow and the expansion ratio (E) of SF, which is defined as the ratio between the outlet (D) and inlet (d) apertures. This study also investigates the effect of inlet aperture d on Re_c for flow in an SF with abruptly changing apertures (SF‐ACA) using the finite volume method. Earlier numerical and experimental results showed that flow is symmetric in respect to the central plane of the SF‐ACA at small Reynolds number (Re) but becomes asymmetric when Re is sufficiently large. Our simulations show that the value of Re_c decreases with the increasing E, and the relationship between the logarithm of Re_c and E can be described accurately using either a quadratic polynomial function or a logarithmic function. However, the relationship of Re_c and d for a given E value is vague, and Re_c becomes even less sensitive to d when E increases. This study also reveals that the hydraulic gradient (J) and flow velocity (v) follow a super‐linear relationship that can be fitted almost perfectly by the Forchheimer equation. The inertial component (J_i) of J increases monotonically with Re, whereas the viscous component (J_v) of J decreases monotonically with Re. The Re value corresponding to equal inertial and viscous components of J (named as the transitional point Re) decreases when E increases, and such a transitional point Re should be closely related to the critical Reynolds number Re_c, although a rigorous theoretical proof is not yet available. Copyright © 2015 John Wiley & Sons, Ltd.