Ab initio molecular orbital calculations for boron isotope fractionations on boric acids and borates

Ab initio quantum chemistry calculations have been performed on the isotopic exchange reaction between B(OH)₃ and B(OH)₄⁻. Several calculation methods have been carefully compared and evaluated. The “water-droplet” method is chosen to investigate this isotope exchange reaction using cluster models with up to 34 water molecules surrounding the solute. HF/6-31G* level calculations coupled with a 0.920 scaling factor are used for the frequency calculations. A larger K value (1.027) is obtained from this study compared to the commonly used 1.0194 (Kakihana et al., 1977).The fractionations for several boric acid polymers and boron minerals are also studied. Our results suggest that assuming the BO₄ bonding in B(OH)₄⁻ is identical to that in borosilicates is wrong. Tetrahedral boron in silicates has a significantly smaller reduced isotopic partition function ratio (RPFR) and hence will be much isotopically lighter than in B(OH)₄⁻.The new theoretical curve of pH vs. δ¹¹B composition of B(OH)₄⁻ using our calculated 1.027 can be used to predict pH values for equilibrium cases such as incorporation into inorganic calcite. We also find that the shape of this curve is very sensitive to both K and pK_a value, giving the possibility of also predicting salinity from the different shapes of the curve.     

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。     

Development of a soil moisture‐based distributed hydrologic model for determining hydrologically based critical source areas

A simple grid cell‐based distributed hydrologic model was developed to provide spatial information on hydrologic components for determining hydrologically based critical source areas. The model represents the critical process (soil moisture variation) to run‐off generation accounting for both local and global water balance. In this way, it simulates both infiltration excess run‐off and saturation excess run‐off. The model was tested by multisite and multivariable evaluation on the 50‐km² Little River Experimental Watershed I in Georgia, U.S. and 2 smaller nested subwatersheds. Water balance, hydrograph, and soil moisture were simulated and compared to observed data. For streamflow calibration, the daily Nash‐Sutcliffe coefficient was 0.78 at the watershed outlet and 0.56 and 0.75 at the 2 nested subwatersheds. For the validation period, the Nash‐Sutcliffe coefficients were 0.79 at the watershed outlet and 0.85 and 0.83 at the 2 subwatersheds. The per cent bias was less than 15% for all sites. For soil moisture, the model also predicted the rising and declining trends at 4 of the 5 measurement sites. The spatial distribution of surface run‐off simulated by the model was mainly controlled by local characteristics (precipitation, soil properties, and land cover) on dry days and by global watershed characteristics (relative position within the watershed and hydrologic connectivity) on wet days when saturation excess run‐off was simulated. The spatial details of run‐off generation and travel time along flow paths provided by the model are helpful for watershed managers to further identify critical source areas of non‐point source pollution and develop best management practices.     

Effects of Enclosure on Plant and Soil Nutrients in Different Types of Alpine Grassland

Enclosure is one of the most widely used management tools for degraded alpine grassland on the northern Tibetan Plateau, but the responses of different types of grassland to enclosure may vary, and research on these responses can provide a scientific basis for improving ecological conservation. This study took one site for each of three grassland types (alpine meadow, alpine steppe and alpine desert) on the northern Tibetan Plateau as examples, and explored the effects of enclosure on plant and soil nutrients by comparing differences in plant community biomass, leaf-soil nutrient content and their stoichiometry between samples from inside and outside the fence. The results showed that enclosure can significantly increase all aboveground biomass in these three grassland types, but it only increased the 10-20 cm underground biomass in the alpine desert. Enclosure also significantly increased the leaf nutrient content of the dominant plants and contents of total nitrogen (N), total potassium (K), and organic carbon (C) in 10-20 cm soil in alpine desert, thus changing the stoichiometry between C, N and P (phosphorus). However, enclosure significantly increased only the N content of dominant plant leaves in alpine steppe, while other nutrients and stoichiometries of both plant leaves and soil did not show significant differences in alpine meadow and alpine steppe. These results suggested that enclosure has differential effects on these three types of alpine grasslands on the northern Tibetan Plateau, and the alpine desert showed the most active ecological conservation in the responses of its soil and plant nutrients.     

Steady‐state analytical solutions of flow and deformation coupling due to a point sink within a finite fluid‐saturated poroelastic layer

An exact steady‐state closed‐form solution is presented for coupled flow and deformation of an axisymmetric isotropic homogeneous fluid‐saturated poroelastic layer with a finite radius due to a point sink. The hydromechanical behavior of the poroelastic layer is governed by Biot's consolidation theory. Boundary conditions on the lateral surface are specifically chosen to match the appropriate finite Hankel transforms and simplify the transforms of the governing equations. Ordinary differential equations in the transformed domain are solved, and then the analytical solutions in the physical space for the pore pressure and the displacements are finally obtained by using finite Hankel inversions. The analytical solutions at some special locations such as the top and bottom surfaces, lateral surface, and the symmetrical axis are given and analyzed. And a case study for the consolidation of a water‐saturated soft clay layer due to pumping is conducted. The analytical solution is verified against the finite element solution. Meanwhile, an analysis of coupled hydromechanical behavior is carried out herein. The presented analytical solution is an exact solution to the practical poroelastic problem within an axisymmetric finite layer. It can provide us a better understanding of the poroelastic behavior of the finite layer due to fluid extraction. Besides, it can be applied to calibrate numerical schemes of axisymmetric poroelasticity within finite domains. Copyright © 2017 John Wiley & Sons, Ltd.     

Geophysical constraints on mesozoic disruption of North China Craton by underplating‐triggered lower‐crust flow of the Archaean lithosphere

The mechanism of the disruption, both lithospheric thinning and oceanization of the commonly accepted long‐term‐stable Archaean craton, is still an open question. The available models, all imply a bottom to top process. With the construction of a 1660‐km‐long transect across the eastern North China Craton (NCC), we demonstrate that both the P‐wave velocity and density in the lowermost crust beneath the central section are significantly higher than in the corresponding parts of the south and north sections on the transect. These features are interpreted as geophysical signature of lower crustal underplating, which supplies sufficiently high gravitational potential energy to trigger lateral flow of the lower crust. This magma underplating‐triggered bilateral lower crust flow may facilitate the lithospheric thinning by means of asthenosphere upwelling and decompression melting, which infill the gap produced by the lower crust flow. The underplating‐triggered lower crustal flow can provide an alternative mechanism to explain the NCC lithosphere disruption, which highlights the crustal feedback to Archaean lithosphere disruption, from top to bottom.     

On the relationship between historical land‐use change and water availability: the case of the lower Tarim River region in northwestern China

Natural ecosystems in the region of the lower Tarim River in northwestern China strongly deteriorated since the 1950s due to an expanding desertification. As a result, the downstream Tarim River reaches became permanently dry land. This historical evolution in land‐use change is typically the result of the anthropogenic impact on natural ecosystems. On the basis of a spatially distributed hydrological catchment model bidirectionally linked with a fully hydrodynamic MIKE11 river model, land‐use changes characterized by historical changes in leaf area index (LAI) of vegetation, as well as the evolution of irrigated surface areas, can be causally related to changes in water resources (groundwater storage and surface water resources). An increased surface area of irrigated (agricultural) land, together with a majority of inefficient irrigation methods, did lead to a strong increase of water resources consumption of the farmlands located in the upper Tarim River area. Evidently, this evolution influenced available water resources downstream in the Tarim basin. As a result, farmland has been gradually relocated to the upstream regions. This has led to reduced flows from the upper Tarim stream, which subsequently accelerated the dropping of the groundwater level downstream in the basin. This study moreover demonstrates that land surface biomass changes (cumulative LAI) along the lower Tarim River are strongly related to the changes in groundwater storage. Copyright © 2012 John Wiley & Sons, Ltd.     

Multiple overpressure systems and their relationship with hydrocarbon accumulation in the Qikou Depression of the Bohai Bay Basin,China

Pressure measurements using drill stem tests and estimates from log data calculation indicate that three vertically stacked regional pressure compartments exist in the Qikou Depression of Bohai Bay Basin, N. China. The compartments comprise hydrostatic, upper weak, and lower overpressure systems. Laterally, overpressure (pressure coefficient > 1.2) occurs in the deeper areas and weakens gradually from the centre to the margin of the depression. The accumulation of oil and gas exhibits the interesting characteristics of oil‐bearing layers above gas‐bearing layers in the Qikou Depression. The pattern can be accounted for by the evolution of overpressure system, the maturity process of the source rock and the main fault activity. In the late Dongying Formation (Ed, 30 Ma), the lower overpressure system began to form shape, and the hydrocarbon sources generated a large volume of oil. However, because there was no migration pathway, the oil only accumulated in the original strata. In the late Guantao Formation (Ng, 12 Ma), the gas was generated, the upper overpressure system formed gradually, and the activity of the main fault gradually increased. Then, the overpressure pushed the early gathered oil to flow from the lower overpressure system into the upper overpressure system. Afterwards, the activity of the main fault decreased again and remains weak until now. Thus, later generated natural gas cannot keep migrating along the main fault and can only accumulate in the lower overpressure system. Copyright © 2014 John Wiley & Sons, Ltd.