扎鲁特地区无烟煤分子结构特征和模型构建

为了构建内蒙古扎鲁特地区无烟煤的分子结构模型,采用工业分析、元素分析、核磁共振碳谱、高分辨率透射电镜和X射线光电子能谱等测试方法对该地区无烟煤的分子结构进行研究。结果表明无烟煤分子结构中以芳香碳为主,脂肪碳以短烷基侧链和环烷烃为主。煤分子结构中氧原子主要以酚羟基和醚氧基的形式存在,氮原子主要以吡咯型氮和吡啶型氮的形式存在,硫原子主要的赋存形态是硫醇硫酚。结合由核磁共振碳谱测得的煤结构参数和由高分辨率透射电镜测得的芳香环尺寸和含量,构建了无烟煤大分子平均结构模型。对构建的模型进行了结构优化与能量分析,发现煤分子结构的芳香片层趋于平行排列,非键结势能中的范德华力是保持煤结构稳定的主要因素。本研究为采用分子动力学模拟从分子尺度研究扎鲁特地区无烟煤在石墨化过程中,其芳香碳层的拼叠过程及其反应路径提供了模型基础。      

The chemical changes of DOM from black waters to coastal marine waters by HPLC combined with ultrahigh resolution mass spectrometry

How dissolved organic matter (DOM) undergoes chemical changes during its transit from river to ocean remains a challenge due to its complex structure. In this study, DOM along a river transect from black waters to marine waters is characterized using an offline combination of reversed-phase high performance liquid chromatography (RP-HPLC) coupled to electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICR-MS), as well as tandem ESI-FTICR-MS. In addition, a water extract from degraded wood that mainly consists of lignins is used for comparison to the DOM from this transect. The HPLC chromatograms of all DOM samples and the wood extract show two major well-separated components; one is hydrophilic and the other is hydrophobic, based on their elution order from the C₁₈ column. From the FTICR-MS analysis of the HPLC fractions, the hydrophilic components mainly contain low molecular weight compounds (less than 400 Da), while the hydrophobic fractions contain the vast majority of compounds of the bulk C₁₈ extracted DOM. The wood extract and the DOM samples from the transect of black waters to coastal marine waters show strikingly similar HPLC chromatograms, and the FTICR-MS analysis further indicates that a large fraction of molecular formulas from these samples are the same, existing as lignin-like compounds. Tandem mass spectrometry experiments show that several representative molecules from the lignin-like compounds have similar functional group losses and fragmentation patterns, consistent with modified lignin structural entities in the wood extract and these DOM samples. Taken together, these data suggest that lignin-derived compounds may survive the transit from the river to the coastal ocean and can accumulate there because of their refractory nature.     

Hydraulic properties of peat soils along a bulk density gradient—A meta study

Our understanding of hydraulic properties of peat soils is limited compared with that of mineral substrates. In this study, we aimed to deduce possible alterations of hydraulic properties of peat soils following degradation resulting from peat drainage and aeration. A data set of peat hydraulic properties (188 soil water retention curves [SWRCs], 71 unsaturated hydraulic conductivity curves [UHCs], and 256 saturated hydraulic conductivity [K_s] values) was assembled from the literature; the obtained data originated from peat samples with an organic matter (OM) content ranging from 23 to 97 wt% (weight percent; and according variation in bulk density) representing various degrees of peat degradation. The Mualem‐van Genuchten model was employed to describe the SWRCs and UHCs. The results show that the hydraulic parameters of peat soils vary over a wide range confirming the pronounced diversity of peat. Peat decomposition significantly modifies all hydraulic parameters. A bulk density of approximately 0.2 g cm^?3 was identified as a critical threshold point; above and below this value, macroporosity and hydraulic parameters follow different functions with bulk density. Pedotransfer functions based on physical peat properties (e.g., bulk density and soil depth) separately computed for bog and fen peat have significantly lower mean square errors than functions obtained from the complete data set, which indicates that not only the status of peat decomposition but also the peat‐forming plants have a large effect on hydraulic properties. The SWRCs of samples with a bulk density of less than 0.2 g cm^?3 could be grouped into two to five classes for each peat type (botanical composition). The remaining SWRCs originating from samples with a bulk density of larger than 0.2 g cm^?3 could be classified into one group. The Mualem‐van Genuchten parameter values of α can be used to estimate K_s if no K_s data are available. In conclusion, the derived pedotransfer functions provide a solid instrument to derive hydraulic parameter values from easily measurable quantities; however, additional research is required to reduce uncertainty.     

Estimation of areal specific yield in sands using the central limit theorem

A new approach is demonstrated that permits a reliable estimate of specific yield using published values of the van Genuchten water retention parameters and effective grain sizes and the measured effective grain sizes of soil samples. The specific yield distribution of the soil texture was computed using the published values of the van Genuchten parameters. The specific yield values and the published values of effective grain sizes were then used to construct a specific yield–effective grain size curve, which estimates the ‘point’ specific yield of the soil samples. Applying the central limit theorem, the point specific yields could be transformed into an ‘areal’ specific yield for a study area. Compared with other commonly used approaches, the present procedure requires relatively low computational efforts and readily obtainable data. It is cost effective and does not depend on soil texture classification. More importantly, it incorporates the depth to water table and the variations in grain sizes inherent in natural soil conditions in the estimation. The approach developed was applied for estimating the specific yield of an unconfined sandy aquifer created by land reclamation in the equatorial region. The values obtained were compared with field measurements and the typical ranges of specific yield from the literature. Instead of a single estimate of the specific yield, the method yields a confidence interval with a high confidence level of 95% and with a narrower range than the typical ranges from the literature. In addition, the estimated values are close to the field measurements; hence, the procedure provides a cost‐effective alternative to field measurement. The applicability of the present approach could be extended to sites with heterogeneity in the horizontal direction. Nevertheless, the applicability of the present approach for layered soil profiles requires further evaluations. Copyright © 2006 John Wiley & Sons, Ltd.     

Shallow sediment transport flow computation using time-varying sediment adaptation length

Based on the common approach,the adaptation length in sediment transport is normally estimated astemporally independent.However,this approach might not be theoretically justified as the process of reaching the sediment transport equilibrium stage is affected by the flow conditions in time,especially for fast moving flows,such as scour-hole developing flows.In this study,the two-dimensional（2D） shallow water formulation together with a sediment continuity-concentration（SCC） model were applied to flow with mobile sediment boundary.A timevarying approach was proposed to determine the sediment transport adaptation length to simulate the sediment erosion-deposition rate.The proposed computational model was based on the Finite Volume（FV） method.The Monotone Upwind Scheme of Conservative Laws（MUSCL）-Hancock scheme was used with the Harten Lax van Leer-contact（HLLC） approximate Riemann solver to discretize the FV model.In the flow applications of this paper,a highly discontinuous dam-break,fast sediment transport flow was used to calibrate the proposed timevarying sediment adaptation length model.Then the calibrated model was further applied to two separate experimental sediment transport flow applications documented in the literature,i.e.a highly concentrated sediment transport flow in a wide alluvial channel and a sediment aggradation flow.Good agreement with the experimental data were obtained with the proposed model simulations.The tests prove that the proposed model,which was calibrated by the discontinuous dam-break bed scouring flow,also performed well to represent rapid bed change and steady sediment mobility conditions.     

土壤水分特征曲线在天然气水合物开采数值模拟中的应用探讨

在使用TOUGH+HYDRATE程序进行水合物开采数值模拟时常用van Genuchten模型计算毛管力,而毛管力大小直接影响水合物开采过程中的产气和产水,因此在数值模拟过程中正确选用模型参数尤为必要。我国某海域天然气水合物储层为未胶结泥质粉砂储层,常规的毛管力测定方法如压汞法、离心法等对该类岩心并不适用,如何测定该类岩心的毛管力并将其应用于van Genuchten模型参数选取具有重要意义。本文探讨了如何应用土壤水分特征曲线测定实验间接获取该类岩心的毛管力数据,为验证该方法的可行性,本文对参考文献[7]中公开的粉砂土壤水分特征曲线测定实验数据进行换算和拟合后得到T+H程序所需的van Genuchten模型参数,结果可为泥质粉砂储层水合物产能研究工作提供参考。     

Anisotropic Cosmological Models with a Perfect Fluid and a Λ Term

We consider a self-consistent system of Bianchi type-I (BI) gravitational field and a binary mixture of perfect fluid and dark energy given by a cosmological constant. The perfect fluid is chosen to be the one obeying either the usual equation of state, i.e., p = ζ, with ζ ∊ [0, 1] or a van der Waals equation of state. Role of the Λ term in the evolution of the BI Universe has been studied.     

并列双圆柱涡激振动的经验性模型研究

建立一种新的预报并列双圆柱涡激振动响应的经验性模型,根据特定间距比条件下旋涡脱落频率出现分支的现象,提出以两个具有不同固有频率的尾流振子来共同描述结构的近壁尾涡动力特性,同时两个振子均满足van der Pol方程,进而得到结构振子和流体振子的耦合方程组。使用该模型分别对中高质量比和低质量比的并列圆柱涡激振动问题进行数值计算,结果表明,结构的位移响应和最大振动幅值等变化规律与实验结果趋势一致,数值基本吻合。     

非饱和粉土路基内水分迁移规律试验研究

动载作用下非饱和粉土路基内部的水分迁移规律,对研究重载铁路在浸水状态下的路基稳定具有重要意义。基于范德堡原理,利用土样的电阻率特性,研制出一套基于GDS动三轴仪的非饱和土样含水率分布规律测试系统。利用该系统开展浸水动三轴试验,并对试验过程中非饱和试样的分层含水率进行连续测试,探究土样的初始压实度、动载的动应力幅值对非饱和土样内部水分迁移的影响规律。结果表明：该测试系统可在动三轴试验过程中对非饱和试样的分层含水率进行实时、无损、连续地测定,测试结果的最大误差为0.7%;非饱和土样在动载作用下随其含水率逐渐增大,土样的初始压实度对电阻率的影响程度减弱,接近饱和含水率时可忽略;土样初始压实度、含水率与土体电阻率具有确定的函数表达式,并具有良好的相关性及唯一性。结合试验结果分析认为：降雨及动荷载共同作用下,路基内水分在某一深度土体积聚,该区域孔隙水压力增大,强度降低,导致翻浆冒泥病害的发生;路基压实度及列车轴重增大,均会抑制路基内水分向下部迁移,有助于路基的稳定,但轴重增加,可能导致路基的失稳,当轴重大于临界动应力时,路基将发生破坏。     

Effect of mineral reactions on the hydraulic properties of unsaturated soils: Model development and application

The selective radius shift model was used to relate changes in mineral volume due to precipitation/dissolution reactions to changes in hydraulic properties affecting flow in porous media. The model accounts for (i) precipitation/dissolution taking place only in the water-filled part of the pore space and further that (ii) the amount of mineral precipitation/dissolution within a pore depends on the local pore volume. The pore bundle concept was used to connect pore-scale changes to macroscopic soil hydraulic properties. Precipitation/dissolution induces changes in the pore radii of water-filled pores and, consequently, in the effective porosity. In a time step of the numerical model, mineral reactions lead to a discontinuous pore-size distribution because only the water-filled pores are affected. The pore-size distribution is converted back to a soil moisture characteristic function to which a new water retention curve is fitted under physically plausible constraints. The model equations were derived for the commonly used van Genuchten/Mualem hydraulic properties. Together with a mixed-form solution of Richards’ equation for aqueous phase flow, the model was implemented into the geochemical modelling framework PHREEQC, thereby making available PHREEQC’s comprehensive geochemical reactions. Example applications include kinetic halite dissolution and calcite precipitation as a consequence of cation exchange. These applications showed marked changes in the soil’s hydraulic properties due to mineral precipitation/dissolution and the dependency of these changes on water contents. The simulations also revealed the strong influence of the degree of saturation on the development of the saturated hydraulic conductivity through its quadratic dependency on the van Genuchten parameter α. Furthermore, it was shown that the unsaturated hydraulic conductivity at fixed reduced water content can even increase during precipitation due to changes in the pore-size distribution.