Wave propagation in nonlinear one-dimensional soil model

The objective of the research conducted by the authors is to explore the feasibility of determining reliable in situ values of shear modulus as a function of strain. In this paper the meaning of the material stiffness obtained from impact and harmonic excitation tests on a surface slab is discussed. A one-dimensional discrete model with the nonlinear material stiffness is used for this purpose. When a static load is applied followed by an impact excitation, if the amplitude of the impact is very small, the measured wave velocity using the cross-correlation indicates the wave velocity calculated from the tangent modulus corresponding to the state of stress caused by the applied static load. The duration of the impact affects the magnitude of the displacement and the particle velocity but has very little effect on the estimation of the wave velocity for the magnitudes considered herein. When a harmonic excitation is applied, the cross-correlation of the time histories at different depths estimates a wave velocity close to the one calculated from the secant modulus in the stress-strain loop under steady-state condition. Copyright © 2008 John Wiley & Sons, Ltd.

Abundance and conservation status of the Yangtze finless porpoise in the Yangtze River, China

middle and lower reaches of the Yangtze River, China. It is the only freshwater population of porpoises in the world and is currently listed as Endangered by IUCN. In November and December 2006 we used two boats and line transect methods to survey the entire current range of the population, except for two lakes (Poyang and Dongting). Sighting results were similar for both boats, so we pooled all data and analyzed them using two line transect models and a strip transect model. All models produced similar estimates of abundance (1111, 1225 and 1000). We then added independent estimates of the number of porpoises from the two lakes for a total estimate of approximately 1800 porpoises. Our findings indicate that the population continues to decline and that its distribution is becoming more fragmented. Our current estimate in the main river is slightly less than half the estimate from surveys between 1984 and 1991 (which was probably an underestimate). We also found an apparent gap in the distribution of porpoises between Yueyang and Shishou (similar to 150 km), where sightings had previously been common. Continued threats to Yangtze finless porpoises include bycatch in unregulated and unselective fishing, habitat degradation through dredging, pollution and noise, vessel strikes and water development. Immediate protective measures are urgently needed to ensure the persistence of finless porpoises in the Yangtze River. The survey design and analytical methods developed in this study might be appropriate for surveys of cetaceans in other river systems. (c) 2008 Elsevier Ltd. All rights reserved.

Amorphous silicon thin film transistor biosensing system

Electronic systems are a very good platform for sensing biological signals for fast point-of-care diagnostics or threat detection. One of the solutions is the lab-on-a-chip integrated circuit (IC), which is low cost and high reliability, offering the possibility for label-free detection. In recent years, similar integrated biosensors based on the conventional complementary metal oxide semiconductor (CMOS) technology have been reported. However, post-fabrication processes are essential for all classes of CMOS biochips, requiring biocompatible electrode deposition and circuit encapsulation. In this work, we present an amorphous silicon (a-Si) thin film transistor (TFT) array based sensing approach, which greatly simplifies the fabrication procedures and even decreases the cost of the biosensor. The device contains several identical sensor pixels with amplifiers to boost the sensitivity. Ring oscillator and logic circuits are also integrated to achieve different measurement methodologies, including electro-analytical methods such as amperometric and cyclic voltammetric modes. The system also supports different operational modes. For example, depending on the required detection arrangement, a sample droplet could be placed on the sensing pads or the device could be immersed into the sample solution for real time in-situ measurement. The entire system is designed and fabricated using a low temperature TFT process that is compatible to plastic substrates. No additional processing is required prior to biological measurement. A Cr/Au double layer is used for the biological-electronic interface. The success of the TFT-based system used in this work will open new avenues for flexible label-free or low-cost disposable biosensors. © 2013 Materials Research Society.

Analysis for temperature and pressure fields in process of hydrate dissociation by depressurization

An improved axisymmetric mathematic modeling is proposed for the process of hydrate dissociation by depressurization around vertical well. To reckon in the effect of latent heat of gas hydrate at the decomposition front, the energy balance equation is employed. The semi-analytic solutions for temperature and pressure fields are obtained by using Boltzmann-transformation. The location of decomposition front is determined by solving initial value problem for system of ordinary differential equations. The distributions of pressure and temperature along horizontal radiate in the reservoir are calculated. The numeric results indicate that the moving speed of decomposition front is sensitively dependent on the well pressure and the sediment permeability. Copyright (C) 2010 John Wiley & Sons, Ltd.

Scaling and the thermal conductivity of the Frenkel-Kontorova model

We have studied the dependence of the thermal conductivity kappa on the strength of the interparticle potential lambda and the strength of the external potential beta in the Frenkel-Kontorova model. We found that the functional relation can be expressed in a scaling form, kappa(proportional to) lambda 3/2/beta(2 center dot). This result is first obtained by nonequilibrium molecular dynamics. It is then confirmed by two analytical methods, the self-consistent phonon theory and the self-consistent stochastic reservoirs method. The thermal conductivity kappa is therefore a decreasing functon of beta and an increasing function of lambda.

UV-photooxidation as pretreatment step in inorganic analysis of environmental samples

Many laboratories deal with the determination of heavy metals, carbon, nitrogen and phosphorus. The first step in chemical analysis is a proper preparation of the investigated samples. The presence of organic substances can cause problems in many analytical methods. This paper describes the application of UV irradiation as a method of destruction of organic matter in the investigated samples.

Structural elucidation and identification of alkaloids in Rhizoma Coptidis by electrospray ionization tandem mass spectrometry

Simple, convenient, sensitive and accurate analytical methods are needed for the structural characterization and identification of alkaloid components in Rhizoma Coptidis in traditional Chinese herbal medicine, which has important bioactivity. In this work, the identification of alkaloid compounds in Rhizoma Coptidis was investigated by obtaining molecular mass information using electrospray ionization mass spectrometry (ESI-MS). Multi-stage tandem mass spectrometric (ESI-MSn) data for the alkaloid compounds were used for detailed structural characterization, then structure information was obtained by comparison of the fragmentation mechanisms of both alkaloids in Rhizoma Coptidis and standard samples of berberine, palmatine, coptisine and jatrorrhizine by MS. Based on the results obtained, the structure of a novel compound was elucidated. The results of the experiments demonstrate that ESI-MSn is a sensitive, selective and effective tool for the rapid determination of alkaloids in Rhizoma Coptidis.

A study of Aconitum alkaloids from aconite roots in Aconitum carmichaeli Debx using matrix-assisted laser desorption ionization mass spectrometry

In the present paper a study of C-19-diterpene type of aconitum alkaloids, extracted from aconite roots in Aconitum carmichaeli Debx has been made using matrix-assisted laser desorption/ionization time of Eight mass spectrometry (MALDI-TOFMS), The results demonstrated that the aconitum alkaloids from aconite roots can be determined simultaneously by this method, which was found to be superior to other analytical methods with regard to speed and sensitivity. Fourteen known aconitum alkaloids, including aconitines, benzoylaconitines and lipoaconitines, were assigned in the methanol extract and three compounds not reported before have been targeted separation. The evaluation of the efficiency of different extractions has been studied. These results suggested that the differences of the polarity and basicity of aconitine, and benzoylaconitines and lipoaconitines result from the C-8 constituent groups that are easily lost under MALDI, (C) 1998 John Wiley & Sons, Ltd.

华北克拉通新生代玄武岩携带的地幔橄榄岩Fe同位素地球化学及含金云母地幔岩岩石学研究

In recent years, thanks to the improvement of analytical methods and the use of MC-ICP-MS, Fe isotope can be measured precisely. Fe isotope shows considerable variation both in biological and inorganic processes (from low T to high T) in nature, Therefore, Fe isotope has become one of the exciting frontier sciences and has favorable prospects of the application to the geosciences and life sciences. Based on a comprehensive review of available references in the related field, this study focuses on the development of techniques for high-precision measurement of iron isotope using MC-ICP-MS, and application of the techniques developed to study the Fe isotopes as well as major and trace element compositions of minerals (Ol, Opx, Cpx and Sp) from spinel peridotitic xenoliths from Cenozoic alkaline basalts to investigate Fe isotopic features of the lithospheric mantle beneath the North China Craton. The minerals from these xenoliths are similar to those off-cratonic peridotites world-wide, but are remarkably different from those on-cratonic peridotites and clinopyroxenes from these spinel lherzolites exhibit two types of chondrite-normalized REE patterns i.e. LREE-depleted and flat or spoon-shaped. It is noted that total abundances of REE in clinopyroxenes from these peridotites show a broad negative correlation with Cr# numbers of Cpx and Sp. The Fe isotope results show that the spinel peridotitic xenoliths have small but distinguishable Fe isotopic variations in minerals (generally Ol < Opx < Cpx) and samples, and the isotopic range in spinel is relatively large. Positive linear relationship with the ε57Fecpx/ε57Feopx ratio close to one unit has been observed between Fe isotopes of coexistent Opx and Cpx, indicating that the Cpx and Opx have generally reached Fe isotopic equilibrium. However, Fe isotopes between the Ol and Sp show apparent disequilibrium. The broadly negative correlation between mineral Fe isotopes and oxygen fugacity (fo2), metasomatic indexes such as spinel Cr#, (La/Yb) N and (La/Sm) N ratios of clinopyroxenes suggest that Fe isotopic variations in different minerals and peridotites were probably produced by melt-peridotite interaction. This study further confirms the previous observation that the lithospheric mantle has distinguishable and heterogeneous Fe isotopic variations at a scale of xenoliths. Mantle metasomatism that induces the interaction of the lithospheric mantle peridotite with metasomatic agent is a most potential mechanism for the Fe isotope fractionation in mantle peridotites. Therefore, Fe isotope could be a new and powerful tool to probe the evolution of the lithospheric mantle. We also report mineral compositions, clinopyroxene trace element concentrations and Sr-Nd isotopes for newly-discovered phlogopite-bearing spinel lherzolite and olivine clinopyroxenite xenoliths from three different localities （Hannuoba, Hebei Province; Jining Sangyitang, Inner Mongolia; Hebi, Henan Province）of the North China Craton. Systematic comparisons with phlogopite-free spinel lherzolite xenolith from the same locality reveals that the phlogopite-bearing peridotitic xenoliths have relatively higher Al2O3, CaO, Na2O, K2O, TiO2 contents and lower MgO contents than those phogopite-free counterparts. The former also has higher LREE concentrations, but relatively less radiogenic Sr-Nd isotopic ratios. This demonstrates that mantle metasomatism can not only enrich the basaltic components and trace element concentrations, but also make a decrease in Mg# of the peridotites and olivines and a relative depletion in Sr-Nd isotopes. 87Rb/86Sr-87Sr/86Sr isochrons of the phlogopite-bearing xenoliths indicate that mantle metasomatism happened in the Mesozoic and/or Cenozoic time. The metasomatic agent was derived from the asthenosphere. The result also manifests that the widespread similarity of the geochemical features such as major and trace elements and isotopic compositions in the Cenozoic lithospheric mantle beneath the North China Craton to those “oceanic” lithospheric mantle could be as a result of the ubiquitous presence of the interaction between the old refractory peridotites and the infiltrated asthenospheric melt, rather than the actually newly-accreted lithospheric mantle.

两种超微细矿物粉体材料的制备及应用研究

Superfine mineral materials are mainly resulted from the pulverization of natural mineral resources, and are a type of new materials that can replace traditional materials and enjoy the most extensive application and the highest degree of consumption in the present day market. As a result, superfine mineral materials have a very broad and promising prospect in terms of market potential. Superfine pulverization technology is the only way for the in-depth processing of most of the traditional materials, and is also one of the major means for which mineral materials can realize their application. China is rich in natural resources such as heavy calcite, kaolin, wollastonite, etc., which enjoy a very wide market of application in paper making, rubber, plastics, painting, coating, medicine, environment-friendly recycle paper and fine chemical industries, for example. However, because the processing of these resources is generally at the low level, economic benefit and scale for the processing of these resources have not been realized to their full potential even up to now. Big difference in product indices and superfine processing equipment and technologies between China and advanced western countries still exists. Based on resource assessment and market potential analysis, an in-depth study was carried out in this paper about the superfine pulverization technology and superfine pulverized mineral materials from the point of mineralogical features, determination of processing technologies, analytical methods and applications, by utilizing a variety of modern analytical methods in mineralogy, superfine pulverization technology, macromolecular chemistry, material science and physical chemistry together with computer technology and so on. The focus was placed on the innovative study about the in-depth processing technology and the processing apparatus for kaolin and heavy calcite as well as the application of superfine products. The main contents and the major achievements of this study are listed as follows: 1. Superfine pulverization processing of mineral materials shall be integrated with the study of their crystal structures and chemical composition. And special attention shall be put on the post-processing technologies, rather than on the indices for particle size, of these materials, based on their fields of application. Both technical feasibility and economic feasibility shall be taken into account for the study about superfine pulverization technologies, since these two kinds of feasibilities serve as the premise for the industrialized application of superfine pulverized mineral materials. Based on this principle, preposed chemical treatment method, technology of synchronized superfine pulverization and gradation, processing technology and apparatus of integrated modification and depolymerization were utilized in this study, and narrow distribution in terms of particle size, good dispersibility, good application effects, low consumption as well as high effectiveness of superfine products were achieved in this study. Heavy calcite and kaolin are two kinds of superfine mineral materials that enjoy the highest consumption in the industry. Heavy calcite is mainly applied in paper making, coating and plastics industries, the hard kaolin in northern China is mainly used in macromolecular materials and chemical industries, while the soft kaolin in southern China is mainly used for paper making. On the other hand, superfine pulverized heavy calcite and kaolin can both be used as the functional additives to cement, a kind of material that enjoys the biggest consumption in the world. A variety of analytical methods and instruments such as transmission and scanning electron microscopy, X-ray diffraction analysis, infrared analysis, laser particle size analysis and so on were applied for the elucidation of the properties and the mechanisms for the functions of superfine mineral materials as used in plastics and high-performance cement. Detection of superfine mineral materials is closely related to the post-processing and application of these materials. Traditional detection and analytical methods for superfine mineral materials include optical microscopy, infrared spectral analysis and a series of microbeam techniques such as transmission and scanning electron microscopy, X-ray diffraction analysis, and so on. In addition to these traditional methods, super-weak luminescent photon detection technology of high precision, high sensitivity and high signal to noise ratio was also utilized by the author for the first time in the study of superfine mineral materials, in an attempt to explore a completely new method and means for the study of the characterization of superfine materials. The experimental results are really exciting! The innovation of this study is represented in the following aspects: 1. In this study, preposed chemical treatment method, technology of synchronized superfine pulverization and gradation, processing technology and apparatus of integrated modification and depolymerization were utilized in an innovative way, and narrow distribution in terms of particle size, good dispersibility, good application effects, low consumption as well as high effectiveness of superfine products were achieved in the industrialized production process*. Moreover, a new modification technology and related directions for producing the chemicals were invented, and the modification technology was even awarded a patent. 2. The detection technology of super-weak luminescent photon of high precision, high sensitivity and high signal to noise ratio was utilized for the first time in this study to explore the superfine mineral materials, and the experimental results can be compared with those acquired with scanning electron microscopy and has demonstrated its unique advantages. It can be expected that further study may possibly help to result in a completely new method and means for the characterization of superfine materials. 3. During the heating of kaolinite and its decomposition into pianlinite, the diffraction peaks disappear gradually. First comes the disappearance of the reflection of the basal plane (001), and then comes the slow disappearance of the (hkl) diffraction peaks. And this was first discovered during the experiments by the author, and it has never before reported by other scholars. 4. The first discovery of the functions that superfine mineral materials can be used as dispersants in plastics, and the first discovery of the comprehensive functions that superfine mineral materials can also be used as activators, water-reducing agents and aggregates in high-performance cement were made in this study, together with a detailed discussion. This study was jointly supported by two key grants from Guangdong Province for Scientific and Technological Research in the 10th Five-year Plan Period (1,200,000 yuan for Preparation technology, apparatus and post-processing research by using sub-micron superfine pulverization machinery method, and 300,000 yuan for Method and instruments for biological photon technology in the characterization of nanometer materials), and two grants from Guangdong Province for 100 projects for scientific and technological innovation (700,000 yuan for Pilot experimentation of superfine and modified heavy calcite used in paper-making, rubber and plastics industry, and 400,000 yuan for Study of superfine, modified wollastonite of large length-to-diameter ratio).

地球化学样品中铂族元素分析方法的研究-以铬铁矿为例

铂族元素和金银统称为贵金属，他们在石油化工、冶金、能源、地球化学、材料、环境科学、电子、航空航天、生物和医学等诸多领域中有广泛的应用。贵金属分析测试是贵金属研究与应用的必要组成部分，具有非常重要的意义。本文以铂族元素标准样品GPt-5（铬铁矿）为主要研究对象，采用阴离子交换树脂和磅共沉淀分离方法富集铂族元素，探索最佳实验条件：其次考察铂族元素的分离富集过程，探讨磅共沉泞分离富焦铂柞矛青的和理。然后通过碱熔、常压酸溶解-碱熔分解不溶物两种方法分解地质样品，在此基础上建立了电感耦奋寺离子体质谱分析钼族元素的方法，为地质地球化学样品中痕量或超痕量铂族元素含量分析提供了可行的途径，并为分析方法的进一步改进提供理论和方法依据。本文通过实验，得到以下结论：1．碲共沉淀具有操作简单，铂族元素的回收率很高能将铂族元素和贱金属彻底分离等诸多优点，便于广泛运用。2．阴离子交换树脂能很好吸附Au、R、Pd、Os、Ir（W），但对Ru、特别是Rh的回收率很低。通过在上柱前加入 SnCl_2能提高Ru、助的吸附率。3．碱熔分解能力强，操作简单，价格低廉，通过改进的分层碱熔法明显提高了Ru的准确度，对其它铂族元素没有影响；酸浸取结合碱熔对Au、Pt、Pd的分析结果较好，但是对于Ru、．Ir的结果偏低，整个流程较长。4．等离子体质谱法能快捷、精确测试铂族元素，一般用内标标准曲线法测单同位素元素Rh、Au，而用同位素稀释法测其它铂族元素。5．铂族元素经过蹄共沉淀后生成能溶于浓HNO_3和王水的产物，Au主要转化为单质Au，Pt、Pd都形成磅化物。其它铂族元素的富集机理需要进一步深入研究。

Métodos de extração de hidrocarbonetos policíclicos aromáticos em amostra de solo, sedimento e lodo.

2009

Analiza specjacyjna arsenu w wodzie techniką wysokosprawnej chromatografii cieczowej połączonej ze spektrometrią mas z jonizacją w indukowanej plazmie

Wydział Chemii: Pracownia Analizy Spektroskopowej Pierwiastków

Nanopartículas e suas aplicações em Ciências Farmacêuticas

Projeto de Pós-Graduação/Dissertação apresentado à Universidade Fernando Pessoa como parte dos requisitos para obtenção do grau de Mestre em Ciências Farmacêuticas

Preparation and characterisation of ceria particles

Cerium dioxide (ceria) nanoparticles have been the subject of intense academic and industrial interest. Ceria has a host of applications but academic interest largely stems from their use in the modern automotive catalyst but it is also of interest because of many other application areas notably as the abrasive in chemical-mechanical planarisation of silicon substrates. Recently, ceria has been the focus of research investigating health effects of nanoparticles. Importantly, the role of non-stoichiometry in ceria nanoparticles is implicated in their biochemistry. Ceria has well understood non-stoichiometry based around the ease of formation of anion vacancies and these can form ordered superstructures based around the fluorite lattice structure exhibited by ceria. The anion vacancies are associated with localised or small polaron states formed by the electrons that remain after oxygen desorption. In simple terms these electrons combine with Ce4+ states to form Ce3+ states whose larger ionic radii is associated with a lattice expansion compared to stoichiometric CeO2. This is a very simplistic explanation and greater defect chemistry complexity is suggested by more recent work. Various authors have shown that vacancies are mobile and may result in vacancy clustering. Ceria nanoparticles are of particular interest because of the high activity and surface area of small particulates. The sensitivity of the cerium electronic band structure to environment would suggest that changes in the properties of ceria particles at nanoscale dimensions might be expected. Notably many authors report a lattice expansion with reducing particle size (largely confined to sub-10 nm particles). Most authors assign increased lattice dimensions to the presence of a surface stable Ce2O3 type layer at low nanoparticle dimensions. However, our understanding of oxide nanoparticles is limited and their full and quantitative characterisation offers serious challenges. In a series of chemical preparations by ourselves we see little evidence of a consistent model emerging to explain lattice parameter changes with nanoparticle size. Based on these results and a review of the literature it is worthwhile asking if a model of surface enhanced defect concentration is consistent with known cerium/cerium oxide chemistries, whether this is applicable to a range of different synthesis methods and if a more consistent description is possible. In Chapter one the science of cerium oxide is outlined including the crystal structure, defect chemistry and different oxidation states available. The uses and applications of cerium oxide are also discussed as well as modelling of the lattice parameter and the doping of the ceria lattice. Chapter two describes both the synthesis techniques and the analytical methods employed to execute this research. Chapter three focuses on high surface area ceria nano-particles and how these have been prepared using a citrate sol-gel precipitation method. Changes to the particle size have been made by calcining the ceria powders at different temperatures. X-ray diffraction methods were used to determine their lattice parameters. The particles sizes were also assessed using transmission electron microscopy (TEM), scanning electron microscopy (SEM), and BET, and, the lattice parameter was found to decrease with decreasing particle size. The results are discussed in light of the role played by surface tension effects. Chapter four describes the morphological and structural characterization of crystalline CeO2 nanoparticles prepared by forward and reverse precipitation techniques and compares these by powder x-ray diffraction (PXRD), nitrogen adsorption (BET) and high resolution transmission electron microscopy (HRTEM) analysis. The two routes give quite different materials although in both cases the products are essentially highly crystalline, dense particulates. It was found that the reverse precipitation technique gave the smallest crystallites with the narrowest size dispersion. This route also gave as-synthesised materials with higher surface areas. HRTEM confirmed the observations made from PXRD data and showed that the two methods resulted in quite different morphologies and surface chemistries. The forward route gives products with significantly greater densities of Ce3+ species compared to the reverse route. Data are explained using known precipitation chemistry and kinetic effects. Chapter five centres on the addition of terbia to ceria and has been investigated using XRD, XRF, XPS and TEM. Good solid solutions were formed across the entire composition range and there was no evidence for the formation of mixed phases or surface segregation over either the composition or temperature range investigated. Both Tb3+ and Tb4+ ions exist within the solution and the ratios of these cations are consistent with the addition of Tb8O15 to the fluorite ceria structure across a wide range of compositions. Local regions of anion vacancy ordering may be visible for small crystallites. There is no evidence of significant Ce3+ ion concentrations formed at the surface or in the bulk by the addition of terbia. The lattice parameter of these materials was seen to decrease with decreasing crystallite size. This is consistent with increased surface tension effects at small dimension. Chapter six reviews size related lattice parameter changes and surface defects in ceria nanocrystals. Ceria (CeO2) has many important applications, notably in catalysis. Many of its uses rely on generating nanodimensioned particles. Ceria has important redox chemistry where Ce4+ cations can be reversibly reduced to Ce3+ cations and associated anion vacancies. The significantly larger size of Ce3+ (compared with Ce4+) has been shown to result in lattice expansion. Many authors have observed lattice expansion in nanodimensioned crystals (nanocrystals), and these have been attributed to the presence of stabilized Ce3+ -anion vacancy combinations in these systems. Experimental results presented here show (i) that significant, but complex changes in the lattice parameter with size can occur in 2-500 nm crystallites, (ii) that there is a definitive relationship between defect chemistry and the lattice parameter in ceria nanocrystals, and (iii) that the stabilizing mechanism for the Ce3+ -anion vacancy defects at the surface of ceria nanocrystals is determined by the size, the surface status, and the analysis conditions. In this work, both lattice expansion and a more unusual lattice contraction in ultrafine nanocrystals are observed. The lattice deformations seen can be defined as a function of both the anion vacancy (hydroxyl) concentration in the nanocrystal and the intensity of the additional pressure imposed by the surface tension on the crystal. The expansion of lattice parameters in ceria nanocrystals is attributed to a number of factors, most notably, the presence of any hydroxyl moieties in the materials. Thus, a very careful understanding of the synthesis combined with characterization is required to understand the surface chemistry of ceria nanocrystals.