酸沉降环境化学与硫同位素示踪研究──以浙江中部地区为例

研究区域降水样品pH值的分布范围为3.64-7.20，pH年均值为4.45。SO4、NO3、NH4、Ca、H是降水中主要的阴、阳离子。降水中SO4对降水酸度的贡献逐渐降低，而NO3的贡献则显著增加。SO4、NH4、Ca、H、NO3的沉降通量相对较大，其它离子则相对较小，同时降水离子成分沉降通量的季节变化非常明显。SO4和NO3、Ca和Mg以及Na和Cl表现出较好的相关关系，另外Ca和SO4、Mg和SO4以及Mg和NO3等酸、碱性离子之间也存在较好的相关性，但H与其它离子间并没有表现出明显的相关关系。降水中SO4、NH4、NO3和F主要来自人为活动的影响，Ca、k和Mg主要来自土壤、沙尘等地壳来源，Na、Cl属于典型的海盐性成分。 浙江中部地区大气降水硫同位素δ34S值的变化范围为+0.53‰－+14.23‰，平均值+5.04‰，区域内各地大气降水硫同位素组成基本一致。大气SO2的δ34S值变化范围在+0.95‰－+7.50‰之间，年均值为+4.73‰，气溶胶δ34S值变化范围则在+6.39‰－+9.83‰之间，年均值为+8.09‰。降水和大气SO2的δ34S值存在冬季高夏季低的季节性变化特征，同位素平衡分馏引起的温度效应和夏季生物成因硫的大量释放是造成季节性变化的主要控制因素。降水中人为来源硫的相对贡献约为53%－91%，年平均为73%，生物成因硫的相对贡献约为8%－44%，年平均为26%。远距离传输硫是研究区域降水中另一个非常重要的硫源，其相对贡献约为27%－44%。大气SO2氧化反应中多相氧化处于相对重要的地位，均相氧化在氧化反应机制中也有其不可低估的作用。研究区域大气环境的相对湿度对大气SO2的氧化机制有着重要的影响。

浙江省矾山明矾石矿床地球化学特征兼论中生代成矿体系

矾山明矾石矿床位于江山－绍兴深断裂南东侧，海西印支褶皱带的南东侧，中国板块东南构造区与太平洋板块的交接处，属于中国板块东南构造区。该矿床产在矾山破火山口内，是一个超大型明矾石矿床，同时矿床中的钒、镓含量也达到了综合利用的品位。该矿床研究程度低，缺少地球化学特征研究。因此，本次工作系统研究了该矿床常量元素、微量元素、稀土元素、硫和铅同位素地球化学特征。本次对明矾石矿床的研究获得以下几点初步认识： 1：成矿物质来源于火山岩。矿区火山岩中的K、Al、Na等矿石元素含量明显比其他地区高，并且从围岩→矿化围岩→矿石呈明显的富集趋势。稀土资料和铅同位素资料也都表明成矿物质来源于中生代火山岩。 2：V、Ga含量达到了综合利用的品位。微量元素资料表明，矿石中V平均含量为211.6ppm，Ga平均含量为16.78ppm，都大于地壳丰度，尤其是V远大于地壳丰度；同时发现，成矿时V以V¬5＋形式通过与Al3＋发生类质同像进入明矾石晶格，而矿石中Ga含量除与Al3＋外还与Fe3＋含量有关。 3：明矾石的稀土元素地球化学特征比较复杂。根据δEu值不同可分为三类： Eu弱负异常型，Eu弱正异常型和Eu强正异常型。影响稀土元素分布的因素主要为成矿原岩中富含碱性长石和成矿时的氧逸度和温度，另外矿石结构（如孔隙度）对稀土元素分布也有影响。研究表明，矿石稀土配分模式为轻稀土富集型，与火山岩基本一致。 4：硫同位素研究发现，黄铁矿的δ34S值为1.9～3.2‰，明矾石的δ34S值为13.62～16.02‰，后者明显大于前者。本次研究认为黄铁矿的δ34S值代表当时的岩浆源硫，而明矾石较大的δ34S值为岩浆硫经过同位素分馏的结果。铅同位素研究发现，明矾石矿石的206Pb/204Pb＝17.963～18.606，207Pb/204Pb＝15.439～15.672，208Pb/204Pb＝38.405～38.796。通过与中生代火山岩和基底变质岩的对比，本次研究认为明矾石的铅源为中生代火山岩来源，与基底变质岩并无直接的来源关系。 5：通过明矾石矿床的地球化学特征研究，结合实际地质特征和前人研究成果，本次研究提出了以下矿床成因：明矾石矿床形成环境为浅成低温氧化环境；成矿物质来源于围岩，成矿所需的硫源为分馏的岩浆硫；矿床形成时期为73～95Ma，比围岩晚10～20Ma；矿床成因为火山热液交代成因。 浙江省中生代火山岩成矿体系主要指受浙江省中生代火山构造、岩浆活动控制的一系列不同类型的矿床组合。成矿体系主要受江绍深断裂带和中生代陆相火山岩控制。前人对成矿体系中的单一矿床研究较多，但是缺少横向对比研究。本次工作主要通过对成矿体系中的两类矿床（金属矿床和非金属矿床）进行对比研究，结合中生代火山岩演化过程，初步探索成矿体系中各类矿床间的联系以及成矿体系与火山岩演变的关系。本次工作取得以下几点初步认识： 1：成矿体系中各类矿床的整体分布受江绍深断裂、温州－镇海大断裂等一些深大断裂控制。各矿床的具体控（容）矿构造都为次级压－压扭性断裂和破火山口构造，其中破火山口构造在成矿过程中占非常重要的作用。 2：成矿体系中各类矿床的成矿温度低，深度浅，为典型的浅成低温矿床。 3：铅同位素资料表明，矿床的铅源为中生代火山岩来源，与基底并无直接联系。氢氧同位素资料表明，各类矿床的成矿流体以中生代大气降水为主，岩浆水占很少部分或并无参与成矿。 4：成矿体系存在明显的成矿成岩时差，金属矿床在12.44～45.6Ma，萤石矿床为25～75Ma，其他非金属矿床为10～20Ma；铅锌（银）金等金属矿床为具有明显的两期成矿特征。

Perovskite-type B-site Bi-doped ceramic membranes for oxygen separation

Novel mixed conducting oxides, B-site Bi-doped perovskites were exploited and synthesized. Cubic perovskite structures were formed for BaBi0.2COyFe0.8-yO3-delta (y less than or equal to 0.4) and BaBixCo0.2Fe0.8-xP3-delta (x=0.1-0.5) The materials exhibited considerable high oxygen permeability at high temperature. The oxygen permeation flux of BaBi0.2Co0.35Fe0.45O3-delta membrane reached about 0.77 x 10(-6) mol/cm(2) s under an air/helium oxygen partial pressure gradient at 900 degrees C, which was much higher than that of other bismuth-contained mixed conducting membranes. The permeation fluxes of the materials increased with the increase of cobalt content, but no apparent simple relationship was found with the bismuth content. The materials also demonstrated excellent reversibility of oxygen adsorption and desorption. Stable time-related oxygen permeation fluxes were found for BaBi0.2CO0.35Fe0.45O3-delta and BaBi0.3Co0.2Fe0.5O3-delta a membranes at 875 degrees C.

A novel method to synthesize amorphous silica-alumina materials with mesoporous distribution without using templates and pore-regulating agents

In this study, a novel sol-gel method is used to synthesize amorphous silica-alumina materials with a narrow mesoporous distribution and various Si/Al molar ratios without using any templates and pore-regulating agents. During the preparation procedure, only inexpensive inorganic salts were used as raw materials, instead of expensive and harmful alkoxides. The precursor sol was dried at room temperature in a vacuum box kept at 60 mmHg until it began to form the gel. The results of a nitrogen sorption experiment indicate that the synthesized materials with different Si/Al molar ratios have similar mesoporous distributions (within 2-12 nm). Moreover, it was found that the material's pore size distribution remains at a similar value during the heat treatment from room temperature to 550 degreesC. On the basis of the nitrogen sorption, TEM, and AFM characterization results, a formation mechanism of mesopores which accounts for the experimental data is also suggested. This suggested mechanism involves rearrangement of the primary particles during the drying process to form the precursors of the similarly sized mesopores. The synthesized materials were characterized by XRD, thermal analysis (TG/DTA), Al-27 and Si-29 MAS NMR spectroscopy, SEM, TEM, and AFM. The results of Al-27 and 29Si MAS NMR indicate that the distribution of silicon and aluminum in the synthesized materials is more uniform and homogeneous than that in the mixed oxides prepared via the traditional sol-gel method even at high alumina contents. The type and density of the acid sites were studied using pyridine adsorption-desorption FTIR spectroscopy. It was shown that the acidity of the synthesized materials is higher than that of the silica-alumina materials prepared by conventional methods.

Templateless synthesis of catalysts with narrow mesoporous distribution

In this study, amorphous silica-alumina nanomaterials with narrow mesoporous distribution can be obtained by two novel sol-gel processes, without the use of any templates. The results of our experiments show that the preparation method has a great influence on the precursor sol structure as well as the specific surface area and mesopore volume of the final product, but has no effect on the pore size distribution.

Ultrasonic synthesis of silica-alumina nanomaterials with controlled mesopore distribution without using surfactants

A novel sol-gel process has been developed for the synthesis of amorphous silica-aluminas with controlled mesopore distribution without the use of organic templating agents, e.g., surfactant molecules. Ultrasonic treatment during the synthesis enables production of precursor sols with narrow particle size distribution. Atomic force microscopy analysis shows that these sol particles are spherical in shape with a narrow size distribution (i.e., 13-25 nm) and their aggregation during the gelation creates clusters containing similar sized interparticle mesopores. A nitrogen physiadsorption study indicates that the mesoporous materials containing different Si/Al ratios prepared by the new synthesis method has a large specific surface area (i.e., 587-692 m(2)/g) and similar pore sizes of 2-11 nm. Solid-state Al-27 magic angle spinning (MAS) NMR shows that most of the aluminum is located in the tetrahedral position. A transmission electron microscopy (TEM) image shows that the mesoporous silica-alumina consists of 12-25 nm spheres. Additionally, high-resolution TEM and electron diffraction indicate that some nanoparticles are characteristic of a crystal, although X-ray diffraction and Si-29 MAS NMR analysis show an amorphous material.

Mesoporous spinel MgAl2O4 prepared by in situ modification of boehmite sol particle surface: I Synthesis and characterization of the unsupported membranes

Mesoporous spinel membranes as ultrafiltration membranes were prepared through a novel sol-gel technique. By in situ modification of the sol particle surface during the sol-gel process, control of the material structure on a nanometer scale from the earliest stages of processing was realized. Nano-particles with a chocolate-nut-like morphology, i.e. spinel MgAl2O4 as a shell and gamma -Al2O3 as a core, were first revealed by HRTEM results. The formation of the spinel phase was confirmed by X-ray diffraction (XRD). N-2 adsorption-desorption results showed that the mesoporous membranes had a narrow pore size distribution. (C) 2001 Elsevier Science B.V. All rights reserved.

Mechanistic studies of methane partial oxidation to syngas over LiNiLaOx/Al2O3 catalyst

Temperature-programmed reduction (TPR) characterization of the LiNiLaOx/Al2O3 catalyst before or after partial oxidation of methane (POM) reaction and a series of O-2, CH4 and CH4/O-2 pulse reaction experiments over the catalyst under different pretreatments were performed. It was found that CH4 dissociatively adsorbs on active center nickel producing H-2 and surface carbon, C(a). The surface carbon reacts with surface lattice oxygen or surface adsorbed oxygen to produce CO. Because the activation barrier for the reaction C(a)+ O(a) =CO(a) is the highest among all the elementary reactions, the rate-determining step of the POM may be the reaction C(a) + O(a) =CO(a).

Alkanes-assisted low temperature formation of highly ordered SBA-15 with large cylindrical mesopores

Highly ordered SBA-15 silicas with large cylindrical mesopores (similar to 15 nm) are successfully obtained with the help of NH4F by controlling the initial reaction temperatures in the presence of excess amounts of alkanes.

Separation of compounds interacting with liposome membrane in combined prescription of traditional Chinese medicines with immobilized liposome chromatography

Immobilized liposome chromatography (ILC), the stationary phase of which has been regarded as a mimic biomembranes system was used to separate and analyze compounds interacting with liposome membrane in Danggui Buxue decoction, a combined prescription of traditional Chinese medicines (CPTCMs), and its compositions Radix Astragli and Radix Angelica Sinensis. More than 10 main peaks in the extract of Danggui Buxue decoction were resolved on the ILC column, suggesting that more than 10 components in the prescription have significant retention on ILC column. Ligustilide, astragaloside, TV and formononetin, three main bioactive ingredients in Danggui Buxue decoction, were found to have relatively significant, while ferulic acid, another bioactive ingredient in the prescription, relatively weak retention on ILC column. Effects of the eluent pH and amount of immobilized phosphatidylcholine (PC) on separation of interactional compounds in the extract of Danggui Buxue decoction were also investigated. It was found that these two factors strongly affected the retention of some interactional compounds. In addition, the fractions partitioned with different solvents from water extract of this combined prescription were evaluated with this ILC column system. (c) 2005 Elsevier B.V. All rights reserved.