STRUCTURE OF CIS-DIAQUABIS(1,10-PHENANTHROLINE)ZINC SULFATE HEXAHYDRATE

[Zn(C12H8N2)2(H2O)2]SO4.6H2O, M(r) = 665.98, triclinic, P1BAR, a = 10.070 (4), b = 12.280 (3), c = 13.358 (2) angstrom, alpha = 109.12 (2), beta = 92.58 (2), gamma = 110.85 (2)-degrees, V = 1433.9 (7) angstrom 3, Z = 2, D(x) = 1.54 g cm-3, lambda(Mo K-alpha) = 0.71069 angstrom, mu = 10.1 cm-1, F(000) = 692, T = 293 K, R = 0.044 for 3985 observed reflections. The Zn atom is coordinated in a distorted octahedral geometry by four N atoms from two 1,10-phenanthroline (phen) ligands and two water molecules. The intermolecular ring-stacking interactions between the phen ligands occur in two forms: infinite chains and discrete dimers. Hydrogen bonds further stabilize the structure.

SYNTHESES OF BIS(TERT-BUTYLCYCLOPENTADIENYL)LANTHANOID CHLORIDE COMPLEXES AND CRYSTAL-STRUCTURES OF BIS(TERT-BUTYLCYCLOPENTADIENYL)CHLORO(BISTETRAHYDROFURAN)-PRASEODYMIUM AND BIS(TERT-BUTYLCYCLOPENTADIENYL)-CHLOROTETRAHYDROFURANYTTERBIUM

Reaction of lanthanoid trichloride with two equivalents of sodium t-butylcyclopentadienide in tetrahydrofuran affords bis(t-butylcyclopentadienyl)lanthanoid chloride complexes (t-BuCp)2LnCl. nTHF (Ln = Pr, Nd, n = 2; Ln = Gd, Yb, n = 1). The compound (t-BuCp)2PrCl.2THF (1) crystallizes from THF in monoclinic space group P2(1)/c with unit cell dimensions a = 15.080(3), b = 8.855(2), c = 21.196(5) angstrom, beta = 110.34(2)degrees, V = 2653.9 angstrom-3 and D(calcd) = 1.41 g/cm3 for Z = 4. The central metal Pr is coordinated to two t-BuCp ring centroids, one chlorine atom and two THF forming a distorted trigonal bipyramid. The crystal of (t-BuCp)2YbCl.THF (2) belongs to the monoclinic crystal system, space group P2(1)/n with a = 7.726(1), b = 12.554(2), c = 23.200(6) angstrom, beta = 97.77(2)degrees, V = 2229.56 angstrom-3, D(calcd) = 1.50 g/cm3 and Z = 4. The t-BuCp ring centroids, the chlorine atom and the oxygen atom of the THF describe a distorted tetrahedron around the central ion of ytterbium.

铜管不锈钢管腐蚀性能及铁牺牲阳极保护研究

铜管一直是电厂凝汽器的主要应用管材，但由于其抗冲刷和抵御污染物腐蚀的能力差，特别不耐氨蚀，美国和欧洲大量使用不锈钢管替代铜管作为冷凝管，然而不锈钢管在我国的运用仅处于初步阶段。 常使用锌、铝阳极对铜管进行牺牲阳极保护，然而存在着电位差过大、阳极溶解过快的问题。铁基牺牲阳极与铜电位差适当、来源广泛、价格便宜，在一些工程上有所应用，但是目前针对铁基牺牲阳极的理论研究报道很少。 本文选用紫铜管、304不锈钢管作为实验用管材，首先运用实验室全浸实验、极化曲线和电化学阻抗研究了二者在海水和淡水中的腐蚀性能以及CO2、溶解氧对其腐蚀的影响。结果表明：CO2会加速二者的腐蚀，溶解氧却对它们的腐蚀影响不同，促进铜管的腐蚀却抑制不锈钢管的腐蚀；随浸泡时间的延长，紫铜管由于表面产物膜的生成耐蚀性提高，304不锈钢管的耐蚀性却降低；淡水中，304不锈钢管和紫铜管都具有很好的耐蚀性能。随后，运用失重法和极化曲线对比研究了紫铜管、304不锈钢管的氨蚀性能，运用SEM分析和电化学阻抗研究了紫铜在不同浓度氨溶液中的腐蚀机理。发现，304不锈钢管的耐氨蚀能力远远好于铜管；溶解氧是影响氨蚀的关键因素，其对二者氨蚀的影响也不同；紫铜管在低氨浓度和高氨浓度溶液中腐蚀机理和产物不同，低氨浓度时形成保护性的产物膜（CuO 和Cu(OH)2），高氨浓度时由活化溶解控制，生成可溶的[Cu (NH3)4]2+。 选用工业纯铁、35钢为牺牲阳极材料。恒电流实验结果表明它们具有良好的牺牲阳极性能；通过极化曲线和自腐蚀电位测试分析，认为将二者用于铜管牺牲阳极保护是可行的；实验室阴极保护效果测试表明，工业纯铁和35钢对紫铜管具有良好的保护效果，保护度达90%以上。

氯离子和硫酸盐还原菌对Q235钢溶解氧还原反应的影响

在海水环境中，溶解氧阴极还原反应是钢铁材料腐蚀的主要因素之一，海水中的氯离子（Cl−）和硫酸盐还原菌（SRB）可能对溶解氧还原反应发生作用从而影响钢铁材料的腐蚀行为。本文以海洋工程材料Q235钢作为研究对象，通过循环伏安法、电化学阻抗谱、旋转圆盘电极和旋转圆盘-圆环电极线性扫描伏安法等电化学方法，研究了Cl−和硫酸盐还原菌对Q235钢电极表面溶解氧还原反应的影响，并对其影响机制进行了探讨。 研究表明：Q235钢在模拟混凝土孔隙液中电极表面氧化物的还原反应和溶解氧的还原反应同时进行；溶解氧还原反应在阴极反应电位范围内最初为混合过程控制的二电子反应，电位较负时为扩散过程控制的四电子反应。当在0.02 M Ca(OH)2溶液中加入Cl−时，随着Cl−浓度的增加，溶液电阻减小，溶解氧还原反应峰电位逐渐正移，即溶解氧还原反应的过电位减小；同时随着氯离子浓度的增加溶解氧还原反应速率逐渐减小。 由于硫酸盐还原菌在电极表面形成的生物膜阻碍了溶解氧到达电极表面，使得溶解氧还原反应与无菌时相比在一定程度上受到抑制，溶解氧还原反应速率降低；同时由于硫酸盐还原菌形成生物膜的作用，使得溶解氧还原机理也发生了改变，在没有硫酸盐还原菌时溶解氧还原以四电子还原为主，当硫酸盐还原菌数量较少时，溶解氧还原反应以二电子反应主，当硫酸盐还原菌数量较多时转为一电子反应为主。

Determination for the different combined-form inorganic carbon in marine sediments

Marine sediment is the important sources and sinks of carbon. The inorganic carbon(IC) in marine sediments plays an important role in carbon cycling. In order to understand IC function in carbon cycling, sequential extraction method based on IC combined chemical strength difference were established to get five phases: NaCl phase (step I), NH3 - H2O phase (step II), NaOH phase (step III), NH2OH . HCl phase (step IV) and HCl phase(step V). The best extraction conditions were obtained by a series of experiments. Extractants were added into plastic centrifuge tubes in Step I - M, the capped tube were placed on a shaker table to keep the solids suspended for two hours. The suspended solution was separated by centrifugal, the residues were washed with water. The two supernatant were combined and the CO, was finally determined by volumetric analysis. The residues were transferred into conical flask in step IV and V, and then the extractants were added. The produced CO2 was adsorbed by saturated Ba(OH)(2) solution, and determined by volumetric analysis. This method for IC has a good precision in the analysis sediment samples.

Assessment of metal contamination in surface sediments of Jiaozhou Bay, Qingdao, China

An assessment of metal contamination in surface sediments of the Jiaozhou Bay, Qingdao, one of the rapidly developing coastal economic zones in China, is provided. Sediments were collected from 10 stations and a total of 15 heavy metals were analyzed. Concentrations of metals show significant variability and range from 210 to 620 ppm for Ti, 2.7 to 23 ppm for Ni, 4.2 to 28 ppm for Cu, 5.2 to 18 ppm for Pb, 12 to 58 ppm for Zn, 0.03 to 0.11 ppm for Cd, 5 to 51 ppm for Cr, 1.5 to 9.9 ppm for Co, 5.3 to 19 ppm for As, 12 to 32 ppm for Se, and 19 to 97 ppm for Sr. Based on concentration relationships and enrichment factor (EF) analyses, the results indicate that sediment grain size and organic matter played important roles in controlling the distribution of the heavy metals in surface sediments of the Jiaozhou Bay. The study shows that the sediment of the Jiaozhou Bay has been contaminated by heavy metals to various degrees, with prominent arsenic contributing the most to the contamination. The analysis suggests that the major sources of metal contamination in the Jiaozhou Bay are land-based anthropogenic ones, such as discharge of industrial waste water and municipal sewage and run-off. Notably, the elevated heavy metal concentrations of the Jiaozhou Bay sediments could have a significant impact on the bay's ecosystem. With the rapid economic development and urbanization around the Jiaozhou Bay, coastal management and pollution control should focus on these contaminant sources, as well as provide ongoing monitoring studies of heavy metal contamination within the bay.

The electrochemical reduction reaction of dissolved oxygen on Q235 carbon steel in alkaline solution containing chloride ions

Cyclic voltammetry, electrochemical impedance spectroscopy, and rotating disk electrode voltammetry have been used to study the effect of chloride ions on the dissolved oxygen reduction reaction (ORR) on Q235 carbon steel electrode in a 0.02 M calcium hydroxide (Ca(OH)(2)) solutions imitating the liquid phase in concrete pores. The results indicate that the cathodic process on Q235 carbon steel electrode in oxygen-saturated 0.02 M Ca(OH)(2) with different concentrations of chloride ions contain three reactions except hydrogen evolution: dissolved oxygen reduction, the reduction of Fe(III) to Fe(II), and then the reduction of Fe(II) to Fe. The peak potential of ORR shifts to the positive direction as the chloride ion concentration increases. The oxygen molecule adsorption can be inhibited by the chloride ion adsorption, and the rate of ORR decreases as the concentration of chloride ions increases. The mechanism of ORR is changed from 2e(-) and 4e(-) reactions, occurring simultaneously, to quietly 4e(-) reaction with the increasing chloride ion concentration.

塞隆骨与虎骨中矿物质元素的比较

目的对比分析国家一类动物药塞隆骨和禁用传统中药材虎骨中的19种矿物质元素的含量.方法骨骼样品经灰化或消解处理后,采用原子吸收光谱法、氢化物原子荧光光谱法、催化极谱法等分析方法测定矿物质元素.结果两种动物骨骼中元素含量差异显著,塞隆骨11种元素高于虎骨,特别是Cu、Zn、Fe、Mn、Se等生命活动必需微量元素塞隆骨极为显著地高于虎骨,而组成骨骼的主要成分Ca、P则为虎骨高于塞隆骨.矿物质元素在头骨、脊梁骨和腿骨中分布非常不平衡,多数元素以头骨中分布最为丰富,而5种常量元素Ca,P,Na,Mg,K的含量为腿骨＞头骨＞脊梁骨.骨骼中主要成分Ca和P的存在形式主要为羟磷灰石Ca10(PO4)6(OH)2.结论塞隆骨骨骼中的矿物质元素与虎骨有可比性,必需微量元素塞隆骨明显优于虎骨.

Two new benzochromone glycosides from the stem of Berchemia racemosa

Two new benzochromone glycosides, rubrofusarin 6-O-alpha-L-rhamnosyl- (1 -> 6)-O-beta-D-glucopyranoside (1) and demethylflavasperone 10-O-beta-D-glucopyranoside (2), have been isolated from the stem of Berchemia racemosa Sieb. et Zucc. (Rhamnaceae). Their structures were elucidated on the basis of spectroscopic evidence.

水热条件下钾长石碱性分解反应机理的实验研究

It is well known that our country is short of water-soluble potassium, but rich in insoluble potassium ores. Based on the work of the formers, using the orthogonal and monofactor experiments, the author optimized the production technology of micro-porous potassium silicon calcium mineral fertilizer by non-stirring hydrothermal chemical reaction when the alkaline earth booster CaO was available. The influences of temperature、time、reactant ratio and water-solid ratio on the dissolution rate of production’s elements were studied by orthogonal experiments, and the production technology was further optimized by monofactor experiments. By XRD、SEM、EDS and dissolving experiments, it was systematically studied that the effects of the reactant ratio、reaction time and reaction temperature on the properties of the production obtained by the hydrothermal reaction between KAlSi3O8 and CaO. The results showed that：when changing of the reaction condition, the reaction productions included tobermorite、 hibschite、α-C2SH and K2Ca(CO3)2; among which, K2Ca(CO3)2 was not the first production containing potassium, but K2Ca(CO3)2 was synthesized by the reaction among KOH、Ca(OH)2 and CO2. Whether the phase was synthesized was related to not only the reaction condition, but also their physicochemical properties; when the reaction condition was changed, the changes of different phases were different. The results of XRD and dissolution rate experiments explained the dissolution characteristic of every element of hydrothermal productions very well, and the relation between the dissolution rate of element and the phase of productions poured a good illumination on the production technology. The results of SEM and EDS showed that: hydrogarnet looked like spherical, and its surface was covered by some productions including K phase and Ca、Si phase; but the morphology of tobermorite was platy or lamellar or needlelike, and parts of Si in the structure of tobermorite were substituted by Al，and some K+ cations were inserted into the Ca interlayer of tobermorite at the same time. It was the first time that the interface between KAlSi3O8 and Ca(OH)2 was observed directly by SEM and EDS after the hydrothermal reaction, and the mechanism of hydrothermal reaction of KAlSi3O8 and Ca(OH)2 was further discussed. These results indicated that: the Ca-KAlSi3O8 intermediate compound was formed at first, and some K was released into the solution and KOH was produced at the same time; the C-S-H phase appeared before hydrogarnet, and then hydrogarnet was synthesized when the chemical reaction was carried on; if the reaction was carried on furthermore, α-C2SH、tobermorite and other C-S-H phases of different atom ratio appeared. The author found that the structure of KAlSi3O8 would be more drastically destroyed if there were some reactants, such as Ca(OH)2 which reacted with KAlSi3O8 and new phases were formed after the hydrothermal reaction between KAlSi3O8 and alkaline solution of equal ionic strength was finished. With the combination of calcination and hydrothermal reaction methods, the dissolution rate of products were greatly improved when the hydrothermal reaction was carried out after KAlSi3O8 and CaCO3 were calcined. Furthermore, the author has tentatively explored how to evaluate the effects of the differences of the activity of lime on the dissolution properties of hydrothermal products.

甘肃金川II号岩体岩浆演化及铜镍硫化物成矿过程探讨

金川矿床是超大型岩浆 Ni-Cu-PGE 硫化物矿床，它赋存有世界第三的镍储量（5.45×106 t，Ni 的平均品位为 1.2%）。该矿床位于华北板块西侧阿拉善地块西南边缘龙首山隆起中。本论文以金川矿区的 II 号岩体为研究对象，在系统整理前人工作的基础上，通过深入细致的野外地质考察和系统采样，选取有代表性的样品，进行详细的显微镜鉴定，并运用元素地球化学等手段，对 II 号岩体的源区特征、岩浆演化过程及其赋存的⑴、⑵号矿体的成矿机制等主要矿床学问题进行了系统成因研究，并尝试提出了二次硫化物熔离成矿模式。本论文主要取得以下几点结论性成果： 1）岩浆起源：起源于上地幔尖晶石－石榴石二辉橄榄岩过渡地带的下部。通过上地幔源岩的柱状部分熔融模式（≥25%）或三角部分熔融模式（10～15%），形成富PGE的S不饱和原始岩浆。 2）地壳同化混染：地壳物质的同化混染主要是由早期下地壳物质的同化混染和晚期上地壳物质的同化混染组成的多阶段同化混染，并且其成分为富钙质围岩。 3）结晶分异演化：金川II号岩体作为橄榄石堆积相，其橄榄石的结晶主要发生在上地壳深部岩浆房，而橄榄石与熔浆的反应及辉石和斜长石的结晶则主要发生在浅部岩浆房，既现今岩体所在位置。 4）S 的饱和机制：岩浆通道内下地壳物质的同化混染，导致岩浆硫饱和，并于岩浆通道中发生了第一次硫化物熔离；上地壳深部岩浆房中地壳物质的同化混染和橄榄石的分离结晶，促使硫饱和的母岩浆发生了第二次硫化物熔离。 5）深部岩浆房的演化：上地壳深部岩浆房中橄榄石分离结晶与硫化物熔离之后，在重力分异作用下，形成了自上而下的硅酸盐岩浆、橄榄石“晶粥”、含硫化物熔体的橄榄石“晶粥”以及矿浆的四层分层格局。同时，底部部分硫化物熔体发生了Pt合金（Pt-Fe）的脱离。 6）侵入期次：上地壳深部岩浆房中，母岩浆分异演化早期，其顶部含有尚未完全成长橄榄石颗粒的“晶粥”在构造应力挤压下首先上侵、成岩形成金川II号岩体顶部、呈“上悬体”的中细粒含辉橄榄岩；分层格局形成之后，橄榄石“晶 VI 粥”、含硫化物熔体的橄榄石“晶粥”以及矿浆依次上侵成岩、成矿，分别形成金川 II 号岩体上部的二辉橄榄岩相、⑴、⑵号矿体的主体以及⑵号矿体底部的块状矿石。

海洋生物碳酸盐硼同位素技术研究及其应用

近些年来，利用海洋生物碳酸盐硼同位素重建古海水pH，计算当时大气CO2含量，进而推测古气候的变化已成为国际同位素地球化学界研究的热点问题，被称为δ11B-pH技术。古海水的δ11Bsw是否恒定、B(OH)4−和B(OH)3间理论的硼同位素分馏系数4/3是多少以及碳酸盐的δ11Bcarb是否等于海水B(OH)4−的δ11B4值是该技术成功的三个关键。但到目前为止以上三项问题还没得到完全证实。 为确定方解石的硼同位素组成与海水pH的依赖关系，已进行过大量实验研究。他们的结果与预期的假设一致，支持了B(OH)4-是掺入方解石结构主要形式的假设。但近期 Pagani(2005)指出B(OH)4-也许不是掺入方解石结构的主要形式，B(OH)3也可能同时掺入进碳酸盐。肖应凯等(2006)的无机碳酸盐沉积实验发现碳酸盐沉积和母液间的硼同位素分馏系数大于1的异常现象，认为碳酸钙中镁或其它微量元素的存在是重要原因，推断这是在高pH生成Mg(OH)2沉积后11B优先掺入的缘故，推断有B(OH)3掺入碳酸盐的可能。 以前进行的沉积实验，只考虑到碳酸钙本身，确实证明了硼只以或主要以B(OH)4-参与进生物碳酸钙。但天然的海洋生物碳酸盐含有镁、锶、铁等微量元素，这些微量元素的存在可能会改变硼的参与行为，从而对硼同位素分馏产生影响。现代珊瑚礁中水镁石普遍存在，这是否会影响珊瑚的硼同位素组成而导致δ11B-pH技术的误差还值得研究。 针对以上问题，主要对硼掺入进Mg(OH)2的形式及分馏机理，现代珊瑚中镁、锶等微量元素与硼浓度及硼同位素的关系进行研究，并用生物碳酸盐的硼同位素对陆相产出有孔虫的沉积环境进行判别。 通过研究，得到以下几点认识： 1. 在Mg(OH)2从pH9.5～13的含硼合成海水中沉积时，Mg(OH)2沉积11B的变化范围为-1.20‰～28.26‰，高于合成海水的11B (-7.00±0.07‰)，沉积和海水间的硼同位素分馏系数固/液变化范围为1.0177～1.0569，平均值为1.0329，这是H3BO3优先掺入的结果，造成11B在Mg(OH)2沉积中富集。 2. Mg(OH)2沉积的硼浓度和硼在Mg(OH)2沉积与滤液间的分配系数Kd的变化范围分别为228.61 g/g～937.79 g/g和9.31～494.20。高pH值时硼掺入Mg(OH)2的过程中吸附作用占有重要位置。 3. Mg(OH)2吸附实验表明，硼掺入Mg(OH)2非常迅速，4 h能达到平衡。平衡后Mg(OH)2中硼浓度[B]固和固相与溶液相间的分配系数Kd随pH设定的升高和固液比的降低而降低。而且最高的[B]固和Kd均远高于硼被金属氧化物或粘土矿物吸附时的对应值，表硼具有很强的掺入Mg(OH)2的能力。 4. 吸附平衡时溶液相的11B液f (-19.2‰～-17.8‰)均低于原始溶液的11B液i (-7.00±0.07‰)，计算的Mg(OH)2与平衡溶液间的硼同位素分馏系数固-液变化范围为1.0186～1.0220，平均值为1.0203。这充分表明，硼掺入Mg(OH)2时11B优先进入固相，这是B(OH)3优先掺入的结果。 5. 硼以B(OH)3和B(OH)4-两种形式同时掺入Mg(OH)2，并以B(OH)3优先掺入为主，pH设定越低掺入的B(OH)3比例越高。 6. 硼将通过吸附和与Mg(OH)2的沉淀反应而掺入Mg(OH)2，两者共同决定了Mg(OH)2中硼同位素分馏特征。 7. Ca、Sr、B和Na在珊瑚中均得到富集，而Mg在珊瑚中却是贫化的。珊瑚的B浓度主要不是由这几种元素决定的。 8. 珊瑚δ11Bcarb的变化范围为22.8‰～27.9‰，平均为25.2‰。除与B浓度相关性明显外，珊瑚δ11Bcarb与其它四种元素的相关性不强。北海涠洲岛、灯楼角和三亚三地珊瑚与海水间的分馏系数carb-sw分别为0.9839、0.9847和0.9850。珊瑚与海水B(OH)3间的分馏系数carb-3的变化范围为0.9772～0.9800，平均值为0.9788，随pH升高carb-3减小。珊瑚的平均δ11Bcarb基本位于采用=0.9772时理论计算的δ11B4曲线之上，而且都低于原始合成海水的δ11Bcarb，表明硼是以B(OH)3和B(OH)4-两种形式同时掺入进珊瑚中的，并以B(OH)4-优先掺入为主。 9. 由于B(OH)4- 和B(OH)3同时进入到珊瑚中，d11Bcarb=d11B4的假设不能成立，由所测定生物碳酸盐的δ11Bcarb值计算的海水pH值会产生误差，使δ11B-pH技术变得更为复杂。 10. 实验模拟与自然的真实情况是有差距的，不能完全用实验模拟来代替自然的真实情况。 11.杨户庄剖面的第四纪早期有孔虫的生存环境是非海相环境，不是“海侵”或“海泛”的结果；同时也表明有孔虫并非是特有的海洋生物，它完全可以在陆相环境中存在。

土壤中重金属活动性的唐南膜测定、模型模拟与污染的原位控制

土壤是自然环境的重要组成部分，是人类赖以生存与发展的宝贵资源。但是近年来我国土壤重金属污染日益严重，重金属污染物与其它类型的污染物相比具有隐蔽性、长期性与不可逆性等一系列特殊性，成为土壤中永久的污染物，最终通过食物链的传递进入人体，对人类的健康造成潜在的危害。因此，研究土壤重金属污染与控制具有很重要的意义。本论文首次将唐南膜平衡法（DonnanMembraneTechnique）和EcosAT（EquilibriumCalculationOfSpeciationAndTransport）模型引入我国土壤重金属活动性研究，并将两种方法获得的结果进行比较，互相验证，取得了较好的结果。还将两种方法结合探讨了贵州铝厂生产的赤泥对土壤中的游离重金属离子浓度的影响。土壤样品采于贵州都匀福锌矿地区，一个位于锅锌矿选厂尾矿坝下农田中的水稻土，以下简称坝下土，为重污染土；另一个位于锅锌矿上游桥边农田中的水稻土，以下简称桥边土，为轻污染土，本研究取得的主要结论与认识包括：1．作者对唐南膜平衡法进行了部分改进，用国内生产的JAM一I型均相离子交换膜替换Brwin等所用的BDH膜，既降低了实验的平衡时间，又经济实惠。另外还用KNO3溶液代替KNO3和Ca（NO3）2混合溶液作为实验的介质溶液，就可以避免由于国内土壤中Ca2+含量差异较大可能造成的误差。其它实验条件为：蠕动泵的流速为2.0ml／min，平衡时间为48小时。2．用柠檬酸体系（液一液体系）和土壤一水体系（固一液体系）检验了唐南膜平衡法，它可以在不扰动体系平衡的基础上同时测定同一体系中的多个游离金属离子浓度，而且各金属离子之间互不干扰。3．桥边土中的游离重金属离子浓度与其中2mol／LHNO3提取的重金属总含量成很好的直线关系，其中Cu和Zn游离离子浓度与其中的总金属含量呈现较好的正比关系，随着重金属总含量的降低，即土液比的降低，游离重金属离子浓度随之降低；而其中的Ni和Cd却相反，随着重金属总含量的降低，游离重金属离子浓度反而增加。添加赤泥后随着土液比的降低各重金属的游离离羲?子浓度的变化趋势与添加赤泥前一样。桥边土中的重金属游离离子浓度在添加联合法赤泥后有所增加，而拜尔法赤泥的加入降低了其中的游离重金属离子浓度，加入的比例越大，变化的量越多，而且其中Ni和cd的变化幅度比Cu和Zn的要大。4．坝下土中Cu、Zn、Ni和Cd元素的游离离子浓度与它们在土壤中Zmol／LHNo3提取的重金属总含量呈很夯的正比关系，随着重金属总含量的降低，游离重金属离子浓度随之降低。添加赤泥后其中Cu和Zn元素的变化趋势与添加赤泥前一样，Ni和Cd元素出现了异常，Ni在赤泥添加比例为0.50％时变化趋势一样，但添加比例为2.00％时其离子浓度先增加，但在土液比为1:100时反而有较大幅度的降低。而其中Cd离子浓度先增加，在土液比为1:100时反而有较大幅度的降低。坝下土中Cu和Zn的游离离子浓度在添加赤泥以后改变很小，赤泥添加比例为2.00％的土壤中的游离离子浓度相对较低一点，而添加比例为0.50％的与未加赤泥的土壤基本上一样；其中Ni和Cd的变化相对来说较大，赤泥添加比例为2.00％的土壤中的游离离子浓度降低得比较明显，拜尔法赤泥添加比例为0.50％的土壤也得到了较大的改善，而联合法赤泥添加比例为0.50％的却比未加赤泥的土壤中的还要高一点。5．利用ECOSAT模型模拟了本论文所涉及的实验中的游离重金属离子浓度，测量值与模拟值取得了较好的一致，除了Zn的误差较大以外，其它三个元素符合的很好，从而表明EC0sAT在土壤一水系统中的模拟取得了较好的结果。6．模拟了不同土液比土壤中各重金属元素在有机质、铁氧化物、粘土和唐南凝胶体这四种吸附相中的分配。发现在所研究的土壤样品中所有元素在粘土相中所占的比例很小，可以忽略不计，Cu主要分布在有机质相中，占80％左右，随着土液比的降低，其在有机质和唐南凝胶体相中的分配比例慢慢变小，而在铁氧化物中的比例越来越大；Zn主要分布在有机质和铁氧化物相中，各占40％左右；随着土液比的降低，Zn在有机质相中的比例增大，铁氧化物比例几乎不变，而唐南凝胶体所占比例逐渐减小；Ni基本上只分布在有机质和铁”氧化物相中，Cd则几乎只存在于有机质相中，它们的分布比例几乎不随土液比的改变而变化。7．无论在桥边土和坝下土中添加何种赤泥，添加的比例是多少，在添加赤泥前后土壤中重金属元素在各吸附相中的分配比变化很小，主要是有机质相所占比例稍微变小，而铁氧化物相相应的有一点增加。而对于不同的土液比，其变化趋势相同，只是变化幅度相对来说较大。

Epoxidation of styrene with NaOCl and catalyzed by nickel(II) complexes

Epoxidation of styrene was catalyzed by some nickel(II) complexes, with NaOCl as the oxygen donor. The catalyst Ni(PA)(2). 2H(2)O has been found to be stable for the epoxidation of styrene. Some additives were introduced in the reaction to improve the "micro-environment" of the catalyst. Radical trap had little influence on styrene epoxidation. It was interesting to find that phase-transfer agent had negative influence on epoxidation in this biphase reaction. A possible mechanism of styrene epoxidation catalyzed by Ni(PA)(2). 2H(2)O has been proposed.

A practical approach to the degradation of polychlorinated biphenyls in transformer oil

A practical and efficient disposal method for hydrodechlormation of polychlorinated biphenyls (PCBs) in transformer oil is reported. Transformer oil containing PCBs was treated by nanometric sodium hydride (nano-NaH) and transition metal catalysts. High destruction and removal efficiency (89.8%) can be attained by nano-NaH alone under mild conditions. The process exhibits apparent characteristics of a first order reaction. The reductive ability of nano-NaH was enhanced by the addition of transition metal catalysts. In the presence of TiCl4, 99.9% PCBs was hydrodechlorinated. The complex reducing reagents, Ni(OAc)(2) + i-PrONa, show extra hydrodechlorinating activity for di-chlorinated biphenyls. (c) 2004 Elsevier Ltd. All rights reserved.