不同施氮水平和杂草清除时间对半湿润地区农田氮素利用及产量的影响

在半湿润地区中等肥力土垫旱耕人为土上进行田间试验,通过对冬小麦不同生育期杂草和作物样品的采集与分析,研究不同施肥及杂草处理对氮肥肥效的影响。结果表明:作物吸氮量随施氮量增加而增加,杂草吸氮量随吸氮量增加而降低;在不同杂草处理全生育期不清除杂草(A)、越冬前清除杂草(B)、返青期清除杂草(C)和拔节期清除杂草(D)的各个处理中,A、B、C和D杂草吸氮量分别占农田植物(作物+杂草)地上部分总吸氮量的1.98%、1.39%、3.99%和3.82%。籽粒产量随施氮量增加而增加,施氮量为135 kg N.hm-2时产量最高,达5 645.1 kg.hm-2,施氮量高于135 kg N.hm-2时,产量趋于稳定。氮肥利用率、氮肥利用效率、氮肥农学效率和氮肥生理效率均随施氮量增加而降低;从不同杂草处理看,以全生育期不清除杂草处理氮肥利用率最高,达到43.8%,返青期清除杂草处理氮肥利用率最低,为26.3%,二者间差异达显著水平;氮肥利用效率以越冬期清除杂草处理最高,为42.8 kg.kg-1N,全生育期不清除杂草处理最低,为40.6kg.kg-1N;氮肥生理效率以返青期清除杂草处理最高,为57.5 kg.kg-1N,显著高...

Self-assembly of diblock copolymer mixtures in confined states: A Monte Carlo study

The self-assembly of diblock copolymer mixtures (A-b-B/A-b-C or A-b-B/B-b-C mixtures) subjected to cylindrical confinement (two-dimensional confinement) was investigated using a Monte Carlo method. In this study, the boundary surfaces were configured to attract blocks A but repel blocks B and C. Relative to the structures of the individual components, the self-assembled structures of mixtures of the diblock copolymers were more complex and interesting. Under cylindrical confinement, with varying cylinder diameters and interaction energies between the boundary surfaces and the blocks, we observed a variety of interesting morphologies. Upon decreasing the cylinder's diameter, the self-assembled structures of the A(15)B(15)/A(15)C(15) mixtures changed from double-helix/cylinder structures (blocks B and C formed double helices, whereas blocks A formed the outer barrel and inner core) to stacked disk/cylinder structures (blocks B and C formed the stacked disk core, blocks A formed the outer cylindrical barrel), whereas the self-assembled structures of the A(15)B(7)/B7C15 mixtures changed from concentric cylindrical barrel structures to screw/cylinder structures (blocks C formed an inside core winding with helical stripes, whereas blocks A and B formed the outer cylindrical barrels) and then finally to the stacked disk/cylinder structures.

Synthesis, characterization, and self-assembly of protein lysozyme monolayer-stabilized gold nanoparticles

Lysozyme monolayer-protected gold nanoparticles (Au NPs) which are hydrophilic and biocompatible and show excellent colloidal stability at low temperature, ca. 4 degrees C, were synthesized in aqueous medium by chemical reduction of HAuCl4 with NaBH4 in the presence of a familiar small enzyme, lysozyme. UV-vis spectra, transmission electron microscopy (TEM), atomic force microscopy, and X-ray photoelectron spectroscopy characterization of the as prepared nanoparticles revealed the formation of well-dispersed An NPs of ca. 2 nm diameter. Moreover, the color change of the An NP solution as well as UV-vis spectroscopy and TEM measurements have also demonstrated the occurrence of Ostwald ripening of the nanoparticles at low temperature. Further characterization with Fourier transform infrared spectroscopy (FTIR) and dynamic light scattering indicated the formation of a monolayer of lysozyme molecules on the particle surface. FTIR data also indicated the intactness of the protein molecules coated on An NPs. All the characterization results showed that the monodisperse An NPs are well-coated directly with lysozyme. Driven by the dipole-dipole attraction, the protein-stabilized Au NPs self-assembled into network structures and nanowires upon aging under ambient temperature.

不同载量Pt/C催化剂制备及其对甲醇氧化的电催化活性

用甲醇作溶剂,SnCl2作还原剂,采用改进的有机溶胶方法制备了用于直接甲醇燃料电池(DMFC)中甲醇氧化的炭载Pt(Pt/C)催化剂。制得的Pt/C催化剂中的Pt粒子具有高度的均一性和良好的分散度。通过控制溶剂的蒸发温度,能够获得Pt粒子平均粒径基本相同、Pt载质量分数为10%～60%的Pt/C催化剂,粒径为3.3～4.3nm。将获得的催化剂通过涂膜-热压法制备成DMFC膜电极,研究了Pt载量对甲醇电催化氧化性能的影响。结果表明,质量分数为40%的Pt/C催化剂对甲醇的电催化氧化显示出优异的电催化性能。

Well defined carbazole-based hole-transporting amorphous molecular materials

Monodisperse carbazole-based oligomers have been synthesized via C-N bonds formation by the modified Ullmann reaction. The full characterization of their structure is presented. These derivatives are highly thermally stable amorphous compounds with glass transition temperatures of 167-171 degrees C and thermal decomposition temperatures of ca. 400 degrees C. Amorphous films of the materials were fabricated and their hole-transporting properties were tested in a light emitting device with Alq(3) as an electroluminescent and electron-transporting material.

Conformational transition of DNA in electroreduction studied by in situ UV and CD thin layer spectroelectrochemistry

Electrochemically induced three conformational transitions of calf thymus DNA from B-10.4 to Z(10.2)-DNA and from B-10.2 to B-10.4 and to C-DNA in 10 mM phosphate buffer solution (pH 7.21) at glassy carbon electrode are found and studied by in situ circular dichroism (CD) thin layer spectroelectrochemistry with singular value decomposition least square (SVDLS) analysis. It indicates that the so-called B-10.2 form and the C-form of DNA may be composed of B-10.4 and left-A DNA and of B-10.4 and right-A DNA, respectively. The irreversible electrochemical reduction of adenine and cytosine groups in the DNA molecule is studied by UV-Vis spectroelectrochemistry. Some electrochemical parameters alphan = 0.17, E-0' = -0.70 V (vs. Ag/AgCl), and the standard heterogeneous electron transfer rate constant, k(0) = 1.8 x 10(-5) cm s(-1) are obtained by double logarithmic analysis and non-linear regression. (C) 2000 Elsevier Science B.V. All rights reserved.

Calculation of chemical bond parameters in La1-xCaxCrO3 (0.0 <= x <= 0.3)

The chemical bond parameters, that is, bond covalency, bond susceptibility, and macroscopic linear susceptibility of La1-xCaxCrO3 (x = 0.0, 0.1, 0.2, 0.3) has been calculated using a semiempirical method. This method is the generalization of the dielectric description theory proposed by Phillips, Van Vechten, Levine, and Tanaka (PVLT). In the calculation of bond valence, two schemes were adopted. One is the bond valence sums (BVS) scheme, and the other is the equal-valence scheme. Both schemes suggest that for the title compounds bond covalency and bond susceptibility are mainly influenced by bond valence and are insensitive to the Ca doping level or structural change. Larger bond valences usually result in higher bond covalency and bond susceptibility. The macroscopic linear susceptibility increases (only slightly for BVS scheme) with the increasing Ca doping level. (C) 1999 John Wiley & Sons, Inc.

Crystal growth and TG-DTA properties of K(2)Ln(NO3)(5).2H(2)O (Ln = La, Ce, Pr, Nd, Sm)

Single crystals of KLnN(Ln=La, Ce, Pr, Nd, Sm) can be grown in water solution with pH approximate to 1 similar to 2 at about 40 degrees C. Crystals of KLnN (Ln=La, Ce, Pr, Nd) are orthorhombic with space group Fdd2. KPrN crystal was grwon and its crystal structure was determined for the first time. The KPrN crystal parameters obtained by the direct method are as follows: a=21.411(3) Angstrom, b=11.2210(10)Angstrom, c=12.208(2) Angstrom, Z=6, R=0.0240. The TG-DTA curves of KLnN(Ln=La,Ce, Pr, Nd, Sm) demonstrate that the processes of dehydration, melt, irreversible phase transition and decomposition of NO3- take place in sequence with the temperature increasing(except KCN). There are three steps in the decomposition of NO3- in KLnN(Ln=La, Nd, Sm) while two steps in KLnN (Ln=Ce, Pr). K(2)Ln(NO3)(5). 2H(2)O are formed at about 225 degrees C by the reaction of the starting materials of KNO3 and Ln(NO3)(3). nH(2)O.

用~(13)C-NMR法研究酚酞/双酚T型聚芳醚砜的序列结构

利用~(13)C核磁共振法研究了酚酞/双酚T型聚芳醚砜共聚物((PP/Bis-T)PES)的序列结构,分析了将双酚T单元引入酚酞型聚芳醚砜(PES-C)聚合物分子中对其酚酞单元的核磁共振谱的影响,并证实了(PP/BiS-T)PES属于无规共聚物。

大洋有孔虫微量元素研究

The most novel aspect of this thesis is the combination analysis of the boron isotopes and trace elements. What’s more, it also provides a reliable analytical technique, which is suitable for both boron isotopes and trace elements. Al/Ca values can be used to monitor the clay removal during the sample preparation. It is found that when Al/Ca>100 mol/mol, the measured boron isotopic compositions are always several permil lower than those properly cleaned. B/Ca ratios can be used to calculate the exact boron loaded for each sample. Otherwise, too much loading will lead to too long time for the whole analytical sequence, and too less loading might incur serious blank problem. One other benefit besides those discussed above is that the combination analysis of boron isotopes and trace elements on the same sample allows reconstruction of the marine carbonate system and atmospheric pCO2 without assumption of the other parameter. In the marine carbonate system, with the seawater pH from the foraminiferal ɧ40;11B, one has to make an assumption on the other variable to obtain the rest four variables. A series studies found that U/Ca and B/Ca are potential proxies for seawater [CO32-]and [HCO3-], respectively. Since they are measured on the same sample with boron isotopes, hence, there is no spatial or temporal ambiguity in the incorporation of the two controlling parameters. With ɧ40;11B and U/Ca, the reconstructed atmospheric pCO2 variations match the atmospheric pCO2 record from the Vostok ice core within ±20 ppm. The incorporations of U and B into foraminiferal carbonates are controlled by the overall growth rate of individual foraminifers and other possible factors. The reliable application of these proxies still require further calibrations. In a similar fashion, the combination analysis of boron isotopes and Mg/Ca also has great advantages. Mg/Ca has been proved to be a reliable proxy for the surface seawater temperature. With the combination analysis, one can determine the phase between changes in atmospheric pCO2 and surface seawater temperature, thus explore the cause and mechanism of the changes in atmospheric pCO2. .

济阳-昌潍坳陷火成岩油气藏体系形成机理和分布规律研究

Jiyang & Changwei depressions are two neighboring depressions in Bahai Bay Basin, the famous oil rich basin in East China. The exploration activities in the past 40 years has proved that, within the basins, there exists not only plentiful sandstone hydrocarbon reservoirs (conventional), but also abundant special reservoirs as igneous rock, mudstone and conglomerate ones which have been knowing as the unconventional in the past, and with the prospecting activity is getting more and more detailed, the unconventional reservoirs are also getting more and more important for further resources, among which, the igneous lithological reservoir be of significance as a new research and exploration area. The purpose of this paper is, with the historical researches and data as base, the System Theory, Practice Theory and Modern Comprehensive Petroleum Geology Theory as guide, the theoretical and practice break through as the goal, and the existing problems in the past as the break through direction, to explore and establish a valid reservoir formation and distribution models for igneous strata in the profile of the eastern faulted basins. After investigating the distribution of the igneous rocks and review the history of the igneous rocks reservoirs in basins, the author focused on the following issues and correspondingly the following progresses have been made: 1.Come to a new basin evolution and structure model named "Combined-Basin-bodies Model" for Jiyang even Eastern faulted basins based on the study on the origin and evolution of Jiyang & Changwei basins, depending on this model, every faulted basin in the Bo-hai Bay Basin is consisted of three Basin-Bodies including the Lower (Mesozoic), Middle (Early Tertiary) and the Upper (Late Tertiary) Bodies, each evolved in different geo-stress setting and with different basin trend, shape and igneous-sedimentary buildings system, and from this one to next one, the basin experienced a kind of process named "shape changing" and "Style changing". 2. Supposed a serious of new realizations as follows (1) There were "multi-level magma sources" including Upper mantel and the Lower, Middle and even the Upper Shell magma Chambers in the historical Magma Processes in the basins; (2) There were "multi-magma accessing or pass" from the first level (Mantel faults) to the second, third and fourth levels (that is the different levels of fault in the basin sediment strata) worked in the geo-historical and magma processes; (3) Three tectonic magma cycles and more periods have been recognized those are matched with the "Basin -body-Model" and (4)The geo-historical magma processes were non-homogeneous in time and space scale and so the magma rocks distributed in "zones" or "belts". 3. The study of magma process's effect on basin petroleum conditions have been made and the following new conclusions were reached: (1) the eruptive rocks were tend to be matched with the "caped source rock", and the magma process were favorable to the maturing of the source rocks. (2) The magma process were fruitful to the accumulation of the non-hydrocarbon reservoirs however a over magma process may damage the grade of resource rock; (3) Eruptive activity provided a fruitful environment for the formation of such new reservoir rocks as "co-eruptive turbidity sandstones" and "thermal water carbonate rocks" and the intrusive process can lead to the origin of "metamorphism rock reservoir"; (4) even if the intrusive process may cause the cap rock broken, the late Tertiary intrusive rocks may indeed provide the lateral seal and act as the cap rock locally even regionally. All above progresses are valuable for reconstructing the magma-sedimentary process history and enriching the theory system of modem petroleum geology. 4. A systematic classification system has been provided and the dominating factors for the origin and distribution of igneous rock reservoirs have been worked out based on the systematic case studies, which are as follows: (1) The classification is given based on multi-factors as the origin type, litho-phase, type of reservoir pore, reservoir ability etc., (2) Each type of reservoir was characterized in a detailed way; (3) There are 7 factors dominated the intrusive reservoir's characteristics including depth of intrusion, litho-facies of surrounding rocks, thickness of intrusive rock, intrusive facies, frequency and size of the working faults, shape and tectonic deformation of rock, erosion strength of the rock and the time of the intrusion ect., in the contrast, 4 factors are for eruptive rocks as volcanic facies, frequency and size of the working faults, strength of erosion and the thermal water processing. 5. Several new concept including "reservoir litho-facies", "composite-volcanic facies" and "reservoir system" ect. Were suggested, based on which the following models were established: (1) A seven reservoir belts model for a intrusive unit profile and further more, (2) a three layers cubic model consisted of three layer as "metamorphic roe layer", "marginal layer" and "the core"; (3) A five zones vertical reservoir sequence model consisted of five litho-facies named A, B, C, D and E for a original lava unit and furthermore three models respectively for a erosion, subsidence and faulted lava unit; (4) A composite volcanic face model for a lava cone or a composite cone that is consisted of three facies as "crater and nearby face", "middle slope" and "far slope", among which, the middle slope face is the most potential reservoir area and producible for oil & gas. 6. The concept of "igneous reservoir" was redefined as the igneous, and then a new concept of "igneous reservoir system" was supposed which means the reservoir system consisted of igneous and associated non-igneous reservoirs, with non-hydrocarbon reservoir included. 7. The origin and distribution of igneous reservoir system were probed and generalized for the exploration applications, and origin models of the main reservoir sub-systems have been established including those of igneous, related non-igneous and non-hydrocarbon. For intrusive rocks, two reservoir formation models have been suggested, one is called "Original or Primary Model", and the another one is "Secondary Model"; Similarly, the eruptive rock reservoirs were divided in three types including "Highly Produced", "Moderately Produced" and "Lowly Produced" and accordingly their formation models were given off; the related non-igneous reservoir system was considered combination of eight reservoirs, among which some ones like the Above Anticline Trap are highly produced; Also, the non-hydrocarbon. Trap system including five kinds of traps was discussed. 8. The concept models for four reservoir systems were suggested, which include the intrusive system consisted of 7 kinds of traps, the land eruptive system with 6 traps, the under water eruptive system including 6 kinds of traps and the non-hydrocarbon system combined by 5 kinds of traps. In this part, the techniques for exploration of igneous reservoir system were also generalized and probed, and based on which and the geological progresses of this paper, the potential resources and distributions of every reservoir system was evaluated and about 186 millions of reserves and eight most potential non-hydrocarbon areas were predicted and outlined. The author believe that the igneous reservoir system is a very important exploration area and its study is only in its early stage, the framework of this paper should be filled with more detailed studies, and only along way, the exploration of igneous reservoir system can go into it's really effective stage.

中国炼锌向大气排汞及其环境影响的初步研究

汞是一种毒性极强的环境污染物。由于汞能在大气中存在并能长距离迁移，因此汞已经被定义为全球性污染物。研究表明有色金属锌的冶炼是大气汞的一个重要的人为汞污染源。西方发达国家在炼锌过程中由于有严格的污染物控制措施，使得这个问题得到有效的控制。由于经济和技术的原因我国大多数锌冶炼企业在冶炼过程中没有进行烟气汞的回收，从而使得我们不能借鉴国外的相关研究成果。我国2005年精锌总产量占到了世界的1/4，是全世界最大的锌锭生产国家，但相关的研究却非常滞后。近年来我国锌冶炼向大气排汞的问题已经引起了国际争议，而且冶炼过程中排放的汞对局部生态系统会产生重要影响，因此锌冶炼过程中释放汞所造成的环境问题已经越来越受到人们的关注和重视。 本研究的目的是通过对不同锌矿山的锌矿石和浮选锌精矿以及冶炼厂不同源锌精矿的研究从而了解我国的矿石汞含量，及矿石浮选过程中汞的分配；通过对冶炼过程向大气排汞的研究，认识锌精矿中汞在锌冶炼过程中的分配，估算不同冶炼方式汞的释放因子。如A、B和C冶炼厂是用不同的工艺来炼锌的，其汞的释放因子也不同。通过对土法炼锌区和工业炼锌区水体、土壤、大气和植物中汞的分布、迁移转化规律的研究，认识锌冶炼对局部生态系统产生的影响。 1.矿石和锌精矿中汞的研究 成因和分类不同的铅锌矿床锌矿石和浮选锌精矿中汞的测定结果表明：凡口矿的矿石和浮选的锌精矿中汞含量比兰坪矿矿石和浮选锌精矿高了2个数量级。凡口矿锌矿石和锌精矿中汞的含量分别是64.5-107 mg∙kg-1，588-602 mg∙kg-1；对应兰坪矿锌矿石和锌精矿中汞的含量分别是0.23~0.40 mg∙kg-1，1.91-3.33 mg∙kg-1。不同冶炼厂不同矿源的锌精矿中汞含量测定结果表明：不同源锌精矿中汞含量在0.10-1100 mg∙kg-1之间，变动范围非常大。而冶炼厂冶炼所用的混合锌精矿中汞含量差别不大，冶炼所用的混和锌精矿汞含量在37-105 mg∙kg-1之间变动。 2.锌精矿中汞在冶炼过程中的分配和汞释放因子的研究 对采用不同炼锌工艺的冶炼厂和有除汞工艺的A、B冶炼厂所用的锌精矿中的汞在冶炼过程分配的质量平衡对比表明，A冶炼厂和B冶炼厂锌精矿中的汞在冶炼过程中的分配显著不同，主要制约因素是是否对烟气中汞进行回收。在烟气到达除汞设备前，A和B冶炼厂在焙砂和尘、酸洗、电除雾等流程对烟气中汞的去除效果相近。不同的是，A厂要进行烟气汞回收，烟气经过汞回收后，50%以上烟气中的汞在这一流程被去除。这使得A、B冶炼厂后续的流程制酸吸收汞和排向大气汞所占的比例有较大的差异。 不同冶炼方式的汞释放因子表明，无任何环保措施的土法炼锌活动的释汞因子为113 g·t-1，不对烟气汞进行回收的B厂和C冶炼厂汞的释放因子分别为49 g·t-1和243 g·t-1，对烟气汞回收的A冶炼厂汞的释放因子为5.7 g·t-1。综合各种不同炼锌方式的汞释放因子及其精锌产量，得出了锌冶炼过程中汞的综合释放因子，从而估算出我国锌冶炼向大气排汞量约61.3-178 t·y-1。 3.锌冶炼对局部生态系统的影响 炼锌区的冶炼废渣是冶炼过程中的主要废弃物，随意堆放的废渣是当地农田土壤的重要汞污染源，大气汞中活性汞和颗粒态汞的沉降也是当地农田土壤另一个汞污染源。土法炼锌区和工业炼锌区土壤分析结果表明，工业炼锌对局部环境的影响更为严重。土壤汞含量对比如下：A冶炼厂周边环境污染土壤汞含量259-2990 μg·kg-1，远高于威宁土法炼锌点污染土壤汞含量72-355 μg·kg-1。威宁土法炼锌点土壤中甲基汞含量的分析表明，在冶炼点附近的土壤中甲基汞绝对含量和甲基汞/总汞的比例都高于其它样点，说明冶炼点附近土壤中汞的甲基化水平提高。A冶炼厂污水处理渣亦没有得到妥善的处理，成为当地潜在的汞污染源。 土法炼锌区水体汞的含量明显受到冶炼渣的影响。工业炼锌过程产生的废水经处理后的水汞含量100%超过国家工业废水排放标准，这些处理后的水的排放是当地重要的汞污染源。A冶炼厂周边稻田水分析表明，溶解态甲基汞占溶解态总汞的的平均比率（5%）远高于一般自然水体（<1%），可能与稻田特殊环境有关。 土法炼锌区大气汞含量测定表明，冶炼点附近大气汞浓度剧增，高达5220 ng·m-3，锌冶炼是当地主要的大气汞污染源。大气汞浓度的提升，是导致农作物玉米叶部位汞含量增高的原因。植物体的地上绿色部分通过叶片吸收大气汞是植物体内汞富集的重要途径之一。 土法炼锌区和工业炼锌区农作物果实中汞含量的测定结果对比如下：A冶炼厂附近稻田产出的部分大米样品中总汞含量已经超过了国家食品限量卫生标准（20 µg·kg-1），所有辣椒中总汞含量全部超出了国家蔬菜卫生限量标准（10 µg·kg-1）。土法炼锌区所取农作物样品未出现果实汞含量超标现象。食用这些汞含量超标的食物将对当地居民带来潜在的危害。

岩石圈伸展对粤北下庄矿田铀成矿的制约机制研究

地球动力学与成矿关系的研究是地球科学研究的前沿领域，而陆内岩石圈伸展与成矿的关系的研究则是该领域相对比较薄弱的环节。 华南地区于白垩—古近纪发生了岩石圈强烈的伸展减薄事件，且岩石圈伸展减薄与该区同时期形成的众多金属和非金属矿床有密切的成因联系，尤其是华南地区的花岗岩型热液铀矿床，显示了与该区岩石圈伸展作用可能有多方面的成因联系。粤北下庄铀矿田位于位于南岭铀-多金属成矿带的南部，是华南地区典型的花岗岩型热液铀矿区，本次研究在深入细致的野外地质工作的基础上，运用流体包裹体地球化学、元素地球化学、同位素地球化学等方法手段，开展了对下庄铀矿田成矿流体性质、成矿过程中元素的活动规律、成矿流体来源及演化等方面的系统研究，初步探讨了岩石圈伸展对该区铀成矿的制约机制，并建立了可能的矿床成因模式。通过研究，本次工作获得了以下几点主要认识： （1）通过对下庄铀矿田部分铀矿床流体包裹体显微测温、激光拉曼光谱及液相成分分析研究，查明了下庄矿田铀矿床矿前期热液属中高温（200℃~350℃）、低盐度（0.72%~5.95%NaCl）、密度中等（0.703~0.830g/cm3）、活动深度较深（2.29km~5.74km）、富∑CO2、相对还原性质的流体；成矿期热液属中低温（主要为154℃ ~250℃）、低盐度（0~1.83%NaCl）、密度中等（0.628~0.867g/cm3）、活动深度较浅（0.19km~1.62km）、富F-、相对氧化性质的流体。 （2）矿石矿矿物电子探针测试分析及岩、矿石的微量元素地球化学分析研研究表明，本区铀矿床主要的原生铀矿物为沥青铀矿、铀石、钛铀矿，铀矿物的形成与Si、Ca���W等元素有密切的关系，而其它金属元素未显示明显地富集。矿石、脉石矿物部分继承了原岩的稀土元素组成，且在原岩基础上又有高度的演化。 （3）进行了矿区内碳酸盐的C、O同位素和黄铁矿的He、Ar稀有气体同位素的分析研究。研究表明，矿化剂∑CO2主要为幔源，大量的He、Ar等稀有气体也来自于地幔。矿区发育的深大断裂构造可能控制了幔源挥发份的加入。 （4）脉石矿物碳酸盐和萤石的Sr、Nd同位素地球化学研究显示，成矿流体中的这些元素主要源于地壳，南区矿床（338、339）的Sr、Nd组成则为富含壳源Sr、Nd的流体与幔源基性脉岩不同程度的水—岩反应所致。另外，碳酸盐铅同位素研究显示，下庄矿区成矿物质铀可能来自帽峰式后期流体交代的花岗岩体。 （5）岩石圈伸展与下庄矿田铀成矿有关系密切：下庄矿田铀矿床明显受伸展构造控制，伸展构造既为导矿构造，又为储矿构造；岩石圈伸展导致的地温梯度升高，大地热流平均值加大，驱动热液流体的流动，为铀成矿提供了主要的热驱动力；岩石圈伸展产生的深大断裂导通了壳幔间的联系，使幔源脱气成因挥发份（主要为∑CO2）沿断裂上升，加入壳源热水循环系统，从而参与了铀成矿。 （6）初步建立了下庄矿田“岩石圈伸展体系下大陆热水系统铀矿床成因模式”。模式认为，华南地区白垩—古近纪岩石圈伸展作用引发区内热水流体的大规模循环，且伸展引起的幔源脱气作用产生的挥发份（主要为ΣCO2）加入了贫铀、贫矿化剂的循环的地下热水中，形成了富矿化剂热水。富矿化剂热水从富铀花岗岩中浸出铀（氧化作用），变为富矿化剂、富铀热液流体，这种热液流体在伸展引起的热驱动下沿构造上升，热液流体上升到浅部时，由于地球化学障、流体压力释放等因素的影响，U被还原沉淀，并在有利部位富集成矿。

贵州碳酸盐岩风化壳次生石英表面结构、裂变径迹测年及其指示意义

我国西南地区分布有广阔的亚热带潮湿区岩溶，以贵州为中心，总面积达50万km2，是世界上连片分布面积最大的岩溶区。贵州高原地处青藏高原东南缘,云贵高原的东翼，是中国大陆“西高东低”地貌格局中重要的过渡区段，对其新生代地质、地貌演化进行研究无疑具有重要的意义，不仅是对贵州薄弱的新生代地质、地貌研究的补充，而且可以直接通过夷平面展开与青藏高原的对比，探讨青藏高原隆升对贵州高原的直接影响。风化壳作为夷平面的组成部分，在过去没有引起足够的重视，但随着成功实例的不断出现，人们逐渐开始认识到风化壳是夷平面识别和重建的重要依据，也是夷平面环境信息的重要载体。贵州作为碳酸盐岩集中分布区，碳酸盐岩风化壳剖面广泛存在，尤其在黔中、黔北等地区各级夷平面上均发育有红色风化壳，利用碳酸盐岩红色风化壳能为夷平面的识别和形成时代的确立提供可靠的证据，特别是风化壳形成年龄的确定对夷平面时标的建立更具有积极意义。有关贵州地区红色风化壳形成时代的确定，多年来已有一些学者对此展开了研究，但贵州红色风化壳形成时代的确定存在着很大争论。虽然存在其它原因的可能性，但造成这种争论的根本原因在于贵州红色风化壳形成时代是依据其它资料(如夷平面、气候事件等)推断出来的，而不是根据直接测年数据界定的。因此，风化壳直接测年才是解决问题的关键。 本文在前人工作研究的基础之上，利用扫描电镜手段对贵州碳酸盐岩地区上覆风化壳土层中的石英颗粒进行观察、统计、分析，为风化壳成土的物质来源寻找新的证据；同时，经地球化学分析、测试等手段，判断风化壳土层中的晶体石英颗粒为风化壳形成初期的新生矿物——次生石英颗粒，并利用裂变径迹测年法对这种次生石英颗粒进行测年，最终探讨贵州碳酸盐岩地区上覆风化壳土层的形成年代。主要取得了以下几点认识： 一、石英颗粒蚀刻条件的优选 由于石英颗粒裂变径迹的长度和数量与晶格、铀含量、年龄等因素有关，所以不同地区的石英颗粒样品的裂变径迹蚀刻条件也存在差别；目前国际上有关石英颗粒的裂变径迹测年应用的实例较少，还没有统一的有关石英颗粒蚀刻条件的国际标准；现有的石英颗粒蚀刻条件有多种，但是缺乏对这些方法的优缺点进行对比评价。因此，我们要进行反复的条件实验，对比不同石英蚀刻剂的蚀刻效率，找寻适合石英颗粒的最佳蚀刻剂。实验结果表明，40%的HF溶液为最佳蚀刻剂，最佳蚀刻时间：温度在4℃左右（冬季）时为40min；温度在29℃左右（夏季）时为30min。 二、石英的外形、表面机械作用特征及其指示意义 我们利用扫描电镜对石英颗粒外形特征进行观察、统计、分析，结果表明本次研究的石英颗粒形态类型主要有两种：棱状-次棱状石英颗粒以及圆状、次圆状石英颗粒，其中棱状-次棱状石英颗粒包含了一部分晶体形态较为完整的石英颗粒。 根据石英颗粒表面机械作用特征分析结果，结合剖面区域地质特征，可初步判断剖面中的石英颗粒有三种物质来源：碳酸盐岩中的原生碎屑石英，有长时间长距离搬运特征；燧石团块石英，有短距离搬运或原位沉积特征；晶形较完整的次生石英，无搬运特征。三种石英均具有原位特征，前两种类型的石英是直接对基岩的继承，第三种类型的石英是风化壳剖面的次生矿物。 三、石英颗粒表面的化学作用特征及其风化强度指示意义 我们通过对石英颗粒表面化学作用形态的观察，发现大兴剖面、新蒲剖面和官坝剖面的石英颗粒表面化学溶解作用和化学沉淀作用都非常强烈，这表明三个剖面均处于湿、热环境中，均处于强烈的化学风化阶段。而且大兴剖面中石英颗粒表面的化学作用最强烈，气候较其他两个剖面更湿热，剖面的风化强度也最大，即各剖面的风化强度由强到弱排序为：大兴、新蒲、官坝。这一结果与矿物组成分析、化学风化强度、硅铝、铝铁硅风化系数比以及相对风化强度等的地球化学分析指标相一致，这也再次证明了我们采用石英颗粒表面形态特征分析手段的可行性和可靠性。 四、石英颗粒的裂变径迹年龄 三种类型石英颗粒的裂变径迹测年数据表明：a、同一样点石英颗粒裂变径年龄呈现一定的规律：F.T.AGE圆状、次圆状＞F.T.AGE不规则状（棱状、次棱状）＞F.T.AGE标准晶形（次生石英）。b、不同剖面的不规则状石英颗粒形成于同一个时期；不同剖面的圆状、次圆状石英颗粒形成于同一个时期。这两种石英颗粒不适于贵州碳酸盐岩风化壳的测年研究。c、不同剖面的标准晶形石英颗粒形成于不同时期，形成于碳酸盐岩酸不溶物原地堆积过程中，即与风化壳剖面同期形成，可用于贵州碳酸盐岩风化壳的测年研究。这一测量结果与我们对石英颗粒表面形态特征的观察、统计、分析结果相一致。 五、风化壳物源的新证据 贵州碳酸盐岩风化壳中的石英颗粒表面形态的分析结果表明，贵州碳酸盐岩风化壳的物质来源于碳酸盐岩中酸不溶物原地风化残积的产物，与其下伏基岩有着明显的继承性。这一分析结果与王世杰等人的碳酸盐岩酸不溶物的提取实验、地球化学、矿物学、粒度特征及区域地质背景等多方面的分析结果相一致，为贵州碳酸盐岩风化壳的物质来源及成因提供新的、更细致的证据。 六、贵州晚新生代地质-环境研究历史轮廓初建 由于目前对贵州及周边地区的风化-气候研究相对缺乏，数据资料较稀少，还没有形成完整的系统，我们本次研究也是建立在对风化壳中次生英颗粒年代学研究的基础上，研究还不是很透彻，因此只能对地质-环境研究历史轮廓进行初建。本文根据本次研究剖面土层中晶体次生石英颗粒的裂变径迹年龄分布情况，结合前人已有资料，对贵州25Ma以来的地质-环境演化历史的轮廓进行初建。从次生石英裂变径迹年龄值来看，中新世以来贵州主要经历了如下构造-风化期：25-19Ma、16-13Ma、10-6.5Ma、5-2Ma、1.7-1Ma。

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ɧ40;11B的变化范围为-1.20‰～28.26‰，高于合成海水的ɧ40;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ɧ40;11B液f (-19.2‰～-17.8‰)均低于原始溶液的ɧ40;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。