无机界矿物天然自净化功能之矿物光催化作用

在简述半导体光催化理论及TiO2多相光催化作用近30年研究现状的基础上，重点对国内外一直处于空白状态的天然含钒金红石光催化性能进行研究。天然含钒金红石中部分Ti^4 被V^5 包括Fe^3 、Cu^2 和Zn^2 等杂质离子替代可引起其晶格畸变与缺陷。机械粉碎到70～80μm后可使其晶胞膨胀0.33％，原位加热700～1100℃其晶胞可膨胀0．93％～2．13％，淬火改性其晶胞收缩0．01％～0．07％。受热改性其体相中V^5 向表面偏析。对晶格畸变的修复可表现为晶面重构和再结晶作用及微应力释放作用。粉碎的金红石对卤代烃三氯乙烯和四氯乙烯具有一定的降解效果而表现出良好的光催化活性。加热1000℃，金红石对卤代烃的降解率明显提高。淬火1000℃和1100℃，金红石对卤代烃的降解速度大大加快。而电子辐射金红石对三氯乙烯的降解率则明显降低。通过52种金属氧化物和金属硫化物半导体矿物的初步研究，发现大多数金属氧化物矿物产生光电子的波长范围是249～777nm，吸收光主要是可见光。而大多数金属硫化物矿物产生光电子的最大波长大于921nm，吸收光主要是红外光，充分表明无机界具有光催化功能的半导体在可见光条件下就可以产生光电子与空穴。系统开展无机界矿物光催化作用研究，对揭示地球生命过程和环境演化有着不可替代的作用，对氧化降解地球表层系统中有机污染物尤其是不能自行降解的持久性有机污染物有着至关重要的作用。     

孕育光催化活性的天然含钒金红石矿物学特征

天然含钒金红石平均含V2O5可达1．22％，Fe2O30．39％，ZnO0．35％，CuO0．22％，这些金属离子可替代八面体中Ti^4 。V以5价形式存在，配位多面体呈三方双锥，其在晶格内部对Ti的替代导致晶格畸变，打破了配位多面体原有的八面体对称而呈四方双锥的几何形态，并产生结构微应力。透射电镜研究表明，该天然金红石结构内部存在位错、晶界等缺陷，可以成为光催化活性位。对其进行受力、受热以及微波辐射等改性作用后，晶胞发生不同程度的膨胀，可能导致晶格畸变及应变能增加，进一步促进光催化活性。研究结果表明，该天然含钒金红石孕育有良好的光催化活性。     

掺铁二氧化钛薄膜的自组装制备、表征与光催化性能研究

采用自组装方法于低温液相反应体系中成功制备出大尺寸二维纳米二氧化钛薄膜和掺铁二氧化钛薄膜。样品通过荧光发射光谱、拉曼光谱、高分辨透射电镜等方法进行表征,并研究了紫外光和可见光下Fe3+/TiO2纳米薄膜对甲基橙溶液(MO)的光催化降解过程,探讨了Fe3+对TiO2的光催化活性的影响。结果表明,此方法不需要高温煅烧即可得到高催化活性的金红石和锐钛矿混合型二氧化钛薄膜,以金红石为主。Fe3+掺杂明显提高了TiO2对甲基橙溶液的光催化降解效率:掺杂Fe3+浓度为0.5 mmol/L时光催化效果最优,且更利于较低浓度甲基橙溶液的降解,在紫外光和可见光下对初始浓度5 mg/L甲基橙溶液的降解率分别达到98.62%和89.24%。     

含钒金红石可见光下催化降解亚甲基蓝实验研究

利用含有钒等杂质的金红石可部分吸收可见光的特性,以500 W卤素灯作为光源,实验研究了其对亚甲基蓝的可见光催化降解,结果表明,该金红石具有催化活性,7 h后亚甲基蓝可降解71 2%。经过加热、粉碎改性方法处理后的金红石光催化活性明显提高,加热1 100 ℃的金红石样品7 h后可使亚甲基蓝的降解率达到90 4%。增加光照强度、加入适当的H2O2 都可提高降解效果。实验为充分开发利用天然金红石提出了新的途径,为环境污染治理提出了新方法。     

紫外光及日光下天然金红石光催化降解苯酚的研究

研究了山西代县天然金红石在紫外光和日光照射条件下对苯酚的光催化降解性能,考察了光照时间、pH值、苯酚初始浓度以及H2O2添加量对降解过程的影响。在紫外光照射下,酸性条件(pH=3.5)利于光催化降解,中性和碱性条件下降解效率较低;当初始浓度为60mg/L时,降解速率可达1.922mg/(L.h);H2O2作为电子捕获剂可提高苯酚降解速率,最佳投加量为2mL/L。在日光条件下,天然金红石对苯酚表现出良好的降解性能,照射7h后,降解率达87.68%,仅略低于P25型TiO2(99.72%),可在14h内完全降解。根据电子探针和X射线衍射分析结果,认为天然金红石晶格中的V、Fe等杂质可能是提高其可见光响应效果和光催化活性的主要原因。     

顶空气相色谱法测定北京市地下水中的氯代烃

以国家标准方法和美国环保局（EPA）方法为基础，建立用自动顶空进样器对饮用水中的氯代烃进行测定的方法，探讨了影响实验空白的因素，所拟方法的检出限为：三氯甲烷0.096μg/L、四氯化碳0.034μg/L，三氯乙烯0.049μg/L，四氯乙烯0.033μg/L。方法回收率控制在82％－106％，其相对标准偏差（RSD，n=7)小于23％，符合国际有机污染物分析的标准，并用此方法对北京市地表水、地下水进行了测定。     

SiO2-TiO2薄膜制备及其光催化性能研究

Sol-gel法制备SiO2-TiO2复合薄膜，进行甲醛的光催化降解实验，研究了SiO2掺杂量、薄膜焙烧温度、甲醛溶液pH值及初始浓度对光催化性能的影响。结果表明，500℃焙烧1h，掺杂质量SiO2：TiO2=12：100时，SiO2-TiO2薄膜的光催化活性最高，150min后甲醛降解率达76％，是单纯TiO2薄膜的1．3倍，该薄膜稳定性较好，经重复8次使用，最大降解率只下降4％。     

热处理对管状埃洛石负载TiO2的光催化降解性能的影响

0 引言 TiO2具有光催化特性,在紫外光照射下产生光氧化还原能力,可以降解有机污染物.在TiO2三种同质多像变体(金红石、锐钛矿、板钛矿)中,锐钛矿(anatase)对有机污染物的光催化降解率最高,在有机污染物降解等环境治理方面应用前景最为广阔.     

铁(氢)氧化物矿物对有机污染物的光催化氧化作用

对水溶液中(氢)氧化铁的光催化氧化反应的发展与机理研究进行了总结,着重对近十年来应用针铁矿／过氧化氢进行光催化氧化环境中有机物的研究进展及其环境矿物学意义作了概述和探讨。采用天然生物矿化的纳米针铁矿／过氧化氢以偶氮染料甲基橙为光解模型物进行了光催化氧化的初步研究,结果表明铁细菌形成的针铁矿具有降解生物难降解的有机污染物的能力。在甲基橙溶液初始浓度为30mg／L,铁细菌矿化的针铁矿用量2．5g／L,反应体系H2O2的初始浓度97mmol／L,pH值为6．92,15W紫外灯照射2h后,甲基橙浓度可降低33％。     

天然金红石光催化降解藏红T实验研究

以低压汞灯为光源研究了天然金红石悬浆体系中藏红T的脱色条件及其光催化反应动力学，讨论了溶液初始pH值、催化剂投入量、光强、气流量、催化剂粒径、反应气氛等实验条件对藏红T脱色速率的影响，阐述了实验过程中无机离子的生成情况。结果表明，该反应基本上符合一级反应动力学；在酸性条件下尤其是当溶液初始pH值为2．5时，藏红T的脱色速率要比在碱性和中性条件下快得多；增加光强度能较大地提高反应的降解速率；催化剂最佳投入量为1．3g／L；在氧化气氛下该反应比在非氧化气氛快得多；通入气体的流量在40L／h最合适；反应溶液中有氯离子溶出说明有机物中的含氯部分被降解。本研究为光催化作用降解有机污染物提供了新的途径。     

The terrestrial fauna of the Late Triassic Pant-y-ffynnon Quarry fissures,South Wales,UK and a new species of Clevosaurus (Lepidosauria: Rhynchocephalia)

Pant-y-ffynnon Quarry in South Wales yielded a rich cache of fossils in the early 1950s, including articulated specimens of new species (the small sauropodomorph dinosaur Pantydraco caducus and the crocodylomorph Terrestrisuchus gracilis), but no substantial study of the wider fauna of the Pant-y-ffynnon fissure systems has been published. Here, our overview of existing specimens, a few described but mostly undescribed, as well as freshly processed material, provides a comprehensive picture of the Pant-y-ffynnon palaeo-island of the Late Triassic. This was an island with a relatively impoverished fauna dominated by small clevosaurs (rhynchocephalians), including a new species, Clevosaurus cambrica, described here from a partially articulated specimen and isolated bones. The new species has a dental morphology that is intermediate between the Late Triassic Clevosaurus hudsoni, from Cromhall Quarry to the east, and the younger C. convallis from Pant Quarry to the west, suggesting adaptive radiation of clevosaurs in the palaeo-archipelago. The larger reptiles on the palaeo-island do not exceed 1.5?m in length, including a small carnivorous crocodylomorph, Terrestrisuchus, and a possible example of insular dwarfism in the basal dinosaur Pantydraco.     

Définition d'une limite multicritère ; stratigraphie du passage Campanien–Maastrichtien du site géologique de Tercis (Landes,SW France)Definition of a multi-criteria boundary; stratigraphy of the Campanian–Maastrichtian interval of the geological site at Tercis (Landes,SW France)

Lithostratigraphy, physicochemical stratigraphy, biostratigraphy, and geochronology of the 77–70 Ma old series bracketing the Campanian–Maastrichtian boundary have been investigated by 70 experts. For the first time, direct relationships between macro- and microfossils have been established, as well as direct and indirect relationships between chemo-physical and biostratigraphical tools. A combination of criteria for selecting the boundary level, duration estimates, uncertainties on durations and on the location of biohorizons have been considered; new chronostratigraphic units are proposed. The geological site at Tercis is accepted by the Commission on Stratigraphy as the international reference for the stratigraphy of the studied interval. To cite this article: G.S. Odin, C. R. Geoscience 334 (2002) 409–414.     

The effect of water on accessory phase solubility in subaluminous and peralkaline granitic melts

The solubilities of columbite, tantalite, wolframite, rutile, zircon and hafnon were determined as a function of the water contents in peralkaline and subaluminous granite melts. All experiments were conducted at 1035 °C and 2 kbar and the water contents of the melts ranged from nominally dry to approximately 6 wt.% H₂O. Accessory phase solubilities are not affected by the water content of the peralkaline melt. By contrast, solubilities are affected by the water content of the subaluminous melt, where the solubilities of all the accessory phases examined increase with the water content of the melt, up to 2 wt.% H₂O. At higher water contents, solubilities are nearly constant. It can be concluded that water is not an important control of accessory phase solubility, although the water content will affect diffusivities of components in the melt, thus whether or not accessory phases will be present as restite material. The solubility behaviour in the subaluminous and peralkaline melts supports previous spectroscopic studies, which have observed differences in the coordination of high field strength elements in dry vs. wet subaluminous granitic glasses, but not for peralkaline granitic glasses. Lastly, the fact that wolframite solubility increases with increasing water content in the subaluminous melt suggests that tungsten dissolved as a hexavalent species.     

Late Wuchiapingian (Late Dzhulfian,early Late Permian) limestone olistolites within the Tertiary flysch of Glypia Unit (Mount Parnon,central–eastern Peloponnesus,Greece)

Some olistolites reworked in a Tertiary flysch of Mount Parnon (Peloponnesus, Greece) exhibit a Late Permian assemblage, dominated by Paradunbarula (Shindella) shindensis, Hemigordiopsis cf. luquensis and Colaniella aff. minima. This association corresponds to the Late Wuchiapingian (=Late Dzhulfian), a substage whose algae and foraminifera are generally little known. Contemporaneous limestones crop out in the middle part of the Episkopi Formation in Hydra, but they are rather commonly reworked in Mesozoic and Cainozoic sequences. The palaeobiogeographical affinities shared by the foraminiferal markers of Greece, southeastern Pamir, and southern China, are very strong (up to the specific level), and are congruent with the Pangea B reconstructions. To cite this article: E. Skourtsos et al., C. R. Geoscience 334 (2002) 925–931.     

PALEONTOLOGY

正20141596 Liu Yunhuan(School of Earth Sciences and Resources,Chang’an University,Xi’an 710054,China);Shao Tiequan Early Cambrian Quadrapyrgites Fossils of Xixiang Boita in Southern Shaanxi Province(Journal of Earth Sciences and Environment,ISSN1672-6561,CN61-1423/P,35(3),2013,p.39-43,3 illus.,20 refs.)     

GEOCHEMICAL EXPLORATION

正20141719 Chen Zhijun(State Key Laboratory of Geological Processes and Mineral Resources,China University of Geosciences,Wuhan 430074,China);Chen Jianguo Automated Batch Mapping Solution for Serial Maps:A Case Study of Exploration Geochemistry Maps(Journal of Geology,ISSN1674-3636,CN32-1796/P,37(3),2013,p.456-464,2 illus.,2 tables,10 refs.)     

MICROPALAEONTOLOGY

正20140962 Chen Fenning(Xi’an Institute of Geology and Mineral Resources,Xi’an710054,China);Chen Ruiming Late Miocene-Early Pleistocene Ostracoda Fauna of Gyirong Basin,Southern Tibet(Acta Geologica Sinica,ISSN0001-5717,CN11-1951/P,87(6),2013,p.872-886,6illus.,56refs.)     

PETROLOGY

正1.IGNEOUS PETROLOGY20142008Cai Jinhui(Wuhan Center,China Geological Survey,Wuhan 430205,China);Liu Wei Zircon U-Pb Geochronology and Mineralization Significance of Granodiorites from Fuzichong Pb-Zn Deposit,Guangxi,South China(Geology and Mineral Resources of South China,ISSN1007-3701,CN42-1417/P,29(4),2013,p.271-281,7illus.,     

ENVIRONMENTAL GEOLOGY

正20141205Cheng Weiming(State Key Laboratory of Resources and Environmental Information System,Institute of Geographic Sciences and Natural Resources Research,CAS,Beijing 100101,China);Xia Yao Regional Hazard Assessment of Disaster Environment for Debris Flows:Taking Jundu Mountain,Beijing as an