黄土高原风尘沉积物中纳米矿物

由黄土-红黏土序列组成的风尘沉积是全球最完整、最连续的陆相古气候载体之一,蕴含了丰富的东亚古季风信息。解读黄土记录的信息以及透彻理解黄土替代指标与古气候的内在联系,都需要从纳米尺度揭示黄土成壤作用过程中碎屑矿物、成壤自生矿物形成与演化。本文利用高分辨透射电镜和场发射扫描电镜,研究了风尘沉积物中磁铁矿氧化的粒径制约、自生磁赤铁矿形成机制,建立了古土壤磁化率增强的成因矿物学理论,为磁化率与古气候的内在联系奠定了矿物基础;发现了第四纪黄土中广泛分布纳米棒状方解石及其含量和微结构显著的规律变化,从生物诱导矿化理论阐述了其形成机制;查明了凹凸棒石在黄土-红黏土序列中的分布规律,提出了古气候变化的黏土矿物响应机制。     

纳米矿物在堆积型铝土矿床研究中的应用*

至少一维尺度上小于100ⁿm的矿物都属于纳米矿物的范畴,自然界中除了大量的人造纳米矿物之外,天然的纳米矿物分布也很广泛。随着透射电子显微镜(TEM)技术在地球科学中的应用,大量的天然纳米矿物在地壳表层和内部被发现。尤其是在矿田区域,与矿体相关的纳米矿物在各种介质中被发现,并且这些纳米矿物在矿床的研究中有着独特的作用。堆积型铝土矿床储量大,是铝土矿的重要来源。在堆积型铝土矿床中发育有大量的纳米矿物,矿石矿物也以纳米级晶体分布于矿床中,并且在纳米尺度上表现出结构和成分的变化,这些纳米矿物以及结构、成分的变化记录了铝土矿成矿过程的物理化学信息,为探究铝土矿的成因提供了独特的窗口。该综述总结了纳米矿物在研究堆积型铝土矿床中的优势,为研究堆积型铝土矿床的提供了新方法,为认识堆积型铝土矿的成因提供了新角度。     

纳米矿物及其环境效应

纳米矿物作为连接原子/分子和块体矿物材料的桥梁,在建立矿物微观反应机制和宏观现象的研究中具有重要的意义.随着纳米地质学的迅速发展,纳米矿物在地表环境中的分布、存在形式及其反应活性引起了越来越多关注.综述了天然环境中常见的纳米矿物的成因、存在方式、特殊的尺寸效应、团聚行为、生物/非生物界面反应的分子机制,及其对地表环境和元素生物地球化学循环的影响;着重介绍了具有重要环境意义的纳米矿物与其对应的大尺寸矿物颗粒在吸附行为、溶解速率、团聚状态、催化活性、界面电子传递效率等方面的差异.对于纳米矿物与其对应的宏观矿物晶体之间差异的研究,有助于全面认识矿物对各种地质过程的作用,对于推动地球科学向更加微观和深入的方向发展具有极其重要的意义.      

纳米矿物与纳米矿物资源

为促进对纳米矿物及纳米矿物资源的认识、深入研究及开发应用,阐述了矿物纳米颗粒、纳米矿物狭义和广义概念、纳米矿物形貌分类和主要类型,并从晶体结构和晶体化学理论讨论纳米矿物形成和稳定的本质,即纳米矿物和矿物纳米颗粒形成分别受内因和外因控制.阐明了纳米矿物学研究内容及其在关键带研究的重要性,提出了纳米矿物资源的概念、属性及其开发利用的方向.      

中国黄土地球化学的若干河题

黄土地球化学是研究黄土中元素的分布、分配和迁移、富集的规律。它的研究不仅有助于进一步了解黄土物质成分的特征,而且对探索黄土堆积的地球化学环境,以及黄土形成过程的地球化学实质有重要意义。这些年来,我们继续以黄河中游黄土为重点,结合有关地区,进行了黄土地球化学的研究。     

一种纳米粒级砭石的矿物学特征与成因

为探究一种灰黑色砭石的矿物学特征及成因,采用X射线粉晶衍射(XRD)、扫描电子显微镜(SEM)、热重-微商热重分析(TG-DTG)及激光诱导离解光谱(LIBS)等分析方法对其矿物组成、结构特征、热力学性质及化学成分进行分析。结果表明,灰黑色砭石主要组成矿物为方解石(>98%),并含有少量石英、云母、长石、黄铁矿及微量石墨(<2%)。晶面尺寸测试及SEM分析结果显示,以上矿物单晶粒径大多处于纳米级别,砭石中矿物主要以块状、棒状及片状等3种集合体形式存在。微晶石墨呈分散态赋存在砭石中是灰黑色砭石致色的主要原因,而石英、云母、长石、黄铁矿及石墨等杂质的存在、纳米级的结构特征和类质同象导致砭石中方解石的热解温度远低于标准的纯方解石。砭石中纳米级方解石微球粒及石墨和黄铁矿微晶的存在,说明纳米级灰黑色砭石的形成可能与微生物的活动密切相关。     

我国不同气候带黄土中粘土矿物组合特征分析

在兰州黄土和下蜀黄土中粘土矿物的X衍射分析基础上,对我国不同纬度和气候带的五个黄土剖面(点)中的粘土矿物组合和空间分布进行了对比分析,并探讨了与古气候的关系。结果表明,黄土中粘土矿物组合具有明显的地带性特征。从西北到东南,随着纬度的逐渐降低,黄土中的粘土矿物组合也发生有规律的变化。主要表现为绿泥石含量的逐渐减少和蛭石含量的逐渐增多。位于温带半干旱区的兰州黄土以伊利石和绿泥石为主要粘土矿物,而位于亚热带湿润区的大港下蜀黄土则以伊利石和蛭石为主要粘土矿物。黄土中含有较多量的绿泥石可作为黄土母质堆积后干冷气候和微弱风化的标志,而蛭石和蛭石/绿泥石混层矿物含量的增加指示了风化强度的增强。因此,黄土粘土矿物组合特征不仅反映物源区古环境信息,而且指示了黄土堆积期后的生物气候环境。     

基于纳米尺度的碎屑岩骨架矿物结构研究

对胜利油田胜坨地区碎屑岩储层岩芯样品和岩石薄晶片分别采用场发射扫描电镜、透射电镜进行镜下观察与能谱测试分析。结果表明：碎屑岩中骨架矿物石英和长石中存在纳米尺度的结构特征;石英镜下可见类蚀像凹坑、雏晶单晶、平行脊线、晶体位错、类包裹体晶内核等5种纳米尺度的结构;长石镜下可见晶面平行凹痕、溶蚀针、纳米级薄层断阶、长石高岭石化、晶体位错和超微包裹体等6种纳米尺度的结构;这些结构大多在几百纳米的尺度范围内,有的甚至只有几十纳米;矿物在纳米尺度上表现出的结构特征与其本身的硬度变化、晶体品格缺陷、晶体生长过程以及成岩作用的显微表现和显微构造应力改造作用有关。对碎屑岩骨架矿物中纳米尺度结构特征的进一步研究有望为岩石显微变形的应力作用机制和方式以及溶解作用等成岩作用模式做出有效分析,进而为油气勘探开发提供新的探索方式。     

纳米颗粒物:独具特性的地球化学组成

至少一维尺度上小于100 nm的颗粒物均称为纳米颗粒物,在人工纳米颗粒物产生的几十亿年前,地球已经通过其特有的生物地球化学过程合成各类天然纳米颗粒物.这些纳米颗粒物及其次生产物具有独特的理化特性,并参与各种地球化学过程,体现其非凡的地球化学意义.从地球化学的角度,解析了环境纳米颗粒物的定义和分类,重点阐述了风化壳与水体中天然和次生纳米颗粒物的形成,并在天然纳米颗粒物中区分了纳米矿物和矿物纳米颗粒物;同时,也讨论了大气纳米颗粒物的来源、成因与环境影响.该综述列举了目前环境中纳米颗粒物表征与鉴别的技术和方法,重点剖析了纳米颗粒物的地球化学功能和环境意义,并对该领域的研究前沿问题进行了概述.      

纳米矿物-水溶液界面过程

在地球环境中普遍存在的纳米矿物-水溶液界面对许多基本的地球化学过程都至关重要,因而是纳米地球化学的前沿核心研究领域.简要介绍了纳米矿物-水溶液界面领域的基本概念和近期研究进展.举例描述了纳米矿物团聚、吸附、溶解和化学反应等几个相互关联的主要过程,具体阐述了纳米矿物自身特征（如组成、结构、尺寸、形貌、表面保护剂等）以及环境介质条件（如pH、离子强度、化学反应物质、天然有机质浓度和组成、微生物、光辐射等）对纳米矿物-水溶液界面过程的影响规律和微观机制.针对本领域发展面临的机遇和挑战,为未来的研究方向提出了一些设想和建议.      

Pleistocene Loess-Paleosol Sequences in Arid Central Asia State of Art

Loess of central Asia is located in a linkage zone between the European and Chinese loess depositional belts. Paleoclimate signatures from loess-paleosol sequences here is a key for completely understanding the spatial-tempo paleoclimate changes of Euro-Asia and for understanding the interactions between westerlies and Asia monsoon system during geological time. However, paleoclimate investigations of loess-paleosol sequences in arid central Asia is relatively weak than those from Europe and Chinese Loess Plateau. Specific, correlations of paleoclimate records with Chinese loess is required for better understanding “westerly regimes” in central Asia and its phase relationship with monsoon Asia on various time scale. In this work, we reviewed new advantages of loess study in central Asia during the last decades. Based on the stratigraphic and paleoclimatic correlations of loess-paleosol sequences between central Asia and the Chinese Loess Plateau, we discussed aridification history of Asia on tectonic time scale, the hydroclimate changes in arid central Asia and its phase relationship with Monsoonal Asia on orbital and millennial time scale during the Pleistocene.     

文石石笋发生矿物重结晶的影响因素及其古气候意义

洞穴沉积物—石笋已成为研究岩溶区环境气候变化历史的重要载体。在我国湘西地区,某些洞穴石笋原始沉积多为不稳定的文石矿物,极易发生重结晶,可能使石笋中相关化学元素含量最终偏离原生矿物的特征,限制了文石石笋某些代用指标在古气候研究中的应用。文章以前人研究成果为基础,总结梳理了文石石笋发生重结晶的影响因素及其对石笋记录古气候的影响:（1）石笋剖面特征、XRD结果、显微镜观察和地球化学元素特征等可作为石笋发生重结晶的判别依据;（2）洞穴滴水和石笋孔隙水饱和度、文石晶体缺陷和晶体之间的方解石胶结物以及岩溶水体中Mg2+浓度等均会影响文石石笋的矿物转变;（3）在文石向方解石转变过程中,石笋铀含量会有一定程度的流失,可导致放射性铀系定年的异常或年代倒序;（4）矿物重结晶可导致δ18O、δ13C及石笋微量元素浓度（或比值）等指标发生改变,其变化特征因洞穴而异,从而影响其作为环境指示器的可靠性;（5）湖南龙山惹迷洞石笋（RM2）发生了不均一的矿物重结晶,自顶部至20.3 cm以放射状为主,20.3 cm至底部主要为糖粒状,并结合年代结果发现文石重结晶对石笋铀系定年产生了影响,而重结晶作用对该石笋其他指标的影响还有待进一步研究。      

The paleosol complex S5 in the China Loess Plateau — A record of climatic optimum during the last 1.2 Ma

Having investigated the loess-paleosol sequence in various loess deposition basins in the China Loess Plateau, authors have found that the paleosol complex S₅ is of special significance in terms of Pleistocene paleoclimate. Paleopedological, micromorphological, palynological and paleomagnetic evidences indicate that this paleosol complex formed in the interval of 460,000 to at least 560,000 years BP, which was a climatic optimum.     

Earthworm Calcite Granule —A New Proxy for Paleoenvironmental Reconstruction

Earthworm calcite granules (ECG), generally produced in Morren's glands of the earthworm Lumbricus terrestris and Lumbricus rubellus, are commonly preserved in Quaternary soils and sediments well. These granules can not only provide radio-carbon dating (Carbon-14) with the efficacious materials, but accurately record a wealth of climatic and environmental information on temperature and precipitation. For instance, researchers from France reconstructed the paleotemperature and paleoprecipitation during the last glacial in west part of Europe by taking advantage of δ¹⁸O and δ¹³C signal contained in ECG. Additionally, scientists from Germany and France carried out radiocarbon dating of ECG from two different loess-paleosol sequences, and the results showed consistency with the dating results of other materials (such as charcoal, bone, plant calcified root cells, etc.). Therefore, this new bio-indicator has been confirmed as a proxy for paleoenvironmental and paleoclimatic reconstruction, hopefully becoming the golden key to understanding the paleoclimate change. This paper, based on the previous literatures, reviewed the present research status of ECG in paleoclimatology, mainly consisting of five aspects: (i) ECGs' production mechanism and their characteristics; (ii) The theoretical foundation of stable carbon and oxygen isotopes in terrestrial fossil earthworm calcite granules for paleoclimatic reconstruction; (iii) The pre-treatment of ECG samples; (iv) Current applications in chronology and paleoclimatology of earthworm calcite granules;(v) Major problems at present regarding paleoclimatic explanation and radiocarbon-14 dating of ECG. Finally, we proposed the future research and development direction in this field, which is expected to make a reference to the future researches.     

黄土地层精确时间标尺的建立——以三门峡黄土地层研究为例

厚度153m的曹村剖面出露了厚145m的完整黄土地层,为L₁-L₃₃的连续风尘沉积,为黄土高原东南部三门峡地区黄土地层的代表。建立曹村黄土地层的精确时间标尺,不仅能在千年时间尺度下探讨黄土高原古季风变迁,而且着眼于全球古气候变化开展海陆对比研究。本文对现有的4种时间标尺模式进行了介绍,应用磁化率模式和粒度模式开展了三门峡黄土时间标尺研究,并进行了校验,说明了几种模式建立曹村黄土时间标尺的可行性。      

中国南方发现大型文石笋

中国南方大量石笋剖面研究表明,石笋矿物组成有方解石、文石、方解石-文石三种类型。石笋沉积纹(微)层结构构造特征大同小异,但是文石石笋的放射状纹(微)层构造更显著。文石石笋沉积生长的气候环境是滴水多而稳定,水温低、气温略高的冷、湿的洞穴气候条件。文石转变为方解石常保留文石的针状、柱状晶形,并存在于石笋沉积生长的始终。文石结构构造转化在常温或低温、常压或低压下自调整作用的成晶成岩环境进行,其强度取决于所在洞穴气候环境、滴水在石笋的渗流和石笋的含水度。转化作用不影响同位素分馏,石笋同时全面记录古气候环境信息。研究文石石笋对重建古气候环境、成岩成矿作用都有重要理论和实践意义。     

Phosphatic precipitates associated with actinomycetes in speleothems from Grand Cayman, British West Indies

Calcitic speleothems from a cave located on the north central coast of Grand Cayman commonly include corrosion surfaces that developed when calcite precipitation ceased and corrosion mediated by condensates became the operative process. Dissolution features associated with these surfaces, including etched crystal surfaces, microcavities, and solution-widened boundaries between crystals, are commonly occupied by microbes and microbial mats that have been replaced by calcium phosphate and/or coated with calcium phosphate. No mineralized microbes were found in the calcite crystals that form the speleothems. The morphology of the mineralized hyphae (eight morphotypes) and spores (nine morphotypes) are indicative of actinomycetes, a group of microbes that are ideally adapted to life in oligotrophic cave environs. Superb preservation of the delicate hyphae, aerial hyphae, and delicate ornamentation on the hyphae and spores indicate that the microbes underwent rapid mineralized while close to their original life positions. Although these actinomycetes were extremely susceptible to replacement by calcium phosphate, there is no evidence that they directly or indirectly controlled precipitation. Nevertheless, the association between the P-rich precipitates and microbes shows that the use of phosphorus as a proxy for seasonal climate changes in paleoclimate analyses must be treated with caution.     

Calcite from the Quaternary spring waters at Tylicz, Krynica, Polish Carpathians

At Tylicz, near Krynica Spa (Polish Carpathians), spelean deposits fill fissures and caverns in Eocene flysch rocks. They occur as: (1) clastic cave sediments transformed into hard crusts due to cementation by finely crystalline low-Mg calcite, (2) drusy calcite that covers crust surfaces and fills voids in the crust and (3) colloform calcite. Two varieties of drusy calcite are distinguished: acicular and columnar. The acicular calcite is built up of crystallites forming spherulitic fans or cones. In places it is syntaxially covered with colloform calcite. The drusy calcite is low-Mg ferroan calcite with non-ferroan subzones, whereas the colloform calcite is a low-Mg non-ferroan variety. The columnar calcite crystals form fan-like bundles. Cross-sections cut perpendicular to the c-axes of columnar crystals are equilateral triangular in shape, although some have slightly curved edges. The columnar crystals have steep rhombic terminations and most have curved triangular faces, i.e. gothic-arch calcite. Saddle crystals have also been observed. The columnar crystals are composed of radially orientated crystallites whose long dimension is parallel to the c-axis. The curved crystal faces of such polycrystals are interpreted as a result of differential growth rates of the crystallites. The spelean calcites precipitated from CO₂-saturated water. The high rate of CaCO₃ precipitation is thought to be responsible for the formation of radial structures. Finely crystalline calcite formed within pore spaces of clastic sediments close to the water-air interface, drusy calcite crystallized beneath the water-air interface, and colloform calcite precipitated from thin films of water.     

Formation of helictite in the cave Dragon Belly (Sardinia,Italy)—Microstructure and incorporation of Mg,Sr, and Ba

In the Dragon Belly cave helictites, a special type of irregular speleothem, are found, which grew on stalactites in all vertical and horizontal directions without any affinity to gravity. Microstructural and mineralogical analyses of this stalactite–helictite system indicate that its evolution is initiated by clogging of the central stalactite channel at its tip, probably when the cave was flooded by muddy water. Clogging caused the formation of secondary channels (≈0.2 mm in diameter) for water passage through the outer surface of the stalactite, where helictites start to grow. The secondary channel passes into the central channel of the helictite.The helictites consist of stacked idiomorphic calcite crystals with uniform orientation. Growth of calcite is essentially controlled by water transfer through the central channel and via canalicules (narrow channels of ≈0.05 mm in diameter) following the crystal boundaries of the calcite mesocrystal induced by capillary hydrostatic forces. At straight parts of the helictites calcite crystals are almost uniform in size, but at bended parts crystals are significantly smaller inside (≤0.1 mm in length) than outside of the bend (≤0.5 mm). It is proposed that the difference in calcite volume (larger crystals) vs. the inside of the bend leads to a helix form, which explains the origin of the term helictite.The Sr and Ba concentrations measured by laser ablation along helictites can be explained by cation incorporation during calcite precipitation close to equilibrium. Dilution effects caused by seasonality control the elemental distribution in the helictite, which result in a positive correlation between Sr and Ba. Variability of Mg is unrelated with Sr and Ba, and is probably due to the incongruent dissolution of Mg–calcite from the host rock.     

Progress in Danube Loess and Paleoenvironment Study

Danube loess, located at the westernmost part of the widespread Eurasian loess belt, is one of the most well-preserved aeolian dust deposits in Europe with the basal age dating back over 1 Ma. Owing to its unique location and formation processes, Danube loess plays an important role in understanding the linkage of climate changes in different climate regimes over Eurasian continent and paleoclimatic changes in middle-high northern latitudes. Major research advances of the Danube loess, including compositions, provenance, chronology, stratigraphy and paleoenvironment changes were systematically reviewed and the focuses of future research were suggested. To better understand loess provenance, the compositions of sediments in all the potential source areas should be investigated, and methodological study of provenance indicators and application of multi-proxies approaches need to be carried out. Chronologically and stratigraphically, feldspar luminescence dating and tephrochronology methods should be widely used, and the establishment of a uniform stratigraphic framework and correlation scheme should be constrained by precise chronology. In terms of the paleoenvironment, it is necessary to conduct high-resolution multi-proxies reconstruction of paleoenviroment for the entire loess-paleosol sequence, extending from the last interglacial period (130 ka to present) to interval of last 1 Ma. The future progress in Danube loess is crucial to improving the study of continental paleoclimate comparison and paleoclimate dynamics over the Eurasian loess region.