Electron Microscopic Study of Manganese Minerals in the Polymetallic Nodules from the Central Pacific Ocean

Manganese minerals in the polymetallic nodules from the Central Pacific Ocean were studied using electron microscopy. The principal Mn minerals, being vernadite and todorokite, exhibit different electron diffraction patterns and morphological features. According to its morphological feature, todorokite shows three phases: fibrous, lamellar and lath-shaped. Both vernadite and todorokite are authigenic minerals. While vernadite was mainly precipitated directly from the relevant solution by microbiological oxidation, todorokite was separated from the solution chemically without the help of microbe. Hence, these two minerals show a close genetic relation.     

初论发现于西太平洋富钴结壳的羟锰矿

大多数研究者认为富钴结壳中的锰矿物主要是水羟锰矿。X-射线衍射数据表明这次所研究的富钴结壳中主要的富锰矿物相是羟锰矿,这是在以往的结核和结壳研究中鲜为人知。探讨了羟锰矿和水羟锰矿的名称由来、化学式、晶胞参数及X射线粉晶衍射值,建议将X-射线衍射特征值为2.4×10^-10 m和1.4×10^-10 m的锰矿物相统称为水羟锰矿;通过研究这两种矿物的成因、产状及环境,认为结壳中羟锰矿的存在表明结壳在生长中后阶段仍处于还原环境。     

太平洋中部多金属结核中锰矿物的电镜研究

利用电子显微术,研究太平洋中部多金属结核中的锰矿物。主要锰矿物为水羟锰矿和钡镁锰矿,它们显示不同的电子衍射花样特征和形貌特征。钡镁锰矿根据形态特征分为三个相:纤维状、片状和板条状。水羟锰矿和钡镁锰矿都是自生矿物,水羟锰矿主要是通过微生物氧化直接从溶液中沉淀生成。而钡镁锰矿则是在没有微生物参加下由溶液中分离出来的。两种矿物之间有着密切的生长关系。     

西太平洋某海域锰结核的矿物学及矿物化学研究

锰结核中的矿物是对结核生长环境反映。对结核进行X射线衍射分析表明:结核中锰矿物主要为水羟锰矿,并含有石英、钙十字沸石、斜长石、以及绿脱石、辉石、方解石和少量的蒙脱石、伊利石、角闪石、绿泥石、白云石、锐钛矿等。锰矿物表明该区为氧化环境,且受到火山、热液活动的影响。定量分析结果表明结核各矿物的含量变化很大,说明结核的生长过程中环境发生了变化。电子探针分析结果表明:结核锰矿物的组分含量变化较大,表明结核的元素来源的不稳定性。     

Mineralogical and geochemical constraints on the origin of ferromanganese crusts from the Rivera Plate (western margin of Mexico)

Marine hydrogenetically precipitated ferromanganese crusts are widespread in the Pacific Ocean. They occur as pavements coating volcanic or sedimentary hard-rock substrates, mainly on the slopes of seamounts, plateaus and hills in ocean basins and continental margins. We studied three ferromanganese crusts from one dredge haul from the Rivera Plate (western margin of Mexico), which are up to 15 mm thick and grow directly on a substrate of pillow basalt fragments. They consist of laminated, botryoidal, porous aggregates mostly of Fe and Mn oxyhydroxides and up to 10% silicates. XRD analysis showed the predominance of poorly crystallized mineral phases in the crusts that include Mn-feroxyhyte and vernadite, and an authigenic smectite-like clay. Detrital minerals probably derive from granodiorites of the eastern wall of the neighboring Middle America Trench. Scattered barite grains occur on the crust surface and suggest plume fall-out derived from hydrothermal vents, although a possible pelagic source cannot be dismissed. Ratios between major (Fe, Mn, Si) and trace (Co, Ni, Cu) elements reveal that such crusts are predominantly hydrogenetic in origin, although they show a hydrothermal influence that increases in the outer layers. Iron contents range from 16.2 to 25.2 wt.%, and manganese from 3.4 to 14.5 wt.%. The Fe/Mn ratio ranges from 1.6 to 7.0. The SiO₂/Al₂O₃ ratio ranges from 4.3 to 6.6, indicating the presence of biogenic silica (radiolarians). The concentrations of copper (up to 383 ppm) and cobalt (up to 534 ppm) are significantly below those of the typical hydrogenetic crusts, whereas Ni (up to 1320 ppm) is about the same or slightly lower. REE normalized profiles and ΣREE values (486 to 732 ppm) match those reported for hydrogenetic crusts, but suggest a hydrothermal contribution for the later crust layers. The inferred crust growth rates using the Co-chronometer (44 and 229 mm/Myr) are higher than those reported for pure hydrogenetic crusts (mostly 1 to 6 mm/Myr), thus indicating an increasing hydrothermal influence. The highest growth rate (229 mm/Myr, corresponding to the outer crust layers) suggests a regional hydrothermal input of iron and manganese to seawater. The intensification of regional submarine hydrothermal activity began about 13,000 yr ago, and may be related to the tectonic activity in the complex junction of the Rivera, Cocos, Pacific and North America plates.     

中太平洋富钴锰结壳水羟锰矿研究

采用场发射电镜（JSM-6700F）和透射电镜（JEM-2000FX）研究了富钴结壳中水羟锰矿的形态和结构。结果表明:水羟锰矿单体片径一般为30～50 nm,集合体成片状或鳞片状;获得了水羟锰矿d=0.142 9 nm的单晶和三连晶电子衍射结构;水羟锰矿中Fe³⁺、Co³⁺、Ni³⁺为高自旋态离子,Co³⁺、Ni³⁺、Cu³⁺易与Mn⁴⁺形成类质同像置换,部分Fe³⁺与Mn⁴⁺可能存在有限的类质同像置换,置换反应为3 Mn⁴⁺=4Co³⁺（Ni³⁺、Cu³⁺、Fe³⁺）,体系总电价平衡。