Main Stages of Evolution of Pacific Ferromanganese Stromatolites and Oncolites

As exemplified by cobalt–bearing Fe–Mn crusts (ferromanganese stromatolite) of the Magellan Seamounts (Clarion–Clipperton Province), the main stages of the structural evolution of bacterial communities have been recognized. It has been demonstrated that the change of the stages is caused by the effect of major tectonic, volcanic, and other geological events.     

The submicroscopic structures of mesozoic-cenozoic Fe-Mn stromatolites

The results of the study of submicroscopic structures of oceanic oxide ores are described. The objects of study were Co-bearing Fe-Mn crusts from the Magellan Seamounts and Fe-Mn nodules from the Clarion-Clipperton province. The evolution of structural elements is traced in the crust section from the Lower Campanian-Maastrichtian to Pliocene-Quaternary layers. It was found that growing nodules actively entrap hosting sediments into the layered cover. The entrapment mechanism of sediments by nodules was revealed.     

Composition of technological sample of ferromanganese crusts from seamounts and products of its processing

Elemental and mineral compositions of cakes (residues left after the acid processing of a technological sample of ferromanganese crusts from the Magellan Seamounts) are investigated. It has been established that hydrosulfuric acid processing of the ferromanganese crust results in the extraction of Mn and associated metals, but a significant part of rare earth and other elements is left in cakes. Electron microscopic investigations of samples after their hydrosulfuric acid processing showed the retention and formation of some rare minerals (monazite, xenotime, coffinite, uranium oxide, molybdite, thallium oxide, and magnetite containing T, Cr, Cu, Pt, and Au). Valuable components can be extracted completely from cakes by the method of combined leaching.     

Nature of co-bearing ferromanganese crusts of the Magellan Seamounts (Pacific Ocean): Communication 1. Geology, mineralogy, and geochemistry

Communication 1 of the present paper is devoted to various aspects of the hydrogenic ferromanganese crusts in the western and eastern clusters of the Magellan Seamounts in the Pacific. It was revealed that crusts are developed on guyots as a continuous sheet of Fe-Mn minerals on exposures of primary rocks. They commonly make up ring-shaped deposits along the periphery of the summit surface and in the upper sectors of slopes. Thickness of the crust varies from n to ～18 cm and shows irregular variations in separate layers. Irrespective of the geographic position, crusts are composed of four layers—two lower phosphatized (I-1 and I-2) and two upper nonphosphatized (II and III) layers. The crusts differ in terms of structure and texture, but they are sufficiently similar within separate layers (I-1, I-2, and others). The major ore minerals in crusts are commonly represented by poorly crystallized and low-ordered minerals (Fe-vernadite and Mn-feroxyhyte); the subordinate mineral, by the well-crystallized and ordered vernadite. It has been established that heavy and rare metal cations are concentrated extremely irregularly in ore minerals of the crusts, suggesting a pulsating mode of their input during different geological epochs.     

The special features of the interaction between iron-manganese stromatolites and the environment

The analysis of the submicroscopic textures of the cobaltiferous crusts from the Magellan Seamounts has shown that biofilms?ferromanganese stromatolite builders absorb petrogenic components (SiO₂, Al₂O₃, P₂O₅, etc.) from the environment and use them for the formation of a columnar structure.     

麦哲伦海山铁锰结壳中氟的古海洋环境意义

碳氟磷灰石的出现是铁锰结壳磷酸盐化的标志,氟是碳氟磷灰石的主要伴生元素.为了解氟作为铁锰结壳磷酸盐化指标的可行性,采用离子选择电极法测定了西太平洋麦哲伦海山区铁锰结壳中氟的质量分数,探讨了铁锰结壳中氟的分布特征、来源及其对磷酸盐化的指示作用.研究结果表明,铁锰结壳中的氟主要来源于海洋有机质的分解,并富集于受到磷酸盐化作用的结壳层中,以碳氟磷灰石为主要赋存相,氟对铁锰结壳的磷酸盐化作用有较为灵敏的指示作用.     

Rare elements and Nd and Sr isotopic composition in micronodules from the Brazil Basin,Atlantic Ocean

The Sr isotope stratigraphy of the biogenic apatite was used to determine the age of pelagic sediments in the Brazil Basin (Station 1541) that contain ferromanganese micronodules, nodules, and coatings on the weathered volcanic rocks. The age of sediments at horizons 0–5 and 86–90 cm was estimated at 24.1 ± 0.2 Ma and 24.8 ± 0.2 Ma, respectively. The average sedimentation rate in the Late Oligocene was about 13 mm/ka. The hydrogenous Fe–Mn nodule on the sediment surface with the Mn/Fe value of 1.05–1.95 was formed at a rate of 1.2–2.4 mm/Ma, which is 1000 times lower than the growth rate of buried nodule (Mn/Fe 0.4) at depth of 83 cm. Diagenesis provoked changes in the mineral composition of the buried nodule (asbolane-buserite partially replaced by goethite), leading to the loss of a part of Mn, Ni, Li, and Tl but accumulation of trace elements linked with iron oxyhydroxides (Ce, Th, Be, As, and V) were retained. The composition of manganese micronodules at two studied depths in sediments evolved in the course of two stages of ore formation: related to the oxic and suboxic diagenesis. The Sr isotopic composition in manganese micronodules from both horizons do not differ from that of dissolved Sr in the ocean water. The ¹⁴³Nd/¹⁴⁴Nd ratio, which reflects the Nd isotopic composition in the paleocean during the micronodule formation, varies in manganese micronodules from different horizons and is constant in different size fractions.     

Assessment of acoustic backscatter intensity surveying on deep-sea ferromanganese crust: Constraints from Weijia Guyot,western Pacific Ocean

Near-bottom observation data from the manned deep submersible Jiaolong with high-precision underwater positioning data from Weijia Guyot, Magellan Seamounts in the Western Pacific Ocean are reported. Three substrate types were identified: Sediment, ferromanganese crust, and ferromanganese crust with a thin cover of sediment. The ferromanganese crusts show clear zoning and their continuity is usually disturbed by sediments on areas of the mountainside with relatively gentle slope gradients. The identified substrate spatial distributions correspond to acoustic backscatter intensity data, with regions of high intensity always including crust development and regions of low intensity always having sediment. Therefore, acoustic backscatter intensity surveying appears useful in the delineation and evaluation of crust resources, although further more work is needed to develop a practicable methodology.     

Paleoceanographic Setting and Preservation of Buried Manganese Deposits in DSDP/ODP Cores

Abstract. The occurrence, lithology, and stratigraphic setting of buried manganese deposits and associated host sediments in cores obtained on Legs 123–210 of the Ocean Drilling Program (ODP) are examined in order to establish the formative environment and conditions of preservation. Fossil manganese nodule and crusts are found to have formed or deposited throughout the period from 100 Ma to the present, with an additional example of formation near 137 Ma, suggesting that the deep-sea environment has been oxic and suitable for the formation of manganese nodules and crusts since the Cretaceous. Many manganese nodules and crusts occur on horizons corresponding to hiatuses in sedimentation or periods of slow sedimentation, consistent with the environment in which modern nodules form (sedimentation rate less than 10 m/m.y.). Sediments overlying the fossil nodules and crusts are oozes or biogenic sediments with sedimentation rates of 1–18 m/m.y. Low total organic carbon (<0.1 wt%) in the overlying sediments and high sulfate content (>25 mM) in interstitial water around the manganese horizon suggest that no strong reduction occurred within the overlying sediments. Coverage by biogenic sediments containing only small amounts of organic matter is therefore considered important for the preservation of manganese nodules and crusts. Manganese carbonate occurs sporadically as nodules, concretions or thin layers in various host sediments, including clay, calcareous ooze and siliceous ooze with sedimentation rates of 6–125 m/m.y. Hiatuses are rare around the host sediments of manganese carbonate. Higher total organic carbon (0.2–1.8 wt%) in the host sediments and lower sulfate content (0–25 mM) in interstitial water around the manganese carbonate horizon suggest that reduction in association with decomposition of organic matter would have proceeded in the host sediments.     

厚结壳的形成条件及控制因素分析

当前对于大洋厚结壳的研究较少,而厚结壳是未来开发利用的重点,同时它记录的地质历史长,控制和影响结壳生长发育的各种因素必然能在厚结壳上充分体现出来。因此,开展厚结壳的形成条件及控制因素的研究,具有重要的理论与现实意义。文章利用GIS空间分析技术与地质统计方法,对厚结壳的定义、结壳厚度与水深、结壳厚度与基岩、结壳生长与构造活动、结壳厚度与沉积速率、结壳厚度与经纬度、结壳厚度与主成矿元素之间的关系进行了分析,结果表明,结壳的厚度变化受控于水深、基岩、构造活动、沉积速率、经纬度等因素,同时结壳厚度与主成矿元素之间存在明显的相关性。     

Mineral resources of the ocean

Major data concerning the history of investigation, distribution, mineral and chemical composition, and formation processes of mineral resources of the ocean, namely ferromanganese nodules, ore crusts, phosphorites, and hydrothermal mineral formations, including ore-bearing and metalliferous sediments, massive sulfides, and hydrothermal ferromanganese crusts are reviewed. The problem of the scale of mineral accumulations in the ocean and their quality, along with prospects of their future recovery, is discussed.     

中太平洋海山富钴结壳主要成壳元素特征

通过大洋一号船DY105--12 /14 航次采集的结壳样品,对中太平洋CL、CM2、CM3、CX、CQ、 CA、CB 海山结壳的主要成壳元素Mn、Fe、Co、Ni、Cu 的含量进行了测试统计,并与邻区的麦哲伦海山、马绍尔群岛、夏威夷群岛和莱恩群岛进行了对比,中太平洋各海山以及不同区域海山结壳的主成分之间存在一些差异,这主要与各海山结壳的物质来源、成壳环境和成壳时代的差异有关。不同形态类型的结壳主成分具有一定的差别,其主要原因可能是生长机制和形成环境不同造成的。     

New data on the structure of the sedimentary section on the Ita Mai Tai Guyot (Magellan Seamounts,Pacific Ocean)

The geological-prospecting investigations carried out by scientists from the Yuzhmorgeologiya State Scientific Center in the eastern segment of the Magellan Seamounts of the Pacific during the cruise of the R/V Gelendzhik in 2003–2010 brought new data on the topography of the Ita Mai Tai Guyot and its Lower Cretaceous-Pleistocene sedimentary section. The guyot is characterized by its complex irregular morphology with angular outlines being complicated by numerous relief mesoforms: spurs, scarps, and volcanic cones and domes. It is shown that the sedimentary cover was formed during a long period. The analysis of the organic macro- and microfaunal remains from the sedimentary rocks made it possible to define transgressive phases in the guyot’s development: the Albian-Cenomanian, the Late Campanian-Maastrichtian, and the late Paleocene-early Eocene. The oolitic limestone sequence recovered by DSDP Hole 202 is determined to be the Albian in age. Based on the original and published data, the geological development of the guyot was analyzed in comparison with other similar structures of the Magellan Seamounts.     

Geochemical zoning in ferromanganese crusts of Ita-MaiTai guyot

Samples of ferromanganese crusts dredged from Ita-MaiTai guyot (Magellan seamounts, Pacific Ocean) were studied. They are made up of a complete stratigraphic section of different-age layers, including unique oldest relict layers in some samples. The study of trace, rare-earth, and noble element (including Pt and Pd) distribution showed that old layers differ from young ones in terms of Co, TR, S, As, and P. In addition, composition of the crusts significantly varies depending on the spatial position of sample in the guyot. In some zones, crusts enriched in trace elements were generated both in the Pleistocene and Paleogene. Significant variations established in trace element composition of different-age layers indicate that trace element composition of the crusts notably evolved with time, which could be caused by productivity of biocenosis or change in the formation depth of crusts on the guyot due to vertical tectonic movements.     

富钴结壳中贵金属元素的特征

对太平洋CL、CM海山调查时获取9个富钴结壳样品,采用化学处理及ICP-MS法进行分析。对贵金属元素含量分布特征、富集因子、标准化模式以及来源进行探讨和研究。结果表明：海山结壳中贵金属元素Ag、Au、Ru、Rh、Pd、Pt等的平均含量分别为： 1.05×10^-6、2.3×10^-6、15.6×10^-9、22.3×10^-9、2.39×10^-9和432×10^-9。与结核、洋壳及陆地矿石的Pd/（Pt+Pd）、Pt/（Pt+Pd）和Pd/Pt等贵金属元素的比值相比,大洋富钴结壳的 Pd/（Pt+Pd） 比值最低,为0.006;其次是结核,为0.06;洋壳为0.08;陆地矿石的Pd/（Pt+Pd）比值较大,为0.35～0.65。结壳的Pt/（Pt+Pd）比值最高,为0.99;其次是结核,为0.95;洋壳为0.93;陆地矿石的Pt/（Pt+Pd）比值相对较低,为0.33～0.65。统计分析显示了不同区域、不同环境中贵金属元素的特征参数变化,并且说明富钴结壳中富铂、金、钌、铑,而贫钯。贵金属元素标准化显示,海山富钴结壳均存在着Pt、Au正异常和Pd的负异常,其中Au异常幅度与结核的Au异常一致。     

First Find of Platinum in Cosmogenic Spherules of Ferromanganese Crusts (Fedorov Guyot,Magellan Seamounts,Pacific Ocean)

Doklady Earth Sciences - More than 250 magnetic spherules 40–200 µm in size were mechanically separated from a ferromanganese crust sample of Fedorov Guyot in the Magellan Seamounts. The...     

Phase associations and potential selective extraction methods for selected high-tech metals from ferromanganese nodules and crusts with siderophores

Deep-sea ferromanganese deposits contain a wide range of economically important metals. Ferromanganese crusts and nodules represent an important future resource, since they not only contain base metals such as Mn, Ni, Co, Cu and Zn, but are also enriched in critical or rare high-technology elements such as Li, Mo, Nb, W, the rare earth elements and yttrium (REY). These metals could be extracted from nodules and crusts as a by-product to the base metal production. However, there are no proper separation techniques available that selectively extract certain metals out of the carrier phases. By sequential leaching, we demonstrated that, except for Li, which is present in an easily soluble form, all other high-tech metals enriched in ferromanganese nodules and crusts are largely associated with the Fe-oxyhydroxide phases and only to subordinate extents with Mn-oxide phases. Based on this fact, we conducted selective leaching experiments with the Fe-specific organic ligand desferrioxamine-B, a naturally occurring and ubiquitous siderophore. We showed by leaching of ferromanganese nodules and crusts with desferrioxamine-B that a significant and selective extraction of high-tech metals such as Li, Mo, Zr, Hf and Ta is possible, while other elements like Fe and the base metals Mn, Ni, Cu, Co and Zn are not extracted to large extents. The set of selectively extracted elements can be extended to Nb and W if Mn and carbonate phases are stripped from the bulk nodule or crust prior to the siderophore leach by e.g. a sequential leaching technique. This combination of sequential leaches with a siderophore leach enhanced the extraction to 30–50% of each Mo, Nb, W and Ta from a mixed type Clarion-Clipperton Zone (CCZ) nodule and 40–80% from a diagenetic Peru Basin nodule, whilst only 5–10% Fe and even less Mn are extracted from the nodules. Li is extracted to about 60% from the CCZ nodule and a maximum of 80% Li is extracted from the Peru Basin nodule.Our pilot work on selective extraction of high-tech metals from marine ferromanganese nodules and crusts showed that specific metal-binding organic ligands may have promising potential in future processing technologies of these oxide deposits.     

利用富钴结壳碳酸盐基岩有孔虫矿物标型重建古海洋温度

重建古海洋海表温度(SST),是研究地质历史时期气候变化控制过程的关键。组成有孔虫化石的矿物Mg/Ca值是海水温度的可靠代用指标,是重建古海洋SST的一个非常好的手段。麦哲伦海山区的富钴结壳和基岩中普遍存在有孔虫化石,这对重建该区的SST有重要意义。利用LA-ICP-MS测得西太平洋麦哲伦海山区富钴结壳碳酸盐基岩中8颗浮游有孔虫化石Globigerinoides sacculifer的Mg/Ca值为3.84±0.36(mmol/mol),通过线性公式:T(℃)=2.898Mg/Ca(mmol/mol)+13.76及已有的定年数据,得到0.91Ma±西太平洋麦哲伦海山区海表温度为24.9+1.1/-1.0℃,未能检索到前人关于该区0.91Ma±前海表温度数据。     

Comparison between Datangpo-type manganese ores and modern marine ferromanganese oxyhydroxide precipitates based on rare earth elements

Datangpo-type sedimentary manganese deposits, which are located in northeastern Guizhou province and its adjacent areas, are Mn carbonate-type deposits hosted in black carbonaceous shale that represent a series of medium to large deposits containing a huge tonnage of reserves. PAAS-normalized rare earth element distribution patterns of manganese ores record “hat-shaped” REY (REE + Y) plots characterized by pronounced middle rare earth element enrichment, evident positive Ce anomalies, weak to strong positive Eu anomalies and negligible negative Y anomalies. These REY geochemical characteristics are different from those of country rocks and record the processes and features of sedimentation and diagenesis. Manganese was precipitated as Mn-oxyhydroxide particles in oxidized water columns with the sorption of a certain amount of rare earth elements, subsequently transforming from Mn-oxyhydroxides to rhodochrosite and redistributing REY in reducing alkaline pore-water during early diagenesis. A number of similarities can be observed through a comparison of Datangpo-type manganese ores and modern marine ferromanganese oxyhydroxide precipitates based on their rare earth elements. The precipitation of Datangpo-type manganese ores is similar to that of hydrogenetic crusts and nodules based on their positive Ce anomalies and relatively higher total REY concentrations. However, several differences also exist. Compared to hydrogenetic crusts and nodules, Datangpo-type manganese ores record smaller positive Ce anomalies, lower total REY concentrations, unobvious fractionation between Y and Ho, and weak to strong positive Eu anomalies. These were caused by quicker sedimentary rates in the oxic water columns of the shallower basin, after which pore water became strongly reducing and alkaline due to the degradation of organic matter in the early diagenetic stage. In addition, compared to typical deposits in the world, Datangpo-type manganese ores are similar to hydrogenetic deposits and different than hydrothermal deposits. All of these characteristics of manganese ores indicate that Datangpo-type manganese ores, the principal metallogenic factors of which include oxidation conditions during deposition and reducing conditions during early diagenetic stages, represent hydrogenetic deposits.     

Mineralogy of morphogenetic types of ferromanganese deposits in the world ocean

The mineralogy and structural features of the main types of ferromanganese deposits—nodules, micronodules, Co-bearing crusts, crustlike nodules, and low-temperature hydrothermal manganese crusts and ferruginous ochers—are considered. The correlation between their mineral composition and structure is shown. The proposed classification of mineral types is based on characteristic assemblages of Fe and Mn minerals.