大洋富钴结壳成因机制的探讨——水成因证据

根据对大洋富钴结壳的分层与年龄、分层与生长速率、生长间断等观测事实,以及大洋富钴结壳主量元素锰、铁元素及钴元素、铂元素、稀土元素、氦同位素、锇同位素等的水成富集,指出大洋富钴结壳是水成因的,进而指出富钴结壳的形成与基岩无关,水动力条件、最低含氧带、生物作用等可能对富钴结壳的形成有控制作用。同时,富钴结壳不一定只生长在岩石裸露的海山上,在沉积物覆盖的海山区也有可能找到富钴结壳。     

西太平洋Kocebu海山铁锰结壳稀土元素地球化学特征

西太平洋麦哲伦海山区是全球重要的铁锰结壳资源分布区,具有丰富的稀土元素资源潜力.本文对采自麦哲伦海山区Kocebu海山的11个铁锰结壳表层样(<1 mm)进行稀土元素地球化学研究,探讨其含量特征、成因和影响稀土元素富集的环境因素.结果表明:Kocebu海山铁锰结壳表层样品ΣREY(Rare earth elements...     

Rare earth elements and yttrium in ferromanganese deposits from the South China Sea: distribution, composition and resource considerations

Ferromanganese nodules and crusts contain relatively high concentration of rare earth elements(REE) and yttrium(REY),with a growing interest in exploitation as an alternative to land-based REY resources.On the basis of comprehensive geochemical approach,the abundance and distribution of REY in the ferromanganese nodules from the South China Sea are analyzed.The results indicate that the REY contents in ferromanganese deposits show a clear geographic regularity.Total REY contents range from 69.1×10~(–6) to 2 919.4×10~(–6),with an average value of 1 459.5×10~(–6).Especially,the enrichment rate of Ce content is high,accounting for almost 60% of the total REY.This REE enrichment is controlled mainly by the sorption of ferromanganese oxides and clay minerals in the nodules and crusts.Moreover,the total REY are higher in ferromanganese deposits of hydrogenous origin than of diagenetic origin.Finally,Light REE(LREE) and heavy REE(HREE) oxides of the ferromanganese deposits in the study area can be classified into four grades: non-enriched type,weakly enriched type,enriched type,and extremely enriched type.According to the classification criteria of rare earth resources,the Xisha and Zhongsha platform-central deep basin areas show a great potential for these rare earth metals.     

过渡金属元素Cu、Co、Ni在铁锰结核(壳)中富集的控制因素

在不同生成环境下生成的铁锰结核(壳)吸收不同的过渡金属元素。在成岩作用形成的铁锰结核中,Cu、Ni主要以锰相形式存在,而Co则以铁相的形式存在;在水成作用形成的铁锰结核(壳)中Cu、Co、Ni均以锰相的形式存在。这些过渡金属元素在成岩作用形成的结核中的存在与铁锰结核(壳)中锰矿物和铁的氧化物、氢氧化物的晶体化学特征密切相关,而在水成作用形成的铁锰结核(壳)中的富集与锰矿物和铁的氧化物、氢氧化物的晶体化。学特征关系不大。同时铁锰结核(壳)中锰矿物和铁的氧化物、氢氧化物又严格地受结核(壳)的生成环境的制约,因此,过渡金属元素Cu、Co、Ni在铁锰结核(壳)中的富集在一定程度上受结核(壳)生成环境的控制。     

Trace elements in ferromanganese nodules from the central indian ocean basin

Thirty-three bulk ferromanganese nodules from the sediment–water interface of siliceous sediment domain from the Central Indian Ocean Basin were analyzed for 50 elements including 6 new (Be, As, Se, Sn, Sb, and Bi) using inductively coupled plasma–mass spectrometer. The Mn/Fe ratio and triangular plot (Fe-Mn-{Cu+Ni+Co?×?10}) suggest that ferromanganese nodules are of hydrogenetic, early diagenetic, and diagenetic origin. In the ferromanganese nodules, Mo, Sb, Bi, and As are highly enriched ～320, 160, 90, and 50 times compared with upper continental crust, respectively. A majority of the elements such as Be, Sc, Ti, V, Co, As, Se, Sr, Y, Zr, Nb, Sn, rare earth elements (REEs), Pb, Bi, P, Th, U, Hf, and Ta are associated with Fe, whereas, Cu, Ni, Zn, Mo, Li, Ga, Sb, Mg, and Cs are associated with Mn in the ferromanganese nodules. Redox proxies such as U/Th (0.14) and Mo/Mn (0.0019) ratio in the ferromanganese nodules suggest their formation under oxic conditions.     

帕里西维拉海盆西缘中段铁锰结核的地球化学特征和成因类型

深海铁锰结核能有效记录海域内重大地质事件和气候环境信息,且富含多种金属物质极具资源潜力,因而广受关注.通过对帕里西维拉海盆西侧边缘中段海域内新发现的12个站位铁锰结核的地球化学特征研究,发现与全球主要成矿区内的铁锰结核相比,Mn及主要赋存在锰氧化物中的Ni、Cu、Mo的含量较低(分别为8.20％～25.24％、0.11...     

Submersible observations of manganese nodule and crust deposits on the Tenpo Seamount,Northwestern Pacific

Pavements of manganese nodules and crusts and outcrops of Miocene limestones were observed on the flanks and flat top of the Tenpo Seamount during three Shinkai 2000 dives. The pre‐Miocene volcano supplied nuclei of volcanic rocks and hydrothermal manganese deposits, and subsequent slow or no sedimentation promoted deposition of abundant hydrogenetic nodules and crusts, mainly on the upper flank of the seamount. Nodule pavements generally cover calcareous sand surface sediments, while crusts cover hard outcrops composed probably of volcanic rocks. The fields of crusts and nodules are sparsely distributed with each other on scales of meters to tens of meters. The on‐site observation suggests the deposits have encountered tectonic and/or mass movements that resulted in unusual occurrences of densely stacked nodules and occasionally the nodules resting directly on crusts or hard substrates. Mineralogical and chemical compositions reveal that for nodules and crusts the encrusting manganese layers of around 1 cm thickness are composed of hydrogenetic vernadite, and diagenetic influence is negligible.     

Influence of substrate rocks on Fe–Mn crust composition

Principal Component and other statistical analyses of chemical and mineralogical data of Fe–Mn oxyhydroxide crusts and their underlying rock substrates in the central Pacific indicate that substrate rocks do not influence crust composition. Two ridges near Johnston Atoll were dredged repetitively and up to seven substrate rock types were recovered from small areas of similar water depths. Crusts were analyzed mineralogically and chemically for 24 elements, and substrates were analyzed mineralogically and chemically for the 10 major oxides. Compositions of crusts on phosphatized substrates are distinctly different from crusts on substrates containing no phosphorite. However, that relationship only indicates that the episodes of phosphatization that mineralized the substrate rocks also mineralized the crusts that grew on them. A two-fold increase in copper contents in crusts that grew on phosphatized clastic substrate rocks, relative to crusts on other substrate rock types, is also associated with phosphatization and must have resulted from chemical reorganization during diagenesis. Phosphatized crusts show increases in Sr, Zn, Ca, Ba, Cu, Ce, V, and Mo contents and decreases in Fe, Si, and As contents relative to non-phosphatized crusts. Our statistical results support previous studies which show that crust compositions reflect predominantly direct precipitation from seawater (hydrogenetic), and to lesser extents reflect detrital input and diagenetic replacement of parts of the older crust generation by carbonate fluorapatite.     

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.     

Ferromanganese Nodules and Crusts from the Christmas Island Region,Indian Ocean

A sampling expedition has shown that largely hydrogenetic marine ferromanganese deposits occur in the Christmas Island region south of Java (~10°S), as small nodules on seamount slopes and abyssal plains (red clay), and as thick crusts on volcanic ridges and seamounts. Vernadite is dominant, with birnessite, jacobsite and todorokite common. Nodules were recovered in 25% of free-fall grab stations in water 4600-5900 m deep, and are not abundant where present. The nodules average 9.6% Fe, 19.7% Mn, 0.51% Ni, 0.49% Cu, and 0.12% Co. Crusts are common in water 1450-3700 m deep, with average deposition rates of 1-1.5 mm / m.y. The crusts average 13.9% Fe, 16.2% Mn, 0.35% Ni, 0.11% Cu, and 0.44% Co. Cobalt grades are higher (~0.8%) in shallower water ( < 2500 m), so future exploration should concentrate on depths of 500-1500 m near the oxygen minimum zone.     

Deposition of hydrogenetic and hydrothermal manganese minerals in the Ogasawara (Bonin) Arc Area,Northwest Pacific

A widespread distribution of hydrothermal and hydrogenetic manganese deposits is described in the results of the Hakurei‐Maru cruises conducted in the Bonin Arc areas of the West Pacific from 1984 to 1989. Manganese deposits occur in the active volcano chains, back‐arc basins, remnant back‐arc ridges, and oceanic seamounts.

The hydrogenetic iron‐manganese deposits commonly form earthly black crusts and nodules on the topographic highs of inactive ridges and old seamounts, sometimes as thick as 10 cm. They are always composed of the iron‐manganese mineral vernadite. Co and Ni contents are relatively high in the crusts from the seamounts in the open Pacific Ocean (up to 1.1% Co and 1.0% Ni). Two generations of distinct chemistry and texture are typical of these crusts, which can be compared to reported thick crusts from the Central Pacific seamounts.

The hydrothermal deposits, characterized by dense, submetallic, and gray appearance, are dominant in the recent and also in past submarine volcanoes of the island‐arc systems. Evidence of past hydrothermal activity was ascertained as fossil hydrothermal manganese deposits inside the hydrogenetic nodules or beneath the hydrogenetic crusts over the Tertiary island arc. Their component minerals are considered to be todorokite and bimessite (stable and contractible upon dehydration), having almost negligible amounts of Fe, Si, Al, Ni, Co, Zn, Pb, Cu, etc. In the small model site, the Kaikata Seamount hydrothermal area, the presumably recent hydrothermal activity has yielded thin slabs of pure manganate deposits growing downward within volcanic and sand layers.

Early diagenetic influence is negligible on nodules of this area.     

Inter-relationship between Nuclei and Gross Characteristics of Manganese Nodules,Central Indian Ocean Basin

More than 200 samples of manganese nodules from the Central Indian Ocean Basin (CIOB) were studied for their different parameters. The study included various aspects such as morphology, texture, mineralogy, and composition of the nodules. The nuclei of the nodules were also examined along with the oxide layers. We attempt to correlate the nucleus (their type and abundance) with the nodule parameters such as their external morphology, chemical composition, and suitable location of formation, amongst others. We found various nucleating materials and these include rock fragments (fresh and altered), clay, pumice and sharks' teeth. In a majority of the cases, rock fragments are dominant in the core of the nodules and these conform to that of the seafloor basalts. The shape of the nuclei influences that of the nodules, especially during their initial period of growth. Irrespective of the kind of nuclei, todorokite is the main mineral of the nodules. The nodules of the CIOB were formed mostly due to hydrogenous accretion of ferromanganese oxides while diagenetic contribution of metals is less common.     

中太平洋海山富钴结壳成矿的空间分布规律研究

海山是富钴结壳主要的成矿载体,结壳成矿分布不仅受到海洋最低含氧带、碳酸盐补偿深度、生物生产力、物质来源、海水氧含量等大尺度宏观因素的影响,同时也受到海山地形、沉积作用和底层海流冲刷等小尺度微观因素的控制。通过对以中太平洋R海山为主的水下结壳成矿与分布的深入研究,发现结壳富集区以海山浅水区域为主;地形地貌上的尖顶高地区、顶坡过渡带、山体鞍部、山脊、斜坡上部等区域结壳质量较好,覆盖率高;下斜坡、山谷、山顶平坦区和斜坡区平缓台地是结壳贫乏区,结壳厚度小、覆盖率也低;15°以下的小坡度地形结壳成矿较好,3°~7°最佳,15°以上的大坡度区质量有所下降,陡崖区最差。地形对结壳分布和成矿起基础性影响作用,沉积作用和底流冲刷分别起到阻滞和促进作用,海流是保持低坡度区结壳长期稳定生长的关键因素,地形控矿本质上是和底层流联合对抗沉积堆积作用的过程。     

The Role of Primary-Producer-Mediated Organic Complexation in Regional Variation in the Supply of Mn,Fe, Co,Cu, Ni and Zn to Oceanic,Non-Hydrothermal Ferromanganese Crusts and Nodules

Oceanic, non-hydrothermal ferromanganese crusts and nodules are variably enriched in Mn, Fe, Co, Cu, Ni and Zn. Comparison of the content of these elements in crusts and nodules with the level of primary productivity in the South Pacific Ocean suggests that primary-producer-mediated complexation of several of these elements by organic ligands in solution may contribute to explaining a pattern of distinctive associations observed between compositional variations for these elements in these deposits and variations in the level of primary productivity.     

西太平洋卡罗琳洋脊CM4海山铁锰结壳矿物学和地球化学特征

2017年8月中国科学院海洋研究所在西太平洋低纬度海区的卡罗琳洋脊CM4海山开展了多学科综合调查,发现该海山山体表面分布着大量的铁锰结壳。本文对该海山的5个铁锰结壳样品进行了矿物学和地球化学研究,利用X射线衍射(XRD)、电感耦合等离子光谱及质谱(ICP-OES、ICP-MS)等测试技术分析了铁锰结壳的矿物组成、主微量元素和稀土元素含量,并进一步探讨了铁锰结壳的成因类型。结果表明,该海山铁锰结壳的矿物组成以水羟锰矿为主,含有少量钡镁锰矿、水钠锰矿、针铁矿、纤铁矿、石英和方解石。该海山铁锰结壳的Mn、Fe、Co、Ni、Cu元素平均含量分别为24.24%、15.14%、0.16%、0.34%、0.01%。与全球各大洋海山区铁锰结壳相比,该海山样品的Cu含量很低。该海山铁锰结壳的稀土元素(REY)含量相对偏低,总体为轻稀土(LREE)富集;稀土(REY)配分模式显示相对平坦的特征,呈明显的Ce正异常,轻微的Y负异常和Ho正异常。样品的矿物组成、元素比值、元素组合等都表明该海山铁锰结壳属于水成成因,未受明显的成岩作用影响。     

Metal flux as an alternative parameter in evaluating the resource potential for co-rich ferromanganese crusts

We propose a geochemical parameter, “metal flux” in evaluating hydrogenetic Co-rich ferromanganese crust deposits in the Pacific seamount area, that is based on physical, chemical, and geological characterization of the integrated growth piles of crusts. We calculated the metal flux for fifteen sites from different depths ranging between 900-6000m from different seamounts. The secular and areal variations of metal flux indicate a strong geological controls, and also can be a reliable tool for estimating an economic potential of the crusts. The Co flux decreases with increasing water depth, followed by almost constant flux of Ni and Mn. The Al and Fe fluxes vary with regions, indicating higher values in the western regions near the island arc probably related to a supply from the Asian continents. The results imply that Co, a redox sensitive metal element, is controlled by redox conditions of seawater, while Fe and Al are by terrigenous input. The metal flux reflects global and regional conditions and controls the compositional diversity of metals, thus consequently, the parameter can be a reliable powerful tool to estimate or single out more potential areas.     

First investigations of massive ferromanganese crusts in the NE Atlantic in comparison with hydrogenetic pacific occurrences

Ferromanganese crusts comparable with central Pacific occurrences with respect to thickness and extension have been discovered at the Tropic Seamount in the subtropical NE Atlantic. A comparison with typical hydrogenetic crusts from a central Pacific seamount revealed lower concentration of the Mn phase with Mn, Co, Ni, Zn, and Cu but a strongly increased terrigenous input of Fe, Pb, Al, and Si in the Atlantic crusts. Growth rates are increased compared with the Pacific crusts, and crust ages average at 10 My. The old phosphatized crust generation that started to grow about 20 My ago on the Pacific seamounts is not pronounced at the Tropic Seamount. The typical hydrographic and morphological parameters for hyrogenetic crust growth have also been found at the Tropic Seamount, which implies that the Tropic Seamount crusts have developed according to the hydrogenetic growth model. There are no indications of hydrothermal influence.     

Relationship between polymetallic nodule genesis and sediment distribution in the KODOS (Korea Deep Ocean Study) Area, Northeastern Pacific

Polymetallic nodule and sediment characteristics were investigated for two blocks (KR2 and KR5) in the Korea Deep Ocean Study (KODOS) area in order to better understand nodule distribution and the potential effects of sediments on nodule genesis. The northern block (KR2) is dominated by hydrogenetic nodules, whereas the southern block (KR5) is dominated by diagenetic nodules. Sediments in the study area are assigned to three major lithologic units which are distinctive in color and texture. The northern block is characterized by a thick, metalpoor Unit 1 sediment, which is thin in the southern block, where metal-rich Units 2b and 3 occur close to the surface. The distribution of different nodule genetic types in the northern and southern blocks can be attributed to topographic variations (topographic high near seamounts in KR2 and abyssal plain in KR5) and different sedimentation rates (0.1 and 0.32 mm/kyr in blocks KR2 and KR5, respectively). The southern block has a geologic setting more conducive to diagenetic nodule formation, such as flat topography and sediment composition. Nodule distribution in the studied blocks might also be explained by the distribution of the sediment units of different metal contents. The northern block, in which Unit 1 is thicker, has more abundant hydrogenetic nodules, possibly because Unit 1 prevents metals that are remobilized from the underlying sediments from reaching the seabed where the nodules are forming.     

稀土元素在成岩型海洋铁锰结核中的富集特征及机制

借助相分析中的偏提取方法对取自东太平洋深海平原上的成岩型铁锰结核进行了选择性提取实验以研究稀土元素在其中各矿物或氧化物相中的分布模式以及铁氧化物和锰氧化物对稀土元素的吸附机制.结果显示,尽管1 nm-水锰矿相对无定形铁的氧化物/氢氧化物而言是成岩型结核中的优势矿物,但是稀土元素主要富集在无定形铁的氧化物/氢氧化物中.虽然稀土元素在海水中主要是以碳酸盐络合物的形式存在,但是无定形铁的氧化物/氢氧化物则是从海水中获得自由稀土元素离子来络合,而1 nm-水锰矿则直接吸附稀土元素的碳酸盐络合物.因此,无定形铁的氧化物/氢氧化物对稀土元素来说具有比1 nm-水锰矿更强的络合能力.成岩型结核的Ce负异常是由于成岩型结核形成于缺氧微环境中,该环境不能把可溶性的Ce~(3+)氧化成不溶性的Ce~(4+)发生沉淀.     

全球三大洋海山钴结壳资源量估算

钴结壳具有Co、Ni、Cu和Mn及其他金属的潜在矿产资源和储存在结壳层中古环境信息的双重意义。与深海多金属结核和热液硫化物矿床相比,具有较高Co、Ni和Pt含量的海山钴结壳有可能成为商业勘探的潜在目标。为合理地估算出全球三大洋海山钴结壳资源量,基于我国西太平洋海山钴结壳拖网采样调查资料和对太平洋海山钴结壳资源分布规律和钴结壳矿区圈定参数指标的深入研究,按海山不同高度、不同洋壳年龄赋予不同结壳厚度,进而计算出全球三大洋海山钴结壳分布面积为3 039 452.14km2和干结壳资源量为(1 081.166 1~2 162.332 2)×108 t。太平洋海山钴结壳分布面积为2 123 087.12km2和干结壳资源量为(513.244~1 026.488)×108 t,大西洋海山钴结壳分布面积为512 509.74km2和干结壳资源量为(116.503 2~233.006 4)×108 t,印度洋海山钴结壳分布面积为403 855.28km2和干结壳资源量为(81.484 9~162.969 8)×108 t。三大洋海山钴结壳的Mn、Co、Ni和Cu金属量分别为(138.848 0~277.696 0)×108 t,(3.967 6~7.935 2)×108 t、(2.793 6~5.587 2)×108 t和(0.825 1~1.650 2)×108 t。根据钴结壳的Co含量、Co通量和厚度相关分析,所赋予的钴结壳厚度占理论推测厚度的6.10%~12.20%,这与Ku等得出"钴结壳生长时间约占其整个生命史4%"的认识非常相近。三大洋海山钴结壳实测厚度与赋值厚度对比分析表明,太平洋海山钴结壳赋值厚度平均值为1.87cm,实测厚度平均值为1.77cm,相对误差为5.35%,大西洋和印度洋相对误差分别为18.18%和23.23%。研究数据表明按海山高度和洋壳年龄所赋的钴结壳厚度基本合理,估算出的钴结壳资源量基本可靠。本文首次估算出三大洋海山钴结壳资源量,为整个海盆和三大洋海山钴结壳资源量估算提供了新方法。