Behavior of Zn<Superscript>2+</Superscript>, Cd<Superscript>2+</Superscript>, Ba<Superscript>2+</Superscript> and Pb<Superscript>2+</Superscript> cations in ferromanganese crusts from the Marcus Wake seamount (Pacific Ocean) in aqueous solutions of metal salts

The behavior of heavy-metal cations in ore minerals of cobalt-rich ferromanganese crusts from the Marcus Wake seamount in aqueous solutions of metal salts was studied in experiments. The Zn²⁺ and Cd²⁺ cations showed high reactivity and Ва²⁺ and Pb²⁺ showed low reactivity. It was found that Zn²⁺ and Cd²⁺ cations within the ore mineral composition are mainly absorbed (up to 66%) whereas Pb²⁺ and Ва²⁺ are chemically bound (up to 70%). Ore minerals in the crusts are characterized by sorption properties and high ionexchange capacity by these cations (1.94–2.62 mg-equiv/g). The capacity values by heavy-metal cations for ore minerals of the crusts from different areas of the Marcus Wake seamount are close to each other.     

南海多金属结壳(核)铁锰矿物/海水界面效应与成矿元素的富集

海底铁锰结壳和结核是重要的海底矿产资源,蕴含着丰富的金属元素并且具有巨大的经济价值。本文主要以南海多金属结壳（核）为研究对象,采用X射线粉晶衍射（XRD）、激光拉曼光谱、红外光谱分析（FTIR）以及X射线光电子能谱对铁锰矿物的矿物学和谱学特征进行了系统的分析和研究。粉晶衍射和拉曼光谱分析结果表明,南海多金属结壳的矿物组成为水羟锰矿、石英和长石,结核的矿物组成为钡镁锰矿、水羟锰矿、石英和长石,铁相矿物均为无定形铁氧化物/氢氧化物,并且锰相矿物和铁相矿物的结晶程度均较差。红外光谱分析结果显示多金属结核和结壳中的铁锰矿物具有大量表面羟基,这些含质子表面羟基官能团,可为海水中各成矿元素的络合提供丰富的活性位点。XPS分析表明多金属结核和结壳中铁锰矿物表面以Fe、Mn和O元素为主,其中Fe呈正三价态,Mn以正四、正三价为主,可能还含有少部分正二价态。对比南海多金属结壳（核）与太平海山结壳,南海多金属结壳（核）具有更为显著的表面羟基氧（-OH）含量,而太平洋海山结壳则以晶格氧（O^2-）为主,表明太平洋海山结壳铁锰矿物结晶程度较南海多金属结壳（核）高。综合研究表明,在海底铁锰结壳和结核中（氢）氧化锰/铁矿物与海水之间界面效应对金属离子的富集机理主要有：（1）金属离子与矿物表面羟基进行络合反应,形成以配位键相连的羟基络合物,或与表面的质子交换生成稳定的内层络合物;（2）矿物的带电表面与金属离子通过静电作用形成双电层,生成外层络合物;（3）金属离子与矿物结构中的Mn、Fe离子同晶置换而成为结构阳离子。     

海山富钴结壳的圈矿方法

对海山富钴结壳的圈矿方法进行了分析和探讨,指出海山富钴结壳圈矿的主要方法和步骤为:(1)挑选富钴结壳发育良好的海山。除大片连续厚层板状分布的结壳发育良好的大型平顶海山是重点调查的目标海山外,规模较小的尖顶海山是近年来新的圈矿目标海山。(2)确定矿块的边界位置。对选定的海山进行深海摄像、电视抓斗、拖网和浅钻等多种手段的调查,通过所取得的综合结果对矿块边界进行判断,确定准确的矿块边界。(3)计算结壳的覆盖率。利用调查所获得的矿块相关的数据和信息对矿块内结壳厚度和结壳覆盖率以及矿区资源量进行评估。     

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.     

麦哲伦海山区MD、ME、MF海山富钴结壳特征

麦哲化海山区MD、ME、MF海山具有三层构造的结壳特征，研究表明，结壳可分为上部较致密层、中部疏松层、下部致密层。致密层构造单一，含很少脉石矿物；疏松层构造杂乱，含有大量脉石矿物；较致密层介于两者之间，壳层矿物有锰相矿物（主要为水羟锰矿）、铁相矿物和次要矿物（粘土矿物、钙十字沸石、石英、方解石、磷灰石等）。不同壳层地球化学特征具有明显差异性，Ce异常表明在结壳从下层到上层的生长过程中，环境的氧化性逐渐减弱，结壳^10Be测年结果表明，疏松层的生长速率最大，其次为致密层，较致密层的生长速率最小。推测区的最老的结壳的生长年代为中新世晚期，在4Ma以前，区内水动力条件很弱，氧化性较强；4－3．1MaBP水动力条件较强，氧化性较弱；2．6MaBP以来，水动力条件为强－弱波动期，氧化性较弱。     

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。     

麦哲伦海山群富钴结壳元素地球化学特征及赋存状态

为探究大洋富钴结壳的元素地球化学特征和赋存状态,以西太平洋麦哲伦海山群5个富钴结壳样品为研究对象,通过X射线衍射法、等离子体发射光谱法、等离子体质谱法及相态分析手段,分析了富钴结壳的矿物组成、主量元素和稀土元素含量。结果表明,富钴结壳样品主要结晶矿物为水羟锰矿,次要矿物包括石英、斜长石和钾长石,同时含有大量非晶态铁氧/氢氧化物。富钴结壳样品中Mn和Fe含量最高, Mn为16.87%～26.55%, Fe为14.34%～18.08%。富钴结壳明显富集稀土元素,其稀土总量为1 287～2 000μg/g,Ce含量为632～946μg/g,约占稀土总量的50%;轻稀土含量为1 037～1 604μg/g,重稀土含量为249～395μg/g,轻稀土元素明显高于重稀土元素。稀土元素配分模式呈现Ce正异常而Eu无异常,具有Ce富集特征。麦哲伦海山群富钴结壳是水成沉积成因,基本没有受到海底热液活动和成岩作用的影响。元素赋存状态与其矿物相密切相关, Na、K、Ca、Mg和Sr主要赋存于碳酸盐相, Mn、Ba、Co和Ni主要赋存于锰氧化物相, Fe、Al、P、Ti、Cu、Pb、V、Zn、Zr和REE主要...     

Minor and rare elements in manganese crusts and nodules and sediments from the Manihiki plateau and adjacent areas: Results of HMNZS Tui cruises

Six manganese crusts, 13 manganese nodules, and 16 sediments were analyzed by instrumental neutron activation analysis. Data were generated on selected major and minor elements but geochemical evaluations are based only on Fe, Sc, U, Th, and the rare earth elements (REE). Manganese crusts and manganese nodules have comparable trivalent REE contents and show a shale‐like distribution pattern. Both crusts and nodules are characterized by a positive Ce anomaly but the anomaly is higher in nodules. REE contents in manganese nodules show a linear dependence on the Fe content, and it is concluded that these elements are incorporated in the Fe‐rich (δ‐MnO₂) phase. In the crusts, the REE correlate with Sc and are therefore assumed to be associated with the clay minerals. Uranium contents are significantly higher in the crusts than in nodules whereas Th is slightly higher in the nodules. There is a clear positive correlation between U and Th in nodules but there are too few data to make a similar conclusion for crusts. Compositional data suggest a division of the sediments into two groups. The carbonate sediments have much lower REE contents and a more pronounced negative Ce anomaly than the clays, while both show a lithogenous component as indicated by a slight negative Eu anomaly.     

西太平洋Lamont海山中新世以来富钴结壳成矿环境的演化

分析了西太平洋Lamont海山12个站位33个富钴结壳样品的主元素和稀土元素,结果表明,该海山富钴结壳成因类型属于水成成因,并且在形成过程中基本未受到磷酸盐化作用的影响。Lamont海山的一个富钴结壳样品剖面的电子探针数据显示,该海山富钴结壳的成矿环境在新第三纪以来至少存在2个演化阶段:第1阶段,23~15 Ma,富钴结壳中Mn相对富集,成矿环境以富氧贫硅为特征;第2阶段,15~0 Ma,富钴结壳中Fe相对富集,成矿环境以贫氧富硅为特征。成矿环境的氧化能力总体上呈现下降的趋势。联系新生代世界大洋,尤其是西太平洋的地质演化背景,认为引起成矿环境演变的原因主要是西太平洋大洋板块的WNW向漂移和新第三纪以来全球水道开合,造成了Lamont海山所处海区最低含氧带逐渐减薄。     

Precious and nonferrous metals in the ferromanganese crusts of the central Sea of Okhotsk

Thin mineral grains of nonferrous and precious metals (Ag, Au, Cu, Ni, Pb, Sn, Zn, Sb, Ti, W, Mo, and Ce) were revealed for the first time by SEM and microprobe studies of polished sections of iron-manganese crusts from the Sea of Okhotsk. The metals form native and intermetallic compounds; less frequently they form mineral oxides or sulfides. The conclusion was drawn that the main part of the native minerals represents a mechanical admixture in the ferromanganese crusts.     

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。     

中太平洋海山富钴结壳与基岩关系的研究

对我国首次取得的中太平洋海山基岩和富钴结壳样品的结构构造、矿物和化学组成特征的研究表明,该区主要基岩类型为碱性玄武岩、磷块岩、磷酸盐化碳酸盐岩和燧石等,碱性玄武岩分布最广,并均有不同程度的风化.观察表明,富钴结壳的载体可以是各种岩性的基岩.玄武岩、风化火山岩和磷块岩上的结壳厚度比燧石的大,有较高的经济价值,是选矿冶炼的主要对象.对于调查区内富钴结壳形态总体上可分为三种类型:板状、砾状和结核状结壳.从以下四个方面探讨结壳与基岩之间的关系:(1)海水、基岩和结壳中主要金属元素含量特点;(2)通过聚类分析方法探讨结壳与基岩之间的亲疏程度;(3)结壳的分布特征;(4)不同基岩类型对结壳生长的影响.分析结果表明,调查区内的火山岩及磷块岩对结壳形成的贡献大(比其他类型岩石).     

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...     

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.     

多金属结壳生长间断期与磷酸盐化事件的关系

磷酸盐化的发生会造成多金属结壳主要成矿元素的贫化,总体上抑制结壳的生长.磷酸盐化作用呈幕式在太平洋内发生,已有研究将其发生期次与多金属结壳中的磷酸盐化层位及其P、Ca等元素地球化学特征对应,为结壳的年代厘定提供证据.然而,由于磷酸盐化多次发生且在结壳多个层位中显现,首先需要厘定出较为可靠的多金属结壳年代框架,才能与磷酸...     

太平洋海山富钴结壳中铂族元素赋存状态与富集机理

通过选择性化学提取法,对太平洋采薇海山富钴结壳样品中铂族元素进行分级提取实验,利用电感耦合等离子体质谱仪(ICP-MS)测定了铂族元素含量。赋存状态结果显示,富钴结壳中铂族元素在各个化学相态中富集比例从大到小依次为:铁氧化物相、残渣态、锰氧化物相、碳酸盐相、吸附态,未磷酸盐化新壳层和磷酸盐化老壳层中铂族元素都主要赋存于铁氧化物相中,其富集比例为59.26%～82.19%,残渣态中磷酸盐对铂族元素具有一定的富集能力,其富集比例为17.23%～35.37%。不同类型地质体中铂族元素的赋存状态结果,也证实了富钴结壳和海山结核中铂族元素富集主要受到铁氧化物相和残渣态的影响。太平洋海山富钴结壳中铂族元素的富集机理推测为铁氧/氢氧化物胶体粒子的吸附作用,使海水中PtC l24-离子被吸附到铁氧化物相中,从而使富钴结壳中铂族元素富集。     

Noble metals in ferromanganese crusts from marginal seas of the Northwest Pacific

Based on data on the concentration of noble metals (Au, Ag, Pt, Os, Ir, and Ru) in bulk samples of ferromanganese crusts, the presence of inclusions of micro- and nanosized grains of Ag, Au, Pd, and Pt, often with impurities of other elements, as well as their chaotic distribution, three sources of incorporation of these metals into ore crusts of Far Eastern seas are suggested: seawater, postvolcanic gas–hydrothermal fluids, and hydrothermal plumes. The presence of grains of platinoids and gold in ferromanganese crusts on only some mounts may result from peculiarities in the formation of volcanic rocks on the ancient continental basement.     

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.     

News from the seabed – Geological characteristics and resource potential of deep-sea mineral resources

Marine minerals such as manganese nodules, Co-rich ferromanganese crusts, and seafloor massive sulfides are commonly seen as possible future resources that could potentially add to the global raw materials supply. At present, a proper assessment of these resources is not possible due to a severe lack of information regarding their size, distribution, and composition. It is clear, however, that manganese nodules and Co-rich ferromanganese crusts are a vast resource and mining them could have a profound impact on global metal markets, whereas the global resource potential of seafloor massive sulfides appears to be small. These deep-sea mineral commodities are formed by very different geological processes resulting in deposits with distinctly different characteristics. The geological boundary conditions also determine the size of any future mining operations and the area that will be affected by mining. Similarly, the sizes of the most favorable areas that need to be explored for a global resource assessment are also dependent on the geological environment. Size reaches 38 million km² for manganese nodules, while those for Co-rich crusts (1.7 million km²) and massive sulfides (3.2 million km²) are much smaller. Moreover, different commodities are more abundant in some jurisdictions than in others. While only 19% of the favorable area for manganese nodules lies within the Exclusive Economic Zone of coastal states or is covered by proposals for the extension of the continental shelf, 42% of the favorable areas for massive sulfides and 54% for Co-rich crusts are located in EEZs.     

Ferromanganese crusts from the Sea of Okhotsk

New data on the microstructures and the mineral and chemical compositions of ferromanganese crusts obtained from the western slope of the Kuril Island Arc in the Sea of Okhotsk during cruises of the R/V Vulkanolog are discussed. The study of the crusts using analytical electron microscopy methods revealed that their manganese phase is represented by vernadite, Fe-vernadite, todorokite, asbolane, and asbolane-buserite, while the iron phase consists of hematite, hydrohematite, ferroxyhite, and magnetite. The assemblage of lithic minerals includes apatite, quartz, epidote, and montmorillonite. According to the chemical analysis, most of the crusts contain a significant share of volcanogenic and hydrothermal material, which is evident from the elevated values of the Mn and Ti modules, the low concentrations of some trace elements, and the positive Eu anomaly in the rare earth elements composition.