基于CC区的多金属结核矿床成因地质模型

通过对东太平洋克拉里恩.克里珀顿区(CC区)和中国多金属结核开辟区(COMRA区)多金属结核的国内外研究资料和数据加以归纳总结,从多金属结核产出的区域地质背景、富集成矿条件以及结核的生长过程及其历史等方面,较全面地阐释了多金属结核的成因机制,深化了对有关多金属结核矿床形成演化控制因素的认识.在明确大洋多金属结核矿床定义基础上,分别建立了基于CC区的宏观、中观和微观三个不同空间尺度的多金属结核区域成矿模型、矿床成矿模型和结核生长模型,完整地提取了多金属结核矿床成因地质模型,为CC区潜在矿产资源的预测和评价提供了重要的科学依据.     

东太平洋CC区多金属结核的地质学特征及形成环境

通过对东太平洋CC区洋底地质取样及实验测试分析,运用洋底照相、多频探测等多种地球物理方法手段,进一步阐明了CC区多金属结核的形态、主要类型、丰度、覆盖率、品位、化学成分及分布特征.通过对CC区区域地质背景及地形地貌的综合研究,深入探讨了多金属结核的形成环境.通过对CC区多金属结核的分布规律与形成环境的综合研究,揭示了该区多金属结核的形成与地质环境之间的内在关系,这对于分析研究该区多金属结核的形成机理,为多金属结核资源评价和开发提供科学依据,对于大力开发与利用洋底多金属矿产资源,具有重要的科学意义和经济意义.     

东菲律宾海多金属结核微区元素赋存特征及成因意义

多金属结核富含Mn、Fe、Co、Ni、Cu和REY(稀土元素和钇)等元素,具有巨大的潜在经济价值。东菲律宾海结核由包壳和核部岩屑(或泥团)构成,其Mn、Fe、Co、Ni和Cu含量介于南海结核和大洋结核之间,但该区域结核的微区特征尚不清楚。本文基于微区元素分析,探究了东菲律宾海结核的元素赋存特征及其成因意义。结果表明,东菲律宾海结核总体为水成成因,主要形成于氧化环境。结核包壳主要由含δ-MnO₂的水成型富铁层(FeO平均为28.7%, MnO平均为21.9%,Mn/Fe值平均为0.93)构成,但边部存在薄层(<100μm)的成岩型富锰层(FeO平均3.41%,MnO平均52.6%,Mn/Fe值平均为17.5),富锰层具有高NiO(2.71%)和CuO(1.45%)含量。根据Co经验公式估算,富锰层可能形成于末次盛冰期(LGM)以来。本研究还发现,结核核部气孔状岩屑中存在成岩成因的富锰矿物,其MnO含量为22.5%～64.7%, FeO含量为0.46%～7.05%,Mn/Fe值为3.96～126。相比包壳中富锰层,核部富锰矿物NiO(1.25%)和CuO(0.5...     

太平洋CC区多金属结核丰度和品位分布特征

太平洋CC区(Clarion-Clipperton Zone)是多金属结核丰度高、品位高的分布区,也是最具有开采价值的区域,本次研究CC区多金属结核丰度和品位分布特征研究的范围为5°N—20°N、110°W—158°W区域,此区域是太平洋多金属结核最富集矿带。CC区东起110°W,西至莱恩海脊,东西延伸约3500km,南北分别以克拉里昂(Clarion)断裂带和克立帕顿(Clipperton)断裂带     

东太平洋CC区多金属结核物质来源和分布规律

对东太平洋CC区(Clarion-Clipperton Zone)多金属结核丰度、品位、多波束地形测量、深拖光学覆盖率探测、地震勘探等一系列调查资料综合研究表明:①东区和西区结核在其化学成分和形态上有差异,但是聚类分析结果表明不能按区域断然分开;②因子分析得出东、西两区结核4种主因子是Mn组元素Mn、Cu、Ni、Zn,Fe组元素Fe、Co、Ti、Sr,岩源组元素Si、Al、K,生物元素Ca、P;③西区结核成矿物质主要来源于上覆海水中金属元素的化学沉淀,火山成矿作用使结核富集和丰度增加,趋势面和人工神经网络分析表明结核主要分布在海底坡度≤5°地区,该地区的结核量占总结核量的89.62％,坡度>5°地区结核量占10.38％;④东区结核丰度、覆盖率、地形三者变化一致,重大相变距离为10～15km,来自地幔成矿物质通过玄武质洋壳裂隙和断层,为多金属结核的形成和生长提供了丰富的物质来源,地球深部地质作用过程如基底岩浆房活动可能对结核分布产生重要影响;⑤东太平洋CC区多金属结核矿带的形成应归于海底板块扩张活动的一种资源效应和经后期表生地质作用改造的结果。     

证据权法在CC区潜在多金属结核资源预测中的应用

运用证据权法,根据东北太平洋Clarion-Clipperton地区(简称CC区)的海底断裂构造、海底沉积物类型、初级生物生产力、水深等主要控矿地质证据资料,对该地区潜在多金属结核资源进行了预测。地质证据与多金属结核矿床的空间相关性研究表明,控制多金属结核的地质证据依次为:海底沉积物类型、初级生物生产力、海底断裂构造和水深。预测结果表明,已发现的多金属结核矿床分布的后验概率区间为0.29~0.73,说明证据权法在大洋多金属结核潜在资源预测中具有良好的应用效果。多金属结核矿床形成的有利后验概率区间表明,在研究区的西南部和南部存在寻找多金属结核资源的潜力地段。     

东太平洋CC区多金属结核矿物学特征及物源

通过对东太平洋CC区洋底地质取样及实验测试分析,运用洋底照相、多频探测等多种地球物理方法手段,进一步阐明了CC区多金属结核的形态、主要类型、化学成分及分布特征.通过对CC区沉积作用、生物作用、洋底火山作用、海水化学成分、南极底流等因素的综合研究分析, 进一步揭示了多金属结核形成的物质来源.通过对CC区区域地质背景及地形地貌的综合研究分析, 进一步探讨了多金属结核的形成环境,并建立了成矿模式.     

东太平洋CC区多金属结核铂族元素（PGE）地球化学及其意义

文章采用火试金分离富集法和等离子发射光谱(ICP_MS)测定了东太平洋CC区多金属结核中PGE和Au元素的含量,结果显示:结核中PGE相对于洋壳明显富集,尤其是Pt含量较高,wPt平均值为100.90×10-9。各种类型的多金属结核PGE和Au的球粒陨石配分曲线及有关参数非常一致,均表现为Pt正异常和Pd负异常,显示其中PGE和Au具有相似的来源。多金属结核与海底海山富钴结壳PGE配分模式及特征元素比值对比表明,两者PGE可能具有相同的来源,可能主要来源于海底玄武岩的水岩反应,部分来源于铁陨石,而并非主要来自海底热液及正常海水。     

南海西北陆缘多金属结核地球化学特征及成因

对取自南海西北陆缘海域的大型多金属结核进行了电子探针、X射线粉晶衍射(XRD)、等离子质谱仪(ICP-MS) 和等离子光谱仪(ICP-AES) 等方面的分析.结核核心部位的主要矿物组成为石英、伊利石、钠长石和绿泥石, 壳层的主要矿物为δMnO₂等.铁、锰组分呈现Fe含量高、Mn含量低和Mn/Fe低的特征.Si含量高, Cu、Co、Ni含量低; 稀土元素(REE) 含量高, 平均为1472.30×10-6, 轻稀土与重稀土的比值(LREE/HREE) 达19.54, 并且存在较强的Ce正异常.元素含量的变化显示: 从结核内壳层到外壳层, Fe、Mn、Cu、Co等元素含量呈不规律变化, 具有典型的边缘海特征, 该特征反映结核在形成过程中受到边缘海沉积环境波动变化的影响, 陆源物质供应量的增加对Fe、REE、Si等元素的富集起到了促进作用, 而对Mn、Ca等元素的富集则产生明显的稀释作用.多金属结核Mn/Fe比及Mn-Fe- (Cu+Ni) ×10三组分图解显示, 南海北部陆缘多金属结核为水成成因, 该成因与结核所赋存的边缘海环境密切相关, 反映了结核成长发育的过程中, 南海典型的边缘海沉积条件和多变的古海洋环境因素对其产生了重要影响.      

我国大洋多金属结核开辟区地形地貌调查

根据大洋金属结核ＤＹ８５－５航次调查所了解的情况,对该航次调查作了简单介绍：根据该航次怕得到的我国大洋多金属结核开辟区地形地貌最新调查结果,对大洋多金属结核开发研究中的矿区放弃和采矿研究方向提出了一些建议。     

Geochemical and mineralogical control of different genetic types of deep-sea nodules from the Pacific Ocean

Deep-sea nodules from the Northeast Pacific nodule belt and the Southeast Pacific (Sonne Basin), being formed in areas bordering the equatorial zone of high biological productivity, accumulate by two basically different growth processes: (A) early diagenetic growth by supply from pore water and (B) hydrogenetic growth by supply from near-bottom sea-water. These growth processes lead to different genetic types of nodules: early diagenetic type A, hydrogenetic type B, and mixed-type AB; a further type A_C, very rich in Mn, is being formed by increasing influence of early diagenesis. These types can clearly be distinguished by their shapes, surface textures, mineral constituents of oxide fraction, internal microstructures, and geochemistry. A genetical classification is being proposed on the basis of statistically computed interelement relationships. Todorokite, very poor in Fe, is the main Mn phase in the early diagenetic substance; -MnO₂ intimately intergrown with FeOOH · xH₂O is the main phase in the hydrogenetic substance. Consequently an important difference can be pointed out: the metal supply for the growth of the early diagenetic nodules is based on an ionic solution of Me²⁺ (e. g. Mn²⁺, Ni²⁺, Cu²⁺, Zn²⁺), whereas the supply for the hydrogenetic nodules is caused by transport of colloidal particles. Mobilization of Mn²⁺ and fractionation from Fe is controlled by the amount of decomposing organic matter in the "peneliquid" layer of the sediments. The main factor controlling the intensity of early diagenesis is the biological productivity in surface waters. The crucial "point of reversal" at a Mn/Fe ratio of about 5, obtained by hyperbolical regression of the analyses of nodules from the Southeast Pacific, represents best concentrations in Ni and Cu. Mn/Fe quotients greater than 5 cause a decrease of Ni and Cu content. Nodules from the Northeast Pacific nodule belt generally contain higher concentrations in Cu than nodules from the Southeast Pacific. This can be explained by an additional supply of Cu transported below CCD by siliceous plankton.     

南海边缘海多金属结核与大洋多金属结核对比

本文通过系统对比分析前人研究成果,研究了南海边缘海多金属结核的成矿特征,结果表明：南海边缘海结核的矿物组成与大洋结核相似,均主要由锰相矿物和铁相矿物组成,其中锰相矿物主要为水羟锰矿和钡镁锰矿,铁相矿物主要以无定型铁氧化/氢氧化物形式存在,另外南海边缘海结核中含有大量硅酸盐矿物,表明在南海结核成矿过程中受到大量的陆源碎屑矿物混杂;相对于大洋主要经济成矿区的多金属结核,南海边缘海多金属结核中主要的经济元素如Mn、Cu、Co、Ni和Zn质量分数较低,而亲陆源性元素如Fe、Ti、P、Nb、Pb、Rb、Sc、Ta、Sr、Th和REY（REE和Y）等质量分数较高;南海边缘海多金属结核的元素地球化学特征和REE配分模式显示其为水成成因,并呈现更低的Mn/Fe值;同时南海边缘海结核也具有较快的平均生长速率及较高的δCe正异常,表明其生长在更为氧化的海水环境。虽然较快的沉积物沉积速率和动荡的海水环境影响了南海边缘海结核的成矿,但大量陆源物质进入海洋也为南海边缘海结核提供了丰富的成矿物质来源,便于南海边缘海结核的快速生长成矿。南海边缘海结核富集有Fe、Ti、Pb、Rb、Th和REY等金属元素,同样可以作为极具潜力的海洋矿产资源。南海边缘海多金属结核具有其独特的地球化学特征,与大洋多金属结核存在着明显差异。     

Geochemistry of ferromanganese nodule–sediment pairs from Central Indian Ocean Basin

Fourteen ferromanganese nodule–sediment pairs from different sedimentary environments such as siliceous ooze (11), calcareous ooze (two) and red clay (one) from Central Indian Ocean Basin (CIOB) were analysed for major, trace and rare earth elements (REE) to understand the possible elemental relationship between them. Nodules from siliceous and calcareous ooze are diagenetic to early diagenetic whereas, nodule from red clay is of hydrogenetic origin. Si, Al and Ba are enriched in the sediments compared to associated nodules; K and Na are almost in the similar range in nodule–sediment pairs and Mn, Fe, Ti, Mg, P, Ni, Cu, Mo, Zn, Co, Pb, Sr, V, Y, Li and REEs are all enriched in nodules compared to associated sediments (siliceous and calcareous). Major portion of Si, Al and K in both nodules and sediments appear to be of terrigenous nature. The elements which are highly enriched in the nodules compared to associated sediments from both siliceous and calcareous ooze are Mo – (307, 273), Ni – (71, 125), Mn – (64, 87), Cu – (43, 80), Co – (23, 75), Pb – (15, 24), Zn – (9, 11) and V – (8, 19) respectively. These high enrichment ratios of elements could be due to effective diagenetic supply of metals from the underlying sediment to the nodule. Enrichment ratios of transition metals and REEs in the nodule to sediment are higher in CIOB compared to Pacific and Atlantic Ocean. Nodule from red clay, exhibit very small enrichment ratio of four with Mn and Ce while, Al, Fe, Ti, Ca, Na, K, Mg, P, Zn, Co, V, Y and REE are all enriched in red clay compared to associated nodule. This is probably due to presence of abundant smectite, fish teeth, micronodules and phillipsite in the red clay. The strong positive correlation (r ? 0.8) of Mn with Ni, Cu, Zn and Mo and a convex pattern of shale-normalized REE pattern with positive Ce-anomaly of siliceous ooze could be due to presence of abundant manganese micronodules. None of the major trace and REE exhibits any type of inter-elemental relationship between nodule and sediment pairs. Therefore, it may not be appropriate to correlate elemental behaviour between these pairs.     

Processes controlling the heavy metal distribution in pacific ferromanganese nodules and crusts

The ferromanganese precipitates existing in deep-sea waters of the Pacific consist of two types of deposits: (1) nodules mainly are distributed in pelagic basins beneath the CCD (Calcite Compensation Depth) where the rate of sedimentation is low; (2) polymetallic encrustations are formed on exposed seamount rocks where currents prevent normal sediment accumulation. Nodules, being formed in areas bordering the equatorial zone of high biological productivity, grow by two different processes: (A) early diagenetic growth by supply of metals and metal compounds from pore water and (B) hydrogenetic growth by supply of colloidal particles from near-bottom seawater. These processes lead to different kinds of oxide and different metal contents. The diagenetic growth process takes place under oxidizing to suboxidizing conditions and is supplied by an ionic solution of Mn²⁺ and other divalent metal ions. The mobilization of Mn is caused by the decomposition of organic matter. The growth features of the early diagenetic nodules show alternating laminae of crystalline and amorphous material. These rhythmic sequences of different microlayers are explained by physico-chemical changes (variation of pH) in the microenvironment of the accreting nodule surface. The hydrogenetic crust growth on seamounts leads to ferromanganese precipitates which are in particular rich in Co. The Co concentration is inversely related to the water depth. Co is positively correlated to Mn which can be derived from the oxygen minimum zone. Contrary to the diagenetic nodule growth, the crust accretion is also a colloidal precipitation process. In the water column below the oxygen minimum zone, a mixture of particles of Mn-Fe-oxyhydroxide and silicate accrete together on the surface of substratum rocks. Surface chemical mechanisms control the enrichment of Ni, Co, Pb, and other metals from the seawater; for Pt, a coprecipitation with MnO₂ caused by a redox reaction is proposed. Distinct oceanographical and geological conditions enable or promote, respectively, the ferromanganese crust formation on seamounts.     

Geochemistry and specific features of manganese ore formation in sediments of oceanic bioproductive zones

Processes of authigenic manganese ore formation in sediments of the northern equatorial Pacific are considered on the basis of study of the surface layer (<2 mm) of ferromanganese nodule and four micronodule size fractions from the associated surface sediment (0–7 cm). Inhomogeneity of the nodule composition is shown. The Mn/Fe ratio is maximal in samples taken from the lateral sectors of nodule at the water-sediment interface. Compositional differences of nodules are related to the preferential accumulation of microelements in iron oxyhydroxides (P, Sr, Pb, U, Bi, Th, Y, and REE), manganese hydroxides (Co, Ni, Cu, Zn, Cd, Mo, Tl, W), and lithogenous component trapped during nodule growth (Ga, Rb, Ba, and Cs). The Ce accumulation in the REE composition is maximal in the upper and lower parts of the nodule characterized by the minimal Mn/Fe values. The compositional comparison of manganese micronodules and surface layers of the nodule demonstrated that the micronodule material was subjected to a more intense reworking during the diagenesis of sediments. The micronodules are characterized by higher Mn/Fe and P/Fe ratios but lower Ni/Cu and Co/Ni ratios. The micronodules and nodules do not differ in terms of contents of Ce and Th that are least mobile elements during the diagenesis of elements. Differences in the chemical composition of micronodules and nodules are related not only to the additional input of Mn in the process of diagenesis, but also to the transformation of iron oxyhydroxides after the removal of Mn from the close association with Fe formed in the suspended matter at the stage of sedimentation.     

Chemical and structural control of the partitioning of Co, Ce, and Pb in marine ferromanganese oxides

The oxidation state and mineral phase association of Co, Ce, and Pb in hydrogenetic, diagenetic, and hydrothermal marine ferromanganese oxides were characterized by X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectroscopy and chemical extraction. Cobalt is trivalent and associated exclusively with the Mn oxide component (vernadite). Cerium is tetravalent in all genetic-type oxides (detection limit for Ce(III) ∼ 5 at. %), including Fe-rich areas (ferrihydrite) of hydrogenetic oxides, and is associated primarily with vernadite. Thus, the extent of a Ce anomaly does not result from variations in redox conditions, but appears to be kinetically controlled, decreasing when the growth rate increases from hydrogenetic to diagenetic to hydrothermal oxides. Lead is divalent and associated with Mn and Fe oxides in variable proportions. According to EXAFS data, Pb is mostly sorbed on edge sites at chain terminations in Fe oxide and at layer edges in Mn oxide (ES complex), and also on interlayer vacancy sites in Mn oxide (TCS complex). Sequential leaching experiments, spectroscopic data, and electrochemical considerations suggest that the geochemical partitioning in favor of the Mn oxide component decreases from Co to Ce to Pb, and depends on their oxidative scavenging by Mn and Fe oxides.     

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.     

Do manganese nodules grow or dissolve after burial? Results from the Central Indian Ocean Basin

Fifty buried manganese nodules at different depth intervals were recovered in 12 sediment cores from the Central Indian Ocean Basin (CIOB). A maximum of 15 buried nodules were encountered in one sediment core (AAS-22/GC-07) and the deepest nodule was recovered at 5.50 m below seafloor in core AAS-04/GC-5A. Approximately 80% of the buried nodules are small in size (2 cm diameter) in contrast to the Atlantic Ocean and Peru Basin (Pacific Ocean) where the majority of the buried nodules are large, 8 cm and >6 cm, respectively. Buried nodule size decreases with core depth and this distribution appears to be similar to the phenomenon of “Brazil Nut Effect”. Buried nodules exhibit both smooth and rough surface textures and are ellipsoidal, elongated, rounded, sub rounded, irregular and polynucleated. Buried nodules from siliceous ooze are enriched in Mn, Cu, Ni, Zn, Mo, Ga, V and Rb whereas those from red clay are enriched in Fe, Co, Ti, U, Th, Y, Cr, Nb and Rare Earth Elements (REE). Buried nodules from siliceous ooze suggest their formation under hydrogenetic, early digenetic and diagenetic processes whereas those from red clay are of hydrogenetic origin.REE are enriched more than 1.5 times in buried nodules from red clay compared to siliceous ooze. However, the mode of incorporation of REE into buried nodules from both sedimentary environments is by a single authigenic phase consisting of Fe–Ti–P. Shale-normalized REE patterns and Ce anomalies suggest that nodules from siliceous ooze formed under more oxidizing conditions than those from red clay. Nodules buried at depths between 1.5 and 2.5 m are diagenetic (Mn/Fe ratio 10–15), formed in highly oxic environments (large positive Ce anomalies) and record aeolian dust (high Eu anomalies). Chemical composition, surface texture and morphology of buried nodules are similar to those of surface nodules from the same basin. Furthermore, buried nodule compositions do not exhibit any distinct patterns within the core depth, suggesting that buried nodules neither grow nor dissolve after their burial in the sediment column.     

太平洋北部铁锰结核富集区沉积物的元素地球化学特征

本文对太平洋北部铁锰结核富集区沉积物的元素地球化学作了较为详细的研究。因子分析提供的信息表明,元素的分布主要受三个因子控制:（1）粘土及Fe、Mn氧化物水化物胶体的吸附作用;（2）生物化学作用过程有关的自生沉积作用;（3）海底页岩风化及附近海区的火山喷发作用。元素的来源:（1）Fe、Mn、Cu、Co、Ni、Zn、Cr、Cr、Mg、Al、Ti、K共生,主要来自粘土吸附;（2）C_有机、N、Sr、Na及Si、Ca、Sr主要来自生物化学过程沉积;（3）Pb主要来源于岩石碎屑（火山喷发碎屑）。