南海东部次海盆海山链多金属结核(壳)地球化学特征及成因

为了进一步解释南海不同区域内多金属结核（壳）的地球化学特征与成因,对东部次海盆黄岩?珍贝海山链上新获取的多金属结核（壳）样品进行了X光衍射、X荧光光谱测试、SEM-EDS分析和X Series2 ICP-MS测试,详细分析了样品的矿物组成、地球化学成分特征. 结果表明,矿物组成为水羟锰矿、石英、斜长石等;主要造岩元素中Si、Al含量较高,与陆缘碎屑物影响较大有关;富含Mn、Fe、Co、Ti、Ni、Pb、Sr等多种金属元素,相比南海其他区域,具有中等的Fe、Mn含量特征,地化元素特征与南海西北陆坡发现的铁锰结核（壳）相似;稀土元素具有总量高（平均2 070.01×10-6）的特点,高于南海北部其他样品,与西太平洋结壳稀土含量接近（接近工业品位）,指示了重要的稀土资源前景. 结核Be同位素结果指示该区铁锰结核生长时代为1.17~8.51 Ma,形成于晚中新世大量火山喷发之后,因此水成作用是南海东部次海盆海山链结核（壳）的主要控制作用,而陆源物质的输入、火山作用和高压富氢离子海水的浸取作用都为结核（壳）的形成提供了有利的沉积环境.      

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.     

太平洋多金属结核和富钴结壳稀土元素地球化学对比及其地质意义

多金属结核和富钴结壳是大洋两类典型的铁锰产物。为探讨不同海区多金属结核和富钴结壳之间稀土元素特点及其揭示的地质意义,利用近年中国在太平洋获取的样品进行对比,采用ICP-AES对稀土元素测试。结果表明,结壳具有正Ce异常明显、LREE富集、∑REE高的特点,而结核表现为HREE相对富集、∑REE相对较低,因成因类型不同,Ce异常或表现为正异常、负异常或异常不明显。结核形成后受到成岩作用的影响,而结壳则为水成作用形成;结核和结壳中REE的存在形式比较复杂,不同海区各不相同,中太平洋东部产出的结壳和位于东太平洋的结核中REE可能主要赋存于铁矿物相,而西太平洋结壳REE可能主要赋存于锰矿物相;结核和结壳REE可能分别来自海水和海山蚀变玄武岩,热液作用影响有限。     

A specific type of Fe-Mn mineralization on the Arctic seafloor

Three samples of Fe-Mn crusts overgrown on the surface of rocks are studied from the Mendeleev submarine rise located in the northern subpolar part of the Chukchi Sea. A massive crust up to 4–5 cm thick consists of an upper dense and lower denser layers similar in composition to the main one and contains 31–37% FeO and 11–13% MnO. Thin crusts and films are depleted in both components. Fe-vernadite is a major mineral of the crusts. The comparison of the major and trace element composition of the crusts with oceanic and marine nodules and hydrothermal crusts shows that they are mostly similar in composition to the nodules of the Bering Sea and are significantly distinct from the oceanic hydrothermal crusts. A small inclusion of the Pt-, Pd-, and Ru-rich (up to 1–2%) rock in one of the thin crusts points to the possible role of igneous rocks as a source of precious metals.     

Rare Earth Elements Composition and Constraint on the Genesis of the Polymetallic Crusts and Nodules in the South China Sea

The rare earth elements(REE) composition of the polymetallic crusts and nodules obtained from the South China Sea(SCS) were analyzed through inductively coupled plasma mass spectrometry.Results revealed great differences in the REE abundances(∑REE) of the SCS polymetallic crusts and nodules; the crusts show the highest ∑REE, whereas the nodules exhibit the lowest ∑REE. The similarity in their NASC-normalized patterns, the enriched light REE(LREE), the markedly positive Ce anomaly(δCe), and the non-or weakly positive Eu anomaly(δEu), suggest that the polymetallic crusts and nodules are of hydrogenetic origin. Moreover, the REE contents and their relevant parameters are quite different among the various layers of the crusts and nodules, which probably results from the different marginal sea environments and mineral assemblages of the samples. The growth profiles of the SCS polymetallic crusts and nodules reveal the tendency ∑REE and δCe to slightly increase from the outer to the inner layers, suggesting that the growth environments of these samples changed smoothly from an oxidizing to a relatively reducing environment; in addition, the crust ST1 may have experienced a regressive event(sea-level change) during its growth, although the REE composition of the seawater remained relatively stable. On the basis of the regional ∑REE distribution in the SCS crusts and nodules,the samples collected near the northern margin were influenced by terrigenous material more strongly compared with the other samples, and the REE contents are relatively low. Therefore, the special geotectonic environment is a significant factor influencing the abundance of elements, including REE and other trace elements. Compared with the oceanic seamount crusts and deep-sea nodules from other oceans,the SCS polymetallic crusts and nodules exhibit special REE compositions and shale-normalized patterns, implying that the samples are of marginal sea-type Fe-Mn sedimentary deposits, which are strongly affected by the epicontinental environment, and that they grew in a more oxidative seawater environment. This analysis indicates that the oxidized seawater environment and the special nano property of their Fe-Mn minerals enrich the REE adsorption.     

太平洋海山钴结壳资源量估算

为合理地估算出太平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以及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, 创造性地按海山不同高度、不同洋壳年龄赋予不同结壳厚度, 进而首次计算出太平洋海山干结壳资源量为(507.06~1 014.11)×108 t, 锰为(111.15~222.29)×108 t, 钴为(3.04~6.08)×108 t, 镍为(2.23~4.46)×108 t, 铜为(0.66~1.32)×108 t, 结壳分布面积为2 062 862 km2.通过Co通量与结壳Co沉积量、结壳厚度的相关分析表明, 赋予不同洋壳年龄段的结壳厚度是理论厚度的6.10%~12.20%, 这与Ku et al.得出"结壳生长时间只占其整个生命史4%"的认识非常相近, 说明所赋结壳厚度基本合理, 得出的结壳资源量基本正确.为整个大洋海盆内海山钴结壳资源量的估算提供了新方法.      

海底金属矿产资源的开发--回顾与未来展望

占地球面积70％的海洋蕴藏着巨量的矿产资源。文章简要回顾了铁锰结核、富钴结壳及热液硫化物等海底金属矿产资源开发研究的进展、经验和挫折,并通过综合分析指出,海洋矿产资源的开发是新世纪的必然趋势,而新近在西南太平洋发现的浅成低温热液金矿可能成为海洋金属矿产开发研究的热点。     

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。     

Comparison of elemental accumulation rates between ferromanganese deposits and sediments in the South Pacific Ocean

Rates of accumulation of Fe and Mn, as well as Cu, Ni, Co, Pb, Zn, Hg, U and Th have been determined for five ferromanganese deposits from four localities in the South Pacific Ocean.Manganese is accumulating in nodules and crusts at a rate roughly equivalent to that found to be accumulating in sediments in the same area. Iron shows a deficiency in accumulation in nodules and crusts with respect to sediments, especially near the continents, but also in the central and south-central Pacific. Copper is accumulating in nodules and crusts at a rate one order of magnitude less than the surrounding sediments.This is interpreted as meaning that most of the Mn is supplied as an authigenic phase to both sediments and nodules while Fe is supplied mostly by ferromanganese micro-nodules and by detrital and adsorbed components of sediments; and Cu is enriched in sediments relative to nodules and crusts most probably through biological activity.     

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。     

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.     

翡翠的皮壳组成及其与内部玉石质量关系初步研究

在对广东南海平洲、广州花都国际翡翠展销会等翡翠原料集散地大量现场考察的基础上,选取了具有黄色色调、白色和灰黑色皮壳的翡翠原石样品,经肉眼和偏光显微镜观察、X射线粉末衍射和电子探针测试,研究了不同颜色系列翡翠原石皮壳的矿物组成和化学成分特征。结果表明,不同颜色翡翠皮壳的主要矿物均为硬玉,次要矿物则有所不同。黄色皮壳含高岭石、三水铝石、软锰矿和赤铁矿等,白色皮壳含高岭石和水钙铝榴石,黑色皮壳则含高岭石和绿泥石类矿物。与内部玉石成分相比,皮壳中的主要化学成分硼（Na2O）和w（SiO2）有所降低,而w（CaO）和w（MgO）及Fe的质量分数则相对增加;黄色皮壳翡翠中Fe的质量分数越高,则皮壳的黄色色调越深,但皮壳的化学成分受环境影响较大,难以用于判断其内部玉石质量。仅初步总结了翡翠皮壳矿物组成与其内部玉石质量的关系。     

Composition and distribution of REE in ferromanganese crusts of the Belyaevsky and Medvedev seamounts in the Sea of Japan

This paper presents the results of the integrated study of ferromanganese crusts from the Belyaevsky (Central Basin) and Medvedev (Honshu Basin) seamounts from the Sea of Japan. The study of the mineral composition using powder diffraction and optical and electron microscopy showed that the crusts are made up of todorokite, birnessite, and pyrolusite minerals typical of hydrothermal ferromanganese deposits of the World Ocean. The composition of the ferromanganese crusts from the Sea of Japan was determined by ICP-MS and ICP-OES. The contents of Mn, Fe, Co, Cu, Ni, and other major and trace elements indicate the hydrothermal genesis of the crusts. The obtained data on the composition of ferromanganese crusts of the Sea of Japan, as well as their comparison with different types of deposits of the World Ocean, suggest the endogenic genesis of the studied crusts. However, the REE and Y distribution patterns testify to a significant admixture of hydrogenic matter, which participated in the growth of ferromanganese crusts from the Belyaevsky and Medvedev seamounts.     

我国深海矿产研究:进展与发现(2011—2020)

深海矿产是地球上尚未被人类充分认识和利用的最大潜在战略矿产资源,近十年我国在该领域的研究取得了重要进展。在太平洋国际海底区域申请到2块多金属结核勘探区、1块富钴结壳勘探区,在西南印度洋中脊申请到1块多金属硫化物勘探区。研究阐明了我国多金属结核和富钴结壳勘探区小尺度成矿规律,揭示了其成矿作用过程及古海洋古气候记录,探讨了关键金属元素富集机制。在西南印度洋、西北印度洋和南大西洋中脊发现了多处热液区,阐述了其成矿作用及控制因素,建立了超慢速扩洋中脊热液循环模型,探讨了拆离断层型热液成矿系统的成矿机制。在太平洋和印度洋划分了4个深海稀土成矿带,在中印度洋海盆、东南太平洋和西太平洋深海盆地发现了大面积富稀土沉积区,初步揭示了深海稀土的富集特征、分布规律、赋存状态和成矿机理。今后在继续加大深海矿产资源调查研究的同时,应聚焦深海关键金属成矿作用研究。     

Structure, chemistry and origins of gypsum crusts in southern Tunisia and the central Namib Desert

Gypsum crusts are broadly defined as accumulations at or within about 10 m of the land surface from 0.10m to 5.0 m thick containing more than 15% by weight gypsum (CaSO₄·2H₂O) and at least 5.0% by weight more gypsum than the underlying bedrock. The deposits are often, but not invariably, consolidated owing to cementation by gypsum. The crusts are found in many of the world's deserts where mean monthly potential evaporation exceeds mean monthly precipitation throughout the year. Using structural, fabric and textural criteria, three main types of crust may be distinguished:(1) bedded crusts, found either at or beneath the land surface, which are made up of discrete horizontal strata up to 0.10 m thick, each showing a gradation in gypsum crystal size from less than 50 μm at the top to more than 0.50 mm at the base; (2) subsurface crusts, of which there are two forms, one made up of large, lenticular crystals (up to 0.50 m in diameter)—the desert rose crusts—and the other, a mesocrystalline form, with gypsum crystals up to about 1.0 mm in diameter; and (3) surface crusts, which are subdivided into columnar, powdery and cobble forms, all of which are made up of predominantly alabastrine gypsum (crystallites less than 50 μm in diameter). In southern Tunisia and the central Namib Desert, bedded crusts are found around ephemeral lakes and lagoons. They are characterized by size-graded beds, gypsum contents of 50–80% by weight and comparatively high concentrations of sodium, potassium, magnesium and iron. They are interpreted as shallow-water evaporites which accumulate when saline pools evaporate to dryness. Desert rose crusts or croûtes de nappe generally contain 50–70% by weight gypsum, and have higher sodium concentrations than the second subsurface form. Texturally they are characterized by poikilitic inclusion of clastic material within large lenticular crystals. They are interpreted as hydromorphic accretions, which precipitate in host sediments at near-surface water tables through the evaporation of groundwater. The second form of subsurface crust—the mesocrystalline—often occurs in close association with the various surface forms. Unlike the hydromorphic crusts, they are not restricted to low-lying terrain. They are characterized by gypsum contents reaching 90% by weight, and have a close chemical and textural similarity to columnar surface crusts. This mesocrystalline form represents an illuvial accumulation; the surface forms—excluding the bedded crusts—are exhumed examples at various stages of solutional degradation. Subsurface precipitation of gypsum from meteoric waters containing salts leached from the surface, results in displacive gypsum accumulation in the soil zone. In southern Tunisia, the gypsum is derived from sand and dust deflated from evaporitic basins; in the central Namib, salts dissolved in fog water are the most likely source. Where other salts are present, differential leaching may form two-tiered crusts, calcrete—gypsum or gypsum—halite, if rainfall is sufficient to mobilize the less soluble salt yet insufficient to flush the more soluble. Gypsum crust genesis is restricted to arid environments, and if their susceptibility to post-depositional alteration is acknowledged, they can provide valuable palaeoclimatic indicators.     

The variation of morphological features and mineralogical components of biological soil crusts in the Gurbantunggut Desert of Northwestern China

Increasingly complex life forms were found in older biological soil crusts in the Gurbantaunggut Desert in Northwestern China. These crusts may play a critical role in mineral erosion and desert soil formation by modifying the weathering environment and ultimately affecting mineralogical variance. To test this hypothesis, variations in the morphological features and mineralogical components of successional biological soil crusts at 1 cm were studied by optical microscopy, SEM and grain size analysis. Concentrations of erosion-resistant minerals decreased with crust succession, while minerals susceptible to weathering increased with crust development. Neogenetic minerals were found in late stage crusts, but not in early stage crusts. Silt and clay concentrations were highest in early formation crusts and soil mean particle size decreased with crust succession. Cyanobacteria, lichen and moss were shown to erode and etch rocks, and secondary minerals produced by weathering were localized with the living organisms. Thus, more developed crusts appeared to contribute to greater mineral weathering and may be a major cause of mineralogical variance seen in the Gurbantunggut Desert. The greater activity and complexity of older crusts, as well as their improved moisture condition may function to accelerate mineral weathering. Therefore, protection and recovery of biological crusts is vital for desert soil formation.     

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.     

西太平洋富钴结壳元素组合特征及其地质意义

海山富钴结壳是一种重要的海底固体矿产。对西太平洋海山的56个结壳样品进行了23种化学组分分析,并利用R型聚类分析和R型因子分析,分别提取四组元素组合和四个主因子。综合特征表明．富钴结壳在形成过程中,经历了一次强度较大的锰矿物相成矿作用,Co、Ni等元素的富集与此有关;铁矿物相的成矿作用强度较小,但表现出多期次的特点;锰、铁矿物是不同成矿作用的产物;结壳形成过程中,可能遭受了二次磷酸盐化作用,结壳中磷酸盐矿物的形成对铁矿物相的形成可能有抑制作用。     

Petrology of recent caliche pisolites, spherulites, and speleothem deposits from central Texas

Recent caliche, including nodules, pisolites, crusts, internal sediment, speleothem deposits, and spherulites, has formed within the dolomitic Cretaceous Edwards Formation of central Texas. As weathering altered the host strata, rhombic crystals of calcite were precipitated concomitantly with dissolution of the dolomite, thereby forming nodules. The highly altered dolomite (i.e. pulverulite) was then removed and spar, internal sediment, and travertine accumulated in the internodular voids. Nodular masses of calcite and dolomite are the most prominent constituent of the caliche. Some of the nodules have a well developed concentric structure as well as other characteristics similar to hypersaline pisolites. Features which appear to be useful in distinguishing caliche from hypersaline pisolites are: regional geological setting, association with other caliche and palaeosoil deposits, types of fossils present, and the presence of rhombic calcite and/or bladed sparry calcite with triangular shaped cross-section. A brick-like calcite texture and relict aragonite rays characterize hypersaline pisolites. Incipient neomorphism of the nodules and pisolites has resulted in the development of a radial pattern of spar within these structures. Geopetal deposits of internal sediment, including terra rossa soil, inhibited spar growth in the upward direction; consequently, spar is much better developed on the undersides of pisolites. Crusts and travertine flowstone (speleothem) deposits are intimately associated with the nodular masses and internal sediment. The brecciated thin crusts and travertine flowstone are end products of the same processes. The crusts formed during times of periodic desiccation of the growing surface while the flowstone formed when water was relatively abundant. Spherulitic bodies within the caliche, commonly 1–2 mm in diameter, display a radial texture and yet are composed of single crystals of calcite. The structures are the product of neomorphosed Microcodium or Microcodium-like globular bodies.     

大洋钻探与海底矿产

深海钻探与大洋钻探发现的许多古海洋事件和古环境变化，控制着海洋矿产的形成与分布，并为研究海底成矿作用提供了大量科学资料，大洋钻探及其他有关研究已经证明，南极底层水和上升流的发育，硅质生物的高生产力，以及始新世、渐新世、中新世与上新世的沉积间断，都有利于多金属结核，富钴结壳和磷灰石的形成。因此，深海钻探和大洋钻探对于海洋成矿理论有重大贡献。