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。     

南海铁锰结核(壳)的元素地球化学研究

本文利用南海11个铁锰结核(壳)样品的化学分析资料,研究了铁锰结核(壳)中Fe,Mn,Cu,Co,Ni,Pb,Zn,Cr,K,Na,Ca,Mg,Si,P,Al,Ti,Sr,Ba及∑REE的元素地球化学特征。结果表明:(1)铁锰结核(壳)以高Fe,∑REE,低Mn,Cu,Co,Ni等元素为主要特征;(2)铁锰结核(壳)中Fe,Mn间无明显相关,而Fe与∑REE,∑Ce,∑Y呈弱的正相关,Mn与∑REE,∑Ce,∑Y呈明显的正相关,结壳中Fe,Mn与Si,Al,Cu Co Ni呈负相关;(3)结核(壳)中Mn/Fe与Cu/Ni,Ce/La呈负相关,Mn/Fe主要受Mn控制;(4)结核(壳)中Fe,∑REE等元素主要来自南海陆源中酸性岩类的风化、淋滤和沉积。     

南海铁锰结核(壳)的稀土元素地球化学

于1987年5—6月间,中、西德在南海进行地球科学调查,获得5个铁锰结壳、6个铁锰结核样品。本文在利用X荧光法测定15个稀土元素的基础上,对南海铁锰结核(壳)的稀土丰度、配分模式与伴生元素的关系以及稀土的来源作了较为详细的探讨。研究表明,南海铁锰结核(壳)的平均丰度为1625×10~(-6),铁锰结核为2167×10~(-6),分别要比太平洋结核高1—2倍,比太平洋北部沉积物高3—4倍,比南海沉积物高10—20倍;结核和结壳的稀土经球粒陨石标准化后的配分模式基本相同,Ce正异常,Eu亏损不明显;与伴生元素、沉积物及岩石稀土对比研究表明,结核(壳)中稀土主要来自南海中酸性岩类风化、淋漓后缓慢沉积。     

第八章 锰结核（壳）资源

(一)南海锰结核(壳)的分布 这次在南海北部陆坡及中西沙地体上进行岩石拖网时,共采集到锰结核(壳)132kg,在较成功的拖网中,几乎每网都获得锰结核(壳),有些是以较厚较大的锰结壳为主,有的采集到较大的锰结核,有的是在采集到的岩样表面有0.5mm左右的锰结皮。联邦德国在南沙地区的SO23和SO27航次中,至少有4个站位取得了锰结核(壳),这是我国首次在南海发现较大量的锰结核(壳)资源。     

南海北部铁锰结核成因及元素的赋存状态

为了解南海北部不同海域铁锰结核中常微量、稀土元素的赋存特点及其富集机制,采用化学淋滤法提取南海北部上陆坡、下陆坡、深海盆3个区域铁锰结核的碳酸盐相、铁锰氧化相、残渣相组分,测定了常微量元素、稀土元素含量,揭示了不同相的元素赋存状态及其意义。Fe-Mn-(Cu+Co+Ni)判别图表明,上陆坡铁锰结核属于与冷泉流体相关的水成成因类型;下陆坡区和深海盆的铁锰结核形成环境相似,属于典型的水成成因类型。结核中K、Ca、Na、Mg、Sr主要富集在碳酸盐相,Fe、Mn、Ni、Cu、Zn、Pb主要赋存在铁锰氧化物相,Al、Ti和Mo主要出现在残渣相。常微量元素赋存状态变化受多种因素影响,钙质生物生产力的强弱和钙质生物碎屑的稀释作用是影响铁锰结核中碳酸盐相态元素变化的重要原因。铁锰结核的稀土元素主要富集在铁锰氧化物相,其次在碳酸盐相,而在残渣相的相对含量极少。不同海区铁锰结核稀土元素进入碳酸盐相的成因和机制基本相似,下陆坡和深海盆铁锰结核残渣相稀土元素配分模式相似,而与上陆坡铁锰结核的明显不同,残渣物质的来源、结核生长环境的氧化还原状态差异是主要影响因素。研究成果可为深入研究铁锰结核的元素迁移与转化、成矿作用与成矿物质来源及其相关的沉积环境、资源潜力评价等提供重要的基础资料。     

铁锰结核结壳生长过程的一种理论假设

铁锰结核成矿物质的直接来源是大洋底层水和沉积物孔隙水，结壳只有底层水，因此，底层水和孔隙水的物理化学特征就成为理解铁锰结核（壳）成矿作用特征与过程的关键。铁锰结核（壳）内部构造的两个明显特征是：①韵律性的环状纹层构造，和②树枝状构造，这两种构造是典型的远离平衡的非线性地质作用的产物。正常情况下，海底水—沉积物界面系统的底层水、孔隙水中Ｍｎ、Ｆｅ是不饱和的。因此，铁锰结核（壳）不可能在平衡状态下连续生长。本文提出铁锰结核（壳）生长的自反馈“振荡式”模型。     

论海洋底铁锰结核（壳）核心物质的起源

本文论述了海洋底铁锰结核（壳）核心物质的起源。不仅剖析了铁锰结核（壳）核心物质的研究历史与现状，时空分布及其属性，而且揭示了铁锰结核（壳）核心物质的起源、演化、现今性状与内在的规律性联系；同时还建立了铁锰结核（壳）五元核心物质分类模式；并且提出了铁锰结核的积成、裂解、再生和再造等一系列观点，指出了在铁锰结核（壳）矿床学研究领域的理论和实际意义。     

南海海盆和陆坡锰结核的特征及地球化学的初步研究

自1979年起,中国科学院南海海洋研究所沉积研究室在南海进行海洋沉积调查以来,多次在南海海盆及陆坡采到锰结核,虽曾作过报道,尚欠系统的分析研究.近几年来,我们对所采集的各种形态的锰结核,分别进行了较系统的显微镜下鉴定,配合扫描电镜观察、电子探针及能谱分析、矿物X射线衍射分析及生长速率的测定,进而对南海海盆及陆坡锰结核的特征、分布规律及形成机制进行分析研究,为进一步普查南海铁锰矿产资源提供资料。     

铁锰结核壳生长过程的一种理论假设

铁锰结核成矿物质的直接来源是大洋底层水和沉积物隙水，结壳只有底层水，因此，底层水和孔隙水的物理化学特征就成为理解铁锰结核（壳）成矿作用特征与过程的关键。铁锰结核（壳）内部构造的两个明显特征是：①韵律性的环状纹层构造，和②树枝状构造，这两种构造是典型的远离平衡的非线地质使用的产物。正常情况下，海底水－沉积物界面系统的底层水，孔隙水中Ｍｎ，Ｆｅ是不饱和的。因此铁锰结核（壳）不可能在平衡状态下连续生长     

南海东北部大陆斜坡铁锰结核的首次发现

继1979年我们在南海东北部33站(117°58＇50″E,21°30＇00″N),水深1450米处发现似铁锰结核后,我们又于1982年在23站(118°00＇4″E,21°31＇07″N),水深1656米的大陆坡发现铁锰结核(含铁29.06％,锰22.27％——电子探针分析)。 关于南海锰结核的报道,在深海盆不断有所发现。六十年代,美国海军海洋局H.W.Dubach提出“…南海整个深水地区所有沉积物中都发现了锰结核或小的结核体,但不     

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。     

中国海域固体矿产资源分布及其区划——砂矿资源和铁锰(微)结核-结壳

综述和研究了我国海域砂矿资源和(微)结核—结壳的分布及其区划。我国的滨海砂矿广泛分布于渤海、黄海、东海和南海,但各省区的砂矿资源分布不同。近年来在我国海域新发现和圈定了多处砂矿品位异常区和矿物高含量区,可分为3个成矿带和24个成矿远景区,资源储量可观。在黄海、东海仅分布铁锰结核,没有发现铁锰结壳,但它们的金属元素含量低,没有潜在资源意义。南海东北陆坡、中央海盆西部和中部是(微)结核、结壳分布较多的区域。南海东北陆坡、海山及其周缘坡脚处的(微)结核、结壳其稀土元素含量较高,可能具有一定的潜在经济价值,今后调查中应引起重视。     

西北太平洋多金属结核铂族元素地球化学特征

Polymetallic nodules and cobalt (Co)-rich crusts are enriched in platinum-group elements (PGEs),especially platinum (Pt) and may be important sinks of PGEs.At present,little information is available on PGEs in polymetallic nodules,and their geochemical characteristics and the causes of PGEs enrichment are unclear.Here PGEs of polymetallic nodules from abyssal basin in the Marcus-Wake Seamount area of the Northwest Pacific Ocean are reported and compared with the published PGEs data of polymetallic nodules and Co-rich crusts in the Pacific.The total PGEs (ΣPGE) content of polymetallic nodules in study area is 258×10~(–9) in average,markedly higher than that of Clarion-Clipperton Zone (CCZ) nodules (ΣPGE=127×10~(–9)) and lower than that of Co-rich crusts in the Marcus-Wake Seamount (ΣPGE=653×10~(–9)),similar to that of Co-rich crusts in the South China Sea(ΣPGE=252×10~(–9)).The CI chondrite-normalized PGEs patterns in different regions of polymetallic nodules and cobalt-rich crusts are highly consistent,with all being characterized by positive Pt and negative Pd anomalies These results,together with those of previous studies,indicate that PGEs in polymetallic nodules and Co-rich crusts are mainly derived directly from seawater.Pt contents of polymetallic nodules from the study area are negatively correlated with water depth,and Pt/ΣPGE ratios in nodules there are also lower than those of the Corich crusts in the adjacent area,indicating that sedimentary water depth and oxygen fugacity of ambient seawater are the possible important controlling factors for Pt accumulation in crusts and nodules.     

Marine mineral resources of the South China sea

Abstract

The South China Sea is located within the domain of a plate triple‐junction and can be divided into five major geotectonic blocks that control the formation and distribution of the mineral resources of the region: (1) the southern China faulted block, (2) the eastern Indochina faulted block, (3) the Nansha‐Borneo faulted block, (4) the Taiwan‐Luzon faulted block, and (5) the central ocean basin faulted block. Apart from oil and gas, the most intensively exploited mineral deposits in the South China Sea are near‐shore placer minerals of titaniferous magnetite, zircon, monazite, tin, gold, and chromite. Based on analyses of submarine morphology and sea level change during the past 15,000 years, the South China Sea continental shelves are considered to be highly prospective for additional placer occurrence associated with such submarine features as: submerged platforms and terraces, drowned rivers and sand bars, ancient beaches, and seafloors covered by relict sediments. Additionally, based on available data, polymetallic sulfides and manganese nodules and crusts are considered as speculative resources of the future in the South China Sea.     

Copper and zinc isotope variations in ferromanganese crusts and their isotopic fractionation mechanism

Ferromanganese(Fe-Mn) crusts are potential archives of the Cu and Zn isotope compositions of seawater through time. In this study, the Cu and Zn isotopes of the top surface of 28 Fe-Mn crusts and 2 Fe-Mn nodules were analysed by MC-ICP-MS using combined sample-standard bracketing for mass bias correction. The Zn isotope compositions of the top surface of Fe-Mn crusts are in the range of 0.71‰ to 1.08‰, with a mean δ~(66) Zn value of 0.94‰±0.21‰(2 SD, n=28). The δ~(65) Cu values of the top surface of Fe-Mn crusts range from 0.33‰ to0.73‰, with a mean value of 0.58‰±0.20‰(2 SD, n=28). The Cu isotope compositions of Fe-Mn crusts are isotopically lighter than that of dissolved Cu in deep seawater(0.58‰ vs. 0.9‰). In contrast, the δ~(66) Zn values of Fe-Mn crusts appear to be isotopically heavy compared to deep seawater(0.94‰±0.21‰ vs. 0.51‰±0.14‰). The isotope fractionation between Fe-Mn crusts and seawater is attributed to equilibrium partitioning between the sorption to crusts and the organic-ligand-bound Cu and Zn in seawater. The Cu and Zn isotopes in the top surface of Fe-Mn crusts are not a direct reflection of the Cu and Zn isotopes, but a function of Cu and Zn isotopes in modern seawater. This study proposes that Fe-Mn crusts have the potential to be archives for paleoceanography through Cu and Zn isotope analysis.     

Deep-sea Fe-Mn Crusts from the Northeast Atlantic Ocean: Composition and Resource Considerations

Eighteen deep-sea ferromanganese crusts (Fe-Mn crusts) from 10 seamounts in the northeast Atlantic were studied. Samples were recovered from water depths of ～1,200 to ～4,600 m from seamounts near Madeira, the Canary and Azores islands, and one sample from the western Mediterranean Sea.

The mineralogical and chemical compositions of the samples indicate that the crusts are typical continental margin, hydrogenetic Fe-Mn crusts. The Fe-Mn crusts exhibit a Co + Cu + Ni maximum of 0.96 wt%. Platinum-group element contents analyzed for five samples showed Pt contents from 153 to 512 ppb.

The resource potential of Fe-Mn crusts within and adjacent to the Portuguese Exclusive Economic Zone (EEZ) is evaluated to be comparable to that of crusts in the central Pacific, indicating that these Atlantic deposits may be an important future resource.     

南海东北部和珠江口沉积物的~(57)Fe穆斯堡尔谱学研究

应用57Fe穆斯堡尔诺学的方法对南海东北部和珠江口沉积物进行了Fe的价态及相对组成的研究，讨论了环境变化对南海东北部沉积物Fe的价态的影响；研究了珠江口沉积物Fe2＋／Fe3＋的比值和溶解态Fe含量与盐度的关系。     

A comparative analysis of compositional variations in and between marine ferromanganese nodules and crusts in the South Pacific and their environmental controls

Regional variation of Mn, Fe, Co, Ni and Cu in ferromanganese oxides (nodules and crusts) in the central south Pacific is related to primary productivity, oxygen minimum layer, and calcium carbonate compensation depth. The largely latitudinal influence of these environmental parameters on nodule and crust composition reflects their predominantly latitudinal variation. Primary productivity is the principal regional environmental control, influencing diagenetic enrichment of these elements in nodules through its effect, mediated by the CCD, on supply and concentration of labile organic matter vs. carbonate remains to the sediments. It influences hydrogenetic enrichment of these elements in nodules and crusts through its effect, mediated by the oxygen minimum layer (mainly in the case of crusts), on their export from surface waters.The elements’ varying susceptibility to being scavenged or organically bound influences the contrasting composition of diagenetic vs. hydrogenetic ferromanganese oxides, which is further influenced by depth. Hydrogenesis is the fundamental process governing nodule and crust formation, superimposed on which is diagenesis under specific circumstances; both are subject to intermittent interruption, diminution and augmentation by changes in environmental parameters. Application of regionally operative environmental controls locally explains local compositional variations and helps refine exploration criteria for economically viable nodules and crusts.