Apatite and associated minerals in ferromanganese crusts from the Magellan Seamounts

The phosphate fraction extracted from a combined technological sample of ferromanganese crusts obtained from the Magellan Seamounts (Northwest Pacific) was studied with analytical electron microscopic methods. The material examined is represented by small rock fragments composed of well crystallized calcium phosphate with pores filled in with Mn oxides consisting largely of vernadite. The rock hosts crystallized barite aggregates, disseminated ultramicroscopic cubic pyrite crystals, filamentous halloysite aggregates, and assemblages of finely dispersed REE minerals represented by cerianite and parisite, which incrust the surface of apatite or are dispersed in the phosphatic matrix. The presence of the latter minerals shows that some REE related to the phosphatic phase do not enter the apatite lattice, which might influence the general pattern of the REE distribution in bulk samples     

铁锰结壳年代学方法及其应用

铁锰结壳记录了丰富的古海洋和古气候信息,要分析这些信息,必须先确定各壳层的生长年龄。目前主要使用的定年方法有:Be同位素定年、U系同位素定年、Os同位素定年、经验公式法、古地磁地层学方法和古生物地层学方法等。每种定年方法均各有利弊,其中10Be是年龄小于10 Ma结壳的最佳定年方法; U系同位素定年精度高,但定年范围小于0.5 Ma; Os同位素定年时间尺度长,且可以判断沉积间断,但需要有区域的海水Os同位素演化曲线; Co经验公式因为简单易行,是结壳估算年龄最为常用的方法,但该法无法判断沉积间断,在使用时需特别谨慎,应确保经验公式适用于所研究的样品;如果结壳厚度大、生长速率较快且不存在沉积间断,古地磁地层学方法可以快速地进行定年;此外,如果结壳中古生物化石较多,可考虑采用古生物地层学方法。在分析铁锰结壳年代学方法利弊基础上,本文利用U系定年法、古地磁地层学法和经验公式计算法分别对南海铁锰结壳进行定年,通过比较,认为目前铁锰结壳较优的定年方法为古地磁地层学方法。     

中太平洋海山区富钴结壳地质特征

应用 X射线衍射分析、穆斯堡尔谱分析、X荧光光谱分析以及超微生物化石定年等方法对 1 998年和 1 999年“大洋一号”调查船 DY95 - 8和 DY95 - 1 0航次采集的富钴结壳样品进行了地质特征综合研究与分析 ,结果表明 :( 1 )该区富钴结壳可划分为板状结壳、砾状结壳和钴结核三类 ,均具有微晶质结构。 ( 2 )该区富钴结壳宏观构造主要呈板层状和圈层状构造 ;显微构造在形态上可大体分为柱状构造、平行纹理状构造和致密块状构造三种基本类型。 ( 3)该区富钴结壳主要由三类矿物组成 :锰矿物、铁矿物和杂质矿物。其中锰矿物为水羟锰矿和少量的钡镁锰矿 ,铁矿物主要为 β-羟铁矿 ,偶见赤铁矿和磁铁矿等 ,杂质矿物有石英、斜长石等。( 4 )该区富钴结壳主要成矿元素含量 :Fe为 1 6.86% ,Mn为 2 1 .2 6% ,Cu为 1 1 0 2 .0 9× 1 0 - 6 ,Co为 62 5 2 .72× 1 0 - 6 ,Ni为 40 64.62× 1 0 - 6 。 ( 5 )该区东部海山 ( N1～ N4海山 )比西部海山( N5、 N6海山 ) Fe元素含量高 ,Mn、 Cu、 Co、 Ni元素含量则低 ,这一差异源于海水中 Fe、 Mn等成矿元素的分离作用 ,其分离程度与海底火山作用时代以及相应的玄武岩海解风化时间长短有密切关系。 ( 6)结壳形成于第三纪古新世至第四纪更新世 :第一阶段从第三纪古新世到中新世 ,     

Cerium anomaly variations in ferromanganese nodules and crusts from the Indian Ocean

Fifty analyses of rare earth elements as well as mineralogical studies have been carried out on a suite of manganese nodules and crusts from the Central Indian Basin and the Western Indian Ocean. The aim was to identify the processes controlling the REE patterns of the phases hosting the REE in the manganese nodules, with an emphasis on an understanding of the Ce anomaly. This has involved separating the encrusting layers and nuclei physically as well as Fe-Mn oxides from the aluminosilicate phase chemically (using a 2 M HCl leach) prior to analysis.

The presence of nodule nuclei seems to have little influence (mostly <5% to a maximum of 30%) on the overall magnitude of the Ce anomalies in these nodules. The ratios of concentrations of elements in the acid leachates and the corresponding bulk values yield flat REE patterns indicating that the aluminosilicate phase contributes very little to the Ce anomalies. Interelement relations indicate that the Ce anomalies are largely controlled by the amorphous mineral phase FeOOH.xH₂O. The relationship of Fe, Ce anomaly and δ-MnO₂ further suggests that Ce is chemisorbed onto iron oxyhydroxides which are epitaxially intergrown with δ-MnO₂.

The regional distribution of the Ce anomaly values appears to depend on many of the factors responsible for the uptake of other minor metals in nodules and crusts.     

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.     

盐场海芽孢杆菌与大洋铁锰结核相互作用

本文研究了盐场海芽孢杆菌(Marinibacilluscampisalis)与大洋铁锰结核的相互作用过程,以及海洋微生物在铁锰结核形成中的作用。实验选取从深海沉积物中分离培养的盐场海芽孢杆菌(Marinibacillus campisalis)和大洋铁锰结核样品进行相互作用实验,设置有菌组和无菌组,培养过程中间隔取样分析。运用X射线荧光光谱(XRF)分析测定大洋铁锰结核元素组成,通过电感耦合等离子体发射光谱(ICP-OES)和电感耦合等离子体质谱(ICP-MS)测定反应过程中Fe、Mn、Co、Ni、Cu等离子浓度的变化,通过透射电镜(TEM)、扫描电镜(SEM)和能谱仪(EDS)观察并分析微生物表面情况,利用X射线衍射(XRD)分析手段测定铁锰结核矿物组成的变化。实验进行1天内细菌处于对数生长期,有菌组的Fe、Mn等离子浓度增加; 2—7天内细菌处于稳定期, Fe、Mn等离子浓度有一定程度降低,但总体浓度均大于无菌组的离子浓度,金属离子被吸附在菌体表面,新形成了简单的含Fe化合物和矿物;实验结束后,XRD分析结果显示样品的矿物含量,如菱铁矿、赤铁矿和针铁矿等有轻微程度的增加。研究表明盐...     

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.     

中太平洋海山铁锰结壳生物地层学研究

用生物地层学方法对位于中太平洋同一座海山上的2块铁锰结壳样品进行了生物地层学详细研究,发现2块样品的生长层位对应,生物组合也相同.经鉴定,2块结壳的主要生长期都是晚古新世、中始新世至晚始新世、中中新世至上新世、上新世至更新世,2个主要的结壳生长间断分别在渐新世和早始新世.     

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.     

西太平洋采薇海山群富钴结壳铂族元素地球化学特征与来源

为探讨富钴结壳铂族元素的来源,以西太平洋采薇海山群富钴结壳样品为研究对象,利用X射线衍射法、等离子体发射光谱法和质谱法,对富钴结壳样品进行了矿物组成、主量元素和铂族元素含量分析。研究表明,富钴结壳的主要结晶矿物为水羟锰矿,次要矿物有石英、斜长石、钾长石和碳氟磷灰石,同时含有大量非晶态铁氧/氢氧化物。富钴结壳中Mn和Fe含量最高,且明显富集铂族元素,铂族总量为142～1 352 ng/g,其中Pt为114～1 268 ng/g,占铂族总量的80%以上。老壳层的铂族元素含量高于新壳层,老壳层发生了磷酸盐化作用。富钴结壳的铂族元素之间发生了分异作用,Pd组（PPGE）含量高于Ir组（IPGE）。铂族元素配分模式显示Pt正异常和Pd负异常,具有Pt富集而Pd亏损特征,推测富钴结壳的铂族元素来源于洋壳蚀变过程中海山玄武岩和海水之间的水−岩反应。富钴结壳的铂族元素与CaO、P₂O₅、Ba和Cu正相关,推测铂族元素赋存于磷酸盐矿物相中。富钴结壳生长剖面从上到下,由新到老,铂族元素含量呈逐渐增加趋势,海水氧化性环境和高海洋生产力可增进磷酸盐化作用,从而进一步促进了铂族元素的富集。该研究对于揭示富钴结壳铂族元素的来源具有一定的参考价值。     

南海东部管事海山铁锰结壳的矿物组成和地球化学特征

对于开阔大洋海山结壳的矿物组成和地球化学特征研究已经比较深入,但对边缘海海山铁锰结壳的研究却较少。以在南海东部管事海山上采集的两块铁锰结壳为研究材料,对其进行了X射线衍射、扫描电镜及电子探针微区的分析,结果显示结壳矿物以水羟锰矿为主,含有少量针铁矿,碎屑矿物主要是石英和长石。结壳的显微结构呈现条带状分布,有10~15μm长的空隙和0.5μm直径大小的孔洞。相对于大洋结壳,结壳的Mn含量较高,与马尼拉海沟附近火山喷发物质有关,但Cu、Co和Ni含量更低,可能与边缘海沉积速率高或有机络合物吸附有关。矿物组成及元素比值表明结壳主要是水成的,但未发生明显磷酸盐化作用。元素比值和相关性表明,Mn主要来源于南海扩张停止后火山喷发、玄武岩风化形成溶解Mn;Fe与Si元素均来自火山碎屑、生源物质和陆源物质,还受到管状蠕虫吸附的影响。南海管事海山结壳是在富氧环境中上升流作用下选择性吸附水体中溶解化学元素缓慢沉积而成。结壳中元素含量随时间变化趋势反映了南海的古环境变化。     

Comparison of internal features and microchemistry of ferromanganese crusts from the Central Indian Basin

SEM/probe analyses of two ferromanganese crusts from the Central Indian Basin, formed on basalt substrate, reveal botryoids and cusps. The botryoids composed of δ-MnO₂, are enriched in Co, and the cusps and laminations with todorokite are enriched in Ni and Cu. Microstructural and elemental variations, from the ferromanganese crust outer surface to the basalt substrate, probably reflect changes in the accretion or in the source of metals. The major source of the crust metals is the seawater, as indicated by the Mn/Fe ratio of unity and by the microstructures.     

Biomineralization of organic matter in cobalt-rich crusts from the Marcus–Wake Seamounts of the western Pacific Ocean

Organic matter in cobalt-rich crust(CRC) from the Marcus–Wake Seamounts of the western Pacific Ocean, Sample CM1D03, has been analyzed to understand the source, geochemistry and mineralization of organic matter, and the mineralization environment. Biomarkers, including n-alkanes, isoprenoids, terpanes and sterols, have been detected in various layers of the CRC sample, using gas chromatography(GC) and gas chromatography–mass spectrometry(GC–MS). The content of organic carbon(OC) and its stable isotope(δ13C), and the combined features of the biomarkers show that the mineralized organic matter in CM1D03 CRC was mainly derived from microorganisms and lower plankton(e.g., bacteria and algae, respectively) from marine surface water, with some terrestrial higher plant components. The ratio of chloroform bitumen "A": OC was high in the CRC, between 10.51 and 20.66, showing significant migration characteristics of n-alkanes. Four mineralization categories of organic matter were recognized based on GC chromatograms of n-alkane molecules:(1) primitive type(bacteria and algae), which is characterized by moderately mature of n-alkanes preserving the original characteristics of the organic matter from microorganisms and lower plankton;(2) microbial degradation type, which is characterized by low contents of n-alkanes and rising baseline in the chromatogram, with the "bulge" being the products of organic matter by biodegradation;(3) organic matter migration type, which is characterized by low carbon number of n-alkanes with n C18 as the main peak carbon, without odd even predominance, and low concentrations of isoprenoids and hydrocarbons with high carbon number; and(4) organic matter hydrothermal type, which is characterized by relatively low concentration of small molecular weight n-alkanes, pristane, and phytane, accompanied by higher concentration of n-alkanes with carbon number greater than n C18. This study shows that biomarkers can record controlling factors of mineralization and their variation.     

九州-帕劳海脊南段铁锰结壳物质组成特征及成因机制

铁锰结壳（又称富钴结壳、多金属结壳）富含Co、Cu、Mn、Ni、Ti、V、REE、Y和Zn等人类日常生活和高新技术产业亟需的关键金属,是一种重要的战略性矿产资源。本文对九州-帕劳海脊南段水深1900～2600 m处获得的9个站位铁锰结壳样品进行了矿物学和地球化学研究,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,研究区铁锰结壳的矿物组成以水羟锰矿为主,同时含有大量非晶态铁氧/氢氧化物;Mn、Fe、Co、Ni、Cu平均含量分别为16.15%、15.38%、0.32%、0.33%、0.10%;CaO/P2O5均值为5.93,表明九州-帕劳海脊南段铁锰结壳样品均未发生磷酸盐化作用;铁锰结壳明显富集稀土元素（含Y,REYs）,平均含量为1194 μg/g,轻稀土显著富集,稀土元素经后太古代澳大利亚页岩（PAAS）标准化后配分模式整体相对平坦,呈现Ce正异常而Eu无异常,与海水呈现镜像关系,说明铁锰结壳稀土元素主要来源于海水。铁锰结壳的矿物组成和元素判别图均表明九州-帕劳海脊南段铁锰结壳属于水成型,未受明显的成岩作用影响。     

Microbial activity promotes the enrichment of cobalt over nickel on hydrogenetic ferromanganese crusts

The different mineral phases of the ferromanganese (Fe–Mn) crusts stem from the interaction of biotic and abiotic components. It is therefore vital to study the activity of these components to decipher their contribution to the enrichment/depletion of metals in the crust. Thus, the present study examined sorption and release of Co and Ni by Fe-Mn crusts with associated microbial communities in the presence and absence of the metabolic poison sodium azide (15?mM). The study was conducted in the presence (G⁺) and absence (G^?) of added glucose (0.1%) at temperatures of 4?±?1°C and 28?±?2°C. Results showed that the microbial community had maximal sorption of Co of 66.12?µg?g^?1 at 4?±?1°C in the absence of added glucose and 479.75?µg?g^?1 at 28?±?2°C in the presence of added glucose. Maximum sorption of Ni in the absence of added glucose was 1.89?µg?g^?1 at 4?±?1°C and release of Ni was 51.28?µg?g^?1 in the presence of added glucose. Under abiotic conditions with 15?mM sodium azide as a metabolic inhibitor, significant amounts of Co and Ni were released in the G⁺ medium. Total cell counts on the Fe-Mn crust in the presence of added glucose increased by an order of magnitude from 10⁶ to 10⁷ cells g^?1 and in the absence of added glucose remained within the order of 10⁶ cells?g^?1 irrespective of temperature of incubation. Microscopic observation of the samples from biotic incubations showed numerous bacterial cells, exopolysaccharides, and structures resembling secondary minerals formed by bacteria. The results indicate that bacteria promote the enrichment of Co and Ni on the hydrogenetic Fe-Mn crusts by sorption processes and release of Ni by reductive dissolution of the oxides. The higher enrichment of Co than Ni is attributed to the way in which microbes interact with the metals.     

Occurrence forms and distribution of precious and base metals in ferromanganese crusts from the Sea of Japan

The examination of polished sections of ferromanganese crusts from the Sea of Japan revealed abundant inclusions of small grains of base and precious metals: Ag, Pd, Pt, Au, Rh, Cu, Zn, Sn, P, Ni, Cr, Ti, Sb, As, W, and Mo. The metals occur in the form of native elements or intermetallic compounds, subordinate sulfides, sulfates, oxides, tungstates, and phosphides. The data on contents, occurrence forms, and distribution of these metals in the ore crusts from this region are discussed.     

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 and yttrium）平均含量为1 366 mg/kg,低于前人在麦哲伦海山区其他海山以及邻近的马尔库斯–威克海山区的分析结果;样品轻稀土富集和Ce正异常（平均值为1.45）特征以及稀土元素成因图解、配分曲线和分配系数曲线等均表明该海山结壳属于水成成因;海水中稀土元素含量和溶解氧含量是控制结壳生长的关键环境参数,二者在Kocebu海山所在海区的浅水环境中含量较低;结壳ΣREY含量偏低与采样点水深较浅导致的海水稀土元素含量和溶解氧含量较低密切相关,受碎屑矿物的稀释作用影响较小。在开展铁锰结壳地球化学特征研究和资源勘探评价时应充分考虑采样水深的分布范围,局部水深样品的分析结果可能导致研究结果出现较大偏差。     

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.     

东菲律宾海深水铁锰结壳发育站位沉积物的粒度及黏土矿物学特征

大洋铁锰结壳是潜在的重要海洋资源,多年来世界各国对此已作了大量调查.传统意义上的铁锰结壳均分布于3000m水深以浅的海山基岩上.中国科学院海洋研究所在对东菲律宾海的地质调查中采集到大量褐黑色深水铁锰结壳.在300多个站位的取样中,在44个站位采集到结壳样品,可见结壳在研究区的分布较为广泛.该结壳发育于4000~5000m水深的致密至半固结沉积物的表层,厚度一般为2~3cm,最厚可达7cm.结壳为板(层)状.     

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.