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.     

中太平洋铁锰结壳碘分布及磷酸盐化对其影响

In the present paper, iodine(I), iron(Fe), manganese(Mn), cobalt(Co), phosphorus(P) and calcium(Ca)contents in three ferromanganese crusts from the Pacific Ocean are measured by spectrophotometric method and inductively coupled plasma atomic emission spectrometers(ICP-AES) to investigate the contents and distribution of iodine in ferromanganese crusts. The results show that iodine contents in three crusts vary between 27.1 and 836 mg/kg, with an average of 172 mg/kg, and the profile of iodine in the three crusts all exhibits a two-stage distribution zone: a young non-phosphatized zone and an old phosphatized zone that is rich in I, P and Ca. The iodine content ratios of old to young zone in MP5D44, CXD62–1 and CXD08–1 are 2.3, 3.4 and 13.7, respectively.The boundary depths of two-stage zone in MP5D44, CXD62–1 and CXD08–1 locate at 4.0 cm, 2.5 cm and 3.75 cm,respectively, and the time of iodine mutation in three crusts ranges from 17–37 Ma derived from 129 I dating and Co empirical formula, which is consistent with the times of Cenozoic phosphatization events. The present study shows that the intensity of phosphatization is the main responsible for the distribution pattern of iodine in the crusts on the basis of the correlation analysis. Consequently, iodine is a sensitive indicator for phosphatization.     

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。     

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.     

Fine-scale compositional variations in a Co-rich Mn crust from the Marcus-Wake Seamount cluster in the western Pacific based on electron microprobe analysis (EMPA)

The internal structure and composition of a 37-mm-thick Co-rich Mn crust from the Lamont Guyot in the Marcus-Wake Seamount cluster have been studied in detail by means of electron-probe microanalysis (EPMA). 184 point analyses for 16 elements were carried out at an average spacing of 0.20 mm and each point was dated using the Co-geochronometer method. Two types of variation in composition were observed in the crust: long-term trends and short-term erratic variations. The long-term trends were identified using the fifth order polynomial. Mn and Ni were shown to increase in concentration from 23.3 Ma to a maximum at about 20 Ma and then decline steadily to the Present, whereas Fe, P and Si showed the opposite trend. By contrast, Co displayed a double humped pattern with maxima at about 19 Ma and 3.5 Ma and minima at 23.3 Ma, about 11 Ma and at Present. The long-term trends in element concentrations in the crust lead us to suggest that much of the Fe in western Pacific Ocean ferromanganese crusts is aeolian in origin and derived from the deserts of central Asia. Cooling of the Asian mainland at about 20 Ma led to an increase in the flux of Fe to the oceans. This was supplemented by an additional input of Fe into the crusts as a consequence of the dissolution of biogenic CaCO₃ tests at 4.5−10.5 Ma. For the short-term erratic variations, three periods of 0.61, 0.96 and 1.65 m.y. were identified by spectral analysis. The second harmonics of these periods are 1.22, 1.92 and 3.30 m.y., which may correspond to the highest-order periods for eccentricity of 1.31, 2.04 and 3.47 m.y. This suggests the possibility that the high-frequency oscillations of the time series data are linked to climatic changes controlled by the highest-order periods of the Milankovitch cycles.     

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.     

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。     

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.     

浅论富钴结壳柱状构造的成因机制

柱状构造为富钴结壳中多种微观构造类型之一。为探讨富钴结壳柱状构造的形成机制,利用高分辨率电子探针技术分析了位于中太平洋某海山的富钴结壳中柱状构造的微观形态和微区元素化学特征,结果表明,柱状构造是由围绕核心的微层呈弓形外延辐射生长逐渐分枝而成。壳层由亮色、暗色微层交替叠置而成,其中亮色微层富锰、钴、镍和氧,而暗色微层富铁和硅;同一微层各部分的生长速率不同,介于0.27~0.92 mm/Ma。柱状构造壳层亮色、暗色微层交替变化以及相应成分的不同是微观氧化还原环境变化的结果,而柱状构造的分枝和同一微层生长速率的差异则与富钴结壳生长界面有界面双电层有关。     

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。     

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.     

东太平洋铁锰结核区微生物的丰度及其成矿作用研究

１９９４ 年 ４～１１ 月在东太平洋铁锰结核区, 使用 “向阳红 ０９”船, 采集 ３９ 个表层沉积物、１２ 个上覆水和 ７ 个结核样。在现场用平板法测定了异养细菌和铁、锰细菌丰度, 用稀释法（ Ｍ Ｐ Ｎ 法） 测定硫酸还原菌丰度。为了探讨微生物在大洋成矿过程的作用, 在实验室对异养细菌和锰细菌作纯化分离, 并进行了多项生理生化实验, 参照伯杰氏手册第八版鉴定至属。使用分光光度法, 测定锰细菌对锰、铁离子的转化作用, 使用 ｐ Ｈ 计测定了ｐ Ｈ 值的变化, 同时测定了不同培养温度对转化作用的影响。结果表明, 沉积物中异养细菌的数量在 ３×１００～９５×１０３个／ｇ; 锰、铁细菌的数量在１×１００ ～１×１０３ 个／ｇ; 硫酸盐还原细菌的数量分布范围在 ０～４×１０３个／ｇ;在上覆水和结核样中各类细菌的数量均较低,比沉积物样中各类细菌数低 １ 个数量级。在细菌的种群组成方面与近海区相比存在差异, 特别是在革兰氏阳性菌的组成上微球菌占了绝对优势。在成矿作用方面, 锰细菌对锰、铁氧化还原的实验结果表明, 在好氧的条件下, 锰细菌使可溶性的 Ｍ ｎ２＋ 氧化为 Ｍ ｎ４＋ , 其氧化速度与环境温度存在密切关系, 锰细菌对铁的氧化速度比对锰的氧化速度来得快。在     

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.