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.     

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.     

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。     

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。     

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。     

Distribution characteristics of seamount cobalt-rich ferromanganese crusts and the determination of the size of areas for exploration and exploitation

In 2001, the International Seabed Authority (ISBA) initiated the consideration relating to the Regulations for Prospecting and Exploration for Hydrothermal Polymetallic Sulphides and Cobalt-rich Ferromanganese Crusts in the Area at its 7th session. Since then, the consideration of the Regulations has been mainly focused on the size of areas to be allocated for exploration and exploitation of the crusts. This paper, based on the investigation data and the analysis of the distribution characteristics of the crusts, suggests a model for determining the size of areas for exploration and exploitation of the crusts, taking into account various factors such as production scale, crust thickness and grade, mineable area proportion, recovery efficiency, exploration venture, and so on. Through the modeling, the paper suggests that the exploration area (the area covered by each application for approval of a plan of work for exploration of cobalt-rich crusts) shall be 4 856 km² and the exploitation area (the mine site area) shall be 1 214 km², for 20 years of 1 million wet tonnes annual production.     

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.     

Kr and Xe isotopic compositions of Fe-Mn crusts from the western and central Pacific Ocean and implications for their genesis

Kr and Xe nuclide abundance and isotopic ratios of the uppermost layer of Fe-Mn Crusts from the western and central Pacific Ocean have been determined. The results indicate that the Kr and Xe isotopic composi-tions, like that of He, Ne and Ar, can be classified into two types： low3He/4He type and high3He/4He type. The low3He/4He type crusts have low84Kr and132Xe abundance, while the high3He/4He type crusts have high84Kr and132Xe abundance. The82Kr/84Kr ratios of the low3He/4He type crusts are lower than that of the air, while the83Kr/84Kr and86Kr/84Kr ratios are higher than those of the air. The Kr isotopic ratios of the high-er3He/4He type crusts are quite similar to those of the air. The128Xe/132Xe,130Xe/132Xe and131Xe/132Xe ratios of the low3He/4He type sample are distinctly lower than those of the air, whereas the129Xe/132Xe,134Xe/132Xe and136Xe/132Xe ratios are higher than those of the air. The low3He/4He type samples have the diagnostic characteristics of the MORB, with excess129, 131, 132, 134, 136Xe relative to130Xe compared with the solar wind. The128Xe/132Xe,130Xe/132Xe and131Xe/132Xe ratios of the high3He/4He type samples are slightly higher than those of the air, and the129Xe/132Xe,134Xe/132Xe and136Xe/132Xe ratios are qiute similar to those of the air. The noble gases in the Fe-Mn crusts are derived from the lower mantle, and they are a mixture of lower mantle primitive component, radiogenic component and subduction recycled component. The helium isotopic ra-tios of the low mantle reservoir are predominantly controlled by primitive He （3He） and U and Th radiogenic decayed He （4He）, but the isotopic ratios of the heavier noble gases, such as Ar, Kr and Xe, are controlled to different extent by recycling of subduction components. The difference of the noble isotopic compositions of the two type crusts is the result of the difference of the noble isotopic composition of the mantle source reservoir underneath the seamounts the crusts occurred, the noble gases of the high3He/4He type crusts are     

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.     

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.     

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。     

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.     

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.     

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.     

海洋铪同位素演化及其对大陆物源与洋流变化的启示

尽管海洋铪(Hf)同位素早在20世纪80年代就有报道,但直到最近几年随着分析测试技术的发展,它作为示踪陆源风化输入和洋流循环改变的新指标才越来越受到关注。综述了全球大洋Hf同位素现代分布以及新生代演化特点,其中最重要的现象是Nd-Hf同位素投影图上海水与岩石具有不一致的趋势线。在这些观测资料的基础上着重讨论了围绕海洋Hf同位素物源争议的一系列问题,阐述了海洋热液系统、大陆差异风化、洋岛陆架沉积物溶解等对海洋Hf的贡献以及Hf,Nd存留时间不一致等对海洋Hf同位素的影响等。弄清Hf的海洋地球化学行为,对深入认识海洋Hf的循环以及古海洋演化具有着重要的意义。     

Chemical fractionation of zinc versus cadmium among other metals nickel, copper and lead in the northern North Sea

Concentrations of dissolved Ni, Cu, Zn, Cd and Pb were measured in water samples collected during a cruise with R.V Pelagia (29-6/14-7-1993) in the northern North Sea and N.E. Atlantic Ocean. At least six depths (0–90 m) were sampled with modified Go-Flo samplers from a rubber zodiac. In the study area, the first 25 m were well mixed and stratification occurred below this depth. The local bloom of Emiliania huxleyi hardly affected the trace metals concentration, except for some removal of Cd as seen from its correlation with nitrate. The mean dissolved concentrations were for Ni (3.66 nM), Cu (1.61 nM), Zn (4.5 nM), Cd (48 pM) and Pb (108 pM). These concentrations are among the lowest reported for the North Sea and are of similar magnitude to those found in the eastern North Atlantic at the same latitude. Zn was the only exception with values 10 times higher compared to those in the Atlantic Ocean, suggesting external inputs, mainly atmospheric and possibly from surrounding land masses. The observed ratio Zn:Cd in the North Sea and estuaries is in between the high ratio 600–900 for continental sources and the low ratio 5–10 for oceanic waters. Latter low ratio is consistent with the 21-fold stronger inorganic complexation of Cd in seawater which, in combination with the preferential biological uptake of Zn, may lead to the observed about hundredfold fractionation of Zn versus Cd in the marine system. Other processes may play a role but would need further investigation. The dissolved Pb values tend to be lower than found before in the North Sea, indicating decreasing inventories due to reduced anthropogenic emissions.     

中太平洋富钴结壳中生物标志物、有机碳同位素地球化学及其古海洋环境意义

利用2003年大洋DY105-12,14航次在中太平洋海山获取的KXD28富钴结壳样品,采用气相色谱(GC)内标法对该结壳样品的分层样进行了可溶有机质(氯仿沥青“A”)及其族组成(饱和烃、芳烃、非烃)、正构烷烃、类异戊二烯烃的定量分析,并结合总有机碳(TOC)及有机碳同位素(δ¹³C)分析,探讨了结壳样品有机质来源及富钴结壳组成与生长环境之间的关系。结果表明:(1)富钴结壳中有机质生物母源主要为海洋生物和菌藻类,并混有少量陆源物质;有机碳同位素同样也指示了海洋水生生物碳同位素特征;(2)KXD28结壳从底层到最外层有机碳同位素发生了很大变化,结壳中有机碳同位素组成变化与结壳生长过程中的海洋环境气候相符合:富钴结壳生长前期δ¹³C组成由正变负,对应全球气候变冷,南极底层流向太平洋挺进;而富钴结壳生长后期δ¹³C逐渐偏正,与全球气候变暖和南极底层流萎缩相关联。     

Chemical forms of copper and zinc in the surficial sediments of Borollos Lake, Egypt

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The Role of Primary-Producer-Mediated Organic Complexation in Regional Variation in the Supply of Mn,Fe, Co,Cu, Ni and Zn to Oceanic,Non-Hydrothermal Ferromanganese Crusts and Nodules

Oceanic, non-hydrothermal ferromanganese crusts and nodules are variably enriched in Mn, Fe, Co, Cu, Ni and Zn. Comparison of the content of these elements in crusts and nodules with the level of primary productivity in the South Pacific Ocean suggests that primary-producer-mediated complexation of several of these elements by organic ligands in solution may contribute to explaining a pattern of distinctive associations observed between compositional variations for these elements in these deposits and variations in the level of primary productivity.     

多接收电感耦合等离子体质谱仪测定沉积物中Cu和Zn同位素

本文介绍了海洋沉积物中Cu和Zn同位素的化学预处理及测定方法,报道了冲绳海槽20件表层沉积物和5件柱状沉积物样品的Cu和Zn同位素组成。采用大孔径阴离子交换树脂AG MP-1M,分别以8.2 mol/L HCl+0.01%HF+0.001%H₂O₂、2 mol/L HCl+0.001%H₂O₂和0.5 mol/L HNO₃作为淋洗液,能有效分离海洋沉积物中的基质元素和Cu、Zn元素,且Cu和Zn的回收率均接近100%。以内标法和标准−样品−标准法联合校正多接收电感耦合等离子体质谱仪的质量歧视,δ⁶⁵Cu和δ⁶⁶Zn的分析精度分别为0.11‰和0.09‰（2SD）。冲绳海槽表层沉积物δ⁶⁶Zn分布范围为0.07‰～0.67‰,δ⁶⁶Zn平均值为0.31‰±0.32‰（2SD）;δ⁶⁵Cu的分布范围为−2.26‰～−0.52‰,δ⁶⁵Cu平均值为−1.21‰±0.55‰（2SD）。表层沉积物δ⁶⁶Zn和δ⁶⁵Cu分布范围较大,柱状沉积物样品δ⁶⁶Zn和δ⁶⁵Cu值随深度存在较显著变化。