Helium isotopes in ferromanganese crusts from the central Pacific Ocean

Helium isotopes have been measured in samples of two ferromanganese crusts (VA13/2 and CD29-2) from the central Pacific Ocean. With the exception of the deepest part of crust CD29-2 the data can be explained by a mixture of implanted solar- and galactic cosmic ray-produced (GCR) He, in extraterrestrial grains, and radiogenic He in wind-borne continental dust grains. ⁴He concentrations are invariant and require retention of less than 12% of the in situ He produced since crust formation. Loss has occurred by recoil and diffusion. High ⁴He in CD29-2 samples older than 42 Ma are correlated with phosphatization and can be explained by retention of up to 12% of the in situ-produced ⁴He. ³He/⁴He of VA13/2 samples varies from 18.5 to 1852 R_a due almost entirely to variation in the extraterrestrial He contribution. The highest ³He/⁴He is comparable to the highest values measured in interplanetary dust particles (IDPs) and micrometeorites (MMs). Helium concentrations are orders of magnitude lower than in oceanic sediments reflecting the low trapping efficiency for in-falling terrestrial and extraterrestrial grains of Fe-Mn crusts. The extraterrestrial ³He concentration of the crusts rules out whole, undegassed 4-40 μm diameter IDPs as the host. Instead it requires that the extraterrestrial He inventory is carried by numerous particles with significantly lower He concentrations, and occasional high concentration GCR-He-bearing particles.     

太平洋富钴结壳中碲元素的地球化学特征及其富集机制探讨

文章通过对采自太平洋海域不同海山上68个结壳样品中Te元素地球化学特征的研究,探讨了富钴结壳中控制Te元素富集的古海洋氧化还原环境及其富集机制。分析表明,太平洋海域中大多数结壳的w（Te）变化于13.4×10^-6~115.8×10^-6,平均50×10^-6,是海水w（Te）的10⁹倍;结壳中w（Te）与Mn/Fe比值呈正相关,相关系数为0.51;与Fe呈负相关,相关系数为-0.61,显示结壳中Te与Co有类似的地球化学特征。古海水氧化还原环境的改变是控制结壳中Te元素含量变化的重要因素;能反映古海水氧化还原环境的Ce异常与结壳中Te含量基本呈同步变化趋势,Te含量具有随古海水氧化程度减弱而降低的特征。结壳中Te元素的富集主要受控于其内的Mn/Fe比值。Te元素的富集机制除被海水中带微弱正电荷的FeOOH胶体以库伦静电吸附外,还可能与δ-MnO₂表面上以一种表面络合物方式的富集机制有关。Te进入结壳的存在形式及其在不同古海洋环境中的富集机制还有待进一步研究和探讨。     

厚结壳的形成条件及控制因素分析

当前对于大洋厚结壳的研究较少,而厚结壳是未来开发利用的重点,同时它记录的地质历史长,控制和影响结壳生长发育的各种因素必然能在厚结壳上充分体现出来。因此,开展厚结壳的形成条件及控制因素的研究,具有重要的理论与现实意义。文章利用GIS空间分析技术与地质统计方法,对厚结壳的定义、结壳厚度与水深、结壳厚度与基岩、结壳生长与构造活动、结壳厚度与沉积速率、结壳厚度与经纬度、结壳厚度与主成矿元素之间的关系进行了分析,结果表明,结壳的厚度变化受控于水深、基岩、构造活动、沉积速率、经纬度等因素,同时结壳厚度与主成矿元素之间存在明显的相关性。     

铁锰结壳中底层洋流活动的地球化学研究

文章以大洋海山铁锰结壳与南极底层流(AABW)之间关系的角度,从铁锰结壳的结构构造、矿物组合,特别是结壳新壳层的Ce异常和Ce/La比值的区域分布来探讨AABW的活动在铁锰结壳中留下的证据。主要对中太平洋和西北太平洋5座海山的17个铁锰结壳新壳层样品进行了结构构造分析和REE含量测定。结果表明,铁锰结壳的REE含量很高,平均为1716.66×10-6,且轻稀土元素明显富集,LREE/HREE平均值为4.82,除MID06样品具微弱的Ce负异常外,其他铁锰结壳样品均具明显的Ce正异常。为了对比研究AABW的影响,除铁锰结壳外,还引用了不同区域的多金属结核的稀土元素平均值资料按不同区域进行了对比研究,结果发现,AABW活动区和非活动区的δCe值和Ce/La比值有显著差异。一般来说,沿AABW流路,从南向北,δCe值和Ce/La比值有逐渐减小的趋势,但在局部地区,如地形复杂的海山区,AABW的强度会发生变化,其Ce正异常和Ce/La比值可能会局部增大。本项研究成果将有助于全面认识大洋成矿作用与海洋环境变迁的内在联系。     

New constraints on the sources and behavior of neodymium and hafnium in seawater from Pacific Ocean ferromanganese crusts

The behavior of dissolved Hf in the marine environment is not well understood due to the lack of direct seawater measurements of Hf isotopes and the limited number of Hf isotope time-series obtained from ferromanganese crusts. In order to place better constraints on input sources and develop further applications, a combined Nd-Hf isotope time-series study of five Pacific ferromanganese crusts was carried out. The samples cover the past 38 Myr and their locations range from sites at the margin of the ocean to remote areas, sites from previously unstudied North and South Pacific areas, and water depths corresponding to deep and bottom waters.For most of the samples a broad coupling of Nd and Hf isotopes is observed. In the Equatorial Pacific ε_Nd and ε_Hf both decrease with water depth. Similarly, ε_Nd and ε_Hf both increase from the South to the North Pacific. These data indicate that the Hf isotopic composition is, in general terms, a suitable tracer for ocean circulation, since inflow and progressive admixture of bottom water is clearly identifiable.The time-series data indicate that inputs and outputs have been balanced throughout much of the late Cenozoic. A simple box model can constrain the relative importance of potential input sources to the North Pacific. Assuming steady state, the model implies significant contributions of radiogenic Nd and Hf from young circum-Pacific arcs and a subordinate role of dust inputs from the Asian continent for the dissolved Nd and Hf budget of the North Pacific.Some changes in ocean circulation that are clearly recognizable in Nd isotopes do not appear to be reflected by Hf isotopic compositions. At two locations within the Pacific Ocean a decoupling of Nd and Hf isotopes is found, indicating limited potential for Hf isotopes as a stand-alone oceanographic tracer and providing evidence of additional local processes that govern the Hf isotopic composition of deep water masses. In the case of the Southwest Pacific there is evidence that decoupling may have been the result of changes in weathering style related to the buildup of Antarctic glaciation.     

西太平洋海山富钴结壳稀土元素(REE)组成原位LA-ICPMS测定

利用激光剥蚀电感耦合等离子体质谱(LA-ICPMS)微区原位分析方法,对采自西太平洋海山具完整三层结构的富钴结壳样品进行了稀土元素(REE)含量测定,结果表明, 虽然均产于西太平洋海山且均具有明显的三层结构,富钴结壳化学组成受地理位置和沉积环境影响很大。绝大多数西太平洋富钴结壳具有高ΣREE、高LREE/HREE、δCe正异常和δEu基本无异常或微弱正异常的特点, 显示它们主要由正常海水沉积形成。结壳不同层圈之间REE组成有较大的区别, 其原因主要在于其形成环境和矿物组成不同。样品0327稀土元素总量(∑REE)由亮煤层到疏松层到外层逐渐升高,且亮煤层δCe和Y/Ho变化非常大,最大值分别为38.61和105.5,显示该层生长环境较为氧化且相对动荡,而样品0346中三层结构的∑REE都非常高,且变化趋势与0327正好相反,从亮煤层到致密层∑REE有降低的趋势。 亮煤层形成时海水相对较氧化的环境有利于铁锰氧化物的形成和Ce⁴⁺等稀土元素的吸附,导致其中ΣREE较疏松层和外层为高,而后期磷酸盐化导致REE元素的迁移和亏损。在结壳生长剖面上,由最外层到疏松层和亮煤层,δCe呈明显上升趋势,且变化范围趋大,说明该结壳所处的海水环境在由老至新的生长过程中由相对动荡和氧化变为相对平静和还原。     

Mineralogy and chemistry of ferromanganese crusts from the Atlantic Ocean

The mineral and chemical compositions of a set of crust samples collected from the North, Central and South Atlantic were examined by means of analytical electron microscopy and ICP-MS, chemical, and microchemical elemental analysis. The dominant mineral phases of the crusts are vernadite, asbolane, and goethite, with minor ferrihydrite, and rare hematite and feroxyhyte. The samples show wide variability in major and trace elements; however, their characteristic geochemical signatures indicate hydrogenetic origin. A comparison between the compositions of oceanic hydrogenetic and hydrothermal crusts and metalliferous hydrothermal sediments from different ocean areas suggests that the geochemical approach may be insufficient in some cases and fail to identify a hydrothermal input in ferromanganese crusts of a mixed composition.     

Composition and characteristics of the ferromanganese crusts from the western Arctic Ocean

Layered ferromanganese crusts collected by dredge from a water depth range of 2770 to 2200 m on Mendeleev Ridge, Arctic Ocean, were analyzed for mineralogical and chemical compositions and dated using the excess ²³⁰Th technique. Comparison with crusts from other oceans reveals that Fe-Mn deposits of Mendeleev Ridge have the highest Fe/Mn ratios, are depleted in Mn, Co, and Ni, and enriched in Si and Al as well as some minor elements, Li, Th, Sc, As and V. However, the upper layer of the crusts shows Mn, Co, and Ni contents comparable to crusts from the Atlantic and Indian Oceans. Growth rates vary from 3.03 to 3.97 mm/Myr measured on the uppermost 2 mm. Mn and Fe oxyhydroxides (vernadite, ferroxyhyte, birnessite, todorokite and goethite) and nonmetalliferous detrital minerals characterize the Arctic crusts. Temporal changes in crust composition reflect changes in the depositional environment. Crust formation was dominated by three main processes: precipitation of Fe-Mn oxyhydroxides from ambient ocean water, sorption of metals by those Fe and Mn phases, and fluctuating but large inputs of terrigenous debris.     

太平洋海底富钴结壳中的烃类有机质及其成因意义

用气相色谱-质谱(GC-MS)联测方法测定了中西太平洋海底海山富钴结壳中的可溶有机质,对其丰度、生源构成、沉积环境、成熟度等方面进行了初步的探讨.富钴结壳的烃类生物标志化合物大多具成熟烃特征,个别具低成熟烃特点."A"/C高达9.81～21.15,显示出运移烃的特征;藿烷C31-R(S JR)为0.43～0.46,Tm/(Tm Ts)为0.40～0.59,C30αβ藿烷/(αβ藿烷 βα莫烷)为0.85～0.89,C29αβ藿烷/(αβ藿烷 βα莫烷)为0.81～0.85,c29甾烷20S/(20S 20R)为0.45～0.60,从而计算出Rsc(%)为0.73%～0.81%,个别达到1.06%;C29αββ/(αββ ααα)为0.35～0.42.甾烷丰度顺序为C29甾烷＞C27甾烷＞C28甾烷,同时检出了孕甾烷和4-甲基甾烷,重排甾烷三角图显示该有机质为Ⅱ型.Pr/Ph值介于0.35～0.82,显示植烷优势.说明烃类形成于强还原环境.链状烷烃、类异戊二烯烷烃、萜烷、甾烷化合物的组成和分布都说明茵藻类低等水生生物和陆源高等植物混合生源输入.洋底热液活动是富钴结壳中有机质热演化的重要热源.有机质在特定的海底条件下生成,并被运移到海山上,通过扩散和浸粢由外层进入结壳.     

Origin and variability of resource-grade marine ferromanganese nodules and crusts in the Pacific Ocean: A review of biogeochemical and physical controls

Marine ferromanganese nodules and crusts containing Mn, Cu, Ni and Co in the most promising resource-grade concentrations and quantities, together with Fe and Zn (all elements of biogeochemical importance) are found far from land on the deep seafloor of the Pacific Ocean. The biogeochemical, chemical and physical mechanisms contributing to their formation, distribution, abundance and – for these six elements – variability in their concentrations in these deposits, are the main focus of the present review. The mechanisms addressed include biological productivity, sedimentation types and rates, bottom water characteristics, the Calcium Carbonate Compensation Depth, the depth and intensity of the oxygen minimum zone, and biogeochemical characteristics of the six focal elements. Particular attention is given to comparisons between the deposits found in the north and the south Pacific, in order to present an overarching view of our current understanding of the mechanisms that apply to both nodules and crusts in both oceanic hemispheres, including examination of the possible existence of a marine ferromanganese oxide continuum. The renewed interest in the commercial exploitation of these deposits has stimulated a welcome increase in scientific research that is essential to informing the public discourse on seabed mining. We briefly reflect on the work addressed in this review in that context.     

The formation of cobalt-bearing ferromanganese crusts under fluid destruction of silicate matter

The processes of fluid destruction of various silicate rocks under diffusion of flows of compressed gases (mainly carbonaceous) were studied. The gas condensate nature was ascertained for the forming alumoslilicate and ore (cobalt–iron–manganese hydroxide) substances produced under this fluid destruction in the forms of microcrusts and microconcretions. The ore condensates contained in high concentrations the typomorphic elements of oceanic ferromanganese formations (Mn, Co, Ni, Cu, Pb, Ce, and Pt). The elemental composition of the ore oxide substance formed under the destruction of various silicate matrices exhibits a definite degree of endemism with prevalence of the Co–Mn association. The pronounced concentration of barium is related to the substantially carbonaceous composition of the fluid systems. A cerium paradox is revealed: Ce³⁺ is oxidized into Ce⁴⁺ and absorbed by ferromanganese hydrogel and the minimum of cerium appears in rare-earth phosphates.     

Peculiarities of the distribution of rare-earth elements and yttrium in mineral phases of the ferromanganese crusts from the Detroit guyot (Pacific Ocean)

The concentrations of rare-earth elements and yttrium (REY) were first determined in four major mineral fractions of cobalt-rich ferromanganese crusts (CMC) from the Detroit guyot at the northern latitudes of the Pacific Ocean. It was shown that REY in the CMC from these latitudes are mainly adsorbed by the manganese phase unlike the crusts of the equatorial part of the ocean where iron hydroxides are the key REY sorbents from seawater. This is caused by the variations in the hydrochemical characteristics of seawater with the latitude of the CMC formation.     

太平洋海山富钴结壳铂族元素（PGE）和Os同位素地球化学及其成因意义

本文分析了中西太平洋海山富钴结壳及其各主要层圈(外层、疏松层、亮煤层)和玄武岩基岩的铂族元素(PGE)和Au含量以及Os同位素组成,发现富钴结壳中PGE和Au含量均较高,且变化很大,∑PGE为(70.09～629.26)×10-9,平均289.48×10-9,Au为(0.60～26900)×10-9.具三层结构的富钴结壳中,疏松层(∑PGE=(339.37～545.82)×10-9)和亮煤层(∑PGE=(280.09～629.26)×10-9)的∑PGE明显高于外层((70.09～133.27)×10-9.单层结壳的∑PGE为(83.94～479.75)×10-9,Au含量普遍高于具三层结构者.结壳的∑PGE和Au含量远高于太平洋多金属结核(分别为(101.57～155.83)×10-9和(1～4)×10.沉积深度和海水氧逸度的不同是导致结壳和结核中PGE含量明显差异的主导因素.富钴结壳∑PGE和Pt与Mn(%)之间呈明显的正相关关系,而与Fe(%)具负相关性,与多金属结核正好相反,显示结壳中的PGE主要赋存在水羟锰矿(8-MnO2)等锰矿物相中,与针铁矿(FeOOH·nH2O)等铁矿物相关系不大,而结核中的PGE主要赋存在铁矿物相中.PGE球粒陨石标准化曲线和各项参数显示富钴结壳的PGE和Au主要来自海底玄武岩的蚀变释放,部分来自铁陨石微粒等地外物质,而与海底热水活动无关.计算显示西太平洋结壳距今42.5 Ma左右开始生长,生长过程中分别在8.OMa和21.8Ma处出现间断,相应形成外层、疏松层和亮煤层,其各自沉积速率为2.64 mm/Ma,1.45 mm/Ma和1.06 mm/Ma,相应海水的187Os/188Os分别为0.948～0.953,0.599～0.673和0.425～0.536,显示外层含有较多的大陆风化尘,而疏松层和亮煤层的沉积物主要来自海底洋壳蚀变和陨石碎屑或宇宙尘等地外物质.     

中太平洋WX海山富钴结壳磷酸盐矿物学研究及成因类型分析

大洋富钴结壳普遍发生磷酸盐化,磷酸盐化对富钴结壳的各种属性存在显著影响,而磷酸盐的成因问题一直没有得到很好解决。中太平洋WX海山富钴结壳老壳层中发育着两期磷酸盐化事件所产生的上下两层磷酸盐,本文运用反光显微镜、扫描电子显微镜、电子探针、微量粉晶X衍射等手段分别对其进行了矿物学特征观察和测试,研究了老壳层上下两层磷酸盐特征并探讨其可能成因。上层磷酸盐由大量形态结构清楚的磷酸质有孔虫和超微化石以及非生物碳氟磷灰石(CFA)组成,成分均一,杂质少,表现出生物成因和原生自沉积特点;下层磷酸盐变化复杂,具有特征的交代结构,混杂较高的Si、Al、K、Fe成分,显示以磷酸盐交代碳酸盐成因为主。这表明不同磷酸盐化期形成的磷酸盐有不同的成因类型。     

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.