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。     

Geochemical features and genesis of continental cobalt-rich ferromanganese crusts

Mass cobalt-rich ferromanganese microcrusts and nodules similar in morphology and chemical composition to cobalt-rich ferromanganese deep-ocean crusts were found in Cenozoic volcanic rocks in southern Primorye. Research has shown that ore genesis of this type is genetically related to argillization and destruction of siliceous rocks by CO₂-rich fluids, which is confirmed by experimental data on carbon erosion of iron-containing materials. Two types of this fluid ore genesis are recognized: (1) relatively high-temperature (vapor-condensate), related to late volcanic processes and fracture gas infiltration, and (2) low-temperature (vapor-liquid-condensate), controlled by degassing followed by carbon mobilization (gasification). Primarily colloidal ferromanganese segregations have high contents of Co, Ni, Pb, Cu, and Ce, typical of oceanic ore genesis. Regardless of the concentrations of these metals in the protoliths, their contents in microcrusts are similar (n-10n wt.%). This indicates the same ore genesis mechanism and similar sorption properties of the colloidal ferromanganese material formed. Barium- and cerium-rich ferromanganese microcrusts and nodules are abundant. Condensed drops of iron-containing platinum were found in apobasaltic nickel-rich ferromanganese segregations. There is a cerium paradox expressed as a minimum or a total lack of cerium among rare-earth phosphates associated with ferromanganese microcrusts. Fluid destruction and oxide metallization of ocean-floor basalts are assumed to be the main source of metals for oceanic ferromanganese crusts and nodules.     

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.     

Trace element and PGE distribution in layered ferromanganese crusts

A collection of layered ferromanganese ores (27 samples) from the Atlantic and Pacific oceans was studied. Trace element and PGE contents were determined layer-by-layer (up to 10 microlayers) in 13 of these samples.The trace, rare earth, and platinum group element distributions, including their layer-to-layer variations, were compared in hydrogenic and hydrothermal crusts from different regions. It was found that the main PGE variations (by a factor of 10–50) are related to their layer-to-layer variations within a given ore field.The distributions of PGE and trace elements are strongly heterogeneous, which is related, first, to different contents of the elements in the layers of different age in ferromanganese crusts (FMC) and, second, to the observed regional heterogeneity and influence of hydrothermal fluids. Geochemical data indicate that CFC formation was mainly caused by the hydrochemical precipitation of material from seawater. This process was accompanied by diagenetic phenomena, water-rock interaction, and influence of volcanic and hydrothermal sources.     

海洋铁锰结壳中碲的富集过程研究进展

碲(Te)元素在工业生产中被广泛应用,但在地壳中含量极低,在海洋铁锰结壳中高度富集。评述了海洋铁锰结壳中Te富集过程的相关研究,结果表明: Te在全球海洋中的分布存在空间差异,其中印度洋东经90°海岭铁锰结壳中的Te含量表现出由南向北逐渐升高的特征; 铁锰结壳中更古老壳层的Te含量更高,结壳中Te的物质通量会随壳层生长速率的变化而改变; Te以多种形式赋存在铁锰结壳中,且来源具有多源性,主要通过物理过程和化学过程进入结壳。研究有助于促进分散元素海底成矿理论的发展。     

Long-term records of erosional change from marine ferromanganese crusts

Ferromanganese crusts from the Atlantic, Indian and Pacific Oceans record the Nd and Pb isotope compositions of the water masses from which they form as hydrogenous precipitates. The¹⁰Be/⁹Be-calibrated time series for crusts are compared to estimates based on Co-contents, from which the equatorial Pacific crusts studied are inferred to have recorded ca. 60 Ma of Pacific deep water history. Time series of ɛNd show that the oceans have maintained a strong provinciality in Nd isotopic composition, determined by terrigenous inputs, over periods of up to 60 Ma. Superimposed on the distinct basin-specific signatures are variations in Nd and Pb isotope time series which have been particularly marked over the last 5 Ma. It is shown that changes in erosional inputs, particularly associated with Himalayan uplift and the northern hemisphere glaciation have influenced Indian and Atlantic Ocean deep water isotopic compositions respectively. There is no evidence so far for an imprint of the final closure of the Panama Isthmus on the Pb and Nd isotopic composition in either Atlantic or Pacific deep water masses.     

Distribution of microelements in ferromanganese crusts of the sea of Okhotsk

The contents of 60 macro- and microelements were determined by inductively coupled plasma mass spectrometry in the samples of ferromanganese crusts collected on submarine slopes of the Kuril Islands. Along with a pronounced variability in the chemical composition of the crusts, the contents of several microelements vary according to the values of the europium anomaly. A positive value points to local volcanogenic hydrothermal activity, which provides for the accumulation of manganese and iron at the expense of the accumulation of some nonferrous and rare metals.     

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.     

Sources of gallium in ferromanganese crusts from the Sea of Japan

Possible sources of gallium in hydrothermal-sedimentary ferromanganese crusts of the Belyaevsky Seamount (Central Basin, Sea of Japan) are considered. Studies with successive selective leaching have shown that ~ 80% of Ga are present in the manganese fraction. The Changbaishan Volcano ash with up to 35.3 ppm Ga has been found in the marine sediment column located in the immediate vicinity of the Belyaevsky Seamount. This suggests that Ga of the Fe–Mn crusts of the seamount was supplied with the ash of volcanic rocks containing up to 300 ppm Ga.     

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。     

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.     

Processes controlling the heavy metal distribution in pacific ferromanganese nodules and crusts

The ferromanganese precipitates existing in deep-sea waters of the Pacific consist of two types of deposits: (1) nodules mainly are distributed in pelagic basins beneath the CCD (Calcite Compensation Depth) where the rate of sedimentation is low; (2) polymetallic encrustations are formed on exposed seamount rocks where currents prevent normal sediment accumulation. Nodules, being formed in areas bordering the equatorial zone of high biological productivity, grow by two different processes: (A) early diagenetic growth by supply of metals and metal compounds from pore water and (B) hydrogenetic growth by supply of colloidal particles from near-bottom seawater. These processes lead to different kinds of oxide and different metal contents. The diagenetic growth process takes place under oxidizing to suboxidizing conditions and is supplied by an ionic solution of Mn²⁺ and other divalent metal ions. The mobilization of Mn is caused by the decomposition of organic matter. The growth features of the early diagenetic nodules show alternating laminae of crystalline and amorphous material. These rhythmic sequences of different microlayers are explained by physico-chemical changes (variation of pH) in the microenvironment of the accreting nodule surface. The hydrogenetic crust growth on seamounts leads to ferromanganese precipitates which are in particular rich in Co. The Co concentration is inversely related to the water depth. Co is positively correlated to Mn which can be derived from the oxygen minimum zone. Contrary to the diagenetic nodule growth, the crust accretion is also a colloidal precipitation process. In the water column below the oxygen minimum zone, a mixture of particles of Mn-Fe-oxyhydroxide and silicate accrete together on the surface of substratum rocks. Surface chemical mechanisms control the enrichment of Ni, Co, Pb, and other metals from the seawater; for Pt, a coprecipitation with MnO₂ caused by a redox reaction is proposed. Distinct oceanographical and geological conditions enable or promote, respectively, the ferromanganese crust formation on seamounts.     

The REE species and their distribution in ferromanganese crusts in the Sea of Japan

Polished sections of ferromanganese crusts on underwater rises in the Sea of Japan were studied with a JXA8100 microprobe analyser. Mineral phases of REE have been detected. They have Ln₂O₃ chemical composition, where Ln is La–Ce–Pr–Nd, La–Ce–Nd, or, much more rarely, La–Ce and La–Ce–Pr. With regard to the same chemical composition of REE grains in the ore crusts and basalts from Medvedev Volcano, it has been concluded that these REE were supplied during postvolcanic gas–hydrothermal processes.     

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.     

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.