Role of Hydrology in the Formation of Co-rich Mn Crusts from the Equatorial N Pacific,Equatorial S Indian Ocean and the NE Atlantic Ocean

Co-rich Mn crusts from four different locations of the world ocean have been studied to understand the role of dissolved oxygen of the ambient seawater in the formation of Co-rich Mn crusts. WOCE (World Ocean Circulation Experiment) oxygen profiles of modern seawater in the Equatorial North Pacific Ocean, Equatorial South Indian Ocean and the North East Atlantic Ocean have been evaluated with respect to the occurrence of Co-rich Mn crusts at depths ranging from 1500 to 3200 m. The oxygen content at these depths varied from ∼90–240 µmol/kg. The oxygen minimum zone (OMZ), with oxygen contents in the range ∼45–100 µmol/kg, is located in the depth range 800–900 m in these regions. The age of the ocean crust on which seamounts formed is in the range 80.3–180 Ma. Profiles of the oxygen contents of seawater with depth in the oceans are shown to be extremely useful in establishing the optimum conditions for the formation of Co-rich Mn crusts. The use of WOCE oxygen profiles to study geochemical processes in the oceans is highly recommended.     

西太平洋富钴结壳的分布、组分及元素地球化学

本文以富钴结壳的研究意义,趋势、西太平洋的地区域地质特征为背景,较为详细地阐述了西太平洋富钴结壳的区域分布特征、局部富集规律及其在水下平顶海山上的产出形态;论述了富钴结壳的物质组分,探讨了其含量变化与古海洋环境的关系;研究了富钴结壳的化学成分特征及其在空间上的变化规律,指出西太平洋富钴结壳成矿的良好前景,这对进一步开展富钴结壳成矿规律以及找矿勘探都有重要指导意义。     

Ore potential of the Marcus-Wake rise (Central Pacific)

The data on the geological structure of different guyots on the Marcus-Wake rise with cobalt-bearing Fe–Mn crusts are discussed. Crusts are represented by three-layer aggregates composed of one lower phosphatized (I-1) and two upper non-phosphatized (II and III) layers. Fe-vernadite and Mn-feroxygite are the major ore minerals in all studied crusts and their layers. Small contents of vernadite, asbolane–buserite, and goethite are registered. Crusts of guyots on the rise are characterized by a stable concentration of heavy and rare metals (Co_tot, Ni, Cu, Zn, Pb, Mo, and Cd) independently of their latitudinal location.     

富钴铁锰结壳的控矿要素和成矿过程——以西太平洋为例

以西太平洋海山的麦哲伦海山群和马尔库斯-威克海山群为例,研究了富钴铁锰结壳（富钴结壳）形成过程中地质要素和海洋要素的作用,重点分析了海山漂移和沉降、水道开合、最小含氧带（OMZ）、大洋环流,以及气候变化等要素对富钴结壳形成的控制作用。基于对麦哲伦海山和马尔库斯-威克海山结壳样品剖面Mn／Fe值曲线的综合研究,结合控矿要素和成矿背景分析,将该区白垩纪以来富钴结壳的成矿过程划分为五个阶段：（1）自垩纪-始新世,（2）始新世末-晚渐新期,（3）晚渐新期-中中新期早期,（4）中中新期早期晚中新期早期,（5）晚中新期早期-现代,其中（2）、（3）阶段有利于发育富钴结壳。     

富钴结壳中的磷酸盐岩及其古环境指示意义

磷酸盐岩是富钴结壳老壳层的主要组分之一。本文对来自中太平洋海山的三块富钴结壳样品中的磷酸盐岩进行了研究,以期对富钻结壳形成环境的变化有所了解。通过扫描电镜发现结壳中磷酸盐岩的形态有六种,磷酸盐岩主要分布在老壳层,新壳层中偶见。结壳中的磷酸盐岩为碳氟磷灰石(CFA),经成分分析及电镜中反射色的差异可以区分出两种成因的CFA：一种为交代碳酸盐岩型的,相对富Si、Al、Fe;另一种为从结壳孔隙水中直接沉淀而成的,基本不含Si、Al、Fe。对CB12样品中磷酸盐岩脉进行生物地层学鉴定,得出其老壳层下部火焰状磷酸盐岩的形成年代为晚渐新世一早中新世(23.2-29．9Ma),而其上部充填脉状磷酸盐岩的形成年代为中中新世(10.8-16Ma)。老壳层中富集磷酸盐岩说明在结壳形成早期,结壳形成环境条件尚不够稳定,底部存在富磷深层储库,当底流突然增强时,可携带磷在海山上交代结壳中的碳酸盐岩或在结壳内部合适条件下直接沉淀形成磷酸盐岩充填脉。新壳层形成时底流已相对髂定,富磷深层储库已消失,不再有广泛磷酸盐化形成。     

Incorporation of Transition and Platinum Group Elements (PGE) in Co-rich Mn Crusts at Afanasiy-Nikitin Seamount (AFS) in the Equatorial S Indian Ocean

Of the 12 elements enriched in Co-rich Mn crusts from the Afanasiy-Nikitin Seamount in the Equatorial S Indian Ocean, Mn, Fe and Co are enriched by a factor of ~10⁹ compared to their concentrations in seawater whereas Ni and Cu are enriched by a factor of ~10⁷ and the PGE and Au by a factor of ~10⁵ to 10⁷ compared to their concentrations in seawater. The relatively high concentration of Pt in the crusts reflects its occurrence as fine-grained particles in the crusts rather than adsorption of the elements from seawater.     

太平洋海山钴结壳资源量估算

为合理地估算出太平洋海山钴结壳资源量, 基于我国西太平洋海山钴结壳拖网采样调查资料以及对太平洋海山钴结壳资源分布规律和钴结壳矿区圈定参数指标的深入研究, 创造性地按海山不同高度、不同洋壳年龄赋予不同结壳厚度, 进而首次计算出太平洋海山干结壳资源量为(507.06~1 014.11)×108 t, 锰为(111.15~222.29)×108 t, 钴为(3.04~6.08)×108 t, 镍为(2.23~4.46)×108 t, 铜为(0.66~1.32)×108 t, 结壳分布面积为2 062 862 km2.通过Co通量与结壳Co沉积量、结壳厚度的相关分析表明, 赋予不同洋壳年龄段的结壳厚度是理论厚度的6.10%~12.20%, 这与Ku et al.得出"结壳生长时间只占其整个生命史4%"的认识非常相近, 说明所赋结壳厚度基本合理, 得出的结壳资源量基本正确.为整个大洋海盆内海山钴结壳资源量的估算提供了新方法.      

初论发现于西太平洋富钴结壳的羟锰矿

大多数研究者认为富钴结壳中的锰矿物主要是水羟锰矿。X-射线衍射数据表明这次所研究的富钴结壳中主要的富锰矿物相是羟锰矿,这是在以往的结核和结壳研究中鲜为人知。探讨了羟锰矿和水羟锰矿的名称由来、化学式、晶胞参数及X射线粉晶衍射值,建议将X-射线衍射特征值为2.4×10^-10 m和1.4×10^-10 m的锰矿物相统称为水羟锰矿;通过研究这两种矿物的成因、产状及环境,认为结壳中羟锰矿的存在表明结壳在生长中后阶段仍处于还原环境。     

Rare elements and Nd and Sr isotopic composition in micronodules from the Brazil Basin,Atlantic Ocean

The Sr isotope stratigraphy of the biogenic apatite was used to determine the age of pelagic sediments in the Brazil Basin (Station 1541) that contain ferromanganese micronodules, nodules, and coatings on the weathered volcanic rocks. The age of sediments at horizons 0–5 and 86–90 cm was estimated at 24.1 ± 0.2 Ma and 24.8 ± 0.2 Ma, respectively. The average sedimentation rate in the Late Oligocene was about 13 mm/ka. The hydrogenous Fe–Mn nodule on the sediment surface with the Mn/Fe value of 1.05–1.95 was formed at a rate of 1.2–2.4 mm/Ma, which is 1000 times lower than the growth rate of buried nodule (Mn/Fe 0.4) at depth of 83 cm. Diagenesis provoked changes in the mineral composition of the buried nodule (asbolane-buserite partially replaced by goethite), leading to the loss of a part of Mn, Ni, Li, and Tl but accumulation of trace elements linked with iron oxyhydroxides (Ce, Th, Be, As, and V) were retained. The composition of manganese micronodules at two studied depths in sediments evolved in the course of two stages of ore formation: related to the oxic and suboxic diagenesis. The Sr isotopic composition in manganese micronodules from both horizons do not differ from that of dissolved Sr in the ocean water. The ¹⁴³Nd/¹⁴⁴Nd ratio, which reflects the Nd isotopic composition in the paleocean during the micronodule formation, varies in manganese micronodules from different horizons and is constant in different size fractions.     

Continuous growth of hydrogenetic ferromanganese crusts since 17 Myr ago on Takuyo-Daigo Seamount,NW Pacific,at water depths of 800–5500 m

Ferromanganese crusts cover all outcrops on Takuyo-Daigo seamount traversed during remotely operated underwater vehicle (ROV) dives, except in places covered by foraminifera sand. Takuyo-Daigo is a Cretaceous seamount located in the northwest Pacific Ocean. Geological and bathymetric mapping provide the framework for this study. Chemical and mineralogical analyses of the hydrogenetic ferromanganese crusts show temporal and spatial variations typical of those found in previous studies. Outcrops from 800 to 5500 m water depths are covered with ferromanganese crusts up to 105 mm thick. Beryllium isotope dating shows that the crusts have apparently been growing continuously at all water depths, even through the modern oxygen minimum zone (OMZ), contrary to some earlier models for deposition. Growth rates vary from 2.3 to 3.5 mm/Myr, with Fe or Mn fluxes of 0.07–0.11 g/cm²/Myr since the early-middle Miocene. Co/Mn ratios decrease with water depth while Fe/Mn and other metallic elements increase or show no change, based on the analysis of the uppermost crust surface. This is probably because Co is the most abundant redox-sensitive element derived from seawater that occurs in crusts.     

Modern Bottom Sediments of Lake Onega: Structure,Mineralogical Composition,and Systematization of Rare-Earth Elements

The results of studying the structure and mineral composition of the Upper Holocene bottom sediments of Lake Onega are presented. It is established that there are two types of columns of bottom sediments, for which stratification of layers and formation of Fe–Mn crusts are determined by the diagenesis processes occurring under physicochemical conditions of sediment accumulation according to two scenarios. The distribution spectra of rare-earth elements (REEs) are different in the indicated types of columns, which is apparently attributed to the differences in the oxidation–reduction conditions at the water–sediment interface during the formation of REEs and possibly to the influence of hydrothermal processes.     

Abnormally high mercury contents in hydrogenic ferromanganese crusts from Seth Guyot (Northwestern Pacific)

Variations in mercury contents in marine sediments have implications for hydrothermal activity, paleoclimate, depositional environments, and primary bioproduction. Mercury contents reach 148 ppb in hydrogenic ferromanganese crusts on flat-topped seamounts. Such crusts, with up to 4120 ppb Hg, were dredged from the slopes of Seth Guyot in the western Marcus-Wake Seamounts in 1982, during the 13th cruise of RV Vulkanolog. The Seth Fe-Mn crusts are of the same origin as hydrogenic Co-rich ferromanganese deposits from seamounts in other oceanic regions. Mercury accumulated in the Cenozoic as Fe-Mn oxyhydroxides in the crusts adsorbed Hg from bottom water. The process was especially rapid during the Pliocene volcano-tectonic rejuvenated stage.     

Strategic and rare elements in Cretaceous-Cenozoic cobalt-rich ferromanganese crusts from seamounts in the Canary Island Seamount Province (northeastern tropical Atlantic)

Thick ferromanganese (Fe-Mn) crusts from four Cretaceous seamounts (The Paps, Tropic, Echo and Drago) at the southern Canary Island Seamount Province (CISP) in the northeastern tropical Atlantic were recovered along the flanks and summits from 1700 to 3000 m water depths. CISP is composed of > 100 seamounts and submarine hills, is likely the oldest hotspot track in the Atlantic Ocean, and is the most long-lived of known hotspots globally. The Fe-Mn crusts grow on basalt-sedimentary rock substrates below the northeastern tropical Atlantic core of the oxygen minimum zone (OMZ) with a maximum thickness of 250 mm at a water depth of 2400 m. The mineralogical and chemical composition of these Fe-Mn crusts indicate a hydrogenetic origin. The main Mn minerals are vernadite with minor interlayered todorokite and asbolane-buserite. Fe oxides are essentially ferroxyhyte and goethite. The Fe-Mn crusts show high average contents in Fe (23.5 wt%), Mn (16.1 wt%), and trace elements like Co (4700 μg/g), Ni (2800 μg/g), V (2400 μg/g) and Pb (1600 μg/g). Rare earth elements plus yttrium (REY) averages 2800 μg/g with high proportions of Ce (1600 μg/g). Total platinum group elements (PGEs) average 230 ng/g, with average Pt of 182 ng/g. Two main types of growth layers form the crusts: 1) a dense laminae of oxides with high contents in Mn, Co and Ni associated with vernadite and Cu, Ni, and Zn associated with todorokite; 2) botryoidal layers with high contents in Fe, Ti, V and REY associated with goethite. The Fe-Mn crusts from the CISP region show higher contents in Fe, V, Pb and REY but lower Mn, Co, Ni and PGEs contents than Pacific or Indian ocean seamount crusts. The oldest maximum age of initiation of crust growth was at 76 Ma (Campanian, Late Cretaceous). Using a combination of high resolution Co-chronometer and geochemical data along an Electron Probe Micro Analysis (EPMA) transect, four stages in morphology, chemical contents and growth rates can be differentiated in the the Cenozoic crusts since 28 Ma, which we interpret as due to changes in the ventilation of the North Atlantic OMZ and to the increase of Saharian dust inputs. An earliest growth period, characterized by similar contents of Fe and Mn in the interval 27.8–24.45 Ma (late Oligocene-early Miocene) reflects slow precipitation related to a thick OMZ. An intermediate laminated zone with higher contents of Fe, Si and P, high growth rates reaching 4.5 mm/Ma, and precipitation of Fe-Mn oxides during the interval 24.5–16 Ma is related to periods of ventilation of the OMZ by intrusion of deep upwelling currents. Significant increase in Fe contents at ca. 16 Ma correlates with the onset of incursions of Northern Component Waters into the North Atlantic. Finally, since 12 Ma, the very low growth rates (< 0.5 mm/Ma) of the crust are related to a thick North Atlantic OMZ, an increase in Sahara dust input and a stable thermohaline circulation.     

大洋富钴结壳资源调查与研究进展

富钴结壳是继多金属结核资源之后被发现的又一深海沉积固体矿产资源,在太平洋、大西洋和印度洋的海底均有分布。据估算,全球三大洋海山富钴结壳干结壳资源量为(1081.1661~2162.3322)×108t。世界各国对富钴结壳的调查始于20世纪80年代初,截至目前,已有日本、中国、俄罗斯和巴西等4个国家与国际海底管理局签订了富钴结壳勘探合同,而韩国的矿区申请也于2016年获得核准。富钴结壳按形态可分为板状结壳,砾状结壳和钴结核3种类型。富钴结壳内部结构构造在宏观上通常表现为三层构造,即底部亮煤层、中部疏松层和顶部较致密层;在微观下主要表现为柱状构造、叠层构造、斑块状构造、纹层状构造等多种类型。富钴结壳的矿物成分主要为自生的铁锰矿物,包括水羟锰矿、钡镁锰矿、羟铁矿、四方纤铁矿、六方纤铁矿、针铁矿等。富钴结壳富含Mn、Fe、Co、Ni、Cu、Pb、Zn等金属元素以及稀土元素和铂族元素,其中Co含量尤为显著。三大洋中,以太平洋富钴结壳的Co平均含量最高。富钴结壳的生长过程极其缓慢,平均仅几毫米每百万年。研究表明,西太平洋富钴结壳最早于始新世-早中新世开始生长。目前通常认为富钴结壳为水成成因,即Co、Fe、Mn等金属元素来源于海水。此外,有研究表明微生物在富钴结壳的形成过程中也起着非常重要的作用。富钴结壳的分布及特征受地形、水深、基岩类型、海水水文化学特征、经纬度等多种因素的影响,其主要分布于碳酸盐补偿深度以上、最低含氧带以下、水深800~2500 m的海山、岛屿斜坡和海底高地上,西、中太平洋海山区被认为是全球富钴结壳的最主要产出区。     

Diagenetic cycling of trace elements in the bottom sediments of the Swan River Estuary,Western Australia

Teflon strips were used in-situ in the bottom sediments at two sites in the Swan River Estuary to collect diagenetic Fe–Mn oxyhydroxides and monitor monthly changes in their morphology and trace element geochemistry. This study demonstrates that substantial concentrations of trace elements accumulate at the redox front during the formation of diagenetic Fe–Mn oxyhydroxides. It is likely that the Fe–Mn oxyhydroxides initially nucleate and grow on the Teflon strips via bacterial activity. Trace element geochemistry of the diagenetic Fe–Mn oxyhydroxides is influenced by changes in the supply of trace elements from either the bottom sediments and/or water column or changes in the physico-chemical status of bottom and porewaters. If sufficient diagenetic Fe–Mn oxyhydroxides are preserved in the upper layer(s) of the bottom sediment it is possible that diagenetic (secondary) trace element enrichment profiles may be produced which modify the historical input of natural or anthropogenic trace element sources. Alternatively, partial or complete dissolution of the diagenetic Fe–Mn oxyhydroxides in response to temporal changes in the redox status of the bottom sediment may lead to a substantial underestimate of trace element fluxes in historical bottom sediment profiles. This study highlights that considerable care must be taken when interpreting short- to long-term geochemical profiles in bottom sediments due to the possible occurrence of rapid, seasonally mediated diagenetic processes.     

中太平洋海山区富钴结壳的钙质超微化石地层学研究

对“大洋一号”调查船在中太平洋采集的N1-15和N5E-06 2个富钴结壳样品进行了钙质超微化石及其生物地层学的研究与分析.这2个结壳从结构上分为3层: 致密型上层、疏松型中层和致密型下层.在研究中对各结构层和各层中有颜色或细微结构变化的层位都进行了详细的取样和分析.在识别了12个新生代钙质超微化石事件的基础上, 确定了2个结壳致密型上层结壳都为晚更新世以来的沉积, 它们的疏松型中层结壳为上新世到中更新世的沉积.对N5E-06富钴结壳来说, 其致密型下层结壳下部形成于中晚古新世到早渐新世的59.7~ 32.8 Ma期间.N1-15富钴结壳致密型下层的形成时代目前暂时定为中新世.研究注意到在2个结壳中都没有发现可信的晚渐新世到中新世的化石记录, 在个别层位之间存在着沉积间断.      

Deep-ocean mineral deposits as a source of critical metals for high- and green-technology applications: Comparison with land-based resources

Ferromanganese (Fe–Mn) crusts are strongly enriched relative to the Earth's lithosphere in many rare and critical metals, including Co, Te, Mo, Bi, Pt, W, Zr, Nb, Y, and rare-earth elements (REEs). Fe–Mn nodules are strongly enriched in Ni, Cu, Co, Mo, Zr, Li, Y, and REEs. Compared to Fe–Mn crusts, nodules are more enriched in Ni, Cu, and Li, with subequal amounts of Mo and crusts are more enriched in the other metals. The metal ions and complexes in seawater are sorbed onto the two major host phases, FeO(OH) with a positively charged surface and MnO₂ with a negatively charged surface. Metals are also derived from diagenetically modified sediment pore fluids and incorporated into most nodules. Seafloor massive sulfides (SMS), especially those in arc and back-arc settings, can also be enriched in rare metals and metalloids, such as Cd, Ga, Ge, In, As, Sb, and Se. Metal grades for the elements of economic interest in SMS (Cu, Zn, Au, Ag) are much greater than those in land-based volcanogenic massive sulfides. However, their tonnage throughout the global ocean is poorly known and grade/tonnage comparisons with land-based deposits would be premature.The Clarion–Clipperton Fe–Mn Nodule Zone (CCZ) in the NE Pacific and the prime Fe–Mn crust zone (PCZ) in the central Pacific are the areas of greatest economic interest for nodules and crusts and grades and tonnages for those areas are moderately well known. We compare the grades and tonnages of nodules and crusts in those two areas with the global terrestrial reserves and resources. Nodules in the CCZ have more Tl (6000 times), Mn, Te, Ni, Co, and Y than the entire global terrestrial reserve base for those metals. The CCZ nodules also contain significant amounts of Cu, Mo, W, Li, Nb, and rare earth oxides (REO) compared to the global land-based reserves. Fe–Mn crusts in the PCZ have significantly more Tl (1700 times), Te (10 times more), Co, and Y than the entire terrestrial reserve base. Other metals of significance in the PCZ crusts relative to the total global land-based reserves are Bi, REO, Nb, and W. CCZ nodules and PCZ crusts are also compared with the two largest existing land-based REE mines, Bayan Obo in China and Mountain Pass in the USA. The land-based deposits are higher grade but lower tonnage deposits. Notably, both land-based deposits have < 1% heavy REEs (HREEs), whereas the CCZ has 26% HREEs and the PCZ, 18% HREEs; the HREEs have a much greater economic value. Radioactive Th concentrations are appreciably higher in the land-based deposits than in either type of marine deposit. A discussion of the differences between terrestrial and marine impacts and mine characteristics is also presented, including the potential for rare metals and REEs in marine deposits to be recovered as byproducts of mining the main metals of economic interest in nodules and crusts.     

西太平洋海山富钴结壳的稀土和铂族元素特征及其意义

为了探讨富钴结壳的稀土和铂族元素是否有相似的形成机制,对西太平洋海山富钴结壳稀土和铂族元素进行了类比研究.结果表明:富钴结壳的∑REY范围为1 433.7×10-6~2 888.0×10-6,其中Ce占到近50%,北美页岩标准化后显示较平坦的稀土模式和显著的Ce正异常特征.根据稀土配分模式及已有的Nd同位素结果,富钴结壳具有亲陆壳属性.富钴结壳具有极高的Pt (115.5×10-9~1 132.0×10-9)、(Pt/Pd)_N和 (Pt/Os)_N值,Ir与Pt及Rh与Pt显示良好相关性.经球粒陨石标准化后显示较一致PGE (platinum-group elements) 配分模式,从Os到Pt逐渐富集,Pd元素强烈亏损.已有的Os同位素研究结果显示物源在地质历史时期从幔源属性向陆源属性变化,但富钴结壳PGE元素内部相对含量仍在一定程度上保持稳定.研究认为:富钴结壳对海水中的稀土清扫具有选择性,Ce的正异常恰恰是结壳对海水稀土中Ce的优先选择造成的,从而导致海水亏损Ce.然而海水中Ce的亏损并未改变新形成富钴结壳的稀土模式,原因是在海洋中存在适量的具有亏损Ce特征的磷酸盐等组分,理论上只需要氧化物类稀土与磷酸盐类稀土消耗的稀土与海水中的补给平衡即可.只是在相关过程中,海洋中氧化物类对稀土的选择更具有主动性,而磷酸盐类表现更多的继承关系.尽管Os同位素显示物源供给发生变化,然而富钴结壳PGE模式相对稳定.因此富钴结壳PGE模式同样可以用富钴结壳对PGE的选择性吸收解释,因富钴结壳优先选择Pt与Ir以及相对排斥Pd和Os,形成了现有独特的PGE模式.      

Rare Earth Elements Composition and Constraint on the Genesis of the Polymetallic Crusts and Nodules in the South China Sea

The rare earth elements(REE) composition of the polymetallic crusts and nodules obtained from the South China Sea(SCS) were analyzed through inductively coupled plasma mass spectrometry.Results revealed great differences in the REE abundances(∑REE) of the SCS polymetallic crusts and nodules; the crusts show the highest ∑REE, whereas the nodules exhibit the lowest ∑REE. The similarity in their NASC-normalized patterns, the enriched light REE(LREE), the markedly positive Ce anomaly(δCe), and the non-or weakly positive Eu anomaly(δEu), suggest that the polymetallic crusts and nodules are of hydrogenetic origin. Moreover, the REE contents and their relevant parameters are quite different among the various layers of the crusts and nodules, which probably results from the different marginal sea environments and mineral assemblages of the samples. The growth profiles of the SCS polymetallic crusts and nodules reveal the tendency ∑REE and δCe to slightly increase from the outer to the inner layers, suggesting that the growth environments of these samples changed smoothly from an oxidizing to a relatively reducing environment; in addition, the crust ST1 may have experienced a regressive event(sea-level change) during its growth, although the REE composition of the seawater remained relatively stable. On the basis of the regional ∑REE distribution in the SCS crusts and nodules,the samples collected near the northern margin were influenced by terrigenous material more strongly compared with the other samples, and the REE contents are relatively low. Therefore, the special geotectonic environment is a significant factor influencing the abundance of elements, including REE and other trace elements. Compared with the oceanic seamount crusts and deep-sea nodules from other oceans,the SCS polymetallic crusts and nodules exhibit special REE compositions and shale-normalized patterns, implying that the samples are of marginal sea-type Fe-Mn sedimentary deposits, which are strongly affected by the epicontinental environment, and that they grew in a more oxidative seawater environment. This analysis indicates that the oxidized seawater environment and the special nano property of their Fe-Mn minerals enrich the REE adsorption.     

Pb isotope variations in hydrogenetic Fe–Mn crusts from the Izu–Bonin fore-arc

Fe–Mn crusts were recovered from the western escarpment of the Bonin Ridge in the Izu–Bonin fore-arc region (dive site #824: 28.612°N, 141.803°E) at water depths of c. 2900 m using the Shinkai 6500 submersible during cruise YK 04–05. Major and trace element data and XRD mineralogy indicate that the crusts are hydrogenetic in origin. We present profiles of variations in Pb isotope composition measured in-situ by laser ablation MC-ICP-MS across two of the crusts. The isotopic variations are systematic and can be matched up between the two crusts, indicating similar growth rates. The crust Pb isotope composition rules out any local source for Pb from within the Izu–Bonin–Mariana arc system, either from hydrothermal activity or through leaching of volcanic detritus. Input of a globally well-mixed volcanic Pb component, either from aerosols or as an absorbed component on aeolian dust, has been proposed as a mechanism to explain the Pb isotope composition of Central Pacific deep water. However, the Izu–Bonin crusts are displaced to lower ²⁰⁶Pb/²⁰⁴Pb and higher ²⁰⁸Pb/²⁰⁴Pb, which requires an additional Pb source. One possibility is that as water is advected from the south, outboard of the Luzon–Ryukyu–Honshu arc system, it is progressively polluted by Pb derived by weathering and erosion of these young island arc volcanic systems. Using a constant Co-flux model, growth rates are estimated at ～ 7–13 mm/Ma, which would suggest that these crusts provide a record of changes in the composition of deep water in the Izu–Bonin fore-arc region of the western Pacific Ocean over the last 4–8 Ma. Over this interval, the main feature has been a progressive decrease in ²⁰⁷Pb/²⁰⁶Pb (0.843 to 0.839) and ²⁰⁸Pb/²⁰⁶Pb (2.088 to 2.080) with time. The interior parts have compositions similar to those of crusts from the Izu–Bonin fore-arc, while the rims have compositions similar to crusts from the central Western Pacific.