Compositional variation and genesis of ferromanganese crusts of the Afanasiy—Nikitin Seamount, Equatorial Indian Ocean

Eight ferromanganese crusts (Fe-Mn crusts) with igneous and sedimentary substrates collected at different water depths from the Afanasiy-Nikitin Seamount are studied for their bulk major, minor and rare earth element composition. The Mn/Fe ratios < 1.5 indicate the hydrogenetic accretion of the Fe-Mn hydroxides. These Fe-Mn crusts are enriched in Co (up to 0.9%, average ∼ 0.5%) and Ce. The Ce-content is the highest reported so far (up to 3763 ppm, average ∼ 2250 ppm) for global ocean seamount Fe-Mn crusts. In spite of general similarity in the range of major, minor, and strictly trivalent rare earth element composition, the dissimilarity between the present Fe-Mn crusts and the Pacific seamount Fe-Mn crusts in Co and Ce associations with major mineral phases indicates inter-oceanic heterogeneity and region-specific conditions responsible for their enrichment. The decrease in Ce-anomaly (from ∼ 8 to ∼ 1.5) with increasing water depth (from ∼ 1.7 km to ∼ 3.2 km) might suggest that the modern intermediate depth low oxygen layer was shifted and sustained at a deeper depth for a long period in the past.     

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.     

Ferromanganese oxide deposits from the Central Pacific Ocean,II. Nodules and associated sediments

Bulk chemical, mineralogical and selective leach analyses have been made on a suite of abyssal ferromanganese nodules and associated sediments from the S.W. equatorial Pacific Ocean. Compositional relations between nodules, sediment oxyhydroxides and nearby ferromanganese encrustations are drawn assuming that the crusts represent purely hydrogenetic ferromanganese material. Crusts, δMnO₂-rich nodules and sediment oxyhydroxides are compositionally similar and distinct from diagenetic todorokitebearing nodules. Compared to Fe-Mn crusts, sediment oxyhydroxides are however slightly enriched, relative to Mn and Ni, in Fe, Cu, Zn, Ti and Al, and depleted in Co and Pb, reflecting processes of non-hydrogenous element supply and diagenesis. δMnO₂ nodules exhibit compositions intermediate between Fe-Mn crusts and sediment oxyhydroxides and thus are considered to accrete oxides from both the water column and associated sediments.Deep ocean vertical element fluxes associated with large organic aggregates, biogenic calcite, silica and soft parts have been calculated for the study area. Fluxes associated with organic aggregates are one to three orders of magnitude greater than those associated with the other phases considered, are in good agreement with element accumulation rates in sediments, and are up to four orders of magnitude greater than element accumulation rates in nodules. Metal release from labile biogenic material in surface sediments can qualitatively explain the differences between the composition of Fe-Mn crusts and sediment oxyhydroxides.Todorokite-rich diagenetic nodules are confined to an eastwards widening equatorial wedge. It is proposed that todorokite precipitates directly from interstitial waters. Since the transition metal chemistry of interstitial waters is controlled dominantly by reactions involving the breakdown of organic carbon, the supply and degradation rate of organic material is a critical factor in the formation of diagenetic nodules. The wide range of (trace metal/Mn) ratios observed in marine todorokite reflects a balance between the release of trace metals from labile biogenic phases and the reductive remobilisation of Mn oxide, both of which are related to the breakdown of organic carbon.     

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.     

富钴结壳关键元素赋存状态与富集机理

富钴结壳是大洋低温海水中的溶解元素在海山边坡沉淀形成的壳状铁锰矿产,广泛分布于全球海山、海底高原斜坡之上,储量巨大。铁锰结壳高度富集Co、Ni、Pt、REE、Te等元素,达到海水丰度的105~1010倍,是未来新能源、高新技术元素的重要来源,具有极大的潜在经济价值。前人通过淋滤实验、吸附实验、现代海洋观测方法、海水化学分析、高分辨率精细矿物学研究等方法对富钴结壳中元素的赋存状态和富集机理进行了广泛而深入的研究。研究结果表明,富钴结壳主要由含铁水羟锰矿和铁氢氧化物组成,在海山附近的海洋化学过程中,含铁水羟锰矿和铁氢氧化物胶体分别优先吸附Co、Ni、Pt、REE和Cu、Pb、Te、REE等元素,表面氧化/置换作用造成了含铁水羟锰矿中Co、Pt、Ni、Ce及铁氢氧化物中Te、Ce的持续积累。富钴结壳极其缓慢的生长速率（1~10 mm/Ma）、超高孔隙度（60%）、极大的体表面积（300 m2/g）都促进了结壳中关键元素的超常富集。对富钴结壳关键元素富集机理的理解是富钴结壳古海洋反演研究的基础,海域富钴结壳地球化学差异的控制因素需要进一步研究,这些关键科学问题的理解有助于富钴结壳资源的勘探工作。     

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.     

Low-temperature hydrothermal deposits in the rift zone of the Mid-Atlantic Ridge

New data on the low-temperature hydrothermal deposits of the Snake Pit, TAG, Broken Spur, and Lucky Strike fields in the rift valley of the Mid-Atlantic Ridge (MAR) obtained during the 47th cruise of the R/V Akademik Mstislav Keldysh are reported. These deposits are related to focused and diffuse flows of hydrothermal solutions and the material precipitated from hydrothermal plumes. Electron microscopy study allowed us to identify protoferrihydrite, ferrihydrite, goethite, hematite, Mn-feroxyhyte, and Fe-vernadite. Fe-free vernadite, akaganeite, opal, nontronite, lepidocrocite, and jarosite occur in subordinate amounts. Bacteria-like forms made up of protoferrihydrite particles replaced with ferrihydrite, nontronite, and goethite along with particles of Fe-free vernadite and opal were found. The contents of major, minor, and noble metals were determined in samples with AAS, INAA, and the direct chromatographic method. Elevated PGE contents were established in the low-temperature hydrothermal deposits of the MAR for the first time. The highest PGE contents were detected in the inner zone of Fe-Mn crusts on the surface of a hydrothermal chimney in the Snake Pit field ((ppm) 0.13 Pd, 0.12 Rh, and 0.03 Pt, along with 16.5 Au, 642 Ag, and 355 Se) and in the Au-depleted crust on the surface of a sulfide ore fragment in the Lucky Strike field (0.12 ppm Pd and 0.04 ppm Rh along with 0.03 ppm Au, 683 ppm Se, and 1.5 wt % Ba).     

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.     

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.     

Comparison between Datangpo-type manganese ores and modern marine ferromanganese oxyhydroxide precipitates based on rare earth elements

Datangpo-type sedimentary manganese deposits, which are located in northeastern Guizhou province and its adjacent areas, are Mn carbonate-type deposits hosted in black carbonaceous shale that represent a series of medium to large deposits containing a huge tonnage of reserves. PAAS-normalized rare earth element distribution patterns of manganese ores record “hat-shaped” REY (REE + Y) plots characterized by pronounced middle rare earth element enrichment, evident positive Ce anomalies, weak to strong positive Eu anomalies and negligible negative Y anomalies. These REY geochemical characteristics are different from those of country rocks and record the processes and features of sedimentation and diagenesis. Manganese was precipitated as Mn-oxyhydroxide particles in oxidized water columns with the sorption of a certain amount of rare earth elements, subsequently transforming from Mn-oxyhydroxides to rhodochrosite and redistributing REY in reducing alkaline pore-water during early diagenesis. A number of similarities can be observed through a comparison of Datangpo-type manganese ores and modern marine ferromanganese oxyhydroxide precipitates based on their rare earth elements. The precipitation of Datangpo-type manganese ores is similar to that of hydrogenetic crusts and nodules based on their positive Ce anomalies and relatively higher total REY concentrations. However, several differences also exist. Compared to hydrogenetic crusts and nodules, Datangpo-type manganese ores record smaller positive Ce anomalies, lower total REY concentrations, unobvious fractionation between Y and Ho, and weak to strong positive Eu anomalies. These were caused by quicker sedimentary rates in the oxic water columns of the shallower basin, after which pore water became strongly reducing and alkaline due to the degradation of organic matter in the early diagenetic stage. In addition, compared to typical deposits in the world, Datangpo-type manganese ores are similar to hydrogenetic deposits and different than hydrothermal deposits. All of these characteristics of manganese ores indicate that Datangpo-type manganese ores, the principal metallogenic factors of which include oxidation conditions during deposition and reducing conditions during early diagenetic stages, represent hydrogenetic deposits.     

The hafnium isotope composition of Pacific Ocean water

The first Hf isotope data for seawater are reported for a series of stations in the Northwestern Pacific and define a range from ε_Hf = 3.5 ± 1.4 to 8.6 ± 1.6. Most samples have values within error of the average of ε_Hf = 5.9, but significant variations are found in intermediate waters at a depth of 600 m, as well as in deep waters. The Nd and Hf isotope compositions of the deep waters fall within the range of values found for surfaces of hydrogenetic ferromanganese crusts in the region, confirming that Hf in the Fe-Mn crusts has been derived from the overlying water column, which thus provide an archive of past seawater compositions. Although the seawater samples are generally close to the global ε_Nd-ε_Hf correlation obtained from ferromanganese crusts, there are significant deviations from this correlation indicating that there is some additional decoupling between Nd and Hf isotope signals, most likely caused by local water mass mixing and differences in residence times. This is not resolved in the crust samples, which integrate seawater signals over 10⁴ years. The combined use of these two isotope systems in seawater therefore provides an additional dimension for tracing water masses in the oceans. Studies of the distribution of oceanic Hf isotope compositions that have been confined to deep water and boundary waters, as recorded in seafloor ferromanganese crusts, can now be extended and aimed at characterising the entire present-day water column. Average Hf concentrations measured in this study are somewhat lower than previously reported, suggesting a shorter residence time for Hf in the global oceans, although the uncertainty in the extent of Hf removal from the water column during estuarine mixing as well as a lack of data on hydrothermal and dust inputs remains a limit on how well the residence time can be defined.     

海洋Nd同位素演化及古洋流循环示踪研究

海洋Nd同位素演化已经成为示踪陆源风化输入和洋流循环改变的最重要的手段之一,得到了越来越多的应用,并取得了许多重要的成果。海水的Nd同位素组成主要受陆源输入物质控制,热液输入几乎可以忽略。由于Nd在海洋中的停留时间(约500～1000a)略小于海水的平均混合时间(约1500a),且各洋盆有不同的Nd同位素风化输入,因此现代各大洋海水具有不同的Nd同位素组成。在陆源输入稳定的情况下,可以利用海水的Nd同位素组成和演化来示踪水体的混合或洋流循环的改变。目前主要依靠对海洋中水成铁锰结壳、海洋钙质有孔虫壳体、磷酸质鱼骨头或鱼牙齿化石以及沉积物中铁锰氧化物组分等的研究来恢复和反演古海水的Nd同位素组成和演化。4种分析材料各有其优缺点。其中,通过对水成铁锰结壳的Nd同位素分析,基本建立了各大洋新生代以来的主要洋流的Nd同位素组成的长尺度演化。通过有孔虫壳体、鱼化石碎片和沉积物中Fe-Mn氧化物组分可以进行高时间分辨率的古海水Nd同位素演化示踪。利用海水Nd同位素演化可以示踪古洋流通道的开启或闭合,以及获得水体交换的直接信息,为研究构造运动与气候变化之间的关系提供指示。同时,将海水Nd同位素演化与气候变化的指标结合起来,可以用于示踪各种气候条件下洋流循环的改变,将洋流循环的改变与气候变化联系起来,研究两者之间的成因关系。对表层水体的Nd同位素组成的研究则可以示踪不同气候条件下大陆陆源风化输入的改变。     

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.     

麦哲伦海山群MK海山富钴结壳稀土元素的赋存相态

利用ICP-OES和ICP-MS,分析了麦哲伦海山群西北端MK海山2 170 m水深的MKD23B-3号富钴结壳样品,获得了其剖面上主元素、稀土元素（REE）和Y含量数据,并基于元素含量间的线性相关关系,研究了REE和Y的赋存相态。结果显示:该样品剖面从基岩到表面可划分为5层,第Ⅰ、Ⅱ层为磷酸盐化壳层,第Ⅲ、Ⅳ、Ⅴ层为未磷酸盐化壳层。在未磷酸盐化壳层中,REE和Y主要赋存在δ-MnO₂相中;而在磷酸盐化壳层中,REE和Y除了赋存在Fe、Mn氧化物相中外,主要赋存在独立于碳氟磷灰石（CFA）的矿物相态中,可能为稀土的磷酸盐。并提出利用磷酸盐中REE/Y 估算富钴结壳磷酸盐化壳层次生稀土的方法,据此估算了MK海山富钴结壳磷酸盐化壳层次生稀土的量。在该样品中,次生稀土占稀土总量的42%~88%,近一半以上的稀土是次生的,磷酸盐化作用对于REE和Y的次生富集具有显著的贡献;因此解读磷酸盐化富钴结壳的稀土元素（特别是Nd同位素）古海洋记录必须排除次生稀土元素的干扰。     

Platinum group elements and gold in ferromanganese crusts from Afanasiy-Nikitin seamount,equatorial Indian Ocean: Sources and fractionation

The major element relationships in ferromanganese (Fe-Mn) crusts from Afanasiy-Nikitin seamount (ANS), eastern equatorial Indian Ocean, appear to be atypical. High positive correlations (r = 0.99) between Mn/Co and Fe/Co ratios, and lack of correlation of those ratios with Co, Ce, and Ce/Co, indicate that the ANS Fe-Mn crusts are distinct from Pacific seamount Fe-Mn crusts, and reflect region-specific chemical characteristics. The platinum group elements (PGE: Ir, Ru, Rh, Pt, and Pd) and Au in ANS Fe-Mn crusts are derived from seawater and are mainly of terrestrial origin, with a minor cosmogenic component. The Ru/Rh (0.5–2) and Pt/Ru ratios (7–28) are closely comparable to ratios in continental basalts, whereas Pd/Ir ratios exhibit values (<2) similar to CI-chondrite (∼1). The chondrite-normalized PGE patterns are similar to those of igneous rocks, except that Pd is relatively depleted. The water depth of Fe-Mn crust formation appears to have a first-order control on both major element and PGE enrichments. These relationships are defined statistically by significant (r > 0.75) correlations between water depth and Mn/Co, Fe/Co, Ce/Co, Co, and the PGEs. Fractionation of the PGE-Au from seawater during colloidal precipitation of the major-oxide phases is indicated by well-defined linear positive correlations (r > 0.8) of Co and Ce with Ir, Ru, Rh, and Pt; Au/Co with Mn/Co; and by weak or no correlations of Pd with water depth, Co-normalized major-element ratios, and with the other PGE (r < 0.5). The strong enrichment of Pt (up to 1 ppm) relative to the other PGE and its positive correlations with Ce and Co demonstrate a common link for the high concentrations of all three elements, which likely involves an oxidation reaction on the Mn-oxide and Fe-oxyhydroxide surfaces. The documented fractionation of PGE-Au and their positive association with redox sensitive Co and Ce may have applications in reconstructing past-ocean redox conditions and water masses.     

Distribution and sources of pre-anthropogenic lead isotopes in deep ocean water from FeMn crusts

The lead isotope composition of ocean water is not well constrained due to contamination by anthropogenic lead. Here the global distribution of lead isotopes in deep ocean water is presented as derived from dated (ca. 100 ka) surface layers of hydrogenetic Fe-Mn crusts. The results indicate that the radiogenic lead in North Atlantic deep water is probably supplied from the continents by river particulates, and that lead in Pacific deep water is similar to that characteristic of island and continental volcanic arcs. Despite a short residence time in deep water (80–100 a), the isotopes of lead appear to be exceedingly well mixed in the Pacific basin. There is no evidence for the import of North Atlantic deep water-derived lead into the Pacific ocean, nor into the North Indian Ocean. This implies that the short residence time of lead in deep water prohibits advection over such long distances. Consequently, any climate-induced changes in deep-water flow are not expected to result in major changes in the seawater Pb-isotope record of the Pacific Ocean.     

U-Th chronology and paleoceanographic record in a Fe-Mn crust from the NE Atlantic over the last 700 ka

Hydrogenetic ferromanganese crusts (Fe-Mn crusts) provide a secular record of the variations of seawater composition responding to changes in ocean circulation and erosion processes. In this respect, the acquisition of an absolute and reliable chronology in Fe-Mn crusts is a prerequisite. Here we combine four different and complementary chronometers (¹⁰Be, ²³⁰Th_ex, ²³⁰Th_ex/²³²Th, ²³⁴U/²³⁸U) in a Fe-Mn crust dredged at ∼2000 m depth in the east Atlantic to first establish a reliable chronology over the Quaternary period. Then, we use EDS chemical analysis to look for correlation between major element chemistry and climate changes. (²³⁰Th_ex), (²³⁰Th_ex/²³²Th), and Be data give very consistent growth rates. In particular, the good match between (²³⁰Th_ex) and (²³⁰Th_ex/²³²Th) data indicates that at the location of crust 121DK, ²³⁰Th and ²³²Th fluxes in the water column change simultaneously and suggests that the normalization of ²³⁰Th_ex to ²³²Th makes (²³⁰Th_ex/²³²Th) a better chronometer. Our best-fit model suggests that crust 121DK experienced changes in growth rates at ∼122 and 312 ka and a growth with a constant ²³⁰Th initial flux. This chronology returns an age of 680 ka for the uppermost 1.5 mm. The (²³⁴U/²³⁸U) depth profile, however, was clearly affected by diffusion of ²³⁴U in the porous crust and can therefore not be used to derive a reliable chronology. One part of the crust seems isolated from pore water diffusion and can be physically recognized as a zone of very small porosity. On the basis of the (²³⁰Th_ex/²³²Th) chronology, major element chemistry is shown to be linked to climate change. Mn/Fe variations compare well with those in a Fe-Mn crust from the Pacific, showing systematic maxima during glacial stages 2 and 4. High Mn/Fe are tentatively interpreted to reflect expansion of the oxygen minimum zone during glacial periods, resulting from higher bioproductivity. In addition we note that the surface (²³⁰Th/²³²Th) activity ratio of crust 121DK is entirely consistent with advection of deep water from the western toward the eastern Atlantic basin.     

太平洋富钴结壳中稀土元素的赋存状态

采用化学提取方法对采自太平洋国际海域的板状和结核状富钴结壳的稀土元素进行了分级提取 ,并利用等离子质谱仪 (ICP MS)测定了稀土元素的质量分数。结果表明 ,结壳中稀土元素在不同结合态中的富集顺序为 :残渣态 >有机结合态 >锰氧化物结合态 >碳酸盐结合态 >吸附态。稀土总质量分数的 5 6 %以上集中在残渣态中 ,并主要赋存于非晶态FeOOH物相中 ,说明FeOOH的形成对稀土元素的富集具有重要作用。水羟锰矿占结壳中X衍射结晶矿物的 95 %以上 ,但其稀土质量分数仅占稀土总质量分数的 1 6 %左右。呈有机结合态的稀土元素含量约占结壳稀土总质量分数的 2 0 % ,表明有机质对于结壳的形成及稀土元素的富集具有显著影响     

Tungsten accumulation in Pacific ferromanganese deposits

Tungsten has often been reported in marine ferromanganese deposits and the question arises as to how the large oxyanionic species (WO ₄ ^2- ) enters the appropriate phases. Very low W concentrations in seawater (less than 0.0002 g/kg) suggest that it is not directly related to precipitation processes. Of all the comparable marine samples, manganese micronodules have the highest W contents, in the range 1.4 to 3.6 times, 3 higher than in the associated macronodules. A depositional record for more than 60 million years obtained for a thick manganese crust shows that the tungsten distribution with depth correlates best with As and to a lesser extent with Fe. The mechanism favoured for enrichment of W is precipitation onto fine hydrothermal manganese-rich particles supplied by ridge volcanic activity. Such particle plumes are usually released in cycles, stay for comparatively long periods in the water column, and are then transported from the hydrothermal centres to the deep basins where they settle and probably contribute to the growth of ferromanganese oxide phases on the ocean floor which is mainly by diagenetic and hydrogenetic processes.     

Rare earth elements in phosphate-ferromanganese crusts on Pacific seamounts

Based on publications devoted to the composition of P-rich ferromanganese crusts on Pacific seamounts, relationships between the REE distribution in the crusts and the contents of phosphates and Fe-Mn hydroxides therein are considered. It is shown that REEs in the crusts are related to all three mineral phases and their contents are variable. In general, the REEs show weak correlations with P, Mn, and Fe in different varieties of ore crust. Average REE contents are comparable in samples with the maximal and minimal phosphorus contents, suggesting irregularity of REE distribution in the phosphates and ferromanganese phases. This fact is consistent with data on the presence of natural REE minerals in the phosphates.