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。     

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。     

西太平洋富钴结壳生长与富集特征

通过对西太平洋麦哲伦海山区富钴结壳的大尺度细致研究 ,笔者较为深入地探讨了该区结壳的生长与富集特征。研究表明 ,该区结壳自古近纪开始生长 ,生长速率变化范围为 1.5～ 12 .3mm/Ma,速率相差近一个数量级 ,平均生长速率为 3.81m m/Ma;生长过程中成矿元素的地球化学行为呈现明显差异 ;环境发生“骤变”的 O/M界面 ,可能是结壳生长过程中其构造和色泽发生“突变”的一个重要年代 ;成矿元素成分的时序演化主要受控于海水化学和各种不同地质作用的综合影响 ,成矿与非成矿地质作用在生长过程中呈现为互为消长的特征。研究发现 ,该区结壳和太平洋深海粘土元素的分配系数间存在着显著的线性相关关系 ,相关系数为 0 .89,显示它们有相近的元素富集机理。此外 ,笔者还从元素的滞留时间、阳离子的电子键能及其在海水中的水解行为与结壳富集特征间的关系进行了探讨。     

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。     

中太平洋海山富钴结壳中水羟锰矿的超结构

采自中太平洋海山富钴结壳主要由水羟锰矿组成,在XRD衍射图谱上,该矿物缺少(001)和(002)底面衍射,其原因是水羟锰矿包含了两种对称型的八面体层,即三斜对称和六方对称的八面体层,它们沿c轴方向无序排列。部分样品中的水羟锰矿在低角度区具有d>2.0nm的超结构衍射峰,它在实质上反映了矿物结构层的长程有序性,即两种层片的排列具有某种周期性或规律性。部分样品原先没有,但在加热后出现超结构衍射峰,可能是因为样品在空气中加热,使三斜层片中的Mn(III)被氧化成Mn(IV),从而转变为六方层片,继而改变了水羟锰矿的有序性。富钴结壳中水羟锰矿的超结构,在一定程度上反映了矿物形成环境的变化。     

中太平洋地区两个铁锰结壳的生长幕研究

通过对3块中太平洋铁锰结壳样品进行的生物地层学及其结构构造、元素地球化学剖面的综合研究发现,铁锰结壳的生长主要集中于两个形成环境存在差异分别由不同因素控制的形成阶段,一个是约25Ma以来其形成环境氧化程度由南极底层流(AABW)控制的对应于结壳新壳层的生长幕,另一个是渐新世之前其形成环境氧化程度由环赤道表中层洋流和高密度温盐表层水下沉控制的对应于结壳老壳层的生长幕,而在早、中渐新世处于两种环境的转换期,也正好是海退期、大洋低生产力期、低CCD和生物碳酸盐低产率期,形成结壳生长的主要生长间断。该研究成果对于进一步了解太平洋的古海洋、古环境演变有一定意义。     

中太平洋YJC海山富钴结壳矿物组成与元素地球化学

运用等离子光谱、等离子质谱、X射线衍射、红外光谱和场发射电镜等分析测试方法,对太平洋威克(Wake)海岭YJC海山中的富钴结壳中不同构造层的矿物组成和元素地球化学研究表明:矿石矿物是水羟锰矿和少量的钙锰矿,脉石矿物是磷灰石、石英和方解石等,微量矿物有蒙脱石、高岭石、钠沸石、斜发沸石、伊利石、水黑云母、磁铁矿和角闪石等。老结壳磷灰石的质量分数>10%,P>1%;新结壳磷灰石<10%,P<1%。老结壳相对富集Cu、Ca、P等元素,新结壳相对富集TMn、TFe、Co、Ni、Ba、Zn、Pb、Mo等元素。结壳内部纹层构造的不同位置及包体内的微区成分变化较大,TMn和TFe呈同消长关系,但TMn/TFe值相对稳定。结壳的稀土元素总量为1761.88×10-6,Ce具明显的正异常。老结壳相对富集稀土元素,新结壳略富Eu。     

西太平洋海山玄武岩的岩石学特征及与上覆富钴结壳的关系

通过对西太平洋海山玄武岩和玄武质火山角砾岩的岩石学特征及其气孔充填物成分变化的研究,讨论了海山玄武岩与上覆富钴结壳的关系。富钴结壳的基岩火山岩主要为碱性玄武岩和玄武质火山角砾岩。碱性玄武岩中气孔充填物为S型和C型,S型和C型气孔充填物不共存在同一个气孔中。S型气孔充填物的物质成分富Si、Fe、K、Mg、Al,Co含量一般为0.17%~0.46%,其成分与碱性玄武岩的组成类似,其物质来源可能与碱性玄武岩有关。C型气孔充填物为O、Ca、C及少量Si、Al、Mg、Fe、K等元素,C型气孔充填物可能与海水中物质的沉积有关。由Si、Al、Fe、Mg、K等元素变化曲线反映出的S型气孔充填物沉积过程与富钴结壳早期的沉积过程具有相似的趋势,说明富钴结壳早期沉积物的物质来源可能与碱性玄武岩有关,富钴结壳物质来源可能是碱性玄武岩和海水共同作用的结果。     

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.     

等离子体发射光谱法同时测定大洋富钴结壳中硅锰铁钙镁铝钛

大洋富钴结壳试样经ＨＣｌ＋ＨＮＯ３＋ＨＦ溶解,在０．２ｍｏｌ／ＬＨＦ和０．１３ｍｏｌ／ＬＨ３ＢＯ３介质中,用感耦等离子发射光谱法同时测定Ｓｉ、Ｍｎ、Ｆｅ、Ｃａ、Ｍｇ、Ａｌ、Ｔｉ元素的含量。方法经国家标准物质ＧＢＷ０７２４９大洋多金属结核验证,其结果与标准值相符,精密度ＲＳＤ〈３．２％（ｎ＝６）;已应用于太平洋富钴结壳中多元素分析。     

Noble Gas Isotopic Compositions of Cobalt-rich Ferromanganese Crusts from the Western Pacific Ocean and Their Geological Implications

1 Introduction Submarine metallic mineral resources consist mainly of polymetallic nodules and cobalt-rich ferromanganese crusts. Despite being discovered much later than the former, the latter are becoming one of the most important submarine polymetallic ore resources, because they containmany valuable metallic elements such as Co, platinum group elements (PGE), rare earth elements (REE), Ni and Cu, besides high contents of Fe and Mn (He et al., 2001). The Co-rich crusts are widely distr…     

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。     

中太平洋YJA海山富钴结壳矿物组成与元素地球化学

研究样品采自马尔库斯（MARCUS）海脊YJA海山。利用等离子光谱、等离子质谱、X-射线衍射、红外光谱、场发射电镜等分析测试方法,对富钴结壳中不同构造层的矿物组成和元素地球化学进行了研究。该结壳为一大型板状新结壳,矿石矿物是水羟锰矿,脉石矿物是石英、斜长石、磷灰石等,微量矿物有蒙脱石、高岭石、钠沸石、水黑云母、片沸石等。从结壳的底部构造层到顶部构造层,TMn,Ni,Cu, Ba,Zn等元素的质量分数逐渐减少,TFe逐渐增加,Co变化不大;在相对疏松的构造层中,Si,Al,K,Na,Ca,Mg,Ti,P,Li,Rb等元素相对富集;结壳的稀土元素总量是1 982.27×10^-6,Ce具明显的正异常。不同构造层稀土元素的演化趋势是：Ce与Mn等元素相同,其他稀土元素（Y除外）与Fe等相似。     

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.     

Formation of diapiric structure in the deformation zone,central Indian Ocean: A model from gravity and seismic reflection data

Analyses of bathymetry, gravity and seismic reflection data of the diffusive plate boundary in the central Indian Ocean reveal a new kind of deformed structure besides the well-reported structures of long-wavelength anticlinal basement rises and high-angle reverse faults. The structure (basement trough) has a length of about 150 km and deepens by up to 1 km from its regional trend (northward dipping). The basement trough includes a rise at its center with a height of about 1.5km. The rise is about 10 km wide with rounded upper surface and bounded by vertical faults. A broad freeair gravity low of about 20 mGal and a local high of 8 mGal in its center are associated with the identified basement trough and rise structure respectively. Seismic results reveal that the horizontal crustal compression prevailing in the diffusive plate boundary might have formed the basement trough possibly in early Pliocene time. Differential loading stresses have been generated from unequal crust/sediment thickness on lower crustal and upper mantle rocks. A thin semi-ductile serpentinite layer existing near the base of the crust that is interpreted to have been formed at mid-ocean ridge and become part of the lithosphere, may have responded to the downward loading stresses generated by the sediments and crustal rocks to inject the serpentinites into the overlying strata to form a classic diapiric structure.     

Linkage between Seasonal Insolation Gradient in the Tropical Northern Hemisphere and the Sea Surface Salinity of the Equatorial Indian Ocean during the Last Glacial Period

Paired stable oxygen isotope and Mg/Ca analyses in calcite tests of the mixed-layer-dwelling planktic foraminifer Globigerinoides ruber has been used to reconstruct equatorial Indian Ocean δ18O of seawater (δ18Osw) over the last ~137 thousand years. On the basis of ice-volume-corrected δ18Osw (δ18Osw–ivc), relative changes in sea surface salinity (SSS) have been estimated. The SSS estimates suggest three episodes of higher SSS (131–113 thousand years before present (kyr BP), 62–58 kyr BP, and 30–24 kyr BP) within the last glacial period as compared with the present. SSS comparison between interglacial episodes reveals that the surface seawater over the core site was significantly saltier during the penultimate interglacial than the Holocene. We suggest that the evolution of a seasonal insolation gradient between the Indian monsoon areas and the equator over the investigated time interval was instrumental in shaping the strength of the Indian winter and summer monsoons that left their imprints on the equatorial Indian Ocean SSS via freshwater input and wind-induced mixing. The study shows that the insolation difference between northern latitudes and the equator during winter affects monsoon strength in the Indian region, especially during cold intervals.     

太平洋中国开辟区铁锰结核稀土元素和铈钕同位素特征

从东太平洋中国开辟区南部挑选了4个铁锰结核(地理坐标,北纬7.7533°～8.6866°,西经143.875°～146.937°),每个结核以内部较容易剥离面和密集的铁锰质纹层为界,分成核部、中部和边部3部分,共12个样品做了Ce、Nd同位素组成和REE浓度测定。另外,从相同站位上又选择了3个结核进行了全结核的常量和微量元素浓度测定。常量与微量元素浓度测定结果证明,被研究结核属于早期成岩型。稀土元素图形特征与以前报道不同,从较广泛区域内挑选出的样品,除一个基本上无Ce异常外,其他都显示弱的负Ce异常,平均δCe为0.85。更重要的特征是,被测定的12个样品ε_(Ce)和ε_(Nd)都呈负值,同时,ε_(Nd)值高于其他大洋,它们分别为-0.80～-1.9和-1.4～-4.6,在ε_(Ne)-ε_(Nd)坐标图上位于第Ⅲ象限。根据这些特征,结合洋底地质环境,可能暗示直接或间接来源于大洋亏损地幔的成矿物质在太平洋结核中占有绝对优势。结核内部壳层之间的Ce、Nd同位素组成和Ce异常强度的变化,可能说明,在整个结核形成期间,成矿组分的来源曾发生过较大变化,幔源组分的强烈活动出现在结核的形成过程中。     

Lipid composition of the pelagic crab Pleuroncodes planipes, its feces, and sinking particulate organic matter in the Equatorial North Pacific Ocean

Fecal pellets from the pelagic crab Pleuroncodes planipes were a substantial portion of the particulate organic matter in a sediment trap deployed at the bottom of the mixed layer in the eastern tropical North Pacific Ocean. The lipids of fresh P. planipes feces were compared to lipids of the sediment trap material, of mixed zooplankton which may comprise part of the diet of the crab, and of the crab itself in order to elucidate the source of organic compounds found in the trap. Hydrocarbons, wax esters, triacylglycerols, steroidal alcohols, steroidal ketones, and fatty acids were determined by capillary gas chromatography and gas chromatography/mass spectrometry. Significant input of lipids via sedimentation of crab fecal material is indicated, and modification of dietary lipid within the gut of the crab is inferred. Labile dietary fatty acids are depleted and sterols enriched in the fecal pellets and trap material relative to the zooplankton and crab. Nuclear saturated and unsaturated 3-ketosteroids and unsaturated steroidal hydrocarbons were detected in the crab, its feces, and in the sediment trap particulate material.     

Final Closure Time of the Paleo‐Asian Ocean: Implication from the Provenance Transformation from the Yangjiagou Formation to Lujiatun Formation in the Jiutai Area,NE China

The Jiutai area is tectonically situated at the eastern segment of the Central Asian Orogenic Belt(CAOB) and is close to the North China Craton(NCC) to the south, serving as an ideal place to investigations of the closure of the PaleoAsian Ocean(PAO). Sandstone samples collected from the Yangjiagou Formation and the Lujiatun Formation in this area have been studied in detail in terms of petrology, geochronology and geochemistry. The maximum depositional time of the Yangjiagou and Lujiatun formations has been constrained to early Middle Triassic(ca. 245 Ma) and middle Late Triassic(ca. 219 Ma), respectively. The Yangjiagou Formation, with a major provenance of dissected island arcs, is dominantly composed of Phanerozoic sediments from Northeastern China(NE China) massifs. The Lujiatun Formation, with major sediments from active continental margins, has a relatively larger proportion of Precambrian sediments, in which the ～1.85 Ga and ～2.5 Ga sediments are typical of the crystalline basements of the NCC and NE China massifs, which were uplifted and eroded during the closure of the PAO. Besides, both formations show the enrichment in LREEs and the depletion in HREEs, the common Eu negative anomalies, and trace element contents similar to that of the upper continental crust. Based on the provenance analysis of these two formations, the final closure time of the PAO in this area is constrained as from the early Middle Triassic(ca. 245 Ma) to the middle Late Triassic(ca. 219 Ma).