太平洋海山成矿系统与成矿作用过程

文中初步探讨了太平洋海山富钴结壳成矿系统的结构与成矿作用过程。海山成矿系统的控矿要素主要包括地质要素和海洋要素,地质要素主要包括海山的形成、迁移、沉降和水道的开合等,海洋要素主要包括大洋温盐环流、最低含氧带(OMZ)、文石溶跃面、碳酸盐补偿深度和海山周围海水的动力情况等。重点分析了海山漂移和沉降、水道开合、最低含氧带变化、大洋环流以及气候变化等要素对富钴结壳成矿的控制作用。海山为富钴结壳成矿提供了一个容矿空间,稳定的基岩,即长期稳定的容矿空间,是富钴结壳成矿的基本条件;海山的形成年龄、海山的迁移和水道的开合决定并改变了富钴结壳的成矿背景条件,促使海山成矿系统发生演化。最低含氧带作为富钴结壳成矿的地球化学障,是直接的矿源层;而海山周边的地形旋涡沟通了最低含氧带与富氧、富铁的深层和底层水,使得最低含氧带中的成矿金属离子得到氧化,进而发生胶体凝聚沉淀,形成富钴结壳。以西太平洋海山成矿系统为例,将该区白垩纪以来富钴结壳成矿作用过程划分为5个阶段:(1)白垩纪—始新世,(2)始新世末—晚渐新世,(3)晚渐新世—中中新世早期,(4)中中新世早期—晚中新世早期,(5)晚中新世早期—现代,其中(2)、(3)阶段有利于发育富钴结壳。     

太平洋海山富钴结壳钙质超微化石生物地层学及生长过程

正确判断富钴结壳生长年代及过程有助于研究结壳形成地质历史和重建古海洋环境.利用生物地层学方法(生物遗留印痕)对太平洋不同海山结壳样品进行生长时代和阶段研究,发现麦哲伦海山CM3D06结壳和中太平洋海山CB14结壳最初形成年代和富集特征差异显著: 前者为白垩纪(或更古老)、晚古新世-早始新世、中-晚始新世、中-晚中新世、上新世-更新世等5个阶段;后者为晚古新世-早始新世、中-晚始新世、中中新世、上新世-更新世等4个阶段.两座海山结壳层内部超微化石组合具有极强的区域性特征,反映了大洋环境对生物的影响以及生物对环境的适应.结壳层间的不整合和结构构造的变化指示在渐新世其生长存在间断期,与成矿作用的间断有关.      

太平洋海山磷酸盐的锶同位素成分及形成年代

作者首次对太平洋不同海山上对富钴结壳伴生的各种产状的磷酸盐的锶同位素成分及其形成年代进行了深入研究。研究表明，我国调查区磷酸盐的^87Sr/^86Sr比值变化于0.70766至0.70842之间，形成年代相当于距今21Ma至39.5Ma。磷酸盐化作用主要发生在晚始新世-早新新世及晚渐新世-早中新世期间。西、中太平洋磷酸盐形成年代的一致性揭示，自晚始新世至早中新世，在太平洋水下海山上曾发生过广泛的磷酸盐化作用，磷酸盐的形成是古海洋环境变迁的一个重要反映。     

富钴铁锰结壳的控矿要素和成矿过程:以西太平洋为例

富钴铁锰结壳(简称富钴结壳)是产出在海山、岛屿斜坡及海底高地上的一种潜在新型矿产资源,由铁锰氧化物和氢氧化物组成,富含Co、Ni、Zn、Pb、Ce、Pt、REE等金属元素,其中Co的平均含量较陆地原生钴矿高几十倍.     

采薇平顶海山群底质类型分布研究

<正>富钴结壳主要生长在水深400~4000 m的中、西太平洋海山山顶边缘和斜坡位置,其中1000~3000m水深范围内最为富集。就具体海山而言,富钴结壳易生长于山顶周边平台和鞍部(Hein,et al.,2000)。海山钙质远洋沉积、碳酸盐岩沉积及重力作用引起的滑塌沉积是海山山顶和斜坡的主要沉积类型。本文利用中国大洋36航次最新获得的EM122多波束测深和回波强度资料,对采薇平顶海山群进行地形     

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。     

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.      

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。     

西太平洋富钴结壳元素组合特征及其地质意义

海山富钴结壳是一种重要的海底固体矿产。对西太平洋海山的56个结壳样品进行了23种化学组分分析,并利用R型聚类分析和R型因子分析,分别提取四组元素组合和四个主因子。综合特征表明．富钴结壳在形成过程中,经历了一次强度较大的锰矿物相成矿作用,Co、Ni等元素的富集与此有关;铁矿物相的成矿作用强度较小,但表现出多期次的特点;锰、铁矿物是不同成矿作用的产物;结壳形成过程中,可能遭受了二次磷酸盐化作用,结壳中磷酸盐矿物的形成对铁矿物相的形成可能有抑制作用。     

中太平洋海山富钴结壳生长习性及控制因素

通过对"大洋一号"调查船DY95-10、DY105-11、DY105-12等航次结壳样品和海底摄像照相资料等综合观测分析,从不同角度对中太平洋海山富钴结壳的生长习性及控制因素进行了初步探讨.结果表明,富钴结壳可以在海山区的各种岩石上生长发育,对岩性没有明显的选择性,载壳岩石类型统计结果与岩石类型区域上的分布不均衡有关,而与岩性本身并没有必然的联系.结壳生长的厚度除受载壳岩石形成年代、物化环境影响外,与其所经受构造活动的强度和频率也有密切联系.水深可能对结壳的生长发育具有一定的控制作用,但由于海山在结壳生长后存在移动和升降运动,因此现在海山上的结壳并不存在截然的水深界限.地形对富钴结壳覆盖率、产状、形态具有明显的控制作用,海山坡度太缓、太陡均不利于结壳的生长发育;在海山坡度较大处生长的结壳多呈平板状,而在坡度较小处生长的结壳多呈波纹状或枕状;海山的斜坡上生长的多为板状结壳,而在平坦低洼处则有利于砾状结壳、钴结核的生长发育.     

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。     

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.     

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。     

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.     

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。     

Geochemistry and genesis of Fe-Mn mineralization in island arcs in the west Pacific Ocean

This paper presents materials on the chemical and mineralogical composition of Fe-Mn mineralization in island arcs (Kurile, Nampo, Mariana, New Britain, New Hebrides, and Kermadec) in the western part of the Pacific Ocean. The mineralization was proved to be of hydrothermal and/or hydrogenic genesis. The former is produced by hydrothermal Fe and Mn oxi-hydroxides that cement volcanic-terrigenous material in sediments. Some Fe oxi-hydroxides can be derived via the halmyrolysis of volcaniclastic material. Crusts of this stage are characterized by fairly low concentrations of trace and rare elements, and their REE composition is inherited from the volcanic-terrigenous material. The minerals of the Mn oxi-hydroxides are todorokite and “Ca-birnessite.” The Mn/Fe ratio increases away from the discharge sites of the hydrothermal solutions. The hydrogenic Fe-Mn crusts are characterized by high concentrations of trace and minor elements of both the Mn group (Co, Ni, Tl, and Mo) and the Fe group (REE, Y, and Th). The hydrogenic crusts consist of Fe-vernadite and Mn-feroxyhyte. Some of the hydrothermal crusts originally had a hydrothermal genesis. The first data were obtained on crust B30-72-10 from the Macauley Seamount in the Kermadec island arc, which contained anomalously high concentrations of Co (2587 ppm) and other Mn-related trace elements in the absence of hydrogeneous Fe oxi-hydroxides.     

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.      

Global occurrence of tellurium-rich ferromanganese crusts and a model for the enrichment of tellurium

Hydrogenetic ferromanganese oxyhydroxide crusts (Fe-Mn crusts) precipitate out of cold ambient ocean water onto hard-rock surfaces (seamounts, plateaus, ridges) at water depths of about 400 to 4000 m throughout the ocean basins. The slow-growing (mm/Ma) Fe-Mn crusts concentrate most elements above their mean concentration in the Earth’s crust. Tellurium is enriched more than any other element (up to about 50,000 times) relative to its Earth’s crustal mean of about 1 ppb, compared with 250 times for the next most enriched element.We analyzed the Te contents for a suite of 105 bulk hydrogenetic crusts and 140 individual crust layers from the global ocean. For comparison, we analyzed 10 hydrothermal stratabound Mn-oxide samples collected from a variety of tectonic environments in the Pacific. In the Fe-Mn crust samples, Te varies from 3 to 205 ppm, with mean contents for Pacific and Atlantic samples of about 50 ppm and a mean of 39 ppm for Indian crust samples. Hydrothermal Mn samples have Te contents that range from 0.06 to 1 ppm. Continental margin Fe-Mn crusts have lower Te contents than open-ocean crusts, which is the result of dilution by detrital phases and differences in growth rates of the hydrogenetic phases.Correlation coefficient matrices show that for hydrothermal deposits, Te has positive correlations with elements characteristic of detrital minerals. In contrast, Te in open-ocean Fe-Mn crusts usually correlates with elements characteristic of the MnO₂, carbonate fluorapatite, and residual biogenic phases. In continental margin crusts, Te also correlates with FeOOH associated elements. In addition, Te is negatively correlated with water depth of occurrence and positively correlated with crust thickness. Q-mode factor analyses support these relationships. However, sequential leaching results show that most of the Te is associated with FeOOH in Fe-Mn crusts and ≤10% is leached with the MnO₂.Thermodynamic calculations indicate that Te occurs predominantly as H₅TeO₆⁻ in ocean water. The speciation of Te in ocean water and charge balance considerations indicate that Te should be scavenged by FeOOH, which is in agreement with our leaching results. The thermodynamically more stable Te(IV) is less abundant by factors of 2 to 3.5 than Te(VI) in ocean water. This can be explained by preferential (not exclusive) scavenging of Te(IV) by FeOOH at the Fe-Mn crust surface and by Fe-Mn colloids in the water column. We propose a model in which the extreme enrichment of Te in Fe-Mn crusts is likely the result of an oxidation reaction on the surface of FeOOH. A similar oxidation process has been confirmed for Co, Ce, and Tl at the surface of MnO₂ in crusts, but has not been suggested previously to occur in association with FeOOH in Fe-Mn crusts. Mass-balance considerations indicate that ocean floor Fe-Mn deposits are the major sink for Te in the oceans. The concentration and redox chemistry of Te in the global ocean are likely controlled by scavenging on Fe-Mn colloids in the water column and Fe-Mn deposits on the ocean floor, as is also the case for Ce.