麦哲伦海山区MA,MC海山富钴结壳元素间关系及成因意义

为探讨富钴结壳中元素的成因,采用了化学容量法、原子吸收、Ｘ－射线衍射分析、电子探针、等离子光谱等技术,对太平洋麦哲伦海山区曲ＭＡ海山、ＭＣ海山上的富钴结壳分老世代和年青世代层进行了矿物成分与元素万分分析。据分析结果,区内主要赋存水成富钴结壳,富钴结壳中的矿物组分以锰相矿物的水羟锰矿为主,其次为铁相矿物（针铁矿等）,还有磷灰石和少量次要矿物（钙十字石、石英等）。老世代富钴结壳,磷酸盐化明显,个别层内     

莱恩海山链MP2海山富钴结壳Co元素的富集/亏损研究

富钴铁锰结壳(简称富钴结壳或海山结壳)是生长在大洋洋底地势较高处(如海山)硬质基岩上的富含铁、锰、钴、铂、稀土等金属元素的"壳状"沉积矿产.与其它深海铁锰沉积相比较,海山结壳的的最主要特征是富Co,其Co含量是大洋铁锰沉积中最高的.但是,同一富钴结壳样品的不同层位Co含量的差异是比较大的,到目前为止,人们并没有充分认识富钴结壳为什么"富钴",即Co发生富集/亏损的原因.本文通过对莱恩海山链MP2海山的一块典型富钴结壳样品电子探针原位化学成分数据的系统分析,对富钴结壳形成过程中Co富集/亏损的原因进行了系统研究,以揭示富钴结壳中的Co富集机制以及富钴结壳成矿作用是否具有时代的特殊性.     

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。     

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。     

磷酸盐化作用对富钴结壳元素相关性的影响

为了探讨磷酸盐化作用对富钴结壳元素相关性的影响,用电感耦合等离子体发射光谱法(ICP-AES)和重量法测试了中太平洋CX海山富钴结壳的主、微量元素及稀土元素.首先以P质量分数和Y异常把富钴结壳分为磷酸盐化型[w(P)＞0.57%且具有正Y异常]和未磷酸盐化型[w(P)＜0.57且具有负Y异常].结果表明,相比于未磷酸盐化型结壳,磷酸盐化型结壳中某些元素出现相对亏损和富集,其中亏损元素的亏损顺序为Si＞Al＞Fe＞Co＞Li＞K＞Pb＞Na＞Mg＞V,而富集元素的富集顺序为P＞Ca＞REE＞Ba＞Sc＞Mo＞Cu＞Ni＞Ti＞Sr＞Zn＞Mn;两类结壳相同元素问的相关性既有共性也有差别,Si-Al、Si-Fe和Si-Ca 等元素间的相关性在两类结壳中变化不大,而P-Mn,P-Fe,Mn-Fe,Fe-Co等元素间的相关性则发生重要改变,这些相关性发生变化的元素对可指示结壳是否遭受磷酸盐化作用,元素丰度以及元素相关性的变化与磷酸盐化作用引起的结壳矿物组成变化有关.     

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。     

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.      

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。     

西太平洋富钴结壳中磷酸盐化的制约因素探讨

富钴结壳是生长在海底岩石或岩屑表面的一种自生壳状沉积物。大洋富钴结壳老壳层在形成后或形成期间曾遭受不同时代的磷酸盐化(Hein J R等,1993),形成多层磷酸盐化壳层。前人关于磷酸盐化作用对富钴结壳的影响多有论著,但主要涉及矿物成分、化学组成、结构构造等方面(Koschinsky A等,1997;Jeong K S等,     

滇黔桂典型锰矿床矿相学特征及其对成矿过程的指示

滇黔桂地区代表性锰矿包括贵州松桃大塘坡锰矿、广西大新下雷锰矿、遵义铜锣井锰矿和云南砚山斗南锰矿.本文利用显微镜、X衍射仪、扫描电镜等仪器,通过研究滇黔桂地区典型锰矿矿相学特征,结合碳酸盐岩研究方法,查明产于南华系大塘坡组第一段(Nh1d1)贵州松桃大塘坡锰矿矿物组合包括菱锰矿、钙菱锰矿、锰白云石、锰方解石、石英、伊利石,微相为SMF2、沉积相FZ1(盆地相),形成于沉积环境伸展阶段;产于上泥盆统五指山组(D3w)广西大新下雷锰矿矿物组合包括褐锰矿、锰钾矿、菱锰矿、钙菱锰矿、蔷薇辉石、透闪石、石英,微相为SMF2和SMF15-M、沉积相FZ7(台地相),形成于沉积环境伸展阶段;产于中二叠统茅口组第二段(P2m2)遵义铜锣井锰矿矿物组合包括菱锰矿、钙菱锰矿、锰方解石、锰白云石、硫锰矿、黄铁矿、闪锌矿、高岭石、伊利石、菱铁矿,微相为SMF15-C和SMF17、沉积相FZ7(台地相),形成于沉积环境收缩阶段;产于中三叠统法郎组(T2f)其矿物成分包括云南砚山斗南锰矿矿物组合包括褐锰矿、水锰矿、钙菱锰矿、含锰方解石、方解石、石英,微相为SMF4和SMF13、沉积相FZ4(斜坡相),形成于沉积环境伸展阶段.     

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.     

东菲律宾海新型铁锰结壳中元素的赋存状态

为了解东菲律宾海新型铁锰结壳中元素的赋存状态, 采用化学提取方法对3个结壳样品进行了物相分析.不同类型结壳中成矿和稀土元素的赋存状态总体一致, 表明它们形成于相近的地质和海洋环境中.成矿元素中的Fe和Cu绝大部分赋存在残渣态中, Mn、Co和Ni则主要赋存在锰氧化物结合态、有机结合态和残渣态中, 并且埋藏型结壳样品锰氧化物结合态中赋存了相对更高比例的成矿元素.三价稀土元素主要集中在锰氧化物结合态中.两个沉积物表层结壳样品中的Ce主要集中在残渣态中.而埋藏型结壳样品中的Ce则主要赋存在锰氧化物结合态中, 这可能与该样品此相态中赋存了相对较多的Mn有关.呈碳酸盐结合态和有机结合态的稀土元素含量仅各占稀土总量的1%左右, 表明两者对结壳中稀土元素的富集作用很小.      

Partizansky base-metal skarn deposit, Dal’negorsk ore district, Russia: Stages of ore formation, mineral assemblages, and typomorphism of fahlore

As indicated by mineralogical, geochemical, and structural-textural data, the base-metal skarn ore at the Partizansky deposit was formed during two stages (base-metal skarn and silver-sulfosalt), which were separated by intrusion of basaltic dikes. The bulk of the base-metal ore was deposited at the first stage, which comprises four sequential mineral assemblages: skarn-silicate, quartz-arsenopyrite, productive galena-sphalerite, and pyrrhotite-pyrite-chalcopyrite. The mineralization of the second stage was mainly confined to the upper margins of orebodies and pertains to the sulfosalt-galena-chalcopyrite assemblage, which was super-imposed on minerals of the first stage. The vertical mineralogical-geochemical zoning of the deposit is telescopic (related to the formation of the late silver-sulfosalt mineralization) and facies (typical of the early skarn and base-metal assemblages). The zoning of the skarn-silicate assemblage is expressed in the metasomatic replacement of skarn by quartz and calcite in the uppermost zone of skarn bodies and is emphasized by variation of the mineral composition throughout the skarn column, for instance, by the distinct updip enrichment of hedenbergite in manganese. The vertical zoning of the productive assemblage is emphasized by variations in the ratio of sphalerite to galena (the Pb/Zn ratio in the ore increases upward from 0.1 to 1), changes in mineral assemblages, and compositional variation of major ore-forming and minor minerals. In particular, galena from the deep levels is extremely enriched in Bi and Ag, while that from the upper levels is almost completely devoid of isomorphic admixtures. Fahlore displays updip enrichment in Sb, Ag, and Fe and corresponding depletion in Cu and Zn. The vertical chemical variations in fahlore are caused by the specific geological setting of ore deposition, the composition of the ore-forming solutions, and the physicochemical conditions of their transportation and ore deposition.     

浙江金衢盆地白垩系衢江群沉积相类型及沉积环境演化

本文在野外露头观察和前人研究成果整理的基础上,通过对金衢盆地白垩系衢江群的岩性组合、沉积构造、地层序列及沉积中心、岩相变化等的研究,将衢江群划分出山麓洪积相、河流相、湖泊相、河湖相4种沉积相类型.认为盆地发育大致经历了3个阶段:形成于中戴期早期,于金华期处于全盛时期,萎缩于衢县期.衢江群岩性总体上反映了盆地的发生、扩展至萎缩各个时期的变化.     

The variation of morphological features and mineralogical components of biological soil crusts in the Gurbantunggut Desert of Northwestern China

Increasingly complex life forms were found in older biological soil crusts in the Gurbantaunggut Desert in Northwestern China. These crusts may play a critical role in mineral erosion and desert soil formation by modifying the weathering environment and ultimately affecting mineralogical variance. To test this hypothesis, variations in the morphological features and mineralogical components of successional biological soil crusts at 1 cm were studied by optical microscopy, SEM and grain size analysis. Concentrations of erosion-resistant minerals decreased with crust succession, while minerals susceptible to weathering increased with crust development. Neogenetic minerals were found in late stage crusts, but not in early stage crusts. Silt and clay concentrations were highest in early formation crusts and soil mean particle size decreased with crust succession. Cyanobacteria, lichen and moss were shown to erode and etch rocks, and secondary minerals produced by weathering were localized with the living organisms. Thus, more developed crusts appeared to contribute to greater mineral weathering and may be a major cause of mineralogical variance seen in the Gurbantunggut Desert. The greater activity and complexity of older crusts, as well as their improved moisture condition may function to accelerate mineral weathering. Therefore, protection and recovery of biological crusts is vital for desert soil formation.     

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.     

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.     

云南兰坪盆地中部白垩系沉积环境及区域构造意义

云南兰坪盆地在白垩纪的演化为其喜马拉雅期的大规模成矿起到了铺垫作用。前人对该时期的沉积相分析较为笼统,一定程度上影响了对盆地演化、盆地性质及成矿方面的深入理解。在兰坪盆地中部开展了实测剖面和路线调查等工作,认为兰坪盆地的白垩系分为扇三角洲-湖泊和辫状河三角洲-残余河湖2个沉积体系,盆地性质应属断陷盆地。结合对特提斯洋演化过程的认识,认为早白垩世兰坪盆地继承了中侏罗世—晚侏罗世沉降的构造背景,早白垩世末中特提斯洋的闭合中断了盆地的沉降作用,晚白垩世新特提斯洋的北向俯冲导致了中生代兰坪盆地演化的终止。结合区域矿产资料,认为早白垩世成矿元素已有初步富集,并为喜马拉雅期成矿提供了必要的矿源层、建造水、运移通道及成矿定位空间。研究可为兰坪盆地的演化过程提供新的实证资料。     

西准噶尔宝贝金矿地质与容矿火山岩的锆石SHRIMP年龄

位于西准噶尔的宝贝金矿主要由石英脉型矿石组成,主要含金矿物为银金矿,以裂隙金和包裹金的形式赋存在毒砂、黄铁矿和石英中。宝贝金矿的黄铁矿普遍含As（最高达3.88%,平均1.49%）。根据脉穿切和矿物共生组合可将宝贝金矿的成矿作用划分出四个成矿阶段：钠长石–石英阶段（I）、银金矿–黄铁矿–毒砂–石英阶段（II）、多金属硫化物浸染状矿化阶段（III）和碳酸盐化阶段（IV）,其中第II和III阶段为主要成矿期。利用锆石SHRIMP方法测定了赋矿围岩（酸性凝灰岩）的形成时代,其U–Pb谐和年龄为328.1±1.8 Ma（MSWD＝1.6, n＝13）。该年龄代表宝贝金矿赋矿围岩的形成时间,即西准噶尔地区大规模中酸性火山岩的喷发时间。