南海边缘海多金属结核与大洋多金属结核对比

本文通过系统对比分析前人研究成果,研究了南海边缘海多金属结核的成矿特征,结果表明：南海边缘海结核的矿物组成与大洋结核相似,均主要由锰相矿物和铁相矿物组成,其中锰相矿物主要为水羟锰矿和钡镁锰矿,铁相矿物主要以无定型铁氧化/氢氧化物形式存在,另外南海边缘海结核中含有大量硅酸盐矿物,表明在南海结核成矿过程中受到大量的陆源碎屑矿物混杂;相对于大洋主要经济成矿区的多金属结核,南海边缘海多金属结核中主要的经济元素如Mn、Cu、Co、Ni和Zn质量分数较低,而亲陆源性元素如Fe、Ti、P、Nb、Pb、Rb、Sc、Ta、Sr、Th和REY（REE和Y）等质量分数较高;南海边缘海多金属结核的元素地球化学特征和REE配分模式显示其为水成成因,并呈现更低的Mn/Fe值;同时南海边缘海结核也具有较快的平均生长速率及较高的δCe正异常,表明其生长在更为氧化的海水环境。虽然较快的沉积物沉积速率和动荡的海水环境影响了南海边缘海结核的成矿,但大量陆源物质进入海洋也为南海边缘海结核提供了丰富的成矿物质来源,便于南海边缘海结核的快速生长成矿。南海边缘海结核富集有Fe、Ti、Pb、Rb、Th和REY等金属元素,同样可以作为极具潜力的海洋矿产资源。南海边缘海多金属结核具有其独特的地球化学特征,与大洋多金属结核存在着明显差异。     

东菲律宾海多金属结核微区元素赋存特征及成因意义

多金属结核富含Mn、Fe、Co、Ni、Cu和REY(稀土元素和钇)等元素,具有巨大的潜在经济价值。东菲律宾海结核由包壳和核部岩屑(或泥团)构成,其Mn、Fe、Co、Ni和Cu含量介于南海结核和大洋结核之间,但该区域结核的微区特征尚不清楚。本文基于微区元素分析,探究了东菲律宾海结核的元素赋存特征及其成因意义。结果表明,东菲律宾海结核总体为水成成因,主要形成于氧化环境。结核包壳主要由含δ-MnO₂的水成型富铁层(FeO平均为28.7%, MnO平均为21.9%,Mn/Fe值平均为0.93)构成,但边部存在薄层(<100μm)的成岩型富锰层(FeO平均3.41%,MnO平均52.6%,Mn/Fe值平均为17.5),富锰层具有高NiO(2.71%)和CuO(1.45%)含量。根据Co经验公式估算,富锰层可能形成于末次盛冰期(LGM)以来。本研究还发现,结核核部气孔状岩屑中存在成岩成因的富锰矿物,其MnO含量为22.5%～64.7%, FeO含量为0.46%～7.05%,Mn/Fe值为3.96～126。相比包壳中富锰层,核部富锰矿物NiO(1.25%)和CuO(0.5...     

深海多金属结核分布与有价元素提取工艺进展

深海多金属结核主要分布在CP区和CC区等不同海域,表层沉积物均以硅质粘土为主,CP区多金属结核丰度一般大于15 kg/m~2,Cu+Co+Ni品位较低,一般小于1.8%;CC区区内丰度大于5 kg/m~2的占45%,主要集中在本区的中部和南部,其对应的品位高于2.5%,基本呈纬向带状分布。外部结核层、内部结核层与核心层w(Fe_2O_3)、w(MnO)分别为9.4%～12.8%、39.7%～46.5%,不同结核层中钠水锰矿、钡镁锰矿、δ-Mn_2等主要矿物的XRD衍射峰强度呈现一定差异。外部结核层较薄,内部结核层较厚表面布满规则裂纹,核心层至少具有一个形核核心。多金属结核中所含金属元素种类丰富、多矿物紧密混杂,难以提取其中的Mn、Fe、Cu、Co和Ni等有价金属元素。火法冶炼有熔炼法与直接还原法,其产品一般为富锰渣与合金,酸/碱法浸出可得到Mn、Fe、Cu、Co和Ni等的金属,其浸出率基本能达到85%以上,甚至可以达到95%以上。生物法可通过微生物浸出多金属结核的Mn、Fe、Cu、Co和Ni等元素。此外,熔炼-锈蚀法、电解法等处理多金属结核同样效果显著。     

中太平洋YJB海山富钴结核矿物组成与元素地球化学

研究样品采自马尔库斯（MARCUS）海脊YJB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,对其富钴结核中不同构造层的矿物组成和元素地球化学研究表明： 该球状结核核部是玄武岩,向外具四层构造。矿石矿物为水羟锰矿和少量的钙锰矿,脉石矿物为磷灰石、石英、斜长石等,微量矿物有蒙脱石、高岭石、钠沸石、方英石、辉石、束沸石等。老结核相对富TMn、Cu、Ca、P等元素,新结核相对富集TFe、Co、Ni、Si、Al等元素。在老、新结核中,从下部构造层到上部构造层,TMn、Co、Ni、Cu、Ba、Zn、Pb、Mo等的质量分数逐渐减少,TFe逐渐增加。核内玄武岩属大洋板内玄武岩,其成因可能与地幔柱有关。结核的稀土元素总量是1 924.07×10^-6,Ce具明显的正异常。在老、新结核不同构造层中,Ce的演化趋势同TMn等元素,其他稀土元素与Fe等相似。     

南海东部次海盆海山链多金属结核(壳)地球化学特征及成因

为了进一步解释南海不同区域内多金属结核（壳）的地球化学特征与成因,对东部次海盆黄岩?珍贝海山链上新获取的多金属结核（壳）样品进行了X光衍射、X荧光光谱测试、SEM-EDS分析和X Series2 ICP-MS测试,详细分析了样品的矿物组成、地球化学成分特征. 结果表明,矿物组成为水羟锰矿、石英、斜长石等;主要造岩元素中Si、Al含量较高,与陆缘碎屑物影响较大有关;富含Mn、Fe、Co、Ti、Ni、Pb、Sr等多种金属元素,相比南海其他区域,具有中等的Fe、Mn含量特征,地化元素特征与南海西北陆坡发现的铁锰结核（壳）相似;稀土元素具有总量高（平均2 070.01×10-6）的特点,高于南海北部其他样品,与西太平洋结壳稀土含量接近（接近工业品位）,指示了重要的稀土资源前景. 结核Be同位素结果指示该区铁锰结核生长时代为1.17~8.51 Ma,形成于晚中新世大量火山喷发之后,因此水成作用是南海东部次海盆海山链结核（壳）的主要控制作用,而陆源物质的输入、火山作用和高压富氢离子海水的浸取作用都为结核（壳）的形成提供了有利的沉积环境.      

夏威夷群岛东南海域多金属结核的物源特征及其对古海水、亚洲季风信息的记录

为深入探讨夏威夷群岛东南海域结核的物源特征及其所记录的古海水、亚洲季风信息,采用电感耦合等离子体质谱(ICP-MS)、X射线荧光光谱仪(XRF)、电子探针(EPMA)方法,对来源于原地质矿产部和国家海洋局"海洋四号"科考船DY85-1航次采集的研究区的4块多金属结核样品进行了详细的元素地球化学分析测试,并对分析结果进行了Fe-Mn-[(Cu+Ni)×10]、Fe-Mn-[(Cu+Co+Ni)×10]图解与元素间相关性分析。结果表明,结核中的成矿元素直接来源于海水;应用Co含量经验公式、结合Mn/Fe值计算方法对其生长速率进行验证,得到结核的Fe/Mn、Al/(Fe+Mn)值变化曲线与太平洋底栖有孔虫的δ18O曲线、亚洲内陆粉尘通量曲线呈现出相似的变化趋势,表明多金属结核可作为古海水氧化程度及亚洲季风演化研究的新载体。     

微量元素在铁、锰氧化物间的分配系数：古环境的新指标

借助顺序提取技术对西太平洋富钴结壳的铁、锰氧化物进行了分级提取,并利用电感耦合等离子体光谱仪测定了其微量元素的组成.结果表明:锰矿物相(δ-MnO2)主要富集Mn、Ba、Co、Ni、Sr;铁矿物相(FeOOH)富集Fe、As、Cu、Mo、P、Pb,V、Zn.计算了Co、Cu、Ni和Zn元素在铁、锰两相之间的分配系数D=(M/Fe)铁相/(M/Mn)锰相,探讨了其作为古环境替代指标的可行性.发现Co、Cu、Ni和Zn的分配系数与其在富钴结壳中的总质量分数无关,而与海洋生产力存在明显的正相关,其作用机理有待于进一步的研究.     

中太平洋WM1和WX海山富钴结壳元素相关性及其层间变化研究

在结壳矿物学等基本特征分析的基础上,对中太平洋WM1和WX海山富钴结壳中的主量元素、微量元素、稀土元素和铂族元素含量、层间变化及其相关性进行了研究,结果表明:本区结壳从下层到上层,粘土矿物和石英等碎屑矿物逐渐增多,很可能与青藏高原的隆升和剥蚀以及亚洲季风演化有关;TFe/Fe2 从结壳下层到上层逐渐增高,反映了结壳的氧化性由下层到上层增强,海山的沉降可能是造成结壳生长后期环境氧化性增强的重要原因;Ti、Co、Pb、As、Mn、TFe等元素与TFe/Fe2 呈正相关,反映结壳中这些元素的富集与氧化环境有关,而Ca、P、Pt和∑REE等元素与TFe/Fe2 呈负相关,反映结壳中这些元素的富集与还原环境有关;Fe与Co显著正相关是本区结壳的重要特点;结壳的Co与(Fe Mn)的相关性大于Co与Fe的相关性及Co与Mn的相关性;P含量小于1%时,Co与P相关性不明显,当P含量大于1%时,Co与P呈明显负相关,磷酸盐化的过程对铁锰结壳吸附Co的能力起到抑制作用。聚类分析将Pt、∑REE与P和Ca分为一组,说明在结壳中Pt和∑REE主要赋存在碳氟磷灰石中,结壳的磷酸盐化的过程对Pt和∑REE的富集起到了重要的作用。     

大洋多金属结核成因的地球化学标志

本文通过对取自太平洋不同地区的近百个多金属结核样品研究表明,不同成矿介质中形成的结核,地球化学特征明显不同,水成型结核矿物成分上富含σ—MnO_2,化学成分上富含Fe、Co、Pb,而贫Mn、Cu、Ni、Zn,TiO_2>1%,ΣREE>1000ppm,σCe>1.5;早期成岩型结核矿物成分上相对富含钡镁锰矿,化学成分上富含Mn、Cu、Ni、Zn,而贫Fe、Co、Pb,TiO_2<1%,ΣREE<1000ppm,σCe≤1.在此基础上通过对Bonatti图解的实际应用和理论分析,证明Mn-Fe-(Cu+Co+Ni)x10图解不具判别意义,并提出Mn/Fe-TiO_2,Mn-Fe-TiO_2×10,Mn-Fe-ΣREE×100和Mn-Fe-σCe×10成因判别图解.     

武汉黄棕壤中铁锰结核的环带构造、元素富集特点与环境变化意义

土壤铁锰结核的环带记录了土壤成土过程和环境条件。文章利用扫描电镜及能谱探针分析测定了铁锰结核剖面上某些元素的含量与分布,研究表明:结核内部为不规则环带,Mn、Fe、Ca呈环带分布,大部分Ca赋存于铁锰结核的外层环带,Si、Al在剖面上呈匀态分布;结核剖面上Mn、Fe、Ca的含量呈波形曲线,根据它们的变幅,推测出该结核经历了10次以上的干湿交替过程,其中在结核生长初期经历了较弱的干湿交替环境,而在其生长后期处于相对较强的干湿交替环境;通过相关分析与因子分析,结核剖面上Ba、Ca、Co、Pb的富集与氧化锰矿物有关,而Ni、P的富集与氧化铁矿物有关     

太平洋北部铁锰结核富集区沉积物的元素地球化学特征

本文对太平洋北部铁锰结核富集区沉积物的元素地球化学作了较为详细的研究。因子分析提供的信息表明,元素的分布主要受三个因子控制:（1）粘土及Fe、Mn氧化物水化物胶体的吸附作用;（2）生物化学作用过程有关的自生沉积作用;（3）海底页岩风化及附近海区的火山喷发作用。元素的来源:（1）Fe、Mn、Cu、Co、Ni、Zn、Cr、Cr、Mg、Al、Ti、K共生,主要来自粘土吸附;（2）C_有机、N、Sr、Na及Si、Ca、Sr主要来自生物化学过程沉积;（3）Pb主要来源于岩石碎屑（火山喷发碎屑）。     

Ship-borne geochemical investigations of deep-sea manganese-nodule deposits in the Pacific using a radioisotope energy-dispersive X-ray system

A radioisotope energy-dispersive X-ray (EDX) system has been used on board the German research vessel “Valdivia” during an exploration expedition in the northern equatorial Pacific in 1973. The instrumentation used consisted of an X-ray detection system incorporating a 30 mm² effective-area Si (Li) detector with a measured energy resolution of 195 eV for Mn Kα X-rays, standard nuclear electronics, a 1024-channel analyser and a data read-out unit. The X-ray spectra in the manganese-nodule samples were excited by a 30-mCi ²³⁸Pu source.The six elements Mn, Fe, Co, Ni, Cu and Zn were analysed on board. Precision values for the analyses were less than 3% for Mn, Fe, Ni, Cu and Zn and about 5% for Co. A total amount of 350 analyses was carried out during a one-month cruise.Average contents of 190 analysed whole manganese-nodule samples from all the sampling sites of the covered area were 23.3% Mn, 6.7% Fe, 0.23% Co, 1.16% Ni, 0.94% Cu and 0.10% Zn. The average content of the base metals expressed as the sum of the Co, Ni, Cu and Zn contents was 2.48%. A linear relationship between Mn and Ni in all analysed samples, including whole manganese-nodule samples, zones of manganese nodules and manganese crusts, was observed. The Mn/Ni ratio calculated by regression analysis was 23.0. Zonal variations of the chemical contents of the six elements in the manganese nodules were found. A size classification of the manganese nodules has been suggested. Geochemical correlations of Cu and Ni versus Mn/Fe in the investigated samples are given.     

Geochemistry of ferromanganese nodule–sediment pairs from Central Indian Ocean Basin

Fourteen ferromanganese nodule–sediment pairs from different sedimentary environments such as siliceous ooze (11), calcareous ooze (two) and red clay (one) from Central Indian Ocean Basin (CIOB) were analysed for major, trace and rare earth elements (REE) to understand the possible elemental relationship between them. Nodules from siliceous and calcareous ooze are diagenetic to early diagenetic whereas, nodule from red clay is of hydrogenetic origin. Si, Al and Ba are enriched in the sediments compared to associated nodules; K and Na are almost in the similar range in nodule–sediment pairs and Mn, Fe, Ti, Mg, P, Ni, Cu, Mo, Zn, Co, Pb, Sr, V, Y, Li and REEs are all enriched in nodules compared to associated sediments (siliceous and calcareous). Major portion of Si, Al and K in both nodules and sediments appear to be of terrigenous nature. The elements which are highly enriched in the nodules compared to associated sediments from both siliceous and calcareous ooze are Mo – (307, 273), Ni – (71, 125), Mn – (64, 87), Cu – (43, 80), Co – (23, 75), Pb – (15, 24), Zn – (9, 11) and V – (8, 19) respectively. These high enrichment ratios of elements could be due to effective diagenetic supply of metals from the underlying sediment to the nodule. Enrichment ratios of transition metals and REEs in the nodule to sediment are higher in CIOB compared to Pacific and Atlantic Ocean. Nodule from red clay, exhibit very small enrichment ratio of four with Mn and Ce while, Al, Fe, Ti, Ca, Na, K, Mg, P, Zn, Co, V, Y and REE are all enriched in red clay compared to associated nodule. This is probably due to presence of abundant smectite, fish teeth, micronodules and phillipsite in the red clay. The strong positive correlation (r ? 0.8) of Mn with Ni, Cu, Zn and Mo and a convex pattern of shale-normalized REE pattern with positive Ce-anomaly of siliceous ooze could be due to presence of abundant manganese micronodules. None of the major trace and REE exhibits any type of inter-elemental relationship between nodule and sediment pairs. Therefore, it may not be appropriate to correlate elemental behaviour between these pairs.     

Geochemistry and specific features of manganese ore formation in sediments of oceanic bioproductive zones

Processes of authigenic manganese ore formation in sediments of the northern equatorial Pacific are considered on the basis of study of the surface layer (<2 mm) of ferromanganese nodule and four micronodule size fractions from the associated surface sediment (0–7 cm). Inhomogeneity of the nodule composition is shown. The Mn/Fe ratio is maximal in samples taken from the lateral sectors of nodule at the water-sediment interface. Compositional differences of nodules are related to the preferential accumulation of microelements in iron oxyhydroxides (P, Sr, Pb, U, Bi, Th, Y, and REE), manganese hydroxides (Co, Ni, Cu, Zn, Cd, Mo, Tl, W), and lithogenous component trapped during nodule growth (Ga, Rb, Ba, and Cs). The Ce accumulation in the REE composition is maximal in the upper and lower parts of the nodule characterized by the minimal Mn/Fe values. The compositional comparison of manganese micronodules and surface layers of the nodule demonstrated that the micronodule material was subjected to a more intense reworking during the diagenesis of sediments. The micronodules are characterized by higher Mn/Fe and P/Fe ratios but lower Ni/Cu and Co/Ni ratios. The micronodules and nodules do not differ in terms of contents of Ce and Th that are least mobile elements during the diagenesis of elements. Differences in the chemical composition of micronodules and nodules are related not only to the additional input of Mn in the process of diagenesis, but also to the transformation of iron oxyhydroxides after the removal of Mn from the close association with Fe formed in the suspended matter at the stage of sedimentation.     

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。     

Geochemical Indication of Sinian Bedded Siliceous Rocks in the Hunan-Guizhou-Guangxi Area and Their Environmental Significance

In the Hunan-Guizhou-Guangxi area there have developed very thick bedded siliceous rocks of the late Sinian. The rocks have a fairly pure composition, with an average content of siliceous minerals exceeding 95%. They are relatively rich in Fe and Mn, and poor in Al, Ti and Mg. The Fe/Ti, (Fe+Mn)/Ti, Al/(Al+Fe+Mn) and U/Th ratios and the Al-Fe-Mn and Fe-Mn-(Ni+Co+Cu)×10 triangle diagrams all show that they are hydrothermal sedimentary siliceous rocks. In the rocks the total amount of REEs is low, the δCe shows an obvious negative anomaly and the 8Eu a weak anomaly, and LREE>HREE, all indicating that they are products of hydrothermal processes. The δ30Si and δ18O values, as well as the formation temperature of the rocks all clearly show that the silica forming the rocks comes from hot water. Besides, analyses of the depositional environment of the rocks using the MnO/TiO2 ratio and the δCe and δ30Si values yield the same conclusion that they are formed in environments from continental marginal slope     

贵州水城二叠系茅口组含锰岩系地质地球化学特征与锰矿成因分析

贵州水城二叠系茅口组内发现新锰矿。通过对含锰岩系的地质地球化学研究,其富集Zn,Ni,As,Sb,Sr,Ba,Ga,Ag,V,U元素;锰含量较高层位,Th/U比值小于1,锰含量较低层位,Th/U比值往往高达4～5。Co/Ni比值小于1。含锰岩石的(Fe+Mn)/Ti均大于47,高于20,特别是含锰高的岩石,其(Fe+Mn)/Ti值在300以上。含锰岩石的Al/(Al+Fe+Mn)均远远低于0.35,一般为小于0.02。稀土配分模式与峨眉山玄武岩相似,∑REE较高,LREE/HREE值偏低等特征。根据锰岩系地球化学和区域构造特征分析,水城二叠系茅口组含锰岩系属于热水喷流沉积的产物。     

大洋磷酸盐化作用对富钴结壳元素富集的影响

中国首次对与大洋富钴结壳密切相关的磷酸盐化作用进行了研究。对取自西太平洋麦哲伦海山区一厚度为 10cm的富钴结壳样品 ,自顶至底以 5mm间距采取了 2 0个分层样品进行了成矿元素和稀土元素分析。结果表明 ,未被磷酸盐化的新结壳和磷酸盐化的老结壳间主要成矿元素的含量相差显著。老结壳中Fe、Mn、Si、Al、Zn、Mg、Co、Ni、Cu元素亏损 ,亏损次序为Co >Ni>Mg >Al>Mn >Si>Cu >Zn >Fe;而Ca、P、Sr、Ba、Pb元素含量增加 ,富集次序为P >Ca >Ba >Pb >Sr。研究认为 ,结壳中磷酸盐化作用的强弱制约着富钴结壳成矿元素含量的变化 ,磷酸盐化作用是造成老结壳中主要成矿元素Co、Ni等贫化流失的根本原因。研究还表明 ,磷酸盐化作用对富钴结壳的稀土元素丰度也产生一定影响 ,使老结壳的稀土总量和Ce含量高于新结壳 ,但未显著改变其稀土配分模式和分馏特征。研究证实 ,老结壳的Y正异常与磷酸盐化作用无关。磷酸盐化作用的研究为富钴结壳矿产资源的评价和综合利用提供了有用信息。