太平洋富稀土深海沉积物及黏土组分(<2μm)的Nd同位素特征及物源意义

太平洋深海沉积物富含稀土元素(∑REY,REE+Y),稀土含量达到或超过中国南方离子吸附型稀土矿品位。富稀土沉积物类型主要为远洋黏土和(含)沸石黏土。为了解富稀土元素深海沉积物的物质来源及其对稀土富集机制的影响,本文对中、西太平洋远洋黏土和(含)沸石黏土分别进行了全岩和黏土组分(2μm)的元素地球化学、Nd同位素及黏土矿物研究。结果表明,沸石黏土的∑REY最高,远洋黏土次之;全岩及黏土组分的∑REY与P_2O_5显示较好的正相关关系,且P_2O_(5全岩)/P_2O_(5黏土)和∑REY_(全岩)/∑REY_(黏土)正相关,说明不同类型沉积物黏土组分及全岩的稀土元素均主要由磷酸盐贡献;沉积物全岩ε_(Nd)值为-5.20～-6.02,表明其中的Nd来自火山源、陆源和自生源物质的混合源区;西太平洋含高REY的沸石黏土较中太平洋同类型沉积物具有较低的ε_(Nd)值,表明火山物质并不是沉积物中稀土元素富集的重要物源,但沸石含量对沉积物中稀土元素含量的高低具有一定指示意义;沉积物ε_(Nd)值接近海水ε_(Nd)值,表明稀土元素更多的直接来自于海水,但是成岩过程中可能受到其他物源或过程的影响。通过对比全岩及黏土组分的稀土元素特征,认为黏土矿物一定程度上可能承担了沉积物中稀土元素过渡载体相的作用。     

太平洋中部富REY深海沉积物的地球化学特征及化学分类

赋存于深海沉积物中的稀土资源是一种潜在的稀土资源。对太平洋中部30个重力活塞柱状样中的1 275个深海沉积物样品的常量、稀土化学分析数据进行了系统研究。在涂片鉴定的基础上,采用Ca O和Al2O3含量把太平洋中部深海沉积物划分为钙质软泥类沉积物、硅质软泥类沉积物、深海黏土类沉积物三种成因类型;这三种类型沉积物的稀土分布模式相似,表现为明显的Ce负异常,一定程度的重稀土元素富集和Y正异常,深海黏土类沉积物的ΣREY明显偏高。采用主要元素(包括Ca O/P2O5比值)与REY的关系图可以有效地判别不同成因类型沉积物的混合状况。太平洋中部富P、富含沸石的深海黏土类沉积物是最有利的富REY的深海沉积物类型。太平洋中部深海沉积物REY富集的主要原因是由于深海沉积物中混入了过量的(鱼牙骨碎屑状)磷灰石组分,而钙质生物组分和硅质生物组分的加入对REY含量起了明显的稀释作用。     

深海沉积物中的稀土矿产资源研究进展

近年发现,太平洋和印度洋的深海盆地中存在大量富含稀土的深海沉积物。主要类型为多金属软泥、沸石黏土和远洋黏土,其中的全稀土含量(∑REY,∑REE+Y)为400×10-6~2000×10-6,最高可达6600×10-6,重稀土含量(HREE)已达到或超过中国南方离子吸附型矿床的重稀土品位两倍以上,是潜在的新型稀土资源,具有重要的经济价值。目前不少学者对富稀土的深海沉积物进行了大量地球化学及部分矿物学的工作,认为多金属软泥中的稀土元素多赋存于与海底热液作用有关的铁锰氧化物和氢氧化物中,而沸石黏土和远洋黏土中稀土元素的富集则与磷酸盐的混入密切相关,其稀土元素主要存在于与磷灰石成分相当的生物鱼骨屑中。深海黏土的北美页岩标准化稀土配分模式与海水相似,表明其中的稀土元素主要来自于海水,REY富集成矿可能主要受控于磷灰石早期成岩阶段,期间稀土元素未发生分异。尽管近些年对深海沉积物中的稀土元素研究取得了不少成果,但是,对于沉积物中的稀土富集机制及影响因素等问题仍然需要更加深入的研究。作为稀土资源大国,为了争取我国在国际海底稀土资源竞争中的话语权,维护中国的稀土利益,中国应加紧开展相关的稀土资源勘查和潜力评价。     

太平洋表层沉积物中稀土元素分布特征及其资源意义

笔者对129°W—88°E,50°S—41°N太平洋区域内的190站表层沉积物中稀土元素进行了研究,结果表明:稀土元素主要赋存于沸石黏土、远洋黏土沉积物中,其稀土元素总量(∑REY)变化范围分别为(169.23~1632.91)×10-6和(48.58~1301.31)×10-6,平均值分别为701.84×10-6和441.65×10-6;硅质、钙质及热液沉积物对稀土元素有明显的"稀释"作用,尤其在钙质软泥和热液沉积物中稀土元素质量分数很低。从分布区域看,稀土元素主要富集于东太平洋CC区(克拉里昂—克里伯顿断裂带),该区域74站样品中有17站沉积物的∑REY质量分数超过530×10-6,且这些站位分布相对集中;在东南太平洋和西太平洋区域仅有零星站位富集,但富集程度极高(最高质量分数可达1632.91×10-6),大多数站位的沉积物中稀土元素质量分数较低(质量分数低于348×10-6);在靠近陆地的环太平洋区域,由于受到陆源物质的严重影响,沉积物中稀土元素质量分数普遍偏低。绝大多数沉积物中稀土元素都存在明显Ce负异常的轻稀土亏损特征(有172站沉积物中δCe小于0.95),稀土元素的配分模式与北太平洋表层海水的亏损轻稀土的"左倾"模式相近,而与代表陆源物质的中国黄土、黄海陆架沉积物的弱富集轻稀土的"右倾"模式差异显著;稀土元素与P2O5、Mn O、Ni、Cu、Zn、Ba等呈明显正相关性,与SiO 2、TiO 2、V、Cr、Ca和Sr等呈负相关。借鉴离子吸附型矿床中稀土元素资源分类标准,将表层沉积物中稀土元素划分为非富集型、弱富集型、富集型和极富集型4个等级,将富集型和极富集型等作为可能具有资源潜力的沉积物。研究发现,可能具有资源潜力的沉积物主要分布于4063~5540 m水深范围内,且以沸石黏土和远洋黏土为主,有极少量的富硅质沉积;在水深浅于4000 m的沉积物中,由于钙质质量分数高而使得稀土元素被"稀释";水深超过5600m则由于黏土质量分数升高,导致沉积物中稀土元素相对富集程度降低。此外,统计还发现,可能具有资源潜力的沉积物中,伴生元素质量分数特征表现为:w(Co)≥33.70×10-6,w(P2O5)≥0.51%,w(Mn O)≥0.12%,w(Ca O)≤20%。     

稀土元素及钇在东太平洋CC区深海泥中的富集特征与机制

东太平洋CC区深海泥具有高的REY(REE+Y)含量,理解其富集机制对于寻找深海稀土资源具有重要意义。本文对WPC1101站位的沉积物柱状样开展了沉积物类型、粒度、黏土矿物和元素组成分析,结合已有资料探讨研究区深海泥的稀土元素富集特征及其形成机制。研究区深海泥主要以远洋黏土和硅质生物组分为主,其∑REY范围主要为400~1 000 μg/g。深海泥北美页岩标准化后的REY配分模式具有显著的负Ce异常,指示富稀土深海泥中海相自生组分贡献较大。根据统计发现,研究区深海泥的∑REY与Al2O3、MnO、P2O5均具有良好的相关性,黏土组分、铁锰氧化物和磷酸盐对REY都有贡献。通过综合分析,提出研究区富稀土泥中高P含量是高∑REY重要的控制因素。     

Comparative study on the geochemical characteristics of rare earth elements in deep-sea sediments from different regions of the Pacific OceanSCIEI北大核心CSCD

太平洋深海沉积物中富集稀土元素(REY,包括钇),被认为是富有潜力的新型稀土资源。(含)沸石粘土、深海粘土和多金属软泥是主要的富含REY的沉积物类型,其中(含)沸石粘土和深海粘土在中、西北太平洋海盆大面积分布,而多金属软泥则多分布于靠近东太平洋洋脊热液活动的深海盆地中。目前关于中、西北太平洋海盆的深海粘土和(含)沸石粘土已有较多的研究,但关于多金属软泥中REY的研究较少。不同区域、不同类型深海沉积物中的稀土元素赋存状态有何差异?影响稀土富集的机制又是什么目前尚不清楚,也就进一步影响了对深海沉积物稀土资源的勘查和开发工作。本文分析对比了太平洋不同区域不同类型深海沉积物的地球化学特征及矿物学特征。结果表明,总体上,中、西北太平洋海盆深海沉积物中,尤其是(含)沸石粘土中的REY含量明显高于东太平洋海盆多金属软泥REY含量,其REY的富集主要与磷酸盐有关。超常富集REY(∑REY>2000×10^(-6))的沉积物中的CaO/P_(2)O_(5)比值趋向于一致(~1.4),几乎接近于磷灰石CaO/P2O5比值(~1.3),因此REY主要赋存载体为磷灰石,该区沉积物中REY的富集可能受到磷酸盐化的影响;东太平洋海盆多金属软泥明显受到热液影响,铁和锰的含量明显增加,但其∑REY含量集中于500×10^(-6)~800×10^(-6),不随铁和锰的增加而变化,REY的富集仍与磷酸盐关系密切,而与铁锰物质和铝硅酸盐关系不大。中、西北太平洋海盆富稀土的深海沉积物形成时处于较强的氧化环境,同时又有充足的含磷物质补给,才造成REY在该区沉积物中的超常富集;而东太平洋海盆多金属软泥虽然处于氧化环境,但缺少足够的磷补给,所以其∑REY含量通常低于中、西北太平洋海盆沸石粘土中∑REY含量。     

太平洋中部富REY深海粘土的地球化学特征及REY富集机制

深海沉积物中的稀土资源是一种新发现的、潜在的海底稀土资源.对太平洋中部重力活塞取样获得的90个深海粘土样品的矿物组分、常量和稀土化学分析结果进行了系统分析,并与中北太平洋以及西北太平洋南鸟岛附近海域深海沉积物稀土元素地球化学特征进行了对比.研究结果表明:太平洋中部深海粘土以富含沸石、富P及富REY为特征,其碎屑矿物中含有较多的鱼牙骨,其P₂O₅与CaO之间、P₂O₅、CaO与∑REY之间呈良好的正相关关系;其稀土分布模式表现为明显的Ce负异常、一定程度的重稀土元素富集和Y正异常.太平洋中部深海粘土REY富集的主要原因是深海粘土中含有过量的磷酸盐组分,推测过量的磷酸盐组分是由于深海粘土中鱼牙骨碎屑的加入引起的.在北太平洋海域,未受到热液活动影响的条件下,富REY的深海沉积物的稀土元素富集机制具有统一性和普遍性,可以归纳为深海沉积物中高REY磷酸盐的混入作用.      

南鸟岛东南部海域沉积物地球化学特征及其稀土资源指示意义

为了深入了解南鸟岛东南部海域表层沉积物的物质来源及其沉积环境和稀土元素富集情况,对大洋40航次在该区获取的深海沉积物岩心进行了主量、微量以及稀土元素含量测试分析。结果表明:沉积物为典型的深海黏土沉积。稀土元素标准化配分模式及La/Yb、La/Tb等结果表明,研究区沉积物物源受陆源物质主导,同时海山玄武岩及其风化产物与硅质沉积也有一定的贡献;结合δCe值与微量元素相关比值分析,研究区总体为稳定的偏氧化环境;区域内稀土元素富集主要受生物磷酸盐控制,并同时受到铁锰氧化物的影响;受陆源物质沉积作用的广泛影响,区域内表层沉积物中稀土元素质量分数偏低,但随深度增加,稀土元素富集程度规律性渐次升高。根据CaO/P_2O_5-w(ΣREY)相关性非线性拟合,推测在710 cm以下深度可能有富稀土元素深海沉积物的分布。     

太平洋西部富稀土深海沉积物的地球化学特征及其指示意义

深海富稀土沉积物已成为潜在的战略资源。为探讨富稀土粘土的地球化学特征及其来源和富集机制,对太平洋西部深海区域进行底层水和深层沉积物的系统采样,分析了样品的主、微量元素和稀土元素地球化学特征,并采用氧化还原环境、稀土元素的迁移和分馏以及海洋稀土循环的分析方法对富稀土沉积物的成因进行探讨。结果显示:沉积物的∑REY与Ce/Ce*表现出负相关关系,并与生物成因的P和Ca关系密切。样品Th/U、V/Sc、(La/Yb)_N、(La/Sm)_N和(Sm/Yb)_N值呈系统的变化,沉积物均处于氧化或次氧化环境。底层海水具重稀土富集的特征,海水-沉积物界面轻、中稀土含量上升,下覆的较深层沉积物表现出中、重稀土富集。初步推断沉积物的稀土元素来源于海水,与生物相关的物质是其REY富集和Ce负异常的主要控制因素。宽的氧化或次氧化环境和生物相关氧化物的强吸附能力导致稀土元素未扩散至海水而引起了沉积物稀土元素的富集。     

大别造山带石关地区变质岩风化壳中REY富集和分异研究

最新的找矿勘查在大别造山带变质岩风化壳中发现稀土元素（REY、REEs+Y）的富集,为揭示高纬度地区变质岩风化壳中REY风化富集规律提供了契机。本文以大别山地区石关变质岩风化壳剖面作为研究对象,通过岩相学、地球化学、XRD、V-SWIR、顺序提取实验等分析,探讨原生矿物-次生矿物转变、REY来源、迁移富集规律及分异机制。研究认为：石关风化壳的基岩为石英二长片麻岩,稀土元素总量（∑REY）范围为280×10-6~310×10-6,呈LREE相对富集的右倾式稀土配分型式,角闪石（∑REY=722×10-6~795×10-6）和榍石（∑REY=12635×10-6~13351×10-6）是基岩中主要的REY载体,也是风化壳内REY的主要来源,风化壳整体的稀土元素配分继承于基岩。风化壳剖面由下至上REY含量逐渐增高（∑REY=469×10-6~535×10-6）,对应的矿物组成上长石类矿物减少、石英和次生矿物（黏土矿物、铁锰氧化物等）增多,其中黏土矿物中伊利石含量逐渐减少,绿泥石、高岭石含量逐渐增多。顺序提取实验表明残余态是风化壳中REY的主要赋存状态（占比69％~88％）,越靠近风化壳上部,可被提取出的、活化的REY占比越高,活化的REY以离子交换、铁锰氧化物结合和有机质结合等方式被固定在风化壳中。(La/Yb)N指示离子吸附态、有机质结合态和铁锰氧化物态均显示HREY相对富集的稀土分异趋势。     

Geochemistry and mineralogy of REY-rich mud in the eastern Indian Ocean

Deep-sea sediments in parts of the Pacific Ocean were recently found to contain remarkably high concentrations of rare-earth elements and yttrium (REY) of possible economic significance. Here we report similar REY-rich mud in a core section from Deep Sea Drilling Project Site 213 in the eastern Indian Ocean. The sediments consist mainly of siliceous ooze, with subordinate zeolitic clay that contains relatively high REY concentrations. The maximum and average total REY (ΣREY) contents of this material are 1113 and 629 ppm, respectively, which are comparable to those reported from the Pacific Ocean. The REY-rich mud at Site 213 shows enrichment in heavy rare-earth elements, negative Ce anomalies, and relatively low Fe₂O₃/ΣREY ratios, similar to those in the Pacific Ocean. In addition, the major-element composition of the Indian Ocean REY-rich mud indicates slight enrichment in lithogenic components, which probably reflects a contribution from southern African eolian dust. A volcaniclastic component from neighboring mid-ocean ridges or intraplate volcanoes is also apparent. Elemental compositions and X-ray diffraction patterns for bulk sediment, and microscopic observation and elemental mapping of a polished thin section, demonstrate the presence of phillipsite and biogenic apatite, such as fish debris, in the REY-rich mud. The strong correlation between total REY content and apatite abundance implies that apatite plays an important role as a host phase of REY in the present deep-sea sediment column. However, positive correlations between ΣREY and elements not present in apatite (e.g., Fe₂O₃, MnO, and TiO₂) imply that the REY-rich mud is not formed by a simple mixture of REY-enriched apatite and other components.     

我国深海矿产研究:进展与发现(2011—2020)

深海矿产是地球上尚未被人类充分认识和利用的最大潜在战略矿产资源,近十年我国在该领域的研究取得了重要进展。在太平洋国际海底区域申请到2块多金属结核勘探区、1块富钴结壳勘探区,在西南印度洋中脊申请到1块多金属硫化物勘探区。研究阐明了我国多金属结核和富钴结壳勘探区小尺度成矿规律,揭示了其成矿作用过程及古海洋古气候记录,探讨了关键金属元素富集机制。在西南印度洋、西北印度洋和南大西洋中脊发现了多处热液区,阐述了其成矿作用及控制因素,建立了超慢速扩洋中脊热液循环模型,探讨了拆离断层型热液成矿系统的成矿机制。在太平洋和印度洋划分了4个深海稀土成矿带,在中印度洋海盆、东南太平洋和西太平洋深海盆地发现了大面积富稀土沉积区,初步揭示了深海稀土的富集特征、分布规律、赋存状态和成矿机理。今后在继续加大深海矿产资源调查研究的同时,应聚焦深海关键金属成矿作用研究。     

Controls on the distribution of rare earth elements in deep-sea sediments in the North Atlantic Ocean

Deep-sea sediments can contain relatively high concentrations of rare earth elements and yttrium (REY), with a growing interest in their exploitation as an alternative to land-based REY resources. To understand the processes that lead to enrichment of the REY in deep-sea sediments, we have undertaken a detailed geochemical study of sediments recovered from the Atlantic Ocean, on a transect along ~ 24°N that includes the deep Nares Abyssal Plain and the Canary and North America Basins.Total REY concentrations (ΣREY) range from 7.99 to 513 ppm, and total concentrations of the heavy REY (Eu - Lu) range from 0.993 to 56.3 ppm. REY concentrations are highest in slowly accumulating pelagic red clays, especially in samples that contain ferromanganese micronodules. Factor analysis reveals that hydrogenous Fe- and Mn-(oxyhydr)oxides are the primary REY carrier phase in the red clays. In situ analysis of individual micronodules confirms that they have high ΣREY (up to 3620 ppm). REY concentrations are higher in micronodules that have a hydrogenous source, characterised by higher Fe/Mn, compared to micronodules that have a diagenetic source.The ΣREY content of North Atlantic deep-sea sediments is ~ 4 times lower than in Pacific deep-sea sediments. We calculate that the area of seafloor required to extract ~ 10% of the global annual REY demand is ~ 100 km², assuming removal of the upper 1 m of sediment.     

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.     

High-resolution LA-ICP-MS mapping of deep-sea polymetallic micronodules and its implications on element mobility

Enrichments of REY (rare earth + yttrium) and other trace metals (Co and Ni) in deep-sea ferromanganese (FeMn) micronodules have received increasing attention in both deep-sea research and mineral exploration. Due to the presence of multiple, easily-crushed and poorly-crystallized phases in micronodules, the genesis of micronodules and their adsorption of various trace elements are poorly understood. To address this gap, we examined the spatial distributions of elements in cross-sections of micronodules from the western tropical North Pacific Ocean using high-resolution (HR) LA-ICP-MS raster mapping coupled with laser Raman and X-ray photoelectron spectroscopy (XPS). The ferromanganese micronodules we studied are dominated by Fe and Mn oxides with minor carbonate minerals, such as siderite, rhodochrosite and calcite. LA-ICP-MS maps show that these micronodules consist of a Mn-rich core and a Fe-rich rim. The Fe-enriched rim is enriched in As and surrounds a Mg, Mn, Cu, Co and Ni concreted core. Laser Raman maps show that the micronodule core contains more birnessite, an important scavenger of trace metals in deep sea sediments, than the rim. The birnessite filled core of these micronodules does not have elevated REY. Indeed, birnessite line channels may feed metal-rich fluid containing REY to adjacent minerals, including well-crystallized bio-apatite and zeolite, as high Ce and Y levels are spatially correlated with these minerals. The observed element profiles and XPS observations showing the coexistence of multiple oxidation states of Mn (+2, +3 and +4), Fe (+2 and +3) and Ce (+3, +4) demonstrate that the FeMn phases of these micronodules are of a diagenetic origin and that they are sites of redox-driven metal enrichment in deep-sea sediment.     

CN ratios in Pacific deep-sea sediments: Effect of inorganic ammonium and organic nitrogen compounds sorbed by clays

Analyses of organic carbon, total nitrogen, and inorganically bound ammonium (exchangeable and fixed ammonium) in two oxic deep-sea sediment cores from the Central Pacific Ocean revealed insufficiently high inorganic ammonium contents of these sediments to explain the low C/N ratios, although representing 20–45% of the total nitrogen.Both, organic carbon/total nitrogen ratios (ranging from 3.9?1.3) and organic carbon/organic nitrogen ratios (5.6?1.9) decrease with increasing sediment depth, the latter indicating a real enrichment of organic nitrogen compounds during diagenesis relative to total organic matter.Organic matter/alumina relationships indicate that this unusual preservation of organic nitrogen compounds is probably caused by sorption to clay minerals protecting them against bacterial attack.     

中太平洋海盆表层沉积物及其与锰结核的关系

通过对中太平洋海盆表层沉积物与相伴生的锰结核的研究表面,丰度、品位等有明显的差异,在深海粘土中锰结核干度最度,钙质软泥多,锰结核的发现聚集与沉积物类型,沉积速率、孔隙度、金属含量及形成时的氧化还原条件,水深、底层流等的影响.锰结核的形成,发育与富集是受多种因素所控制,是一个模式内的约制。