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。     

中印度洋海盆表层沉积物稀土元素分布特征及富集规律

对中印度洋海盆14个站位的表层沉积物进行了稀土元素(REE+Y,简称REY)分布特征和富集规律研究.结果表明,样品中REY主要富集于沸石黏土和远洋黏土中(稀土元素总量最高为1239×10?6),且明显富集钇(Y)等重稀土元素(Y富集系数高达14.1,重稀土元素和Y富集系数最高为11.6);富稀土沉积物呈明显Ce亏损,发...     

深海沉积物中稀土元素的富集成矿作用

我国虽是稀土大国,但重稀土仍是十分紧缺的关键金属资源。2011年日本学者Kato等在太平洋深海盆地中发现了大规模富含稀土元素的沉积物,引起世界各国高度重视。深海富稀土沉积物广泛分布于海底,其富集稀土元素尤其是相对富集重稀土元素等关键金属,是继大洋结核结壳、洋中脊热液硫化物、天然气水合物之后一种重要的海洋矿产资源。目前太平洋和印度洋中都证实有大面积富稀土沉积物的存在,我国科学家将深海稀土资源分为4个主要成矿远景区,其中太平洋3个,印度洋1个。富稀土沉积物的矿物组分主要包括生物成因磷灰石（鱼牙和鱼骨）、微结核（铁锰氧化物或氢氧化物）、沸石、黏土矿物等,其中生物磷灰石是最重要的稀土载体。稀土元素直接来源于上覆海水和孔隙水,热液和火山活动可能也有贡献。水深、沉积速率和氧化还原环境等是控制深海稀土元素富集的重要因素,强底流、海底火山和热液活动以及气候事件所导致的陆源输入的变化也会对深海稀土富集产生重要影响。深海稀土成矿作用仍然存在一些尚未解决的科学问题,需进一步加强深海富稀土沉积物成因及超常富集机制等的研究,以丰富和完善深海稀土的成矿模型,为我国在深海稀土富集区的勘探研究与实践提供重要借鉴。     

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.      

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。     

富稀土深海沉积物中稀土元素载体矿物的研究进展与展望

广泛分布于太平洋与印度洋的深海富稀土沉积物是一种重要的稀土资源,其储量远超陆地稀土资源的储量,并具有富含中-重稀土元素、易于浸出等优点。已有研究表明,稀土元素的含量、赋存状态和成矿机制与载体矿物的类型、结构和性质之间的关系密切,且载体矿物本身是未来勘探开采深海稀土资源和进行稀土选冶的直接对象。本文回顾了深海富稀土沉积物中的主要载体矿物类型及其稀土元素赋存机制等方面的研究结果,并展望了未来富稀土沉积物中载体矿物的研究方向。太平洋和印度洋深海沉积物中最主要的载体矿物包括磷灰石、铁锰（氢）氧化物、粘（黏）土矿物以及钙十字沸石。稀土元素以耦合替代的形式进入磷灰石结构中,在铁锰结核中,稀土元素主要通过表面络合吸附的形式赋存,而有关钙十字沸石与粘土矿物对稀土元素的富集作用仍有待通过深入的微区矿物学分析厘清。未来相关研究的重点应是海洋沉积物中稀土元素载体矿物的定量分析,以及稀土元素载体矿物溶解-重结晶过程对稀土元素富集迁移的影响等。     

富稀土磷酸盐及其在深海成矿作用中的贡献

中国最近几年对中北太平洋海域开展了系统调查,在中太平洋海盆新发现了稀土含量高达2000×10~(-6)的富稀土泥。深海泥样品稀土与各主要氧化物相关图解中,∑REY与P_2O_5含量始终保持良好的相关性。在太平洋各沉积物柱状样中,∑REY随着P2O5变化非常敏感。如果将P_2O_5含量高于0.25%的样品剔除,深海泥的∑REY不高于400×10~(-6),指示了磷对稀土元素的控制。海洋磷酸盐能够继承海水的负Ce异常及高Y/Ho比值特征,深海泥样品具有相似特征,且表现为稀土含量越高,其稀土配分模式越接近磷酸盐。酸淋滤实验显示,滤液中萃取出大部分的P及∑REY,且∑REY与P含量具有良好的正相关关系。无论∑REY高低,滤液稀土配分均呈现出显著的负Ce异常;而难溶残留物的∑REY普遍较低,且无负Ce异常特征。根据12组滤液中PO_4~(3-)与∑REY,估算出深海泥中的磷酸盐具有的∑REY含量范围为9495×10~(-6)~28287×10~(-6),这与深海泥中生物磷灰石的稀土含量和稀土模式均吻合。综上所述,我们认为深海泥中的磷酸盐主要以富稀土磷酸盐的形式存在,其稀土含量远高于深海泥中的铁锰氧化物和铝硅酸,因此磷含量的变化对于深海泥的稀土含量和模式影响至关重要。相较于碳酸盐沉积环境下容易形成贫稀土的磷块岩,深海环境下的化学沉积以及有机P的成岩作用容易形成富稀土磷酸盐。     

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.     

Geochemical and mineralogical characteristics of recent clastic sediments from lower Godavari river: Implications of source rock weathering

The major, trace and rare earth elements geochemistry and clay mineral compositions in the river bed sediments from lower reaches of Godavari river suggest that they are derived from weathering of felsic rocks. Trace and rare earth elemental compositions indicate evidence of sedimentary sorting during transportation and deposition. Lower concentrations of transition elements, such as V, Ni and Cr imply enrichment of felsic minerals in these bed sediments. The REE pattern in lower Godavari sediments is influenced by the degree of source rock weathering. The light rare earth elements (LREE) content are indicating greater fractionation compared to the heavy rare earth elements (HREE). A striking relationship is observed between TiO₂ and gZREE content suggesting a strong control by LREE-enriched titaniferous minerals on REE chemistry. Shale-normalized REE pattern demonstrate a positive Eu anomaly, suggesting weathering of feldspar and their secondary products, which are enriched in Eu. Chondrite-normalised REE pattern is characteristic of felsic volcanic, granites and gnessic source rocks. Trace elemental compositions in sediments located near urban areas suggest influence of anthropogenic activity. Chemical Index of Alteration (CIA) is high (avg. 65.76), suggesting a moderate chemical weathering environment. X-ray diffraction analysis of clay fraction shows predominance of clay minerals that are formed because of the chemical weathering of felsic rocks.     

Geochemistry of mineralization with exchangeable REY in the weathering crusts of granitic rocks in South China

Mineralization with exchangeable rare earth element (REE) and yttrium (MEX-REY) has been recognized in the weathering profiles in South China since the early 1970's. This type of REY mineralization occurs in weathering profiles of parent rocks ranging in composition from granite to acidic volcanic rocks and lamprophyre. The majority of the known resources occurring in the weathering profiles of granitic rocks. Total resources of this type of REY amount to millions tons of rare earth oxides, and therefore represent one of the most important types of rare earth resources in China, particularly for heavy rare earth elements (HREE) and yttrium.Accumulation of REY in the weathering profiles of granitic rocks is strongly controlled by the resistance to weathering of the principal REY-bearing accessory minerals in the parent rocks; only a limited proportion of total REY (< 30%) is incorporated in the rock-forming minerals. MEX-REY more commonly occur in weathering profiles developed on granitic rocks within which most of the REY are incorporated in accessory minerals weakly resistant to weathering (doverite, parisite, etc.). For the well-developed weathering profiles, three horizons can be distinguished from surface downwards: the lateritic horizon (A), the weathered horizon (B), and the weathering front (C). Continuous leaching, coupled with low rate of denudation, results in the accumulation of REY in the subsurface horizons (the B and C horizons), and thus results in REE differentiation within the well-developed, layered, and mature weathering profiles. Exchangeable REY, which can be replaced by cations like NH⁴⁺ and Na⁺ etc. in electrolyte solutions and can be removed by complexing agents such as EDTA, are commonly the major form of REE occurrence in the B horizon. Cerium is enriched in the top layer (A horizon) and depleted in the subsurface horizons of the weathering profiles, most likely due to the oxidation of Ce(III) to Ce(IV) followed by cerianite formation or absorption onto clays and/or Fe and Al oxyhydroxides.     

中国大陆架海底沉积物中的稀土元素

选择渤海、黄海、东海和南海有代表性的大陆架沉积物样品,利用X射张荧光光谱法测定了15个稀土元素。中国大陆架沉积物稀土元素的丰度为156ppm,相对接近于中国黄土和花岗岩的丰度,而与太平洋沉积物的丰度相差较远,具有明显的“亲陆性”。稀土的配分模式旦显著的负斜率,属陆壳稀土的典型特征。稀土含量受沉积物粒度控制。实验表明稀土主要以类质同像存在于粘土矿物之晶体构造中。根据数理统计,稀土与亲陆源粘土矿物的元素为一类,彼此呈正相关;与亲海洋生物的元素为负相关。事实说明中国大陆岩石的风化和搬运,是中国海大陆架沉积物中稀土的主要物质来源。     

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.     

Bacterial dissolution of fluorapatite as a possible source of elevated dissolved phosphate in the environment

In order to understand the contribution of geogenic phosphorus to lake eutrophication, we have investigated the rate and extent of fluorapatite dissolution in the presence of two common soil bacteria (Pantoea agglomerans and Bacillus megaterium) at T = 25 °C for 26 days. The release of calcium (Ca), phosphorus (P), and rare earth elements (REE) under biotic and abiotic conditions was compared to investigate the effect of microorganism on apatite dissolution. The release of Ca and P was enhanced under the influence of bacteria. Apatite dissolution rates obtained from solution Ca concentration in the biotic reactors increased above error compared with abiotic controls. Chemical analysis of biomass showed that bacteria scavenged Ca, P, and REE during their growth, which lowered their fluid concentrations, leading to apparent lower release rates. The temporal evolution of pH in the reactors reflected the balance of apatite weathering, solution reactions, bacterial metabolism, and potentially secondary precipitation, which was implied in the variety of REE patterns in the biotic and abiotic reactors. Light rare earth elements (LREE) were preferentially adsorbed to cell surfaces, whereas heavy rare earth elements (HREE) were retained in the fluid phase. Decoupling of LREE and HREE could possibly be due to preferential release of HREE from apatite or selective secondary precipitation of LREE enriched phosphates, especially in the presence of bacteria. When corrected for intracellular concentrations, both biotic reactors showed high P and REE release compared with the abiotic control. We speculate that lack of this correction explains the conflicting findings about the role of bacteria in mineral weathering rates. The observation that bacteria enhance the release rates of P and REE from apatite could account for some of the phosphorus burden and metal pollution in aquatic environments.     

Geochemistry of Rare Earth Elements in the Ocean

This work briefly outlines modern ideas on geochemistry of rare earth elements (REE) in the ocean. Sources of REE and chemical properties of these elements, which govern their migration ability in natural processes, are considered. The REE behavior in the river water–seawater mixing zone is analyzed. The fractionation of dissolved and suspended REE in oceanic water in both aerobic and anaerobic conditions is also considered. It is shown that the variability of REE composition in pelagic sediments reflects the fractionation of these elements in the oceanic water as a consequence of material differentiation in the ocean. The REE distribution in terrigenous, authigenic, hydrothermal, and biogenic constituents of sediments, such as clay, bone debris, barite, phillipsite, Fe–Mn oxyhydroxides (ferromanganese nodules and micronodules), Fe–Ca hydroxo-phosphate, diatoms, and foraminifers, is considered.