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.     

桂西南柳桥地区上二叠统大隆组层状硅质岩成因和沉积环境

对桂西南上二叠统大隆组层状硅质岩地球化学的研究发现:陆源主量元素Al、Ti等含量较高,并呈很好的相关性（R>0.90）;热液来源的主量元素Mn和Fe等含量偏低,并具有较小的负相关关系（R=－0.30）;陆源元素(Al、Ti、Hf、Zr、Th等)与总稀土元素含量具有较高正相关性（R为0.70～0.83）;Al Fe Mn三角图解指示研究区的硅质岩为非热液成因。这些说明陆源物质是硅质岩形成的重要物源,结合硅质岩中含有大量的硅质生物（放射虫和海绵骨针等）的事实,我们认为研究区硅质岩是在生物作用为主,并有大量物源物质和少量热液物质（可能与大断裂导致的玄武岩喷发有关）和火山物质混入的条件下形成的。Ce/Ce*、(La/Yb)Shale、(La/Ce)Shale和∑REE与细粒沉积物沉积环境的关系以及(La/Ce)Shale—Al2O3/(Al2O3 +Fe2O3)图解等说明研究区硅质岩沉积环境为大陆边缘的中下部。Th/U和Ceanom指示了硅质岩形成于氧化环境。      

华北陆块南部古元古代熊耳群硅质岩地球化学特征及其沉积环境

华北陆块南部古元古代熊耳群中的硅质岩主要发育于马家河组沉积岩中,有少量与火山岩共生。通过分析硅质岩的主、微量元素特征,把熊耳群硅质岩分为热水成因和非热水成因两类。热水成因硅质岩表现为低TiO2、MgO、Al2O3和∑REE含量,以及低的A1/(A1+Fe+Mn) 比值的特征;其北美页岩标准化的稀土分配模式平坦,但具有Ce负异常与Eu正异常,U/Th>1,反映沉积速率快,受陆源物质的影响小。非热水成因的硅质岩的∑REE含量高,轻稀土富集(LaN/YbN=1.41~9.04),U/Th<1,受陆源物质影响较大。熊耳群硅质岩的Cr/Th比值变化小,表明物源区成分比较单一;其与熊耳群火山岩具有相似的REE配分模式图和蛛网图,也说明物源为熊耳群的英安—流纹质火山岩和玄武—安山质火山岩的混合。硅质岩的Al2O3/(Al2O3+Fe2O3)比值为0.44~0.64、以及Ce/Ce*(0.77~0.94)、LaN/CeN(1.18~1.47)的特征表明,熊耳群硅质岩主要形成于被动大陆边缘环境。熊耳群硅质岩主要形成于海相、海陆交互相等环境。早在古元古代熊耳群时期,熊耳—中条拗拉谷发生强烈的扩张裂解作用,华北陆块南部遭受海水入侵,豫南有些地区已经处于海相环境,晋南垣曲有些地区处于海陆交互相环境,局部地区还处于陆相环境。     

Geochemistry,Paleoenvironment and Mechanism of Organic-Matter Enrichment in the Lower Silurian Longmaxi Formation Shale in the Sichuan Basin,China

To investigate the mechanism of the organic-matter enrichment in the Lower Longmaxi Formation shale, the geochemistry and total organic carbon(TOC) of the Longmaxi Formation black shales in the Jiaoshiba, Zhaotong, and Weiyuan areas of the Sichuan Basin were analyzed. Paleoproductivity proxy parameters(Babio, Siex, and Ni/Al), clastic influx proxies(TiO_2 and Ti/Al), redox indices(V/Cr, Ni/Co, V/(V+Ni), and U/Th), and hydrothermal indicators(Fe, Mn,and Y concentrations; Fe/Ti ratio and a Ni-Zn-Co diagram) were employed to decipher the paleoenvironment of the Lower Longmaxi Formation shales. TiO_2 and Ti/Al indicated low terrigenous detrital influx in all three areas. However, Babio, Siex,and Ni/Al indicated high productivity in the Jiaoshiba area. V/Cr, Ni/Co, and U/Th indicated higher oxygen content with larger fluctuations in the Zhaotong and Weiyuan areas. Fe, Mn, and Y concentrations and the Fe/Ti ratio implied greater active hydrothermal activity in the Weiyuan area. These heterogeneities were considered to be closely related to the paleoenvironment and paleogeography, and the large basement faults that developed during the Chuanzhong paleo-uplift could have provided vents for deep-hydrothermal-fluid upwelling. The redox indices(V/Cr, Ni/Co, and U/Th) and a paleoproductivity proxy(Ni/Al) displayed a significant correlation with the TOC, suggesting that both excellent preservation conditions and high paleoproductivity were the controlling factors for the enrichment of organic matter in the Longmaxi Formation shale. There was no obvious correlation between the clastic influx proxy(Ti/Al) and the TOC due to the extremely low supply of terrigenous debris. The hydrothermal indicator(Fe/Ti) was negatively correlated with the TOC in the Weiyuan area, indicating that hydrothermal activity may have played a negative role in the accumulation of organic matter. This study suggests that the enrichment of organic matter in the Longmaxi Formation marine shale varied according to the paleogeography and sedimentary environment.     

Rare earth element studies of surficial sediments from the southwestern Carlsberg Ridge,Indian Ocean

The rare earth element (REE) contents of sixteen surficial calcareous sediments from the southwestern Carlsberg Ridge, Indian Ocean, have been determined. The total REE vary from 35 ppm to 126 ppm and are inversely related to the calcium carbonate content. REEs show a strong positive correlation with Al + Fe + K + Mg + Na (r ²= 0.98) and Mn + Fe + Cu + Ni (r ²= 0.86) suggesting that the REE is associated with a combined phase of clays (mainly illite) and Mn-Fe oxyhydroxides. The aeolian input into these sediments is suggested from the weak positive Eu/Eu* anomaly. Shale-normalized (NASC) pattern along with La_(n)/Yb_(n) ratio suggest enrichment of heavy REE (HREE) relative to the light REE (LREE) with a negative Ce/Ce* anomaly implying retention of a bottom water REE pattern. An erratum to this article is available at .     

Geochemistry of rare earth elements in bottom sediments of the Brazil Basin, Atlantic Ocean

The sedimentation and ore formation were studied in sediments from nine stations located in the 24°W profile in the Brazil Basin of the Atlantic Ocean. The sediments are represented by mio- and hemipelagic muds, which are variably enriched in hydrothermal iron and manganese oxyhydroxides. As compared to the sediments from other basins of the Atlantic Ocean, these rocks are marked by extremely high manganese contents (up to 1.33%) and maximal enrichment in Ce. It was shown that the positive Ce anomaly is related to the REE accumulation on iron oxyhydroxides. Influence of hydrothermal source leads to the decrease of Ce anomaly and LREE/HREE ratio. In the reduced sediments, preservation of positive Ce anomaly and/or its disappearance was observed after iron and manganese reduction. The REE contents were determined for the first time in the Ethmodiscus oozes of the Brazil Basin. Ore deposits of the Brazil Basin are represented by ferromanganese crust and ferromanganese nodules. Judging from the contents of iron, manganese, rare, and trace elements, these formations are ascribed to the sedimentation (hydrogenic) deposits. They are characterized by a notable positive Ce anomaly in the REE pattern. The extremely high Ce content (up to 96% of total REE) was discovered for the first time in the buried nodules (Mn/Fe = 0.88).     

Provenance and accumulation rates of opaline silica,Al, Ti,Fe, Mn,Cu, Ni and Co in Pacific pelagic sediments

Accumulation rates and chemical compositions have been obtained for pelagic sediments for 73 locations in the Pacific and for 11 in the Indian Ocean. The data for the Pacific show that many elements accumulate rapidly close to the continents and slowly in the central part of the ocean. This pattern is interrupted by two major zones of relatively high accumulation rates, one along the Equator and one along the East Pacific Rise. Deposition of opaline silica is almost completely restricted to areas of known high biological productivities at the Equator and at very high latitudes. Cu and Ni show stronger tendencies than Fe and Mn to precipitate with opaline silica. The highest accumulation rates of Fe and Mn in the open Pacific occur along the East Pacific Rise, to some extent also Cu and Ni are enriched there due to volcanic processes. Al and Ti show high accumulation rates only close to the continents; these elements appear to be almost completely terrigenous.Provenance studies of minerogen fractions, using the relations between Fe, Ti, Al and Mn, show that significant quantities of basaltic matter (oceanic crust) are incorporated into the sediments only in areas of very low total sedimentation rates in the vicinity of oceanic island groups such as Polynesia and Hawaii, whereas hydrothermal processes act as a major sediment source only on the East Pacific Rise. Sediments in the north as well as in the southernmost part of the Pacific are nearly entirely terrigenous. A balance estimate of the minerogen fraction of the deep-sea sediments from the open Pacific suggests that between 75 and 95% of all sediments in the Pacific are terrigenous and that submarine weathering (and release of basaltic debris in general) and submarine exhalations each account for only a small fraction of the sediments.     

Geochemistry and genetic model of the ore-bearing sediments of the Parnok ferromanganese deposit, Polar Urals

The Parnok ferromanganese deposit is confined to the black shales of the western slope of the Polar Urals. The deposit area is made up of weakly metamorphosed terrigenous-carbonate rocks formed in a marine basin at a passive continental margin. Ore-bearing sequence is composed of coaliferous clayey-siliceous-calcareous shales comprising beds and lenses of pelitomorphic limestones, and iron and manganese ores. The iron ores practically completely consist of micrograined massive magnetite. The manganese ores are represented by lenticular-bedded rocks consisting of hausmannite, rhodochrosite, and diverse manganese silicates. With respect to relations between indicator elements (Fe, Mn, Al, Ti), the shales are ascribed to pelagic sediments with normal concentrations of Fe and Mn, the limestones correspond to metalliferous sediments, ferruginous sediments are ore-bearing sediments, while manganese rocks occupy an intermediate position. It was found that the concentrations of trace elements typical of submarine hydrothermal solutions (As, Ge, Ni, Pb, Sb, Zn, etc.) in both the ore types are in excess of those in lithogenic component. At the same time, the indicator elements of terrigenous material (Al, Ti, Hf, Nb, Th, Zr, and others) in the ores are several times lower than those in the host shales (background sediments). REE distribution patterns in iron ores show the positive Eu anomaly, while those in manganese ores, the positive Ce anomaly. In general, the chemical composition of the ores indicates their formation in the hydrothermal discharge zone. The peculiar feature of the studied object is the manifestation of hydrothermal vents in sedimentary basin without evident signs of volcanic activity. Hydrothermal solutions were formed in terrigenous-carbonate sequence mainly at the expense of buried sedimentation waters. The hydrothermal system was likely activated by rejuvenation of tectonic and magmatic processes at the basement of sedimentary sequences. Solutions leached iron, manganese, and other elements from sedimentary rocks and transported them to the seafloor. Their discharge occurred in relatively closed marine basin under intermittent anaerobic conditions. Eh-pH variations led to the differentiation of Fe and Mn and accumulation of chemically contrasting ore-bearing sediments.     

Quantitative parameters of Pleistocene pelagic sedimentation in the World Ocean: Global trends and regional features

A comparative analysis of Pleistocene pelagic sedimentation in the Pacific, Indian, and Atlantic oceans revealed the predominance of terrigenous sediments, while carbonate and siliceous sediments are second and third in abundance. During Pleistocene, the mass of terrigenous and siliceous sediments increased, while that of carbonates slightly decreased. The latter is related to the fact that the bottom waters aggressive to carbonates became increasingly generated at high latitudes, thus exceeding an increase in the productivity of plankton carbonate organisms. The peculiarities of accumulation of the main types of bottom sediments in the Pleistocene are considered. It is concluded that the Pleistocene geological history of continents, especially neotectonic uplift and continental glaciations, played an important role in pelagic sedimentation.     

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.      

南秦岭富钠长石岩石的岩石学和地球化学研究

钠长石岩是秦岭造山带中的一类特色岩石,主要分布于南秦岭凤-太、山-柞和镇-旬盆地的泥盆纪和志留纪地层中,与秦岭众多大中型铅锌矿、金矿成矿关系密切。钠长石岩呈层状、似层状产于碎屑岩或碳酸盐岩岩系中,与区域地层整合产出,渐变过渡。具有条带状、块状、角砾状构造;XRF分析数据显示钠长石岩化学成分以富Na2O、Al2O3、SiO2等常量元素及Pb、Zn、Au、Ag、Cu等微量元素为特征;富含元素Ba和Fe-Mn-(Co+Cu+Ni)×10分布图投影表明钠长石岩具有热水沉积的特征。而TiO2与Al2O3关系图解又反映出钠长石岩中有陆源碎屑物混入的特点,其Ti、Al可能来自水成沉积物中的粘土;ICP-MS分析所得稀土元素数据显示,钠长石岩与地层稀土元素在稀土总量、轻重稀土量和配分模式均十分相似,其较高∑REE就是成岩过程中水成沉积物混入造成的。富钠长石岩石在形成时间上发生在沉积和早期成岩阶段,与正常沉积岩同时形成。兼具有正常沉积岩石和热水沉积岩石的特点,是一种有别于二者的混合型非典型热水沉积岩石。研究认为钠长石岩是由一种富钠和金属元素的热水通过对地层元素的萃取并与海底未固结沉积物混合而成的混合热液经沉积成岩作用形成的。     

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。     

桂北泗里口老堡组硅质岩的常量、稀土元素特征及成因指示

桂北泗里口老堡组为一套埃迪卡拉纪—寒武纪过渡时期（大约550～540 Ma）深水盆地沉积的硅质岩。它们的SiO2含量普遍高（平均93.8%）;Al2O3含量为0.17%～4.92%,沿剖面自下而上明显增加,上部超过2%;Al/(Al+Fe+Mn)比值多高于0.42;Fe/Ti比值大都小于16.3;Al2O3/( Al2O3+Fe2O3)比值多高于0.4,剖面上部样品的比值为0.8～0.9;Y/Ho比值为26.4～36.9,中、下部样品较高（多高于32）,上部样品的比值接近地壳值（27）;Eu/Eu*平均值为1.0,正异常不明显。剖面下部样品的∑REE含量低（15.9×10-6～27.1×10-6）,具有与现代海水相近的REE配分,没有正的Eu异常,不同于海底的热液流体和与其有关的碧玉的REE配分;中部样品的∑REE含量为26.2×10-6～49.4×10-6,由于所含陆源碎屑的增加,REE配分变得平坦,但仍有海水REE的某些特征;上部样品的∑REE含量为40.5×10-6～59×10-6,显示与平均页岩相似的平坦的REE配分,但∑REE含量仅为平均页岩的大约1/4～1/3。这些常量和稀土元素特征表明,海底热液和陆源碎屑都不可能成为泗里口老堡组硅质岩的重要物源。埃迪卡拉纪—寒武纪过渡时期华南深水盆地厚层硅质岩沉积反映了这一时期大气高CO2浓度,大量陆源化学风化的硅质流入海洋和大量生物的降解可能是造成这些硅质岩形成的基本原因。     

Rare earth elements in the sedimentary cycle: A summary

The relative and absolute concentrations of rare earth elements (REE) in authigenic and biogenic phases of deep-sea sediments are quite different. Competition between these phases for REE has resulted in fractionation from the parent material, the latter consisting predominantly of terrigenous material, but with a contribution from marine volcanism. The strongest feature of this fractionation is a depletion of Ce, relative to La, in CaCO₃, opalline silica, phillipsite, phosphorite, barite, and montmorillonitic clays; and a Ce enrichment in Fe/Mn nodules. The distribution of REE in different masses of seawater strongly reflects their fractionation in sediments. Whereas the relative concentration of REE in rivers resembles that of shale, their removal from seawater by authigenic and biogenic phases results in: (1) a decrease of their total concentration; (2) a depletion of Ce; and (3) an enrichment of heavy REE relative to light REE. The order of fractionation for water masses in the Atlantic Ocean is:Antarctic intermediate water > North Atlantic deep water > Antarctic bottom water> shelf water > river water ～ shale.The shale-normalized pattern for the sum of REE in the authigenic and biogenic phases of pelagic sediment and in seawater resembles that of an admixture of shale and basalt corresponding presumably to the realtive inputs from continents and marine volcanism respectively. The estimated rate of accumulation of each REE in the sediment, however, is approximately 12 times the estimated rate of input of REE from these two sources.     

Geochemistry of trace and minor elements in sediments and manganese micronodules from the Angola Basin

Indicator role of trace elements in sedimentation and ore formation is considered for sediments from Station 2182 in the Angola Basin. It is shown that pelagic sediments were formed from two main sources: biogenic calcium carbonate and lithogenic sediment component compositionally similar to the miopelagic clay. Increase of the Mn/Al ratio, Ce anomaly in the REE composition, Co/Ni and Mo/W ratios, and anomalous accumulation of Tl, Pb, Bi and other microelements indicate that sediments from horizons 15–20 and 30–35 cm contain significant amounts of hydrogenic material as Fe-Mn oxyhydroxides. Manganese micronodules (MN) were extracted from different horizons (10–15, 15–20, and 30–35 cm) and analyzed to study the hydrogenic component. Their development is related to retardation of biogenic and lithogenic sedimentation. The studied manganese micronodules are represented by the hydrogenic-diagenetic formations >100 μm in size with Mn/Fe = 2.0–2.8, Co/Ni = 0.2–0.4, Ce an = 4.2–5.7, and Mo/W = 5.2–7.9. The MN content is too low to affect the major and trace element composition of sediments. The main part of Fe and Mn is confined to fraction <10 μm.     

Uranium and Thorium in Phosphatic Bone Debris from the Ocean Bottom

Uranium and thorium content, as well as their distribution patterns are studied in biogenic phosphates from the Atlantic and Indian oceans. The material studied is represented by differently lithified fish remains (bones, scales, teeth) and marine mammal bones (ribs, vertebras, earbones) collected from both reduced shelf sediments and oxidized pelagic ones. The U content in the material varies from 0.7 to 700 ppm, and the Th content ranges from less than 0.5 to 14 ppm. The U/Th ratio varies from 0.16 to 400. Contents of both elements increase with the lithification of biogenic phosphates. The U concentration is more intense on shelves, whereas the thorium concentration increases in pelagic areas. A partial positive correlation of U and Th with Fe but a negative correlation of U with organic carbon are noted. The latter corresponds to increasing lithification of biogenic phosphates. Calcium phosphate, which is transformed from hydroxyapatite to fluorcarbonate-apatite serves as the main carrier of U, while transformed organic matter is a minor agent. Thorium is mainly bound with Fe.     

The origin of clay minerals in active and relict hydrothermal deposits

Samples of Fe-oxide-rich hydrothermal sediments were collected from active and inactive portions of the TransAtlantic Geotraverse (TAG) hydrothermal field on the Mid-Atlantic Ridge. Clays separated from TAG metalliferous sediments in this study all consist of Al-poor nontronite. Oxygen isotope thermometry of the clays yields formation temperatures of 54-67°C for samples from the inactive Alvin mound compared with 81-96°C for samples from the active TAG site. The latter are the highest recorded temperatures for authigenic hydrothermal clays. Sr isotope analysis of the clays from the active mound suggests that they precipitated from seawater-dominated fluids, containing less than 15% hydrothermal end-member fluid. In contrast, nontronite from the inactive Alvin mound has ⁸⁷Sr/⁸⁶Sr values that closely resemble that of detrital North Atlantic clays, suggesting a dominantly continental source for the Sr. Rare earth element data are consistent with a significant detrital input to the inactive site but also demonstrate the extent of hydrothermal input to the low temperature fluid. Crystallographic fractionation of the trivalent REE is apparent in the heavy REE enrichments for all nontronite samples. The inferred formation-mechanism for nontronite-rich Fe-oxyhydroxide deposits at the surface of the active mound is by direct precipitation from low temperature fluids. At the inactive Alvin site, in contrast, the deposits form during alteration of pelagic sediments by diffuse fluids and replacement of biogenic carbonate with nontronite and Fe-oxyhydroxide. These two modes of formation are both important in seafloor hydrothermal settings where clay minerals are a significant component of the hydrothermal deposit.     

塔西北地区早寒武世玉尔吐斯组热液作用及沉积模式

埃迪卡拉纪-寒武纪之交全球沉积了一套黑色泥页岩和硅质岩组合,塔里木盆地早寒武世玉尔吐斯组即包含这样一套组合,并被认为是塔里木古生界主力烃源岩之一,然而目前对这套岩石组合的成因及沉积过程的研究还相对薄弱。在野外研究的基础上,将玉尔吐斯组分为5段,分为两个海进-海退旋回,认为其总体沉积于缓坡背景之上。对第一段硅质岩进行主量元素及稀土元素分析,结果显示其含有较低的Al/(Al+Fe+Mn)和较高的Fe/Ti值(均值分别为0.29和108.24)。在Al-Fe-Mn和Fe/Ti-Al(Al+Fe+Mn)图解上,多数样品落入热液作用范围,表明硅质岩主要受热液作用控制。硅质岩REE配分模式显示其不具有Eu的正异常和LREE富集的特征,这显示了海水对热液的稀释作用。靠近热液盆内口的库勒和什艾日克剖面发育较厚的硅质岩和一系列滑移变形构造。早寒武世时期,南天山洋已经打开,硅质热液广泛发育于整个塔北的深水和浅水区,这些迹象表明该区早寒武世仍然有很强的伸展构造活动。     

Metalliferous sediments from DSDP Leg 92: The East Pacific Rise transect

The carbonate-free metalliferous fraction of thirty-nine sediment samples from four DSDP Leg 92 sites has been analyzed for 12 elements, and a subset of 16 samples analyzed for Pb isotopic composition. The main geochemical features of this component are as follows: i) very high concentrations of Fe and Mn, typically 25–39% and 5–14%, respectively; ii) Al and Ca contents generally less than 2% and 5%, respectively; iii) high Cu (1000–2000 ppm), and Zn and Ni (500–1000 ppm) values; and iv) Co and Pb concentrations of 100–250 ppm. In terms of element partitioning within the metalliferous fraction, amorphous to poorly crystallized oxide-oxyhydroxides removed by the second leach carry virtually all of the Mn, and about 90% of the Ca, Sr and Ni. The well-crystallized goethite-rich material removed by the third leach carries the majority of Fe, Cu, and Pb. These relations hold for sediments as young as ~ 1–2 Ma, indicating early partitioning of hydrothermal Fe and Mn into separate phases.Calculated mass accumulation rates (MAR) for Fe, Mn, Cu, Pb, Zn and Ni in the bulk sediment show the same overall trends at three of the sites, with greatest MAR values near the basement, and a general decrease in MAR values towards the tops of the holes (for sediments deposited above the lysocline). These relations strongly support the concept of a declining hydrothermal contribution of these elements away from a ridge axis. Nevertheless, MAR values for these metals up to ~200 km from the ridge axis are orders of magnitude higher than on abyssal seafloor plains where there is no hydrothermal influence. Mn/Fe ratios throughout the sediment column at two sites indicate that the composition of the hydrothermal precipitates changed during transport through seawater, becoming significantly depleted in Mn beyond 2&#x0303;00–300 km from the axis, but maintaining roughly the same proportion of Fe.Most of the Pb isotope data for the Leg 92 metalliferous sediments form approximately linear arrays in the conventional isotopic plots, extending from the middle of the field for mid-ocean ridge basalts toward the field for Mn nodules. The array of data lying between these two end-members is most readily interpreted in terms of simple linear mixing of Pb derived from basaltic and seawater end-member sources. The least radiogenic sediments reflect the average Pb isotope composition of discharging hydrothermal solutions and ocean-ridge basalt at the EPR over the ≈4–8 Ma B.P. interval. Pb in sediments deposited up to 250 km from the axis can be almost entirely of basaltic-hydrothermal origin. Lateral transport of some basaltic Pb by ocean currents appears to extend to distances of at least 1000 km west of the East Pacific Rise.     

Formation conditions and rare-earth mineralization of Riphean carbonaceous shales of the Upper Nyatygran Subformation,Russian Far East

Graphitic and graphite varieties are distinguished in the carbonaceous shales of the Riphean Upper Nyatygran Subformation in the Melgin fragment of the Turan block, eastern Bureya Massif. The protolith of the graphitic shales had a terrigenous source related to island-arc volcanism. Pelagic sedimentation played a great role in the formation of the protolith of the graphite shale. These rocks were juxtaposed during the formation of an accretionary wedge on an active continental margin. The carbonaceous shales are characterized by high (>600 ppm) REE + Y contents, especially in the zones of brecciation and hydrothermal reworking. Detrial monazite enriched in LREE and MREE is the main carrier of REE mineralization in the graphitic shales. The main REE carrier in the graphite shales is REE phosphate (xenotime) formed during lithogenesis of sediments. Preliminary experimental treatment of the graphite shales of the Upper Nyatygran Subformation by ammonium hydrofluoride shows their potential for economic extraction of REE and Y.