Rare Earth Elements Composition and Constraint on the Genesis of the Polymetallic Crusts and Nodules in the South China Sea

The rare earth elements（REE） composition of the polymetallic crusts and nodules obtained from the South China Sea（SCS） were analyzed through inductively coupled plasma mass spectrometry.Results revealed great differences in the REE abundances（∑REE） of the SCS polymetallic crusts and nodules; the crusts show the highest ∑REE, whereas the nodules exhibit the lowest ∑REE. The similarity in their NASC-normalized patterns, the enriched light REE（LREE）, the markedly positive Ce anomaly（δCe）, and the non-or weakly positive Eu anomaly（δEu）, suggest that the polymetallic crusts and nodules are of hydrogenetic origin. Moreover, the REE contents and their relevant parameters are quite different among the various layers of the crusts and nodules, which probably results from the different marginal sea environments and mineral assemblages of the samples. The growth profiles of the SCS polymetallic crusts and nodules reveal the tendency ∑REE and δCe to slightly increase from the outer to the inner layers, suggesting that the growth environments of these samples changed smoothly from an oxidizing to a relatively reducing environment; in addition, the crust ST1 may have experienced a regressive event（sea-level change） during its growth, although the REE composition of the seawater remained relatively stable. On the basis of the regional ∑REE distribution in the SCS crusts and nodules,the samples collected near the northern margin were influenced by terrigenous material more strongly compared with the other samples, and the REE contents are relatively low. Therefore, the special geotectonic environment is a significant factor influencing the abundance of elements, including REE and other trace elements. Compared with the oceanic seamount crusts and deep-sea nodules from other oceans,the SCS polymetallic crusts and nodules exhibit special REE compositions and shale-normalized patterns, implying that the samples are of marginal sea-type Fe-Mn sedimentary deposits, which are strongly affected by the epicontinental environment, and that they grew in a more oxidative seawater environment. This analysis indicates that the oxidized seawater environment and the special nano property of their Fe-Mn minerals enrich the REE adsorption.

Rare earth elements and yttrium in ferromanganese deposits from the South China Sea:distribution,composition and resource considerations

Ferromanganese nodules and crusts contain relatively high concentration of rare earth elements（REE） and yttrium（REY）,with a growing interest in exploitation as an alternative to land-based REY resources.On the basis of comprehensive geochemical approach,the abundance and distribution of REY in the ferromanganese nodules from the South China Sea are analyzed.The results indicate that the REY contents in ferromanganese deposits show a clear geographic regularity.Total REY contents range from 69.1×10^-6 to 2 919.4×10^-6,with an average value of 1 459.5×10^-6.Especially,the enrichment rate of Ce content is high,accounting for almost 60% of the total REY.This REE enrichment is controlled mainly by the sorption of ferromanganese oxides and clay minerals in the nodules and crusts.Moreover,the total REY are higher in ferromanganese deposits of hydrogenous origin than of diagenetic origin.Finally,Light REE（LREE） and heavy REE（HREE） oxides of the ferromanganese deposits in the study area can be classified into four grades： non-enriched type,weakly enriched type,enriched type,and extremely enriched type.According to the classification criteria of rare earth resources,the Xisha and Zhongsha platform-central deep basin areas show a great potential for these rare earth metals.

Geochemical Characteristics of the Trace and Rare Earth Elements in Reef Carbonates from the Xisha Islands(South China Sea): Implications for Sediment Provenance and Paleoenvironment

Based on the concentrations of the trace elements,rare earth elements(REE),and Sr isotopic compositions in reef carbonates from the well‘Xike-1’reef core of the Xisha Islands,the constraints on sediment provenance and paleoenvironment were defined.Variations of the terrigenous input into the paleoseawater were traced in detail and the paleoenvironment and sediment provenance were further investigated.The results show that the HREE/LREE values in the reef carbonates are negatively associated with their Th and Al concentrations;however,their Al and Th concentrations show positive correlation.The lowest 87 Sr/86 Sr values in the reef carbonates generally coincide with the lowest values of Al,Th concentrations and the highest values of HREE/LREE.These data indicate that the HREE/LREE,Al concentrations,and Th concentrations of the reef carbonates are useful indexes for evaluating the influence of the terrigenous inputs on the seawater composition in the study area.From top to bottom,the changing process of the HREE/LREE values and Al,Th concentrations can be divided into 6 intervals;they are H1(0–89.30 m,about 0–0.11 Myr),L1(89.30–198.30 m,about 0.11–2.2 Myr),H2(198.30–374.95 m,about 2.2–5.3 Myr),D(374.95–758.40 m,about 5.3–13.6 Myr),L2(758.40–976.86 m,about 13.6–15.5 Myr),and H3(976.86–1200.00 m,about 15.5–21.5 Myr).Moreover,the changing trend of the HREE/LREE values coincides with that of the seawater δ^13C values recorded by benthonic foraminiferal skeletons from the drill core of ODP site 1148 in the South China Sea(SCS),but not with that of the seawaterδ18O values.The high uplifting rates of the Qinghai-Tibet Plateau coincide with the high Th and Al concentrations and the low HREE/LREE values in the reef carbonates.These data indicate that the main factors controlling the changes of terrigenous flux in the SCS are the tectonic activities associated with Qinghai-Tibet Plateau uplifting and the variations of uplifting rates rather than paleoclimatic changes.

Zhujiang Refinery The Largest Rare Earth Plant in South China

Zhujiang Refinery is located in the east suburb of Guangzhou city, the People’s Republic of China. Thegeographical advantage makes it convenient both in communications and in foreign trade. The refinery cov-ers an area of 15 hectares and has nearly 1000 staff members, more than 200 of whom are engineering andtechnical personnel. Established in 1966, Zhujiang Refinery has engaged in the production and scientific re-search of rare earths for more than 20 years. Having fixed assets of about RMB 20 million yuan, ZhujiangRefinery is the largest base for producing and exporting rare earths in the south of China.

RARE EARTH ELEMENT DISTRIBUTION PATTERN OF COALS IN SOUTH CHINA

In this article, 15 coal samples from South China have been systematically analyzed. Combining the geological features of coal seam and wall rocks,especially the distribution of hydrothermal veins and thermally metamorphosed minerals, the rare earth element distribution patterns of unmetamorphosed, low-grade-metamorphosed, regional-metamorphosed,thermal-contact metamorphosed and hyd rothermally-metamorphosed coals tell us that REE in the regional-metamorphosed, thermal-contact metamorphosed and hydrothermally-metamorphosed coals have been mobilized and fractionated to varying degrees. All these reseaches will become judging evidences for coal geochemistry.

Rare earth elements distribution in marine sediments of Malaysia coasts

In the east coast Peninsular Malaysia region,sediments are transported by several rivers from the east Malaysia into the South China Sea estuary.In the vicinity of the five river estuaries core sediments were collected in order to investigate rare earth elements(REEs) profile.Core sediments were divided into strata of between 2 to 4 cm intervals and prepared for analyzing by ICP-AES.REE concentrations of 54.3 μg/gr at 24–26 cm in EC4 increased to 114.1 μg/gr at 20–22 cm in EC5.The measured concentration of ...

Contribution of Mountain River Materials to the Continental Shelf off Southeastern Hainan Island Since the Mid-Holocene

The concentrations of rare earth elements(REEs)in the bulk sediment of Core X2,which was collected from southeastern Hainan Island,were analyzed to investigate the relative contributions of various provenance regions since mid-Holocene.The results show that sediments in Core X2 were primarily derived from Hainan Island with lesser amounts from Taiwan and limited input from the Pearl River.Based on the application of quantitative inversion to model the REE data,the average contributions of river materials from southeastern Hainan Island and southwestern Taiwan to the study area were 68%and 32%,respectively.Furthermore,starting at 4.0 kyr BP,the transport of fluvial sediments from Taiwan to the study region increased due to enhanced hydrodynamics in South China Sea(SCS).These results indicate that the contributions of mountain river materials from Hainan Island and Taiwan to the continental shelf of northern SCS are non-negligible.Furthermore,these results demonstrate that mountain rivers can play an important role in the material cycle of continental margins and may feature a greater impact than large river systems in specific continental shelf areas.

Trace and Rare Earth Element Characteristics in Fe-Mn Carbonates Associated with Stratiform Ag-Pb-Zn Mineralization from the Lengshuikeng Ore District, Jiangxi Province: Implications for Their Genesis and Depositional Environment

We performed a systematic trace and rare earth element analysis for the bedded Fe-Mn carbonate rocks related to the stratiform Ag-Pb-Zn mineralization in the Lengshuikeng ore district, Jiangxi Province, South China. Three types of Fe-Mn carbonates are distinguished, namely, the massive, breccia, and vein types. Both carbonate and silicate fractions in the samples are analyzed for their trace and rare earth element concentrations using a step acid-leaching technique. Our results show that the carbonate fractions in the massive type samples have the lowest REE concentrations but pronounced positive Eu and Y anomalies with Eu/Eu＊ value from 1.3 to 6.2 and Y/Ho value from 40.1 to 59.5, and similar characteristics are also shown for the silicate fractions in the massive type samples（Eu/Eu＊=1.0-6.7, Y/Ho=20.7-55.1）. These REE characteristics are similar to those of Sedex type massive sulfide deposits worldwide, and we suggest that the massive type Fe-Mn carbonate rocks were likely formed from an exhalative volcanic-hydrothermal fluid feeding the depression basin of a volcanic lake. The high concentrations of redox-sensitive elements and ratios such as U/Th, V/Cr and V/（V＋Ni） indicate a dysoxic environment for the Fe-Mn carbonate deposition. In contrast, the breccia type and vein type Fe-Mn carbonate samples show different trace and rare earth element features from those of massive type samples, and they are more similar to the volcanic rocks and magmatic-hydrothermal fluids in the Lengshuikeng ore district and may reflect strong overprinting from volcanic and sub-volcanic magmatism related to the porphyry type mineralization in the district.

Compositional Variations and Its Implications of a Bastnaesite Crystal,Mianning County,Sichuan Province

A bastnaesite crystal about 12×20 mm 2 in size collected from a pegmatitic aegirine augite barite bastnaesite vein of the Maoniuping rare earth deposit, Mianning County, Sichuan Province, has been analyzed for La, Ce, Pr and Nd by synchronous radiative X ray fluorescence(SRXRF) technics at the National BEPC Laboratory. The results show an apparent compositional variation along vertical and horizontal sections accross the crystal which may be divided into three compositional zones(A, B and C). Significant difference exists between the inner portion(zone A), averaging at 28 35% La 2O 3, 35 04% CeO 2, 2 01% Pr 6O 11 and 5 44% Nd 2O 3, and the outer portion(zone B), averaging at 32 81% La 2O 3, 42 26% CeO 2 3 30% Pr 6O 11 and 7 08%. Nd 2O 3, of the crystal. Only one analysis is available on the egde of the crystal(zone C) yielding 14 50% La 2O 3, 21 41% CeO 2, 4 19% Pr 6O 11 and 16 71% Nd 2O 3, which demonstrates probably fractionations between LREE and HREE. The La/Ce ratio, however, is nearly constant around 0 84±0 08 among the three zones, while the La/Pr and La/Nd ratios erratically fluctuate due to low and variable contents of Pr and Nd. These results indicate that the REE bearing hydrothermal system underwent a significant compositional change during the stepwise growth of the bastnaesite crystal.

REEs fractionation and sedimentary implication in surface sediments from eastern South China Sea

To get features of rare earth elements （REEs） fractionation, 106 surface sediment samples from eastern South China Sea were determined for REEs combined with major and trace elements by ICP-MS. The distribution pattern of REEs, strong correlation between REEs and Al, North American shale composite （NASC） normalization all suggest a dominant crustal source for REEs in the research area. However distinct fractionation among REEs was observed in surface sediment from area with water depth over 2000 m, confirmed by the strong positive correlation among light rare earth elements （LREEs） and among heavy rare earth elements （HREEs） but weaker relationship between LREEs and HREEs. Eluviation by Cl- might be a key role on the fiactionation of REEs, comparing with factors such as grain size, co-precipitation with Fe and Mn hydroxide, calcareous and siliceous biogenic precipitation. The fractionation among REEs could be used as index to illustrate the sedimentary environment in reverse.

Geochemistry of the Middle to Late Permian limestones from the marginal zone of an isolated platform(Laibin,South China)

Major, trace and rare earth elements were measured in 27 samples of the Middle to Late Permian limestones from the Tieqiao section located on the marginal zone of an isolated platform （Laibin, South China）. Shale-normalized REE＋Y patterns of all samples show notably negative Ce anomalies （0.21-0.66, average 0.33）, slightly positive Gd anomalies （1.08-1.30, average 1.20）, and positive Y anomalies with superchondritic Y/Ho ratios （36-91, average 55）, which are consistent with those of modern shallow seawater. Their relative LREEs enrichment with higher NdsN/YbsN ratios （0.58-1.80） than those of modern shallow seawater （0.21-0.50） suggests complicated sources of REEs for all samples. Compared with geochemical features of sediments influenced by terrigenous particles and hydrothermal fluids, it is concluded that ambient shallow seawater was the primary source of REEs in these limestones. Comparing the indicators of REE＋Y elements （ZREE, NdsN/YbsN, Ce/Ce＊, Gd/Gd＊, Eu/Eu＊ and Y/Ho） in limestones with those in bedded cherts from the Tieqiao section, we consider that limestone and bedded chert have similar sources of REE＋Y elements： ambient shallow seawater with more or less hydrothermal fluids. In addition, there is a completely negative correlation between CaCO3 and SiO2 contents in limestones and bedded cherts. These results imply that precipitation of CaCO3 was inhibited by that of SiO2 which was derived mainly from hydrothermal fluid, es- pecially in bedded cherts from the Tieqiao section.

华南热水沉积硅质岩建造及其成矿效应

华南地区热水沉积建造发育。文中介绍该地区热水沉积建造 ,特别是震旦系顶部、泥盆系榴江组和二叠系当冲组 3个重要层位的硅质岩建造 ,分析它们的地质地球化学特征。研究表明 ,华南三层位沉积硅质岩的共同特征是TiO2 、Al2 O3 和K2 O含量一致偏低 ,大部分微量元素含量偏低 (与地壳克拉克值相比 ) ,但Ba、As、Sb富集 ,具有较为典型的热水沉积成因特点。多元统计分析显示 ,大部分微量元素在第一个主因子上均有显著因子载荷 ,与它们在基底的富集或亏损无关 ,代表了古地热系热水循环中的淋滤因子。华南三层位热水成因硅质岩具有相似的REE地球化学特征。REE总量低 ,稀土配分模式落在典型热水沉积物的上、下限之间 ,多数样品呈现δCe和δEu负异常。正常沉积的混入使部分硅质岩的REE配分模式复杂化。最后 ,讨论了与热水沉积建造相关的成矿效应 。

华南热水成因硅质岩建造的稀土元素地球化学特征

本文在华南地区若干个重要层位热水成因硅质岩建造的稀土元素地球化学数据的基础上,讨论了热水成因硅质岩的REE特征及其与形成环境的关系。指出典型热水沉积建造的δCe为负异常,而δEu为正异常,且LREE>HREE;这种热水成因的硅质岩REE总量普遍较低,且有从热水喷口向外REE总量增高的趋势。热水成因硅质泥岩与正常沉积成因硅质泥的混合存在使稀土元素分布状况变得更复杂。

南方废弃稀土矿区生态失衡状况及其成因

本文综述了我国南方废弃稀土矿区大面积植被破坏,水土流失严重、滑坡、泥石流危险,重金属污染,水体污染,土壤污染和氟污染的生态失衡状况;并详细分析了造成南方废弃稀土矿区生态失衡状况的成因,如采用池浸、堆浸和原地浸取工艺提取稀土的不足,稀土矿的矿床厚度薄且分布较为广泛、稀土品位较低同时资源利用率低,南方离子型稀土资源未充分进行整合、相关部门对稀土矿开采的准入和监管不到位,针对离子型稀土矿区生态恢复的研究滞后、未形成可推广的稀土废弃地生态修复模式等;最后,从以下诸方面提出了改善南方废弃稀土矿区生态失衡状况的建议,如:开发提取稀土的新工艺、加快稀土资源整合的步伐、加大稀土废弃地生态修复研究的投入等。

南海北部陆坡海洋沉积物稀土元素及物源和成岩环境

通过对ODP184航次 114 6站位海底岩心沉积物中稀土元素含量及其配分模式的研究 ,确立了其分配规律 ,即相对富集轻稀土 ,Eu亏损等 ,并且与东海大陆架及中国黄土的稀土分布模式相似 ,表明本区沉积物物源主要来自陆源 ,是大陆岩石分化过程的产物。对富集因子的研究也证明了沉积物主要来自陆源。δCe的弱负异常值与∑REE和δEu值一样 ,主要受陆源源区气候环境变化控制 ,而与海水关系不大。稀土元素与生物作用基本无关 ,可能主要是赋存于陆源碎屑矿物的晶格中。通过对岩心沉积物间隙水成分的研究 ,表明成岩环境主要为还原环境。6 8m(mcd)以上主要为硫酸盐的还原作用 ,6

贵州瓮安陡山沱组磷块岩的稀土元素地球化学特征与沉积古环境

晚元古代末的陡山沱期(550～600Ma)是地球历史生物、化学和气候变化的剧烈时期。通过对贵州瓮安陡山沱组磷矿的稀土元素研究,确定上矿层磷块岩的北美页岩标准化稀土模式具负Ce异常、轻和重稀土亏损及中稀土富集特征。下矿层磷块岩稀土模式为轻微负Ce异常、轻微的轻和重稀土亏损及中稀土富集。下矿层磷块岩的Ceanom 值为-0 065～-0 077,上矿层磷块岩的Ceanom 为-0 26～-0 291,表明瓮安磷矿沉积古环境从下矿层的还原条件转变为上矿层的氧化条件。这种南沱冰期之后的环境变化可能为瓮安动物群的大爆发提供了必要的条件。

南海西南海域表层沉积物微量和稀土元素地球化学特征及其意义

分析了南海西南海域表层沉积物的微量元素和稀土元素组成,结果表明,这些沉积物与大陆上地壳相比,具有相对低的Zr、Sc、V、Nb、Hf、Th、REEs含量,而Co、Cu、Ni、Ta、Rb、Cs、Sr、Ba的含量稍高;深海区表层沉积物比陆坡区具有较高的Co、Zr、Sc、V、Nb、Hf、Ta、Th和REEs,陆坡区表层沉积物相对高的生物碎屑组分对这些元素起到了一定程度的稀释作用。因子分析和相关分析显示绝大部分微量元素和稀土元素主要受陆源组分的控制,Th、Cr、Co、Sc、Nb、Zr、Hf和REEs等不活动元素之间的比值特征,并没有受到风化作用、海流搬运作用和海洋自生组分稀释作用的影响,较好地保存了源岩的化学组成特征。因此,南海西南海域表层沉积物的La/Sc、Th/Sc、Th/Cr、Th/Co比值和稀土配分曲线特征,指示这些沉积物的源岩具有陆壳成分的特点,以长英质岩石为主,缺乏深源的基性和超基性岩,火山碎屑物质成分很低,其源区主要为南海西部的印支大陆。陆架区和深海区表层沉积物具有十分相近的微量元素和稀土元素组成特征,指示它们的碎屑物质来源较为相同。

南海神狐海域表层沉积物稀土元素地球化学

南海神狐海域表层沉积物稀土元素总量变化较大,分布范围为66.8～218.3μg/g,平均值为128.1μg/g,相对接近于中国黄土(w(∑REE)=170.66μg/g);∑REE受"粒度效应"控制,主要富集于黏土质粉砂中;各类沉积物及与中国黄土、上陆壳和珠江口沉积物的稀土元素标准化曲线的变化趋势基本一致,表明这些沉积物具有相同的物源区,且具有大陆地壳性质。铈的负异常主要受陆源源区气候环境变化控制,而与海水关系不大。∑REE与CaO、CaCO3和Sr元素呈负相关,与Al2O3、K2O、SiO2呈正相关,表明稀土元素与生物作用基本无关,可能主要吸附于黏土矿物表面和赋存于陆源碎屑矿物的晶格中。

贵州瓮安陡山沱组磷块岩稀土元素地球化学特征与沉积期后变化

贵州瓮安陡山沱组磷块岩保存了可能是全球最早的后生动物化石 (瓮安动物群 ) ,对于瓮安动物群出现过程中的古海洋环境重建具有重要科学意义。但必须对成岩后生作用对磷块岩中的稀土元素改造进行评估。通过对贵州瓮安陡山沱组磷块岩的磷质碎屑、磷质和白云质胶结物、磷条带和泥条带等的稀土元素地球化学特征研究 ,确定沉积期后变化对稀土元素的改造影响不大。上矿层磷块岩沉积期形成的磷质碎屑、成岩期形成的白云质和磷质胶结物具相同的稀土元素配分模式 ,暗示了沉积期后的改造作用对瓮安陡山沱组磷块岩保存的原生沉积信息影响不大。瓮安陡山沱组磷块岩具有显著的重稀土亏损特征。磷块岩的磷质和白云质胶结物、伴生磷质碎屑、强风化磷块岩相近的ErN/LuN 比值 ,表明沉积期后的改造作用不是重稀土元素亏损的主要原因。磷块岩的ErN/LuN、LaN/NdN 与Ce/Ce 间的相关性 ,表明越氧化的沉积环境中 ,轻和重稀土元素亏损越强。

赣南花岗岩风化壳型稀土矿床中纳米级稀土矿物的研究

为揭示次生风化成因稀土矿物的赋存形态和分布特征,对赣南安远岗下稀土矿区花岗岩风化壳剖面进行了研究。采集风化壳不同层位的样品进行分选、提纯,场发射扫描电镜和透射电镜研究结果表明,与稀土矿物紧密相关的粘土矿物是高岭石和埃洛石等,风化壳中发现的纳米级稀土矿物既有附着于其他矿物表面的微细颗粒,也有呈集合体存在的稀土矿物(可能为方铈石),这一现象有助于进一步认识风化壳稀土矿床的形成过程。