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).     

Distribution of rare earth elements in waters and bottom sediments of mineralized lakes in the eastern Transbaikal region (Russia)

Contents of rare earth elements in waters and bottom sediments are maximum in the most mineralized soda lakes. It is shown that REE occur in waters mainly as carbonate (LnСО₃)⁺ and oxyhydroxide LnO₂H, LnO⁺, (LnO₂)^– complexes, whose activity in the La → Lu series changes in opposite directions. It has been determined that increase of mineralization leads mainly to higher concentrations of the dissolved HREE. Prevalence of the absolute values of MREE and HREE is recorded in basins with the development of bacterial processes. Geochemical barrier for the accumulation of LREE in waters can be represented by fluorcarbonates, whose saturation degree in the soda lake waters can be several orders of magnitude higher than the solubility products (SP). Oxidative and reductive settings in lakes are favorable for the formation of Ce(OH)₄ and Ce(OH)₃, respectively.     

Kiglapait geochemistry VII: Yttrium and the rare earth elements

Based on 51 wholerock analyses by XRF and summation over the layered group, the Kiglapait Intrusion contains 4.7_?1.6^+1.2 ppm Y, which resides principally in augite and apatite. Using liquid compositions calculated by summation, the partition coefficient D^AUG/L_Y is 0.95 ± 0.12 from 84 to 97 PCS (percent solidified) and 1.5 ± 0.4 above 97 PCS. For feldspar, the most likely value for D is 0.028 ± 0.02 (N = 6).REE analyses for 13 whole rocks were interpreted with the aid of yttrium models to yield trends for wholerocks and liquids vs PCS. Summations over the rocks of the layered group gave La = 2.5, Ce = 5.8, Nd = 3.9, Sm = 1.0, Eu = 0.8, Tb = 0.17, Yb = 0.37, and Lu = 0.06 ppm, with 2 s.d. errors near ± 30%. All these elements are highly incompatible until the arrival of augite, which affects chiefly the HREE, and apatite, which affects all (but more strongly, the LREE). The net result is that after apatite arrival at 94 PCS, the liquid compositions are nearly constant, hence D^WR/L_REE ≈ 1.0. These results are compatible with the mineralogy of the intrusion and the estimated partition coefficients for feldspar, olivine, augite, apatite, and Fe-Ti oxide minerals. For pre-apatite liquids, D^FSP/L_REE vary regularly with the normative di content of the liquid and change by an order of magnitude, hence the bulk liquid composition must be considered in any attempt to invert the compositions of feldspars to parent liquids.The Eu anomaly at first decreases in Kiglapait liquids due to plagioclase fractionation, but then increases due to removal of augite and apatite with negative Eu anomalies. The features dominantly responsible for Eu partitioning are liquid structure and, for monoclinic ternary feldspars, crystal structure. The former is best monitored by the augite or diopside content of the liquid and the latter, by the K content of the feldspar.The chondrite-normalized REE pattern for the intrusion has La_N = 7.4, Lu_N = 1.6, (Ce/Yb)_N = 3.6, and Eu/Eu* = 2.4, indicating its feldspar-rich nature. The chilled margin of the nearby Hettasch Intrusion has a similar but more evolved pattern, corresponding roughly to the Kiglapait liquid at 70 PCS. As with other data, those for the REE suggest source differences for the two intrusions rather than a relationship due to fractionation.     

华北平原高氟地下水中稀土元素分布和分异特征

高氟地下水是世界各国研究者广泛关注的重大环境问题。尽管对高氟地下水的化学特征、形成机理和扩散机制等已有不少研究,但其稀土元素(REE)的含量和分异特征以及这些特征能否反映高氟地下水的形成和分布尚不清楚,这在一定程度上限制了REE在高氟地下水中的运用。本研究以地下水氟离子异常严重地区——华北平原为研究区,沿地下水流向采集浅层和深层地下水样,研究分析了水中氟离子和REE的地球化学特征。浓度分析结果表明地下水氟离子浓度介于0.28 mg/L和9.33 mg/L之间,其中55%超出我国饮用水标准规定值1.0 mg/L;PHREEQC计算结果反映地下水中氟以NaF、CaF⁺、MgF⁺和自由态F^-形式存在,其中自由态F^-含量占主导(85.42%99.39%);高氟地下水主要分布于中部冲积湖积平原以及东部冲积海积平原,60%高氟地下水样分布在180 m深度以下;水化学图件分析结果指示浅层高氟地下水的形成主要受蒸发浓缩作用的控制,而深层高氟地下水是水岩相互作用下的矿物溶解和离子竞争吸附共同作用的结果。研究区地下水REE含量处于pmol/L至nmol/L级别,PHREEQC模拟计算结果表明REE主要以碳酸络合物( {\mathrm{REECO}}_3^{+}和$REE(CO_{3})_{2}^{-})$的形式存在,与氟离子络合的稀土元素(REEF²⁺和 {\mathrm{REEF}}_2^{+})占01.18%;上陆壳(UCC)标准化结果显示,所有地下水均呈重REE(HREE)和中REE(MREE)相对于轻REE(LREE)富集的模式,且具有显著Ce负异常(0.11* = Ce_UCC/(La_UCC×Pr_UCC)^0.5<2.29)特性;地下水富HREE主要归因于HREE比LREE优先与碳酸根络合,并且形成更加稳定的碳酸络合物。沿地下水流向,深层地下水中总REE含量与地下水中氟浓度均呈现不断上升的变化趋势,同时高氟地下水比低氟地下水更易富集重稀土元素,说明稀土元素对深层含水层富氟行为具有一定的指示作用。     

深海稀土分布规律与成矿作用

深海稀土是近年发现的一种富集中-重稀土的新型海洋矿产资源,其资源量远超陆地稀土储量,具有重要的潜在应用价值。中国是继日本之后在国际上第二个开展深海稀土调查研究的国家,2011年以来,先后在中印度洋海盆、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,在全球大洋中初步划分出4个深海稀土成矿带：西太平洋深海稀土成矿带、中—东太平洋深海稀土成矿带、东南太平洋深海稀土成矿带和中印度洋海盆-沃顿海盆深海稀土成矿带。深海富稀土沉积主要发育在深海盆地的沸石粘土和远洋粘土中,属于自生成因;部分发育在洋中脊附近的盆地中,受到热液作用的影响。研究发现,深海粘土中稀土元素主要赋存于生物磷灰石中,海水是稀土元素的主要来源;在早期成岩阶段,稀土元素在深海沉积物中发生转移和重新分配,并最终富集于生物磷灰石中;大水深（CCD面之下）、低沉积速率和强底流活动是深海稀土大规模成矿的主要控制因素。今后需要继续加大深海稀土基础调查,加强深海稀土调查探测技术研发,并开展海陆稀土成矿作用对比研究,揭示深海稀土成矿机制和规律。     

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...     

Distribution of titanium and the rare earth elements between peridotitic minerals

The concentrations of titanium and rare earth elements (REE) in olivines, orthopyroxenes, clinopyroxenes and spinels from four anhydrous, spinel-bearing peridotite xenoliths have been determined. The distribution of titanium (used as an analogue for the high field strength elements: HFSE) relative to the REE between clinopyroxenes and orthopyroxenes varies as a function of the whole rock composition and modal mineralogy. The distribution coefficients for titanium and the REE in these peridotites do not reflect mineral-melt equilibria. It is believed that subsolidus distribution coefficients for HFSE relative to REE vary with temperature. Ratios of various incompatible elements (e.g., Ti/Eu, Zr/Sm, Hf/Sm and P/Nd) in peridotite minerals differ from those in most primary basalts. However, the abundance ratios of incompatible elements in the bulk peridotite are comparable to those found in modern basalts. Given this and the differing contribution of melt from each phase during melting, near constant ratios of such incompatible elements in primary and primitive basalts and komatiites reflect the buffering of the melt by its residue. These ratios are fixed in the magma during the initial stages of melting because of similar and low distribution coefficients between melt and bulk residue for these element pairs. Differences in the relative abundances of titanium and REE in clinopyroxenes and orthopyroxenes demonstrate that mantle normalized abundance patterns for clinopyroxene are not equivalent to those of the whole rock. Therefore, claims of a widespread HFSE-depleted reservoir in the upper mantle base solely on the relative abundances of incompatible elements in peridotitic clinopyroxenes are invalid.     

Distribution of selected trace elements in sediments of Pamlico river estuary,north Carolina

Sixty-eight samples of sediment collected on a variably-spaced grid pattern from Pamlico River Estuary of North Carolina were analyzed for As, Cd, Co, Cr, Cu, F, Ni, Pb, U, Zn, clay, and organic matter. The major objectives of the study were to determine background and anomalous levels of trace elements in the sediments, and the effects of human activities on concentration and distribution of trace elements in the sediments. Clay and organic matter are more concentrated near the center of the estuary. This causes the highest concentration of trace elements in the sediments to be located there also owing to their preferential uptake of these elements. Highest trace element concentrations were observed in clay and organic matter near industrial sites, housing developments, and tributary mouths that drain areas of human activity. The apparent increase in trace element contents of fine sediments in Pamlico River Estuary owing to human activities is 4 to 1,750 times normal background levels.     

State of rare earth elements in the rare earth deposits of Northwest Guizhou,China

We studied the states of rare earth elements in ore of the Xianglushan rare earth deposit. Rare earth ore samples were tested and examined by scanning electron microscope, electron probe, and chemical leaching. No independent rare earth minerals were detected by scanning electron microscope. Elements detected by the electronic probe for the in situ micro-zone of the sample included: O, Al, Si, Ca, Mg, Fe, Ti, K, Na, S, Cl, C, Cu, Cr, V, and Pt. Rare earth elements were not detected by electron probe. (NH4)₂SO₄, (NH₄)Cl, NaCl, and H₂SO₄ were used as reagents in chemical leaching experiments that easily leached out rare earth elements under the action of 10% reagent, indicating that the rare earth elements in ore are mainly in the ionic state rather than present as rare earth minerals.     

长江沉积物稀土元素的粒度效应研究

依据Stokes定律,将小于63μm的长江沉积物分成小于2、2～4、4～8、8～16、16～32、32～63μm6个粒级,采用ICP-MS法分别测试了分粒级沉积物的REE含量,结果显示:长江沉积物REE的丰度遵循元素的"粒度控制律",即随粒度变细,∑REE含量依次增高;北美页岩标准化分布曲线均呈右倾的近"W"型,轻、重稀土分馏明显,相对富集LREE,明显的Ce负异常和弱Eu亏损。对长江沉积物不同粒级样品进行X射线衍射分析和体视镜下观测,结果表明:长江沉积物随粒度增大石英和长石含量逐步增加,碳酸盐和重矿物在各个粒级中含量甚微并且随粒级变化不大;长江沉积物REE随粒度变细逐渐增加的特征主要受控于沉积物随粒度变化而变化的矿物成分,黏土粒级及细粉砂中较高的∑REE主要是黏土矿物吸附作用的结果,粗粉砂中较低的∑REE主要为长石和石英的稀释作用结果,而碳酸盐和重矿物因其较低的含量对稀土元素含量影响较小。     

Authigenic associations between selected rare earth elements and trace metals in lacustrine sediments

Surficial sediment samples were collected at 47 stations in Little Traverse Bay, Lake Michigan, to determine the geochemical associations between certain rare earth elements (REE's) and trace metals. Each sample was analyzed for carbonate carbon, organic carbon, grain size, and the elements Al, Ca, Ce, Co, Cr, Eu, Fe, Hf, La, and Mn. Two distinct Ce subpopulatins were identified by graphical analysis, and an R-mode factor analysis was applied to data from the “enriched” Ce subpopulation (18 samples). Results show that the REE's and trace metals are primarily enriched in the authigenic phase of these sediments. Partial correlation analyses indicate that the REE's are primarily associated with hydrous Fe oxides relative to organic matter in this phase. The ratio of Ce/La concentrations increased markedly from the bay margins to the central trough of the bay, indicating that Ce, similar to Fe, exhibits a variable oxidation state in the authigenic phase of nearshore fine-grained sediments. The results of the present study suggest that the REE's and trace metals behave coherently in the authigenic phase of recent lacustrine sediments, and the REE's may be useful as geochemical tracers to differentiate between trace metal enrichments in surface sediments as a result of diagenesis and pollution loadings.     

中国南方红壤中稀土元素分布的研究

中国南方红壤中稀土元素总量主要集中在１５０￣２００μｇ／ｇ范围内,且土壤剖面层的底土层含量较高;稀土元素分布模式表明,红壤中轻稀土元素间略有分异,而轻,重稀土元素间以及重稀土元素间没有明显分异,稀土元素含量与红壤中有机质,粘粒含量及阳离子交换量间的相关性很弱,而与红壤中铁锰氧化物及磷酸岩呈显著的正相关关系。     

鄂尔多斯盆地西缘煤中稀土元素特征

煤中稀土元素是煤地质领域研究源岩和沉积环境的良好地球化学指示剂,也是一种重要的矿产资源。运用ELEMENT XR等离子体质谱分析仪对鄂尔多斯盆地西缘石炭-二叠系和侏罗系延安组煤样中稀土元素进行测试,计算了多种化学参数并绘制了稀土元素分布类型曲线。在对稀土元素（REY）的地球化学特征分析的基础上,探讨了其物质来源。结果表明,石炭-二叠系煤中REY含量明显高于中国和世界煤中的均值,也高于上地壳值,呈铕（Eu）负异常,铈（Ce）负异常,这可能因为石炭-二叠系处于海陆交互相,与其处于强的还原环境有关;而侏罗系煤中REY含量却低于中国和世界煤中的均值,也低于上地壳值,呈轻微Eu负异常,轻微Ce正异常,侏罗系延安组主要为氧化的陆相环境,所以δCe在煤中的不亏损才会普遍存在。通过煤中稀土元素的分配模式、平面展布与其构造环境的综合分析,推测石炭-二叠系的物源为研究区西北部的阿拉善地块和北部的阴山古陆,南部的秦-祁造山带为侏罗系煤中稀土元素提供了主要的物质来源。     

溶解态稀土元素在离子吸附型稀土矿区周边地表水中的分布特征及影响因素

选择赣南典型稀土矿区,即寻乌(以轻稀土为代表)、安远(以中稀土为代表)和龙南(以重稀土为代表)为研究区域,于生产期和停产期(停产后半年)分别采集了矿区上游、矿区淋滤废水、矿区山泉水、生活用井水、近矿支流、矿区下游等地表水共90件,分析了溶解态稀土元素在离子吸附型稀土矿区周边地表水中的含量、空间分布特征及影响因素。结果表明:稀土矿的开采对矿区周边地表水中DREE含量影响较大。此外,水粒作用、区域地质背景与风化作用、水化学因素都是影响离子吸附型稀土矿区周边水体DREE行为的主要因素。矿区周边地表水中稀土含量高是我国离子吸附型稀土矿山开采引发的特殊问题。     

Distribution of Rare—earth Elements in the Shenzhen Bay and Dapeng Bay Modern Sediments

The aim of this paper is to study the REE geochemistry of the Shenzhen Bay (SZB) and Dapeng Bay(DPB) modern sediments, discuss their REE distribution patterns, reveal the REE geochemical difference between the two bays which share the same material source but are deposited in different sedimentary environments, and expound their dynamic changes.It can be concluded that the SZB and DPB sediments are essentially of continental source.Their REE distribution patterns are quite different from those of Pacific pelagic sediments, but are very similar to those of South Chi-na granites.Because of different sedimentary environments prevailing in the SZB and DPB, some REE fractionation would have taken place in the sediments of the two bays.     

Specific features of the distribution of trace and rare earth elements in recent bottom sediments in the lower course of the Severnaya Dvina River and White Sea

The paper discusses results of the lithogeochemical examination of recent bottom sediments in the lower course of the Severnaya Dvina River and White Sea. It has been established that the average concentration of several trace elements (Hf, Sc, Co, Y, Ni, V, Cr, Zr, Ba, and others) therein correlates with the content of the silt-pelite fraction. Maximal concentrations of the majority of above elements are confined to the silty-clayey sediments at the Basin/Dvina Bay boundary. They localized near the coastal zone only for some clastophile (Zr, Cr, and others). Typical values of the hydrolyzate module, chemical index of alteration, and Al₂O₃/SiO₂ ratio in the aleuropelitic and pelitic sediments of the Severnaya Dvina River delta, Dvina Bay, and the Dvina Bay Basin boundary suggest that these sediments are confined to sufficiently cold climate settings. Data points of sediment composition in discriminant paleotectonic diagrams are scattered over a large field probably due to high contents of the weakly weathered plagioclases, micas, and amphiboles, as well as the hydrogenic process promoting the accumulation of Fe and Mn. The PAAS-normalized spectra of rare earth elements (REE) in bottom sediments of the Pinega and Severnaya Dvina rivers, marginal filter of the latter river, Dvina Bay, and the Dvina Bay Basin boundary are similar to the REE distribution in clayey rocks of the ancient platform cover (except for a slight positive Eu anomaly). The REE systematics and distribution pattern of compositional data points of recent bottom sediments in the Gd_N/Yb_N-Eu/Eu* and Eu/Eu*-Cr/Th diagrams and values of several indicator ratios of trace elements suggest that the studied rocks were formed by the mixing of clastic materials from geochemically contrast provenances: northwestern provenance (Kola-Karelia geoblock), which is mostly composed of the Archean and Early Proterozoic crystalline complexes, and the southeastern provenance (northwestern periphery of the Mezen syncline), which is almost totally composed of Phanerozoic sedimentary rocks. The latter provenance likely played a crucial role in the geochemical signature of recent bottom sediments over a significant area of the White Sea.     

云南安宁磷矿中稀土元素分布规律和赋存状态研究

磷矿伴生稀土元素是获取稀土资源的重要途径。我国磷块岩型稀土矿分布广,稀土含量高,具有综合回收价值,是仅次于独立稀土矿床的伴生稀土资源。本文主要研究云南安宁磷矿中稀土元素分布规律和赋存状态,并比较了磷矿石中稀土元素总量与磷含量的关系,结果表明磷矿石中稀土氧化物总量为72×10^-6～1 050×10^-6,与磷含量呈一定的正相关关系。另外通过光学显微镜及电子显微镜观察发现,安宁磷矿中缺乏独立的稀土矿物,只在部分海绿石中找到了独立的稀土矿物(可能为独居石和褐帘石)。LA-ICP-MS分析结果表明,胶磷矿单矿物稀土元素含量在770×10^-6～920×10^-6之间,而白云石单矿物稀土元素含量均低于34×10^-6,石英单矿物的稀土元素平均含量为180×10^-6。由于部分独立的稀土矿物的存在,海绿石矿物中稀土元素总量可高达2 947.27×10^-6～3 159.87×10^-6。综合分析结果表明,安宁磷矿中稀土元素主要以类质同像的...     

Dominants and accumulation of rare earth elements in sediments derived from riparian and depressional marshes

The rare earth elements (REEs) in the sediments of the Xianghai wetlands were measured by inductively coupled plasma spectrometry. The REEs accumulation rates in two sedimentation cores derived from the riparian and depressional marshes were determined by ²¹⁰Pb method. The results showed that REEs concentrations in the Xianghai wetland sediments (∑REEs, 116 mg kg⁻¹) were lower than the corresponding values in Chinese soils (181 mg kg⁻¹) and river sediments (∑REEs, 158–191 mg kg⁻¹). Under alkaline conditions (with pH, 8.2–10.3), the light REEs were more enriched than the heavy REEs. Cerium is the predominant element, and accounts for 30–33% of the total REEs. REEs in the depressional marsh sediments were relatively high (∑REEs, 127 vs. 104 mg kg⁻¹), especially light REEs contents. A significantly positive correlation was found between the neighboring elements except Pr and Dy. The different types of vertical distribution of REEs between the riparian and the depressional marsh can partly result from long-term differing hydrological regimes. Generally, depressional marsh had accumulated much more REEs than riparian marsh (the mean accumulation rates of ∑REEs, 102.98 vs. 48.89 μg cm⁻² year⁻¹).     

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.     

Distribution of rare earth elements in crystalline bedrock groundwaters: Oslo and Bergen regions,Norway

One hundred and fifty Norwegian bedrock groundwater samples, from Bergen and from Vestfold (Oslofjord), have been analysed by ICP-MS techniques at two laboratories for a large suite of trace elements including rare earth elements (REEs) and Y. The bedrock lithologies include granites (dominated by the Permian Drammen Granite) and Permian latites/rhomb porphyries from Oslofjord, and Caledonian/Precambrian granitic and gneissic lithologies in the Bergen area. The REEs show good correlation with each other, with the exception of Eu. REEs generally show a weak negative correlation with pH. REE concentrations are highest in waters in acidic lithologies and generally decrease with increasing atomic weight. Yttrium, La, Ce and Nd are the most abundant REEs in the waters, with median concentrations exceeding 0.1 μg/l. On crustal (PAAS)-normalised plots, distinct geochemical signatures are observed for the different lithologies. Most groundwaters exhibit negative Eu anomalies on such plots, except for latitic waters from the Oslo area which show a positive Eu anomaly. Aquifer host-rock-normalised plots for groundwaters from Vestfold indicate minor enrichment in heavier REEs and depletion in Ce during water–rock interaction.