Rare earth element partitioning between titanite and silicate melts: Henry’s law revisited

We present detailed experimental results on the partitioning of rare earth elements (REE) between titanite and a range of different silicate melts. Our results show that Henry’s law of trace element partitioning depends on bulk composition, the available partners for heterovalent substitution, crystal composition, and melt composition. We illustrate that the partition coefficients for Sm depend very strongly on the bulk concentration of Sm in the system. The substitution mechanism, by which rare earth elements are incorporated into the crystal structure, plays an important role for trace element partitioning and also for the onset of Henry’s law. Our data show that there are clear differences between substitution mechanisms of major elements compared to elements which are present only as traces. Our experiments also clearly show that the onset of Henry’s law depends on the concentrations of the sum of all trace elements which are incorporated into the crystal by the same substitution mechanism. For geochemical modelling of magmatic processes involving titanite, and indeed other accessory phases, it is of crucial importance to first evaluate whether the REE, and other trace elements, are present as traces or as major elements, only then appropriate D values may be chosen.     

The aquatic chemistry of rare earth elements in rivers and estuaries

Laboratory experiments were carried out to determine how pH, colloids and salinity control the fractionation of rare earth elements (REEs) in river and estuarine waters. By using natural waters as the reaction media (river water from the Connecticut, Hudson and Mississippi Rivers) geochemical reactions can be studied in isolation from the large temporal and spatial variability inherent in river and estuarine chemistry. Experiments, field studies and chemical models form a consistent picture whereby REE fractionation is controlled by surface/solution reactions. The concentration and fractionation of REEs dissolved in river waters are highly pH dependent. Higher pH results in lower concentrations and more fractionated composition relative to the crustal abundance. With increasing pH the order of REE adsorption onto river particle surfaces is LREEs > MREEs > HREEs. With decreasing pH, REEs are released from surfaces in the same order. Within the dissolved (<0.22 µm) pool of river waters, Fe-organic colloids are major carriers of REEs. Filtration through filters and ultrafilters with progressively finer pore sizes results in filtrates which are lower in absolute concentrations and more fractionated. The order of fractionation with respect to shale, HREEs > MREEs > LREEs, is most pronounced in the solution pool, defined here as <5K and <50K ultrafiltrates. Colloidal particles have shale-like REE compositions and are highly LREE enriched relative to the REE composition of the dissolved and solution pools. The addition of sea water to river water causes the coagulation of colloidal REEs within the dissolved pool. Fractionation accompanies coagulation with the order of sea water-induced removal being LREEs > MREEs > HREEs. While the large scale removal of dissolved river REEs in estuaries is well established, the release of dissolved REEs off river particles is a less studied process. Laboratory experiments show that there is both release and fractionation of REEs when river particles are leached with seawater. The order of sea water-induced release of dissolved REE(III) (LREEs > MREEs > HREEs) from Connecticut River particles is the same as that associated with lowering the pH and the same as that associated with colloidal particles. River waters, stripped of their colloidal particles by coagulation in estuaries, have highly evolved REE composition. That is, the solution pool of REEs in river waters are strongly HREE-enriched and are fractionated to the same extent as that of Atlantic surface seawater. This strengthens the conclusions of previous studies that the evolved REE composition of sea water is coupled to chemical weathering on the continents and reactions in estuaries. Moreover, the release of dissolved Nd from river particles to sea water may help to reconcile the incompatibility between the long oceanic residence times of Nd (7100 yr) and the inter-ocean variations of the Nd isotopic composition of sea water. Using new data on dissolved and particle phases of the Amazon and Mississippi Rivers, a comparison of field and laboratory experiments highlights key features of REE fractionation in major river systems. The dissolved pool of both rivers is highly fractionated (HREE enriched) with respect to the REE composition of their suspended particles. In addition, the dissolved pool of the Mississippi River has a large negative Ce-anomaly suggesting in-situ oxidation of Ce(III). One intriguing feature is the well developed maximum in the middle REE sector of the shale normalized patterns for the dissolved pool of Amazon River water. This feature might reflect competition between surface adsorption and solution complexation with carbonate and phosphate anions.     

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.     

Geochemistry of rare earth elements in oceanic phillipsites

The behavior of rare earth elements (REE) was examined in oceanic phillipsites collected from four horizons of eupelagic clay in the Southern Basin of the Pacific. The REE concentrations were determined in the >50-μm-fraction phillipsite samples by the ICP-MS method. The composition of separate phillipsite accretions was studied using the electron microprobe and secondary ion mass-spectrometry. Rare earth elements in phillipsite-only samples are related to the admixture of ferrocalcium hydroxophosphates. The analysis of separate phillipsite accretions reveals low (<0.1–18.1 ppm) REE (III) concentrations. The Ce concentration varies between 2.7 and 140 ppm. The correlation analysis shows that REE (III) are present as an admixture of iron oxyhydroxides in separate phillipsite accretions. Based on the REE (III) concentration in iron oxyhydroxides, we can identify two generations of phillipsite accretions. Massive rounded accretions (phillipsite I) are depleted in REE, while pseudorhombic (phillipsite II) accretions are enriched in REE and marked by a positive Ce anomaly. Oceanic phillipsites do not accumulate REE or inherit the REE signature of the volcaniclastic material and oceanic deep water. Hence, the REE distribution in phillipsites does not depend on the sedimentation rate and host sediment composition.     

Distribution of rare earth elements and oxyhydroxide phases within a weathered felsic igneous profile in Hong Kong

Variation in type and abundance of oxyhydroxide phases and the fractionation of rare earth elements (REE) within a weathered felsic pyroclastic profile in Hong Kong were investigated in order to assess the key factors and micro-environmental conditions controlling their distribution during weathering at rock and mineral scales. Three types of oxyhydroxide phases (Fe-, Mn- and Ce-rich) were recognized based on their most abundant elements. The Fe-rich types appeared in all samples at different stages of weathering. The Mn-rich types, however, were limited to samples at advanced stages of weathering, while the Ce-rich types were found solely in samples from oxyhydroxide-rich zones. Fractionation of REE likely started at the early stages of weathering, but became evident only at the advanced stages. Characteristics of REE patterns, especially the direction (negative or positive) and extent of Ce-anomalies, correlated very well with the appearance and abundance of Mn-oxyhydroxides, and were attributed to the co-existence of distinct micro-environmental conditions within the profile. These conditions resulted from two major competing processes, “leaching and fixation” and “oxidation (precipitation) and reduction (dissolution)”, which operated simultaneously within the profile at any given stage of weathering.     

Stabilisation of divalent rare earth elements in natural fluorite

Summary ?The occurrence of divalent rare earth elements (Sm²⁺, Yb²⁺, Tm²⁺, and Ho²⁺) in natural fluorite is evaluated using a suite of 37 samples deriving mainly from Sn–W deposits in the Erzgebirge (Germany), Central Kazakhstan, and the Mongolian Altai. Trace element composition was determined by ICP-AES and ICP-MS. The defect structure of the samples was studied by cathodoluminescence (CL), electron paramagnetic resonance (EPR), and optical absorption spectroscopy. Reduction of cubic Sm³⁺, Yb³⁺, Tm³⁺, and Ho³⁺ under radioactive irradiation produces the corresponding divalent centres. Our data suggest a preferable formation of Sm²⁺ and Yb²⁺ under thorium and of Tm²⁺ and Ho²⁺ under uranium irradiation. Irradiation (indicated by intense brownish (thorium) and deep purple (uranium) coloration of fluorite) gives rise to a population of divalent centres in equilibrium with their decay. However, sporadic radioactive irradiation and stabilisation of the divalent state of the REE by other electron defects were found in most cases. Three models of stabilisation of Sm²⁺, Yb²⁺, Tm²⁺, and Ho²⁺ are discussed. The most effective mechanism for Sm, Yb, Tm, and Ho is coupling with Fe³⁺ centres (REE³⁺+Fe²⁺ → REE²⁺+Fe³⁺). Accordingly, the occurrence of Fe³⁺ centres in natural fluorite is regarded to indicate not an oxidising, but rather a reducing environment during fluorite precipitation. Originally incorporated in the divalent form, Fe²⁺ was converted to Fe³⁺ by radioactive irradiation. Such a conclusion is in agreement with the finding of high contents of interstitial fluorine providing tetragonal local compensation of trivalent REE centres in crystals with high Fe³⁺. If Fe is not present, compensation of divalent Sm, Yb, and Tm is achieved by radiogenic oxidation of Ce(Pr, Tb)³⁺ accompanied by charge transfer (REE³⁺+Ce(Pr, Tb)³⁺ → REE²⁺+ Ce(Pr, Tb)⁴⁺). Ho²⁺ is sometimes stabilised by a hole trapped by an electron localised on a F vacancy (Ho³⁺+e⁻ on □_F → REE²⁺+ self-trapped exciton). Because Sm²⁺ is optically active, the stabilisation by Fe³⁺ (stable up to temperatures above 350 °C) or Ce(Pr, Tb)⁴⁺ (unstable even under visible light) in samples may be determined by careful observations in the field. Institut für Geotechnik, ETH Zürich, ETH-H?nggerberg, Zürich, Switzerland Stanford Linear Accelerator Center, Menlo Park, CA, USA Received January 8, 2002; revised version accepted June 10, 2002     

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。     

Rare earth elements in ferromanganese nodules and other marine phases

The concentrations of rare-earth elements (REE) have been measured in 31 ferromanganese nodules from the Pacific and Indian Oceans and vary by almost a factor of 5. Too few nodules have been analyzed to define possible regional trends. The shale-normalized patterns, however, permit division of nodules into two groups: those from depth greater than 3000–3500 m and those from less depth. The factors that determine this change in the relative concentration of REE may be related to the mineralogy of manganese phases and/or the transport of REE to the deep ocean by particulate matter.Comparison of the REE patterns of nodules with those of phillipsite, phosphorite, clays, CaCO₃ and seawater suggests that the patterns of these phases reflect fractionation from an initial pattern closely resembling that of shale. By assuming that the accumulation rate of REE in clays, CaCO₃ and nodules is represented by that for surface sediments, it has been possible to estimate an accumulation rate of phillipsite in pelagic sediments of the Pacific of 0.02 mg/cm²/yr.     

淮北煤田煤的稀土元素地球化学

采用仪器中子活化分析法（ＩＮＡＡ）测试了淮北煤田６、３煤层１个煤样的稀土元素含量,并探讨了稀土元素地球化学特征,得出以下认识：１１个样吕的平均ΣＲＥＥ为８１．９５３５ｕｇ／ｇ;稀土元素分布模式呈左高右低的、具Ｅｕ负异常的“Ｖ”型曲线。相关分析、聚类分析的结果表明：稀土元素与灰分、陆源碎屑的元素（Ｓｉ、Ａｌ、Ｔｉ、Ｃｒ、Ｃｏ、Ｎｉ、Ｔｈ、Ｔａ、Ｓｃ和Ｒｂ等）的关系密切,而与海相元素（Ｃａ、Ｓｒ等）关     

马坑铁矿床稀土元素地球化学研究

引言七十年代以来,许多研究者对马坑铁矿进行过深入的研究。关于该矿床的形成机制,特别是含矿建造中一套中一基性岩石和矿体底板岩石的成因,以及矿石的形成方式等问题,曾引起研究者们的特别关注,并开展了热烈讨论。笔者曾对该矿床的地质一地球化学特征进行了较为详细的研究,并指出它是与石炭纪海底火山活动有关的喷气-热液沉积矿床,成矿流体来源于地热对流海水与玄武岩的反应。本文是上述研究的继续和深入,目的在于为     

含稀土磷矿稀土元素赋存特性

采用化学分析、X射线衍射分析和MLA矿物自动检测技术等手段,对湖北地区伴生稀土磷矿选矿精矿进行元素赋存特性研究,分析了该矿物的化学成分、矿物组成、稀土元素的赋存状态等理化特征。结果表明,稀土元素Ce、Nd、Sm主要赋存在独居石中,Gd、La全部赋存在独居石中,Dy则全部赋存在磷灰石矿物中,Pr全部赋存在磷灰石和独居石的复合矿物中,Y主要赋存在易解石中。独居石是含有稀土元素最多的矿物。磷灰石与稀土矿物相互交生,独居石主要呈稀疏星散浸染状充填于黑云母、萤石和赤铁矿等脉石矿物的粒间、边缘及孔洞中,多数粒度过于细小而与脉石构成极为复杂的镶嵌关系。     

Mineralogical control of rare earth elements in acid sulfate soils

Major, trace and rare earth element concentrations were measured in porewater, surface water and sediments at an acid sulfate soil site. The concentrations of La and Ce in porewater are up to 1-3 ppm. There is a strong correlation between REE concentration and acidity, except that the maximum concentrations were consistently found below the horizon of maximum acidity, associated with an increase in pH (to ca. 4) and change in mineralogy from jarosite-dominated to goethite-dominated mottles. Jarosite replacement by goethite is as expected with the rise in pH, which in turn is due to the occurrence of a fossil shell bed just below. The rare earth element patterns in the porewaters are enriched in the MREE with respect to Post-Archaean Australian Shale (PAAS). Measurements and calculations show that this is in accord with experiments on low-degree partial dissolution of jarosite, even when the jarosite itself is highly enriched in LREE. There is a clear fractionation in the patterns between the clay-rich soil matrix, which is slightly depleted in the LREE when normalized to PAAS (La/Yb_PAAS ∼0.5), and the secondary mineral phase jarosite, which is enriched in the LREE (La/Yb_PAAS = 15-50). The REE pattern in the porewater changes with the transition from jarosite- to goethite-rich mottles, becoming relatively more enriched in the LREE compared to the HREE, which is consistent with the incongruent dissolution of jarosite to form goethite and the release of greater amounts of jarosite REE to solution, including proportionately more of the jarosite-compatible LREE.Maximum surface water REE concentrations in acidic water were 100-200 ppb La and Ce. REE patterns in surface water were very similar to the porewater transition zone, enriched in the MREE, but asymmetric, relatively enriched in the LREE compared to the HREE.     

Geological significance of rare earth elements in Japanese geosynclinal basalts

Rare earth elements (REE), Ba, Sr as well as major elements in 47 pre-Cenozoic geosynclinal volcanics in Japan have been determined. The types of chondrite-normalized REE patterns can be classified into two large groups viz. log-linear REE pattern group and convex REE pattern group. Each group thus classified is also closely related to major element features. Although the REE pattern of the latter group is observed in the island arc tholeiite as well as abyssal tholeiite, the relative content of Ba to La indicates that the Japanese geosynclinal volcanics of this group are more akin to those of abyssal tholeiites than are the island arc ones. Two distinct types of REE fractionation are found in the volcanics of the Japanese geosyncline. The geographical distribution of two groups of the geosynclinal volcanics is different from that of the Cenozoic volcanics in Japan, and the petrochemical features of volcanics from northeast Japan can be distinguished from those of southwest Japan. By analogy with the current knowledge concerning a close relation between the tectonic settings and the geochemical features of the present-day volcanics, the geosynclinal basalts in question are inferred to have been formed during a tensional tectonic movement and have erupted along a local rift zone like the marginal seas and inter-arc basins in the Western Pacific Ocean or along part of a global rift system such as the Red Sea Trough.     

Concentrations of rare earth elements in topsoil from East China

Fifty topsoil samples collected from 12 different regions of East China have been analyzed for rare earth elements (REEs). The average REE concentrations of the 50 topsoil samples are much higher than world average and are characterized by LREE-enrichment, HREE-depletion, Eu-depletion and Ce-enrichment. However, the REE concentration is not strongly affected by the climate of the sampling site; it is controlled mainly by parent materials. The plot of Ce/Eu against Eu/Sm is proved to be useful to distinguish different parent materials of topsoil. Each element in the 50 topsoil has a good correlation with its neighboring element. Seven of the 13 values are above 0.987.     

巴尔哲超大型稀有稀土矿床成矿机制研究

巴尔哲矿床中的矿化和非矿化碱性花岗岩主要造岩矿物均为微斜长石、石英、钠闪石和钠长石,但其相对含量及颗粒大小明显不同,且两类岩石中包裹体的组成特征及锆石的结晶习性也有显著差异.主量元素分析显示,矿化与非矿化碱性花岗岩均以富硅、富碱、贫镁和钙为特征,为较典型的非造山A型花岗岩.尽管矿化碱性花岗岩中K_2O和Na_2O的含量均没有明显的增加,但其Na+K/Al、Na_2O+K_2O/CaO、FeO~*/MgO及K_2O/MgO等岩石化学参数与非矿化碱性花岗岩明显不同.在矿化碱性花岗岩中除了矿化的稀土元素及Nb、Zr强烈富集外,U、Th及Y也明显富集,而Ba、Sr、P、Eu和Ti表现为强烈的亏损.在非矿化碱性花岗岩中除了大离子亲石元素Rb略有富集外,稀土元素、Nb、Zr、U、Th、Ta及Y并无明显富集,虽然Sr、P、Eu和Ti也表现为亏损,但与矿化碱性花岗岩相比其亏损程度明显降低.岩相学、岩石化学及微量元素地球化学特征显示,矿化碱性花岗岩不可能是非矿化碱性花岗岩硅化和钠长石化作用的产物,二者应是同一岩浆体系不同演化阶段熔体固结的产物.K/Rb、Rb/Sr及δEu等地球化学参数显示,矿化碱性花岗岩是高演化A型花岗质熔体固结的产物;而岩石学、包裹体及地球化学特征则显示,这种高演化的A型花岗质熔体已经进入了岩浆一热液过渡阶段.巴尔哲矿床稀有稀土元素的超常富集和成矿与A型花岗岩的高演化过程密切相关.     

陈家山矿煤中微量元素和稀土元素地球化学特征

通过对陈家山煤矿中下侏罗统延安组4^#主采煤层中微量元素和稀土元素的测试分析,发现煤中富集亲花岗岩的钨钼族元素W、Mo、Bi、Sn、Ba、Sr和Li,说明该区煤系形成期间的陆源碎屑主要来自花岗岩和花岗片麻岩等中、酸性岩石。4^#煤中ΣREE平均值为98.2×10^-6,稀土元素分布模式十分相似,呈左高右低的宽缓“V”型曲线,Eu负异常明显,反映出稀土元素与陆源碎屑岩关系密切,成煤期间稀土元素来源一致,陆源物质的供应相对稳定。     

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。     

Monazite solubility and dissolution kinetics: implications for the thorium and light rare earth chemistry of felsic magmas

A series of monazite dissolution experiments was conducted in a hydrous (1–6 wt.%) granitic melt at 8 kbar over the temperature range 1,000–1,400° C. A polished cube of monazite was immersed in a natural obsidian melt and allowed to partially dissolve. Electron microprobe traverses perpendicular to the crystal-melt interface revealed concentration gradients in the LREEs and P. Diffusivities of the LREEs and P were calculated from these profiles, yielding the following Arrhenius relations for the LREEs: D=0.23 exp(–60.1 kcal mol^–1/RT) at 6% water D=2.30×10⁷ exp(–122.1 kcal mol^–1/RT) at 1% water These results demonstrate the importance of dissolved water on REE diffusion. Phosphorus diffusivities are nearly identical to those of the rare-earths, suggesting that P diffusion charge-compensates REE diffusion. The concentration of LREEs required for monazite saturation in these melts is given by the level of dissolved LREEs at the crystal-melt interface. These values also show a dependence on dissolved water, with LREE_sat=60 ppm at 6% H₂O when extrapolated down to 700° C, and LREE_sat=30 ppm at 1% H₂O. Calculated dissolution rates based on the above parameters indicate that minute (<30 m diameter) monazite crystals will be readily digested by an enclosing anatectic magma under reasonable geologic conditions (i.e., T=700–800° C and >2% H₂O), whereas larger (> 50 m) crystals will likely be residual over the duration of an anatectic event. The low solubility of monazite in this melt suggests that the LREE depletion observed in some felsic differentiation suites may be the result of monazite crystallization. Limited experimental and geochemical/petrologic evidence indicates that compositional changes in the melt accompanying differentiation decrease the solubility of monazite drastically. Kinetic and chemical constraints may also lead to localized monazite saturation and inclusion in major phases or even other accessories. Variations in the REE composition of monazite from different parageneses probably reflects the REE pattern of the parent melt, and may be due to gradational differences in the stability of individual or subgroup REE-complexes as a function of melt composition. Particularly important in this regard seems to be the lime+alkali/alumina balance of the melt and its volatile content.     

Behaviour of rare earth elements in geothermal systems of New Zealand

Rare earth element (REE) patterns of hydrothermally altered rhyolite from geothermal systems located in the Taupo Volcanic Zone in the North Island of New Zealand provide evidence of REE mobility. REE trends of unaltered rhyolites are characterised by moderate LREE enrichment ((La/Lu)_cn = 3.84 to 5.62) and pronounced negative Eu anomalies. In contrast, REE patterns of hydrothermally altered rhyolites commonly exhibit different signatures and may be placed into four chemically and petrographically distinct categories. Rocks with clay + quartz + feldspar + calcite (±zeolites, epidote, sphene, chlorite, opaque minerals) assemblages typically display patterns subparallel to fresh rock, whereas, samples which contain quartz + chlorite, or quartz + clay + zeolite assemblages have flat patterns without Eu anomalies, and highly silicified samples are characterised by depleted, bowed REE trends. These patterns may be produced by interaction with alkaline or acid fluids. A fourth group of very intensely altered samples, affected by interaction with acid fluids, exhibits unusual REE trends with highly enriched HREE and depleted LREE, or depleted HREE.These results indicate that some of the REE released by the breakdown of primary phases during alteration are transported away in the fluid. In addition, the degree of depletion is positively correlated with alteration intensity and the fluid/rock ratio. The similarity of REE patterns resulting from alteration by alkaline and acid fluids suggests that the shape of the REE trends is controlled principally by fluid/rock ratios and secondarily by mineralogy. The REE are retained in rocks with a diverse alteration mineralogy, whereas in samples with only one dominant alteration phase (e.g. quartz) it is more probable that not all REE liberated during alteration can be accommodated in the altered rock. Eu commonly behaves differently from the other REE, possibly due to the dominance of Eu²⁺.