Ligand extraction of rare earth elements from aquifer sediments: Implications for rare earth element complexation with organic matter in natural waters

The ability of organic matter as well as carbonate ions to extract rare earth elements (REEs) from sandy sediments of a Coastal Plain aquifer was investigated for unpurified organic matter from different sources (i.e., Mississippi River natural organic matter, Aldrich humic acid, Nordic aquatic fulvic acid, Suwannee River fulvic acid, and Suwannee River natural organic matter) and for extraction solutions containing weak (i.e., CH₃COO⁻) or strong (i.e., ) ligands. The experimental results indicate that, in the absence of strong REE complexing ligands in solution, the amount of REEs released from the sand is small and the fractionation pattern of the released REEs appears to be controlled by the surface stability constants for REE sorption with Fe(III) oxides/oxyhydroxides. In the presence of strong solution complexing ligands, however, the amount and the fractionation pattern of the released REEs reflect the strength and variation of the stability constants of the dominant aqueous REE species across the REE series. The varying amount of REEs extracted by the different organic matter employed in the experiments indicates that organic matter from different sources has different complexing capacity for REEs. However, the fractionation pattern of REEs extracted by the various organic matter used in our experiments is remarkable consistent, being independent of the source and the concentration of organic matter used, as well as solution pH. Because natural aquifer sand and unpurified organic matter were used in our experiments, our experimental conditions are more broadly similar to natural systems than many previous laboratory experiments of REE-humic complexation that employed purified humic substances. Our results suggest that the REE loading effect on REE-humic complexation is negligible in natural waters as more abundant metal cations (e.g., Fe, Al) out-compete REEs for strong binding sites on organic matter. More specifically, our results indicate that REE complexation with organic matter in natural waters is dominated by REE binding to weak sites on dissolved organic matter, which subsequently leads to a middle REE (MREE: Sm-Ho)-enriched fractionation pattern. The experiments also indicate that carbonate ions may effectively compete with fulvic acid in binding with dissolved REEs, but cannot out compete humic acids for REEs. Therefore, in natural waters where low molecular weight (LMW) dissolved organic carbon (DOC) is the predominant form of DOC (e.g., lower Mississippi River water), REEs occur as “truly” dissolved species by complexing with carbonate ions as well as FA, resulting in heavy REE (HREE: Er-Lu)-enriched shale-normalized fractionation patterns. Whereas, in natural terrestrial waters where REE speciation is dominated by organic complexes with high molecular weight DOC (e.g., “colloidal” HA), only MREE-enriched fractionation patterns will be observed because the more abundant, weak sites preferentially complex MREEs relative to HREEs and light REEs (LREEs: La-Nd).     

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...     

岩石－土壤－脐橙系统中稀土元素迁聚特征

在赣南稀土高背景区和稀土低背景区不同地质环境脐橙果同,系统采集岩、土、脐橙植物样,用ICP-MS法测定样品中15种稀土元素的含量,并对稀土元素在岩石、土壤和脐橙植物体内的分布、迁移、累积特征进行了研究.结果表明:a.基岩的稀土元素含量影响(决定)土壤各层位的稀土元素含量;b.土壤环境中稀土元素含量高低直接影响脐橙植物体稀土元素含量,但不完全成正比;c.基岩的稀土元素配分模式基本上贯穿土壤各层位、脐橙植物体各器官;d.岩、土、脐橙三大环节稀土无素的百分含量,总的趋势是轻稀土比重逐渐增高,重稀土比重逐渐降低,但重稀土在脐橙植物体末稍器官比例有所增加;e.岩土脐橙生态系统立体刮面中,稀土元素的垂直方向运动呈向量关系;f.由于土壤-植物壁垒作用和脐橙植物体自身的选择性吸收、控制性积累功能,高、低稀土背景区脐橙果肉的稀土含量均低于国家食品卫生限量标准.     

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。     

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.     

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).     

南黄海NT1孔沉积物稀土元素组成与物源判别

为研究黄河、长江以及韩国河流输运的大陆物质对南黄海沉积的贡献,对南黄海中部泥质区NT1孔沉积物做了稀土元素分析和物源判别。研究发现,南黄海NT1孔沉积物物源主要为长江源和黄河源,NT1孔上部0—7．70m沉积物以长江源为主,中部7．70．16．60m和40．00～50．70m沉积物以黄河源为主,其间夹近24m厚的沉积物则以长江源为主,底部50．70～69．76m沉积物以长江源为主。结果表明,长江从晚更新世早期到现代对南黄海中部泥质区沉积起着主要作用,而黄河则在晚更新世晚期的早玉木冰期时已开始对南黄海陆架沉积作用有明显影响。     

Geochemical characteristics and provenance implication of rare earth elements in surface sediments from bays along Guangdong Coast, Southeast China

A systematic study of the granulometric properties and the occurrence and distribution of rare earth elements (REE) within surface sediments from ten bays situated along the coast of Southeast China has facilitated a more rigorous understanding of constraints on sediment provenance in the area. The results show that REE concentrations are similar within a single bay, but vary considerably (133.58–251.77 mg/kg) among the bays. The chondrite-normalized distribution patterns show the typical enrichment of light REEs (LREEs: La–Eu) relative to heavy REEs (HREEs: Gd–Lu), and an apparent depletion of Eu, which is diagnostic of a terrigenous sediment source. Obvious enrichments of the middle REEs (MREEs: Sm–Ho) in the PAAS-normalized (Post-Archean Australian Shale) distribution patterns of these bay sediments are similar to results reported from large rivers in China. Comparing the REE composition of the bay sediments with those of adjoining fluvial sediments and with the bedrock of the surrounding drainage basins, the latter are indicated as the dominant sediment source. The uniform REE distribution patterns, and MREE enrichments, prove that the sediments are derived from the material transported by the streams and rivers that discharge into the bays.     

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.     

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.     

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。     

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.     

四川稀土精矿的稀土元素和微量元素地球化学特征及开发利用意义

产自广东省梅州市玉水铜矿的景文矿,属于含水、重稀土-矾-铝硅酸盐矿物(简写为HREE-V-铝硅酸盐矿物),其化学结构式为Y₂Al₂V₂⁴⁺(SiO₄)₂O₄(OH)₄,该矿物在全球属首次发现,暂未开展相关研究。相对于含轻稀土矿物,含重稀土矿物在电子探针分析过程中,当被高压电子束轰击时,被激发出来的特征X射线线系繁多,线系之间分布更加密集,彼此之间相互重叠的现象也更为严重,要获得理想数据的难度很大,是亟待解决和突破的技术难题。本文对该矿物进行了精细的电子探针定量分析,获得理想的化学成分数据,为新矿物命名提供了理论数据技术支撑。通过对实验方法的探索和总结获得以下结果：①利用15kV加速电压、100nA束流对试样进行全元素扫描,以此确定出17种元素;②在定量分析过程中,对重叠峰进行了剥离;③利用仪器软件中的Zoom-Peak ID程序,选择出17种元素的分析线系、精确的峰位及上下背景值;④选取合适的标样及测试时间等定量分析条件,最终获得理想的定量分析结果(平均总量97.41wt%)。上述四条也是确保获得理想定量分析数据的关键因素。

     

淮南采煤沉陷区表层沉积物稀土元素地球化学特征

稀土元素由于其独特的化学特征被广泛应用于环境地球化学分析过程研究。以淮南采煤沉陷区表层沉积物中稀土元素(REEs)为研究对象,采集研究区潘一、顾桥、谢桥沉陷区的表层沉积物样品共12个,采用ICP-MS对样品的稀土元素含量进行测试分析,探讨了表层沉积物中稀土元素的含量分布特征、控制因素及其物质来源。结果表明:研究区表层沉积物中稀土元素含量为54.63~130.45 μg/g,平均102.60 μg/g;LREE/HREE比值为11.89~20.55,平均14.29,轻稀土呈现明显富集现象;相关性分析结果显示,REEs趋向于黏土组分中富集;研究区养殖和捕捞活动导致表层沉积物中稀土元素含量的降低;球粒陨石标准化结果表明,研究区稀土元素呈现不同程度的La和Gd正异常,其中,Gd正异常主要是受到燃煤的影响,而La正异常主要与燃煤和化肥有关。结合Pearson相关性、球粒陨石标准化和(La/Yb)_N-(La/Sm)_N-(Gd/Yb)_N三元图判别,认为研究区水体表层沉积物中稀土元素与人类活动(燃煤和化肥)有关,研究认识为污染物的源头控制和煤矿区环境的生态治理提供参考依据。      

Patterns of rare earth and other trace elements in Paleogene and Miocene clayey sediments from the Mondego platform (Central Portugal)

In the present study the origin of clay deposits occurring in an inland platform, in central Portugal, was investigated by their mineralogical and chemical composition. The clay deposits, exploited for ceramic industry are composed of silt-clay facies, the Monteira Member and the Arroça Member, which are assigned to the Coja Formation (Paleogene) and the Campelo Formation (Miocene), respectively. These clayey facies show almost compositional homogeneity, especially concerning texture. The mineralogical composition of the Monteira Member displays slightly higher content in smectite and interstratified clay minerals, which is supported by the chemical composition of samples analyzed. Both members present similar REE patterns, displaying an intense weathering record and little variation in the source area composition. Minor element geochemistry suggests low content in heavy minerals and transition metals. REE patterns and ratios of geochemical parameters support the dominant metasedimentary provenance, with a granite source contribution and also mature recycled sediments of continental origin. The study results’ suggest that the clays of these two members have the same source in terms of lithology and recycled sediments from the Hesperian massif. During the deposition of the Arroça Member, a major remobilization of the Monteira Member is suggested, explaining the geochemical similarity of both facies.     

大青山煤田煤系高岭岩稀土元素地球化学特征

采用中子活化法对采自内蒙古大青山煤田石炭-二叠纪煤系的12个高岭岩样品进行了稀土元素(REE)含量测定。结果表明,样品的稀土元素含量变化很大,ΣREE最低31.98×10^-6,最高616.3×10^-6,平均178.6×10^-6,与NASC的173.21×10^-6相近;ΣLREE/ΣHREE介于6.32~46.14之间,平均17.5,明显高于NASC;中—弱Eu亏损,弱Ce正异常。通过不同对比样品(北美页岩、超基性岩、基性岩、中性岩、酸性岩以及偏碱性岩等)所作的标准化分析结果表明,研究样品不具有典型的沉积型泥岩特征;结合薄片鉴定及前人分析结果推论,高岭岩可能由中—基性或偏碱性火山碎屑物质原地蚀变而成,泥炭化所提供的酸性介质条件对火山灰向高岭岩转化以及稀土元素的分异提供了必要的条件。     

Rare earth elements in pore waters of marine sediments

The rare earth elements (REEs) were measured in pore waters of the upper ∼25 cm of sediment from one site off Peru and three sites on the California margin. The pore water REE concentrations are higher than sea water and show systematic down core variations in both concentration and normalized pattern. From these analyses and from comparison to other chemical species measured (dissolved Fe, Mn, Ba, oxygen, nitrate, phosphate), it is suggested that pore water REEs can be grouped into three categories: those that are from an Fe-source, those that are from a POC-source, and cerium oxide. REEs from the Fe-source appear where anoxia is reached; they have a distinctive “middle-REE (MREE) enriched” pattern. The concentrations in this source are so elevated that they dominate REE trends in the Fe-oxide reduction zone. The net result of flux from the POC-source is relative enrichment of heavy-REEs (HREEs) over light-REEs (LREEs), reflecting remineralizing POC and complexation with DOC. A common “linear” REE pattern, seen in both oxic and anoxic sediments, is associated with this POC-source, as well as a “HREE enriched” pattern that is seen in surficial sediments at the Peru site. Overall, the pore water results indicate that Mn-oxides are not an important carrier of REEs in the oceans.A REE biogeochemical model is presented which attempts to reconcile REE behavior in the water and sediment columns of the oceans. The model proposes that POC, Fe-oxide and Ce-oxide sources can explain the REE concentration profiles and relative abundance patterns in environments ranging from oxic sea water to anoxic pore water. The model is also consistent with our observation that the “Ce-anomaly” of pore water does not exceed unity under any redox condition.