长期喷施稀土对土壤-植物(小麦)系统中稀土元素分布、累积及运移的影响

在我国施用稀土时间最长的黑龙江省花园农场,研究比较了施用稀土12 a和不施稀土的对照处理上小麦和土壤中的稀土元素的分布、累积及运移.结果表明,长期叶面喷施稀土并未造成耕层土壤和下部土层的稀土元素的累积.成熟期小麦植株各部位的稀土元素含量顺序为根>叶>茎、壳;稀土元素主要累积在根部,其次是叶,茎和壳累积较少.喷施处理小麦根部的稀土元素累积量高于对照,叶部也有此趋势,而茎、壳等部位差异不大.根、茎、叶、壳稀土元素分布模式与土壤中相似,与施用的常乐稀土差别较大;长期喷施稀土未曾造成籽粒中稀土元素的明显累积.     

Bioaccessibility and health risk assessment of rare earth elements in Porphyra seaweed species

In this study, the content and bioaccessibility of rare earth elements (REEs) in Porphyra spp. Samples before and after thermal treatments were investigated. Additionally, the risks of REEs exposure to human health were assessed. REEs content significantly reduced after thermal processing (P < 0.01), and the removal rate of REEs was approximately 30%. Thermal treatment increased REEs bioaccessibility from 44% to 64.34%. The concentration and bioaccessibility of Ce, La, Y, Nd were high in raw and thermally treated Porphyra samples, and there was no correlation between REEs content and bioaccessibility. Based on the following parameters: highest content of REEs in the studied seaweed samples (13.45 mg/kg), the highest daily seafood consumption (44.9 g/day), and the highest bioaccessibility (64.34%), the ratio of the calculated daily intake (DI) to daily allowable intake by diet (DAI_diet) of REEs did not exceed the reference value in rare earth mining areas or under extreme conditions. The DI via seafood consumption would be exceeded when the content of REEs in the seafood sample is greater than 15.77 mg/kg. In this study, the concentration of REEs did not exceed 15.77 mg/kg in any sample. Thus, the human health risks of REEs associated with seafood are low.     

Interactions of microorganisms with rare earth ions and their utilization for separation and environmental technology

In recent years, rare earth elements (REEs) have been widely used in various modern technological devices and the global demand for REE has been increasing. The increased demand for REEs has led to environmental exposure or water pollution from rare earth metal mines and various commercial products. Therefore, the development of a safe technology for the separation and adsorption of REEs is very important from the perspective of green chemistry and environmental pollution. In this review, the application and mechanisms of microorganisms for the removal and extraction of REEs from aqueous solutions are described. In addition, the advantages in using microorganisms for REE adsorption and future studies on this topic are discussed.     

Urinary Monitoring of Exposure to Yttrium, Scandium, and Europium in Male Wistar Rats

On the assumption that rare earth elements (REEs) are nontoxic, they are being utilized as replacements of toxic heavy metals in novel technological applications. However, REEs are not entirely innocuous, and their impact on health is still uncertain. In the past decade, our laboratory has studied the urinary excretion of REEs in male Wistar rats given chlorides of europium, scandium, and yttrium solutions by one-shot intraperitoneal injection or oral dose. The present paper describes three experiments for the suitability and appropriateness of a method to use urine for biological monitoring of exposure to these REEs. The concentrations of REEs were determined in cumulative urine samples taken at 0?C24?h by inductively coupled plasma atomic emission spectroscopy, showing that the urinary excretion of REEs is <2?%. Rare earth elements form colloidal conjugates in the bloodstream, which make high REEs accumulation in the reticuloendothelial system and glomeruli and low urinary excretion. The high sensitivity of inductively coupled plasma?Cargon emission spectrometry analytical methods, with detection limits of <2???g/L, makes urine a comprehensive assessment tool that reflects REE exposure. The analytical method and animal experimental model described in this study will be of great importance and encourage further discussion for future studies.     

有机配体对稀土元素在小麦体内积累和分异的影响

采用营养液培养和添加外源混合稀土等方法,研究了有机配体柠檬酸、EDTA和DTPA对稀土元素在小麦的根和叶中积累与分异的影响。结果表明,低浓度有机配体对小麦根和叶中的稀土元素,尤其是轻稀土元素的积累有轻微的促进作用,随浓度的升高则表现出显著的降低作用。有机配体对重稀土的作用比轻稀土强,使根和叶中稀土元素的分布曲线向重稀土相对亏缺的方向发展。3种配体对轻、重稀土分异的作用强度为:EDTA>DTPA>柠檬酸。通过VM INTEQ计算表明,在EDTA和DTPA作用下小麦叶中稀土元素的积累与轻、重稀土的分异主要由溶液中呈自由离子态稀土元素的含量和组成控制;柠檬酸作用下小麦叶中稀土元素的变化与自由离子态稀土的含量和组成关系较弱,推测REE-柠檬酸络合物可被小麦直接吸收并运转到小麦的叶中。     

Bioaccumulation of rare earth elements in cultured hela cells

HeLa S-3 cells were grown in minimal essential medium supplemented with 10% calf serum and 1 mM L-glutamine without adding any rare earth elements (REEs). Exponentially growing cells were collected, and dried materials were used to analyze their REE content by inductively coupled plasma-mass spectrometry. The results showed that the cells accumulated REEs in individually different manners; namely the accumulation ratio was higher in the lighter REEs than in the heavier REEs. To deduce the implication of the accumulation of REEs in HeLa cells, the accumulation ratios for REEs were compared with those of other biologically important elements. It was seen that the accumulation ratios obtained for REEs (from 31.8 [Ce] to 14.7 [Lu]) were intermediate among those of many bioelements: Fe (124), Mg (54.5), K (38.8), Cr (12.7), Na (11.8), Mn (11.3), Zn (10.7), Ca (8.8), and V (6.7).     

稀土元素在赣南非稀土矿区和不同稀土矿区土壤-铁芒萁(Dicranopteris linearis)系统中的分布、累积和迁移

ICP-M法测定了江西赣南地区非稀土矿区和4处不同稀土矿区内,土壤-铁芒萁系统中15个稀土元素的含量,并对稀土元素在土壤剖面层及铁芒萁植物体内的分布、迁移特征进行了研究.结果表明,稀土元素总量在土壤剖面层的底土层含量最高,但表土层铈相对富集.稀土元素在铁芒萁植物体内的分布规律是叶、根＞茎＞叶柄.铁芒萁根中稀土元素的丰度与其母土表土层,尤其是母土表土层可溶态稀土元素的分布模式基本相似.稀土元素在铁芒萁体内的迁移过程中,发生了明显的分馏作用,茎、叶柄、叶中的重稀土相对贫乏.     

Accumulation and fractionation of rare earth elements (REEs) in the naturally grown Phytolacca americana L. in southern China

The widespread use of rare earth elements (REEs) has resulted in problems for soil and human health. Phytolacca americana L. is a herbaceous plant widely distributed in Dingnan county of Jiangxi province, China, which is a REE mining region (ion absorption rare earth mine) and the soil has high levels of REEs. An investigation of REE content of P. americana growing naturally in Dingnan county was conducted. REE concentrations in the roots, stems, and leaves of P. americana and in their rhizospheric soils were determined. Results showed that plant REEs concentrations varied among the sampling sites and can reach 1040 mg/kg in the leaves. Plant REEs concentrations decreased in the order of leaf > root > stem and all tissues were characterized by a light REE enrichment and a heavy REE depletion. However, P. americana exhibited preferential accumulation of light REEs during the absorption process (from soil to root) and preferential accumulation of heavy REEs during the translocation process (from stem to leaf). The ability of P. americana to accumulate high REEs in the shoot makes it a potential candidate for understanding the absorption mechanisms of REEs and for the phytoremediation of REEs contaminated soil.     

Effects of rare earth elements and REE-binding proteins on physiological responses in plants

Rare earth elements (REEs), which include 17 elements in the periodic table, share chemical properties related to a similar external electronic configuration. REEs enriched fertilizers have been used in China since the 1980s. REEs could enter the cell and cell organelles, influence plant growth, and mainly be bound with the biological macromolecules. REE-binding proteins have been found in some plants. In addition, the chlorophyll activities and photosynthetic rate can be regulated by REEs. REEs could promote the protective function of cell membrane and enhance the plant resistance capability to stress produced by environmental factors, and affect the plant physiological mechanism by regulating the Ca2? level in the plant cells. The focus of present review is to describe how REEs and REE-binding proteins participate in the physiological responses in plants.     

Rare earth elements,aluminium and silicon distribution in the fern Dicranopteris linearis revealed by μPIXE Maia analysis

BackgroundThe fern Dicranopteris linearis is a hyperaccumulator of rare earth elements (REEs), aluminium (Al) and silicon (Si). However, the physiological mechanisms of tissue-level tolerance of high concentrations of REE and Al, and possible interactions with Si, are currently incompletely known.MethodsA particle-induced X-ray emission (μPIXE) microprobe with the Maia detector, scanning electron microscopy with energy-dispersive spectroscopy and chemical speciation modelling were used to decipher the localization and biochemistry of REEs, Al and Si in D. linearis during uptake, translocation and sequestration processes.ResultsIn the roots >80 % of REEs and Al were in apoplastic fractions, among which the REEs were most significantly co-localized with Si and phosphorus (P) in the epidermis. In the xylem sap, REEs were nearly 100 % present as REEH₃SiO₄²⁺, without significant differences between the REEs, while 24–45 % of Al was present as Al-citrate and only 1.7–16 % Al was present as AlH₃SiO₄²⁺. In the pinnules, REEs were mainly concentrated in necrotic lesions and in the epidermis, and REEs and Al were possibly co-deposited within phytoliths (SiO₂). Different REEs had similar spatial localizations in the epidermis and exodermis of roots, the necrosis, veins and epidermis of pinnae of D. linearis.ConclusionsWe posit that Si plays a critical role in REE and Al tolerance within the root apoplast, transport within the vascular bundle and sequestration within the blade of D. linearis.     

Distribution of rare earth elements in seaweed: implication of two different sources of rare earth elements and silicon in seaweed

Rare earth elements (REEs) and Si in five species of seaweed, ambient surface seawaters, and suspended solid particles in the seawaters were determined separately. Inductively coupled plasma mass spectrometry (ICP-MS) was used for REEs and inductively coupled plasma emission spectrometry (ICP-ES) was used for Si in order to evaluate REEs as a tracer in seaweeds and to understand the source of inorganic elements, especially Si, in seaweeds. Two different REE patterns, one similar to that of the seawater solution and another resembling that of suspended particles, were observed in seaweeds, and the variation of REE patterns seems to show a clear dependence on the abundance of Si. The REE pattern and Si concentration seem to vary depending on the division: green and red algae showed REE patterns similar to that of suspended particles, but brown algae showed patterns closer to that of seawater solutions and relatively lower Si concentration. The possibility of contamination from silicate particles on the surface of seaweeds was ruled out for several reasons. Silicate particles, not dissolved silicate, have been identified as the direct source of REEs and Si in plants ( Fu et al. 1998 ), and seaweeds are no exception. We have to consider that seaweeds can take up Si from suspended particles through their blade or branches. From the appearance of tetrad-effect-like variation of REEs, Si is assumed to enter a dissolved state just before the particles are taken up. From the results of a sonication experiment, REEs, once taken up as silicate particles, seem to be separated from Si in the thallus.     

Accumulation of rare earth elements in human bone within the lifespan

For the first time, the contents of rare earth elements (REEs) in a rib bone of a healthy human were determined. The mean value of the contents of Ce, Dy, Er, Gd, La, Nd, Pr, Sm, Tb, and Yb (10 elements out of 17 total REEs), as well as the upper limit of means for Ho, Lu, Tm, and Y (4 elements) were measured in the rib bone tissue of 38 females and 42 males (15 to 55 years old) using inductively coupled plasma mass spectrometry (ICP-MS). We found age-related accumulation of REEs in the bone tissue of healthy individuals who lived in a non-industrial region. It was calculated that during a lifespan the content of REEs in a skeleton of non-industrial region residents may increase by one to two orders of magnitude. Using our results as indicative normal values and published data we estimated relative Gd accumulation in the bone tissue of patients according to magnetic resonance imaging with contrast agent and La accumulation in the bone tissue of patients receiving hemodialysis after treatment with lanthanum carbonate as a phosphate binder. It was shown that after such procedures contents of Gd and La in the bone tissue of patients are two to three orders of magnitude higher than normal levels. In our opinion, REEs incorporation may affect bone quality and health similar to other potentially toxic trace metals. The impact of elevated REEs content on bone physiology, biochemistry and morphology requires further investigation.     

Rare earth elements and relation between their potential bioavailability and soil properties, Nidda catchment (Central Germany)

Rare earth elements (REEs) are widely used in industry and the entry of REEs into the pedosphere is assumed. Data about REEs in soils are scarce since only a few studies discuss their ecologically relevant behavior. Hence, we investigated total contents (aqua regia digestion) and potentially bioavailable contents (EDTA extraction) of REEs in soils from the Nidda catchment in Hesse (Central Germany). The study site covers a 1,600 km² sized area and 232 soil samples from 63 soil profiles were examined. The total REE content varied considerably, ranging from 544 mg kg^?1 to 41 mg kg^?1 (mean 201.1 mg kg^?1) with a high proportion of light REEs. Highest REE contents were found in the soilscape VB, followed by LVB, WNE, T, WSW and BF with the smallest concentrations. With respect to the parent material the contents decreased in the following order: basalt > clay slate > loess > sandstone. On average 15.9% of the total REEs belong to the potentially bioavailable fraction. They range greatly by a factor of 100, between 1.3 and 171.3 mg kg^?1 (average 33.5 mg kg^?1). Remarkably, Yttrium has a maximum available proportion of 75%. In contrast, Ce showed the highest total contents with the smallest potentially bioavailable proportion of all elements. Regression analyses established relation between soil properties and the potential bioavailability of REEs. Around 53% (range from 29.9 to 76.8%) of the REE’s potential bioavailability variations could be explained by the chosen variables (pH, clay and C_org contents and the total element concentrations). Occurrence patterns and concentrations of REEs lie within the range of the results found in the available literature. Bioavailability is linked to soil properties and varies greatly according to the individual element. In comparison with the chosen soil properties the pH value shows the least impact on bioavailability.     

稀土元素在小麦体内分配行为的研究

采用水培,土培试验及中子活化分析技术,在作物生长效应曲线研究的基础上,系统地研究了稀土远征顷作物体内的含量、吸收、分布和转移等行为。所获结果表明,名稀土元素在作物体现人的分配行为受生物的内外因素与稀土来源、自身特征和元素间关系的影响,是作物稀土元素分配行为已有研究成果的重要补充与深化,并为土壤施用稀土元素提供促进一步的科学依据。     

Effects of citric acid and the siderophore desferrioxamine B (DFO-B) on the mobility of germanium and rare earth elements in soil and uptake in Phalaris arundinacea

Effects of citric acid and desferrioxamine B (DFO-B) on the availability of Ge and selected rare earth elements (REEs) (La, Nd, Gd, Er) to Phalaris arundinacea were investigated. A soil dissolution experiment was conducted to elucidate the effect of citric acid and DFO-B at different concentrations (1 and 10 mmol L^?1 citric acid) on the release of Ge and REEs from soil. In a greenhouse, plants of P. arundinacea were cultivated on soil and on sand cultures to investigate the effects of citric acid and DFO-B on the uptake of Ge and REEs by the plants. Addition of 10 mmol L^?1 citric acid significantly enhanced desorption of Ge and REEs from soil and uptake into soil-grown plants. Applying DFO-B enhanced the dissolution and the uptake of REEs, while no effect on Ge was observed. In sand cultures, the presence of citric acid and DFO-B significantly decreased the uptake of Ge and REEs, indicating a discrimination of the formed complexes during uptake. This study clearly indicates that citric acid and the microbial siderophore DFO-B may enhance phytoextraction of Ge and REEs due to the formation of soluble complexes that increase the migration of elements in the rhizosphere.     

Fractionations of rare earth elements in plants and their conceptive model

Fractionations of rare earth elements (REEs) and their mechanisms in soybean were studied through application of exogenous mixed REEs under hydroponic conditions. Significant enrichment of middle REEs (MREEs) and heavy REEs (HREEs) was observed in plant roots and leaves respectively, with slight fractionation between light REEs (LREEs) and HREEs in stems. Moreover, the tetrad effect was observed in these organs. Investigations into REE speciation in roots and in the xylem sap using X-ray absorption spectroscopy (XAS) and nanometer-sized TiO2 adsorption techniques, associated with other controlled experiments, demonstrated that REE fractionations should be dominated by fixation mechanism in roots caused by cell wall absorption and phosphate precipitation, and by the combined effects of fixation mechanism and transport mechanism in aboveground parts caused by solution complexation by intrinsic organic ligands. A conceptive model was established for REE fractionations in plants based on the above studies.     

Indicator species drive the key ecological functions of microbiota in a river impacted by acid mine drainage generated by rare earth elements mining in South China

Acid mine drainage (AMD) generated by rare earth elements (REEs) deposits exploration contains high concentrations of REEs, ammonium and sulfates, which is quite different from typical metallic AMD. Currently, microbial responses and ecological functions in REEs-AMD impacted rivers are unknown. Here, 16S rRNA analysis and genome-resolved metagenomics were performed on microbial community collected from a REEs-AMD contaminated river. The results showed that REEs-AMD significantly changed river microbial diversity and shaped unique indicator species (e.g. Thaumarchaeota, Methylophilales, Rhodospirillales and Burkholderiales). The main environmental factors regulating community were pH, ammonium and REEs, among which high concentration of REEs increased REEs-dependent enzyme-encoding genes (XoxF and ExaF/PedH). Additionally, we reconstructed 566 metagenome-assembled genomes covering 70.4% of identifying indicators. Genome-centric analysis revealed that the abundant archaea Thaumarchaeota and Xanthomonadaceae were often involved in nitrification and denitrification, while family Burkholderiaceae were capable of sulfide oxidation coupled with dissimilatory nitrate reduction to ammonium. These indicators play crucial roles in nitrogen and sulfur cycling as well as REEs immobilization in REEs-AMD contaminated rivers. This study confirmed the potential dual effect of REEs on microbial community at the functional gene level. Our investigation on the ecological roles of indicators further provided new insights for the development of REEs-AMD bioremediation.     

Ecotoxicological assessment of lanthanum with Caenorhabditis elegans in liquid medium

With their widespread applications in industry, agriculture and many other fields, more and more rare earth elements (REEs) are getting into the environment, especially the aquatic systems. Therefore, understanding the aquatic ecotoxicity of REEs has become more and more important. In the present work, Caenorhabditis elegans (C. elegans) was used as a test organism and life-cycle endpoints were chosen along with elemental assay to evaluate the aquatic toxicity of lanthanum (La), a representative of REEs. The results show La3+ had significant adverse effects on the growth and reproduction of worms above a concentration of 10 μmol L?1. The elemental mapping by microbeam synchrotron radiation X-ray fluorescence (μ-SRXRF) illustrated how La treatment disturbed the metals distribution in the whole body of a single tiny nematode at lower levels. Our results suggested that the high-level REEs in some polluted water bodies would lead to an aquatic ecological crisis. The assessment we performed in the present work could be developed as a standardized test design for aquatic toxicological research.     

Fractionations of rare earth elements in plants and their conceptive model

Fractionations of rare earth elements (REEs) and their mechanisms in soybean were studied through application of exogenous mixed REEs under hydroponic conditions. Significant enrichment of middle REEs (MREEs) and heavy REEs (HREEs) was observed in plant roots and leaves respectively, with slight fractionation between light REEs (LREEs) and HREEs in stems. Moreover, the tetrad effect was observed in these organs. Investigations into REE speciation in roots and in the xylem sap using X-ray absorption spectroscopy (XAS) and nanometer-sized TiO₂ adsorption techniques, associated with other controlled experiments, demonstrated that REE fractionations should be dominated by fixation mechanism in roots caused by cell wall absorption and phosphate precipitation, and by the combined effects of fixation mechanism and transport mechanism in aboveground parts caused by solution complexation by intrinsic organic ligands. A conceptive model was established for REE fractionations in plants based on the above studies.     

Adsorption of Rare Earths(Ⅲ) Using an Efficient Sodium Alginate Hydrogel Cross-Linked with Poly-γ-Glutamate

With the exploitation of rare earth ore, more and more REEs came into groundwater. This was a waste of resources and could be harmful to the organisms. This study aimed to find an efficient adsorption material to mitigate the above issue. Through doping sodium alginate (SA) with poly-γ-glutamate (PGA), an immobilized gel particle material was produced. The composite exhibited excellent capacity for adsorbing rare earth elements (REEs). The amount of La³⁺ adsorbed on the SA-PGA gel particles reached approximately 163.93 mg/g compared to the 81.97 mg/g adsorbed on SA alone. The factors that potentially affected the adsorption efficiency of the SA-PGA composite, including the initial concentration of REEs, the adsorbent dosage, and the pH of the solution, were investigated. 15 types of REEs in single and mixed aqueous solutions were used to explore the selective adsorption of REEs on gel particles. Scanning electron microscopy (SEM) and Fourier transform infrared (FT-IR) spectroscopy analyses of the SA and SA-PGA gel beads suggested that the carboxyl groups in the composite might play a key role in the adsorption process and the morphology of SA-PGA changed from the compact structure of SA to a porous structure after doping PGA. The kinetics and thermodynamics of the adsorption of REEs were well fit with the pseudo-second-order equation and the Langmuir adsorption isotherm model, respectively. It appears that SA-PGA is useful for recycling REEs from wastewater.