The variation of REE (rare earth elements) patterns in soil-grown plants: a new proxy for the source of rare earth elements and silicon in plants

Rare earth elements (REEs) in five species of soil-grown plants (Taxodium japonicum, Populus sieboldii, Sasa nipponica, Thea sinensis and Vicia villosa) and in the soil on which each plant grew were determined with an inductively coupled plasma mass spectrometer (ICP-MS) in order to observe the variation in the distribution of REEs and to elucidate their source in soil-grown plants. The plant samples were divided into root (secondary root and main root), trunk (stem) and leaf; the soils into water soluble (soil_{soluble fraction}), HCl and HNO₃ soluble (soil_{non-silicate fraction}) and HF soluble (soil_{silicate fraction}). The REE abundances of samples were compared using REE patterns where the abundances were normalized to those of a chondrite and plotted on a logarithmic scale against the atomic number. All the plants showed similar REE patterns independent of species and location, and a W-shape variation (W-type tetrad effect) and abundance depletion of cerium (negative Ce anomaly) were found in each REE patterns of plants, more conspicuous tetrad effect being observed in HREE (heavier rare earth elements) region than in LREE (lighter rare earth elements) region. The overall variation of REE patterns of each secondary root was not similar to that of soil_{soluble fraction}, but similar to that of soil_{silicate fraction} except for the tetrad effect and Ce anomaly. The REE patterns can be interpreted by the idea that plants of different species take in REEs and Si from different parts in the soil. The results of this study seem to imply that Sasa nipponica and Vicia villosa take in free REEs and Si rather directly from silicate in the soil, and that a majority of REEs and Si in Taxodium japonicum and Thea sinensis are originated from the soluble fraction in the soil.     

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.     

稀土元素对红霉素发酵的影响

通过对红霉素发酵培养基中添加稀土元素的研究,确定了几种能对发酵效价有提高作用的稀土元素及其浓度,当其中镧La^3＋、钕Nd^3＋和铈Ce^4＋离子浓度分别为50mg／L、50mg/L和100mg／L时对提高红霉素效价水平最显著,提高了32％、25％和25％,并且对改善红霉素组分也有明显作用,红霉素A组分相对百分含量分别提高18．9％、32．7％和34．4％,红霉素B组分分别减少24．1％、58．6％和62．1％。     

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。     

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.     

Distribution pattern of rare earth elements in fern

All the lanthanide elements (REE) in fern (Matteuccia) and in soil were determined with inductively coupled plasma mass spectrometer (ICP-MS) in order to discuss REE behavior in fern. The fern sample was divided into three parts: root, stem, and leaf; the soil of the same site was also sampled and the soil sample was divided into two parts: HCl and HNO₃ soluble part (soil[HCl]) and HF soluble part (soil[HF]). REE in each part was determined by ICP-MS after solvent extraction separation. The overall variation of the REE pattern of the root does not resemble that of the whole soil, but that of the HF soluble part. A tetrad effect variation (W-type) was found in the REE patterns of root, stem and leaf; more conspicuous tetrad effect variation was observed in HREE region than in LREE region, and was so in stem and leaf than in root. Negative anomalies of Ce were observed in the REE patterns of root, stem and leaf, with bigger anomalies in stem and leaf than in root. The results of this study suggest that REE in fern has come from silicates of soil and has once been in dissolved state.     

Accumulation of rare earth elements in maize plants (Zea mays L.) after application of mixtures of rare earth elements and lanthanum

Rare earth elements are applied in China to improve crop production, and the distribution patterns of individual rare earth elements in native plants have widely been reported. But our knowledge is still limited about the dose-dependent accumulation of individual rare earth elements in agricultural crops after application of rare earth elements. Effects of lanthanum and mixtures of rare earth elements were studied in pot experiments on the accumulation of individual rare earth elements in maize plants. All plant samples were divided into plant tops and roots. On addition of mixtures of rare earth elements and lanthanum to the soil, a significant dose-dependent accumulation of individual rare earth element(s) was found in the roots and in the plant tops. Application of mixtures of rare earth elements at >10 mg kg^–1 soil, resulted in a significant increase in contents of light rare earth elements in the roots, and at a dose of 50 mg kg^–1 soil, a similar phenomenon was found in the plant tops. When mixtures of rare earth elements were replaced by lanthanum alone, at a dose higher than 10 mg La kg^–1 soil, a significant increase in La content occurred in the roots and in the plant tops. The content ratio of La to Ce in maize plants appeared to increase as the application doses of rare earth element(s) increased. At a highest dose (50 mg kg^–1soil), the transport of the absorbed La from the roots to the plant tops might be substantially reduced after treatment with lanthanum alone, compared with mixtures of rare earth elements. Increasing the application doses of rare earth element(s) appeared to cause a positive Gd and negative Ce anomaly in the roots and in the plant tops, and the anomaly was more obvious in the plant tops than in the roots. The results indicated that the Gd and Ce anomaly in corns might be considered as important parameters for the safety assessment of agricultural application of rare earth elements.     

Contents and the biogeochemical characteristics of rare earth elements in wheat seeds

Contents of fifteen rare earth elements (REEs) in the seeds ofsixty breeds of wheat collected from seed bank were measured byinductively coupled plasma mass spectrometry (ICP-MS). The distributionpatterns of contents of REEs in wheat seeds (n = 58) wereobserved and compared with their average level in soils (n =364). Differences among regions and between spring and winter wheat weretested. Comparison with literature data was also made. The results showthat the content of REEs in wheat seed ranges between10^–11 g · g^–1 and10^–8 g · g^–1, 3–4 orderof magnitudes lower than that in soils. The distribution patterns arethat light REEs enriched and the Eu-anomaly is weak, similar to the soilcase. No obvious differences were found among different regions andbreeds. The data obtained in this study represent the contents of thefifteen REEs in wheat seeds.     

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。     

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.     

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.     

南方稀土采矿恢复地土壤稀土元素含量及植物吸收特征

通过野外取样调查和室内ICP-MS测定,研究了福建省长汀县稀土矿治理地土壤和主要植物中稀土元素的含量、分布以及转移特征.结果表明:稀土矿治理地的土壤养分含量较低;土壤中稀土元素的含量为507.40～841.37 mg· kg-1,高于对照地土壤的含量.稀土矿治理地土壤中稀土元素主要为交换态,其含量占总量的61％～98％.稀土矿治理地土壤中稀土元素从原来偏单一的交换态转变为多种形态共存,其中有机态含量显著升高.植物根、茎、叶中稀土元素含量分别为40.27～986.01、5.14 ～ 206.58、6.81 ～ 2364.51mg·kg-1.稀土元素在植物各器官中含量水平除芒萁为叶＞根＞茎,其他植物均表现为根＞叶＞茎.根据不同植物吸收和积累稀土元素的差异,可将矿区治理地植物分为富集型和根部囤积型植物.芒萁属于富集型植物,桉树、高羊茅、宽叶雀稗、木荷和油茶属于根部囤积型植物.     

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).     

酸雨胁迫下,稀土元素对菠菜膜保护系统作用

利用盆栽实验,探讨了酸雨胁迫下对菠菜膜保护酶系统的防护效应,实验结果表明,单一酸雨处理会造成超氧化物歧化酶（ＳＯＤ）,过氧化酶（ＣＡＴ）活性总体水平下降,其变化曲线呈“Ａ”形,并使过氧化物酶（ＰＯＤ）活性明显增加,施用稀土元素后酸雨胁迫下的植株叶片中ＳＯＤ,ＣＡＴ活性总体水平上升,变化曲线的峰值向酸度较大的方向移动,ＰＯＤ活性上升幅度减小,３种膜保护酶的活性与单一酸雨处理组相比,处在一种结稳定的状     

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.     

稀土对蚯蚓体内氨基酸含量的影响

采用滤纸接触染毒法,分别进行了氯化稀土、氯化镧与土居动物蚯蚓接触染毒不同时间和不同浓度的试验。研究其对蚯蚓体内氨基酸含量的影响变化。结果表明。Re、La对蚯蚓体内的氨基酸含量影响较显著,在低浓度时总体表现为促进蚯蚓体内氨基酸的形成,而在高浓度状态下则使蚯蚓体内氨基酸含量下降,产生抑制作用,两种稀土在400mg·L^-1浓度时,蚯蚓体内氨基酸含量除脯氨酸外开始上升,随着作用时间延长,氨基酸含量逐渐下降,在100～1200mg·L^-1浓度范围,两种稀土均引起蚯蚓体内脯氨酸含量的下降,产生抑制作用。     

稀土元素对红豆杉细胞悬浮培养及紫杉醇合成的影响

研究了在250mL摇瓶中,不同浓度的硝酸镧、硫酸铈铵、硝酸亚铈3种稀土化合物对细胞生长及紫杉醇分泌和释放的影响。结果表明,在培养初期加入稀土元素。3种不同稀土化合物对细胞生长影响强弱不同,但趋势相似,均使细胞的延迟期缩短。1ppm的Ce^4 促进细胞生长的效果最明显。细胞干重第17d达到10.9g/L。在指数期加入稀土元素。10ppmCe^3 刺激细胞生长的效果最明显,细胞干重最高值达到11.5g/dL,比对照高1.5g/L,而10ppm的La^3 抑制细胞的生长。经稀土元素处理后,细胞胞内和胞外紫杉醇含量都有大幅度的提高,其中以10ppmCe^3 处理,胞外紫杉醇释放率最大,达37.7%。     

Mapping first to final uses for rare earth elements,globally and in the United States

Estimating the material flows of rare earth elements (REEs) is essential to understanding which industries are most vulnerable to potential REE supply disruptions which, in turn, may inform policy recommendations aimed at reducing the supply risk. However, the REEs are a group of mineral commodities characterized by highly uncertain estimates of supply and demand due to the REE market's complexity, opacity, and small size. In this study, a streamlined methodology was applied to map mineral commodity first-use to final-use applications and to estimate total requirements at the national level based on available industrial data for final-use finished goods. This analysis examines REEs both as a group and individually, showing that total US requirements are between 15% and 16.5% of world requirements for the year 2015, the latest year with the most complete information available. The findings shed light on US industrial capabilities by revealing the discrepancy between the types of REEs that go into US raw material consumption and those that are contained in embedded consumption. For instance, given the United States’ large oil refining industry, US raw material consumption of lanthanum is quite high. In contrast, US raw material consumption of neodymium is relatively low, whereas embedded demand is comparatively high. This reflects the lack of industrial capacity to process REE concentrates into magnet material combined with the US's high imports of products that contain rare earth permanent magnets.     

Promotion of the growth of Crocus sativus cells and the production of crocin by rare earth elements

La3+ and Ce3+, either singly or a mixture, promoted crocin production of Crocus sativus callus but Nd3+ had little effect and all metal ions were toxic above 100 microM. La3+ (60 microM) promoted growth of callus significantly but increased crocin only slightly. Ce3+ (40 microM) significantly promoted crocin production but had little effect on cell growth. La3+ (60 microM) and Ce3+ (20 microM) together gave the highest dry weight biomass (20.4 g l(-1)), crocin content (4.4 mg g(-1)) and crocin production (90 mg l(-1)) which were, respectively, 1.7-fold, 4.2-fold and 7.1-fold of those without additions. Nd3+ (40 microM) only slightly promoted cell growth and crocin production.     

稀土元素对甘草细胞生长及甘草酸合成的影响

以胀果甘草根愈伤组织为材料,研究了在150mL摇瓶中,不同浓度的两种稀土离子镧、亚铈对甘草细胞生长及甘草酸分泌和释放的影响。结果表明,在悬浮培养初期、指数期加入稀土元素,改变了细胞生长状况,均使细胞在整体上生物量减少;不同种类的稀土离子、不同的稀土浓度对细胞生长影响强弱不同,但趋势相似。其中,培养指数期,加入500μL镧溶液的培养液中,所得甘草细胞生物量较多,利用薄层-紫外分光光度计法检测到甘草酸含量为67.68mg/g。