Determination of rare earth elements in fern leaves using instrumental neutron activation analysis

The lanthanides (REE) in 142 fern leaves collected from several sampling sites in Japan have been determined by neutron activation analysis, and the correlations between any two REEs in the logarithmic scattering diagram were examined. The relationship was expressed by the general formula, Y=aX+b with a correlation coefficient R. A strong positive correlation was seen between any two REEs in the diagram with a regression coefficient and a correlation coefficient close to unity. However, between Eu or Tb and other REEs the relationship was split into two lines with the same correlation coefficient. From the intercept b, the relative abundance of the two elements was determined for each REE and compared with those in hickory and tobacco leaves. These findings indicated that the abundance pattern of fern leaves is quite different from those of hickory and tobacco leaves. Namely, the relative abundance of La and Ce was quite similar in the three plants, but the abundance of the other REEs (Nd, Sm, Gd, Dy and Lu) was considerably lower in ferns than in hickory and tobacco leaves. For Eu and Tb the higher values obtained in fern leaves coincided with those of the two plants.     

Rare earth element concentrations in mature and developing leaves of fern, Blechnacea, collected in the University Forests of Ashiu, Kyoto University

We have investigated the concentrations of REEs in fern leaves collected indifferently to the fern species from 9 sampling sites in Japan using INAA. The results indicated a large variation in the values obtained between fern leaves. In the present investigation we applied the same analytical method on the samples (Blechnaceae, a kind of fern, mature and developing leaves were collected from the same plant) restrictively gathered from the University Forests in Ashiu, Kyoto University. It was demonstrated that the variations in the REE concentrations decreased by one to two order of magnitude, and that the REE contents in developing leaves were also one to two orders of magnitude lower than those in mature leaves. It can be considered that fern accumulates REEs with their growth stages.     

Unusual interrelationship between care earth element and calcium contents in fern leaves

Since the rare earth elements (REE) are most informative as isomorphic replacements of Ca²⁺ in organisms, we analyzed these elements in 142 fern leaves collected from several sampling sites in Japan by instrumental neutron activation analysis (INAA), and the correlation between the REE and Ca contents was examined. In most cases, between any particular REE and the Ca contents, the correlation in the logarithmic scattering diagram was expressed as a single line parallel to the vertical (Y) axis. However, the detailed analysis of the diagrams characterized with respect to the sampling site revealed that the 142 ferns could be separated into two or three groups on the basis of their different REE/Ca ratios. The sampling sites where the different REE/Ca ratios were observed completely agreed with those found in the preceding report, i.e., regarding the unusual correlation between Eu and the other REEs. The present work was supported in part by a Grant-in-Aid from the Ministry of Education, Science, Sports and Culture, Japan.     

土壤-植物体系稀土元素的分异现象

用仪器中子活化分析测定了从同一地点采集的9种不同植物根和叶中8个稀土元素（La,Ce,Nd,Sm,Eu,Tb,Yb和Lu)的含量，研究了稀土元素在植物根、叶及相应母土中的分布特征。结果表明，同一植物的根、叶和母土中稀土分布模式均有较大差异。生长在同一地点不同植物根中稀土分布模式非常相似，而叶中分布规模差别较明显。说明根对单一稀土元素的吸收主要取决于这个元素在土壤中有效态的含量，而在稀土从根到叶的运输和积累过程中出现的分异则由植物自身的结构特征决定。     

Determination of nitrite with a nano-gold modified glassy carbon electrode by cyclic voltammetry

Abstract

Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) was employed to determine the concentration of rare earth elements (REEs) in plants and soils. Sample preparation and analytical conditions were investigated to set up a simple routine procedure for measuring rare earth elements. For prompt sample decomposition, a microwave digestion technique was successfully used with an acid mixture of HCl+HNO₃+HF. Detection limits, reproducibility, accuracy and possible interference were also studied. ICP-MS provided extremely low detection limits for REEs (0.6–6ng/l). Precision was typically better than 6% RSD (relative standard deviation) for soil and 10% for plant. The potential of the method was evaluated by analysis of standard reference materials of soils and plants. A good agreement between the experimental results and certified values was observed. The spectroscopic interference of Ba with Eu and light REEs(LREEs, La-Eu) with heavy REEs(HREEs, Gd-Lu) were eliminated by the algebra correction.

The results suggested that REEs in soil samples existed mainly as light REEs, and the same concentration distribution patterns of Oddo-Hakins law were observed, showing negative gradient from La to Lu concentrations. The REE contents in plants were very low, less than 20μg/g and varied with plant species. Apart from rape leaf(Brassica juncea), the REE distribution patterns in other plant leaves were consistent with soils, indicating that these plants generally absorbed REEs from soil without selectivity. Rape leaf showed selective absorption for LREEs, especially for La. The REE concentration distribution in parts of hot pepper(Capsicum annuum) was characteriaed by root>leaf>stem>fruit. The REEs absorbed by hot pepper concentrated mainly in roots and leaves, very little migrated into fruit. Transfer factors(TFs) of REEs in plants were very low. Although the contents of LREEs were relatively more than those of HREEs, no distinct difference of TFs between LREEs and HREEs was observed, meaning that LREEs and HREEs have the same abilities of transportation. However, for rape leaf, the TFs of LREEs were one or two orders of magnitude higher than those of HREEs.     

Determination of the contents and distribution characteristics of REE in natural plants by NAA

The concentration of 8 REEs (La, Ce, Nd, Sm, Eu, Tb, Yb and Lu) in 17 species of plants and their host soil, which were collected from a rare earth ore area located in the south of China, have been determined by INAA. The chondritic normalized REE patterns for different parts of plants (e.g., leaf stem and root) and their host soils were studied. The results showed that the concentration levels of REE for most plants in the sampling area were elevated. Particularly, the leaves of the fern (Dicranopteris dichotoma) contain extremely high concentration of the total REE (675–3358 g/g) Generally, these REE distribution patterns in every part of plants were very similar and reflected the characteristics of their host soils. However, the chondritic normalized REE patterns in some plants relative to the host soil revealed obvious fractionation, such as the depletion of the heavy REE (for fernCitrus reticulata andBrassia campestris), the heavy REE enrichment (forCamellia sinensis, Camellia oleifera andZiziphus) and the Ce positive anomaly (forGardenia jasminoides).     

Distribution characteristics of rare earth elements in plants from a rare earth ore area

The contents of eight rare earth elements (La, Ce, Nd, Sm, Eu, Tb, Yb and Lu) in various plant species taken from a rare earth ore area were determined by instrumental neutron activation analysis. For a given plant, the REE patterns in root, leaf and host soil are different from each other. The REE distribution characteristics in roots of various species are very similar and resemble those in the surface water. The results of this study suggest that there is no significant fractionation between the REEs during their uptake by the plant roots from soil solution. However, the variation of the relative abundance of individual REE occurs in the process of transportation and deposition of REEs in plants.     

稀土元素在植物中的分异研究进展

有关对稀土农用的理论和实践、天然和农业生态系统中稀土的地球化学行为及稀土的增产生理过程与毒理等方面已开展了大量研究,而对稀土进入植物体内的迁移过程、分布分异现象和机制缺乏必要的了解。稀土元素在植物中的分异研究有助于“示踪”稀土元素在土壤(溶液)-植物系统中的迁移路径,进而查明控制稀土元素迁移和积累的体外和体内敏感因素。本文结合近5年的研究工作,就近年来国内外有关稀土元素在植物中的分异现象、机制及其研究意义进行了综述,并展望了此方面的研究趋势,期望能为稀土以及重金属的生物有效性研究开辟一条新思路。     

Variation of the rare earth element concentrations in the soil, soil extract and in individual plants from the same site

Samples of various types (spruce needles, blackberry leaves, soils, and soil extracts) have each been taken at 6 places from the same site. In addition, 4 whirls each from 2 spruce trees were sampled. Rare earth elements (REEs) were determined in these samples by neutron activation analysis with a chemical group separation. Variations between places were found to be small with soils and soil extracts, but large with plants. Variations between whirls were small. Plants neither reflected the soil nor the soil extract. Both plant species were dissimilar, but the logarithm of their ratio was a linear function of the atomic number of the REE. A negative Ce anomaly (with respect to soil) was found in both plant species.     

稀土元素在植物中的分异机制 (I) 小麦不同器官中的稀土元素分异模式及形成机制

以小麦为植物材料，利用外源稀土添加、营养液培养等人工控制手段，研究了稀土元素在植物体内的分异效应，并探讨了分异效应产生的机制。结果表明，稀土元素在小麦不同器官中出现显著分异。根系出现中稀土(MREE)富集特征和“M”型四重效应，分析是由稀土元素与PO4^3-的选择性沉淀造成。小麦地上部分稀土元素分布出现“W”型四重效应，分析也是由根部磷沉淀造成。与此同时，小麦茎部相对富集轻稀土(LREE)，叶中相对富集重稀土(HREE)。运用VMINTEQ程序计算了木质部溶液中稀土元素的结合形态主要有LnEDTA^-和Ln^3 (Ln指稀土元素)，但仅有LnEDTA^-表现出HREE相对富集特征，其他形态则表现出LREE相对富集特征。分析叶部LREE／HREE分异是吸收LnEDTA^-造成，而茎部LREE／HREE分异则是吸收Ln^3 和其他形态稀土的结果。细胞壁对Ln^3 的吸附也是导致以上分异特征的重要因素。     

Bioaccumulation pattern of lanthanides in pteridophytes and magnoliophytes species from Atlantic Forest

The availability of chemical elements for plants is mainly dependent on the nature of the soil and characteristics of each species. The transfer factors of lanthanides from the soil to the tree leaves of the Atlantic Forest, Brazil, were calculated for one fern species (Alsophila sternbergii—Pteridophyta division) and four magnoliophytes species (Bathysa australis, Euterpe edulis, Garcinia gardneriana and Guapira opposita—Magnoliophyta division) obtained in two areas of Serra do Mar State Park and collected in two different seasons. Samples were analyzed by instrumental neutron activation analysis (INAA). The soil-to-plant transfer factor (TF = C_plant:C_soil) in magnoliophytes species was correlated to the mass fraction of lanthanides in the soil, described by a exponential model (TF = a.C_soil^−b). Despite the tree fern Alsophila sternbergii presented a hyperaccumulation of lanthanides, this species did not have a significant relationship between TF and mass fraction in soil. Results indicated that plants of Magnoliophyta division selected the input of lanthanides from the soil, while the same was not observed in Alsophila sternbergii.     

REE bound DNA in natural plant

The binding of rare earth elements (REEs) with nucleic acids in the leaves of fern Dicranopteris dichotoma (DD) has been studied by molecular activation analysis (MAA). The REEs bound DNA (REE-DNA) was obtained from the leaves of DD. The CTAB-based procedure was modified for extraction of total DNA. The purity of DNA was examined by UV spectroscopy. The DNA obtained was separated and determined by agarose gel electrophoresis further. Meanwhile, the contents of eight rare earth elements (La, Ce, Nd, Sm, Eu,Tb, Yb and Lu) in REE-DNA were detected by instrumental neutron activation analysis (INAA). The results showed that REE-DNA with higher purity could be extracted from plant using this method. It was also found that REEs were bound firmly with DNA in the leaves of DD. The molecular weight (MW) of REE-DNA band was about 22 kb in agarose gel electrophoresis.     

湖南辰溪特高有机硫煤的稀土元素特征及其成因

采用高分辨率电感耦合等离子质谱(HR-ICP-MS)技术测定辰溪晚二叠世高有机硫(7.75%)煤中的稀土元素(REEs)。辰溪煤中∑REE变化较大,从38.84 μg/g至305.85 μg/g,加权平均值为104.57 μg/g,高于世界煤均值,与中国煤相近。辰溪煤中有明显的Ce负异常(δCe=0.74~0.84)和Eu的负异常(δEu=0.55~0.69)。煤层剖面上稀土元素含量和分布模式的变化反映了成煤环境的波动,从底板到顶板陆源物质的影响减弱,而海水的影响增强。沉积环境的阶段性变化是导致剖面上下有机硫与黄铁矿硫比值相差悬殊的原因。辰溪煤中稀土元素与铁呈现了显著的正相关性(n=11,r=0.95),说明其物质来源和富集条件有一定相似性,即陆源物质和海水共同影响的结果。稀土元素的分布模式以及∑REE与灰分、Si、Al的相关性说明了其主要来源于陆源物质;辰溪煤中δCe与δEu在剖面上变化很小,说明海水对煤中的稀土元素存在重新改造的作用。     

稀土元素日允许摄入量与农用安全性探讨

稀土农用是我国独立开创的稀土应用领域,30年来,取得了巨大的经济效益。然而,作为元素周期表中第ⅢB主族的重金属,稀土元素不是动植物的必需微量元素,其生理效应的机制还不清楚,稀土农用的安全性问题一直受到密切的关注。本文从稀土元素分析方法与人均总膳食摄入量、稀土元素毒理实验方法与日允许摄入量、稀土农用对土壤中稀土元素含量和化学形态的影响、以及稀土农用对食物中稀土元素含量影响的4个方面,对文献报道作了分析、整理和评定,结论是只要对使用的范围、剂量及施用方式进行限制,稀土农用是一种安全的农业增产方式。     

REE bound polysaccharides in leaves of Dicranopteris dichotoma by MAA

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Determination of rare earth and other elements in algae by ICP-MS and neutron activation analysis

Several rare earth elements (REEs) and other elements in algae were investigated by ICP-MS and INAA. Algae materials were supplied from an IAEA Intercomparison Study:Chlorella vulg. grown under reduced levels of toxic elements (IAEA-391) and IAEA-393 algae was grown in a medium to which certain toxic elements were added. 34–691 mg of algae samples were dissolved in conc, nitric acid using a microwave sampleppreparation system. REEs could be detected in the order of magnitude of 10⁻³ ng/g by ICP-MS. Activation analysis failed to detect any REEs because of a strong interference due mainly to²⁴Na and³²P. The distriubtion patterns of these REEs in algae slightly differed from those ofCarya sp. and tobacco leaves, and differed significantly from that of fern leaves. The distribution pattern was rather similar to that found in the North American shale composite (NASC).     

Determination of rare earth elements in carbonatites from the Kangankunde Mine, Malawi by instrumental neutron activation analysis

Nine rare earth elements (REEs) in African carbonatite samples were determined by instrumental neutron activation analysis (INAA). The geochemical behavior of REEs in carbonatites, especially REE pattern (chondrite-normalized), is studied in relation to carbonatite formation at the Kangankunde Mine, Malawi. REE-rich phosphate minerals, particularly monazite, and the other unusual minerals such as strontianite, are observed during the stages of carbonatite formation. Four kinds of carbonatites exhibit similar chondrite-normalized REE distribution patterns in spite of the marked difference of their REE contents. All these carbonatites are characterized by the strong fractionation between light and heavy REEs and by the very high La/Yb ratio (1000-2800).     

Peculiarities of rare-earth-element distribution in environmental objects

The effect of the production of phosphorus fertilizers on the pollution of the environment by rare-earth elements is reviewed. The main sources of rare-earth element pollution in the environment are described. The levels of REEs in components of the environment — atmosphere, snow, different types of soil, native and agricultural types of vegetation — that provide evidence for their participation in the biological cycle of plants are considered. The high values of the correlation coefficients lead one to think that the REE distribution in vegetation occurs under specific laws true for this family of elements.     

Determination of rare earth elements in Indian kimberlite using inductively coupled plasma mass spectrometer (ICP-MS)

A method has been developed for the analysis of rare earth elements (REEs) in kimberlite samples using inductively coupled plasma mass spectrometer (ICP-MS). The samples were dissolved using sodium peroxide fusion and after appropriate dilutions the solutions were analyzed using ICP-MS. The paper presents the concentration of rare-earth elements as determined by ICP-MS in eight kimberlite samples from Central India. The method was validated using certified reference materials STSD-1 and STSD-2 from Canadian Certified Reference Material Project. The method detection limit of various REEs varies from 0.12 to 1.54?mg?kg^?1. The total REE concentrations range from 418 to 726?mg?kg^?1 and fall within the interval of those reported in the literature for kimberlites. Despite the marked difference in the REE contents, all the analyzed samples show similar REE patterns that resemble those for kimberlites. In order to compare ICP-MS results, the samples were analyzed using instrumental neutron activation analysis which is a reference method for determination of REEs in geological samples.     

Distribution of the rare earth elements in sediments of the Northwestern Iberian Continental Shelf

The temporal and spatial distribution of the REEs was determined, by INAA, in sediment cores collected at Northern Iberian shelf along the area between the Finisterra Cape and the mouth of Minho river, to contribute to the understanding of the origin and sedimentation processes of sediments deposited at the Continental Shelf. The distribution pattern of the REEs were flat and similar to the shales. A negative Eu anomaly was found for all the sections of the analyzed cores. Significant positive correlations between the REE and Zr and Hf contents suggest that zircon is responsible for hosting both light and heavy REEs.