Rare earth elements in soil and in soil-grown plants

Concentrations of the rare earth elements (REEs) La, Ce, Nd, Sm, Eu, Gd, Tb, Yb and Lu were determined in leaves of 6 plant species (Norway spruce, silver fir, maple, ivy, blackberry, and wood fern), and in pertinent soils and soil extracts, also taken from the same site. The distribution of the individual REEs in plants showed little or no agreement with that in the soil or the soil extracts. Ce had a negative anomaly with respect to the soil in all plants. The REE distribution patterns of fir and spruce were almost identical, but differed profoundly from that of the other species. In most cases, concentration ratios between species were a smooth function of the atomic number of the REE. Very similar results were obtained at 2 additional sites.     

The accumulation of the rare earth elements and of scandium in successive needle age classes of Norway spruce

The endogenous concentrations of Sc, La, Ce, Sm, Eu, Tb, Yb, and Lu were determined by neutron activation analysis in up to five successive needle age classes of Norway spruce (Picea abies). Trees from nine sites over different bedrocks were sampled individually. Concentration values found are generally much lower than those reported in the literature. This is attributed to the careful removal of any aerosols or soil particles from the needle surface prior to analysis. The concentration of each element increases linearly with the needle age class, i.e., the accumulation can be characterized by just one parameter, the yearly increment. This pattern is followed at small as well as at large concentrations. The accumulation behavior of the investigated elements is identical to that of Si. The relative concentrations of the rare earth elements (REE) in the needles are similar to those in the earth crust. There are significant correlations between the individual REE and between Sc and La.     

Evaluation of trace elements in lung samples from coal miners using neutron activation analysis

In this study, instrumental neutron activation analysis was applied to the determination of Sc, La, Ce, Nd, Sm, Eu, Tb, Yb, Lu, Hf, Th, and U in lung samples from miners working in coal mines located in the state of Santa Catarina, Brazil. These results were compared to those from a control group constituted of healthy individuals. The results showed that the elements determined exhibit considerable intersubject variability within a single group of individuals and the mean values of concentrations in miners’ lungs were higher than those of normal individuals. Lung samples presented U concentrations varying from 11 to 890 Μg/kg. Therefore, for some samples, the contribution of the uranium fission products in the analysis of La, Ce, Nd, and Sm was considered by determining the interference correction factors. The accuracy of the results was evaluated by analyzing certified reference materials.     

Multielement compositions of marine phytoplankton samples from coastal areas of japan by instrumental neutron activation analysis

Phytoplankton samples were collected during spring bloom of diatoms from three coastal areas of Japan using a NORPAC P-25 net (25-Μm opening) with a NGG52 prenet (335-Μm opening), and 25 major and trace elements have been analyzed by INAA. Concentration ranges of analyzed phytoplankton samples are much wider than the concentration ranges compiled by Bowen (1979) except for As, and data of marine phytoplankton samples for Br, Sb, Hf, Sc, La, Ce, Sm, and Eu were not included in the compilation. The 25 analyzed elements have been categorized into three groups: elements showing positive correlation with Br, positive correlation with Al, and no positive correlation with Br or Al. The marine phytoplankton samples have been plotted on a Masuzawa-Koyama-Terazaki (MKT) plot and it proved that the MKT plot is applicable to marine phytoplankton samples.     

Rare earth elements in forest-floor herbs as related to soil conditions and mineral nutrition

Mixtures of rare earth elements (REEs) in fertilizers are widely used in Chinese agriculture to improve crop nutrition. REE concentrations in wild-growing plants, especially herbs, are little known. This study describes differences in the concentrations and proportions of REEs in eight forest-floor herbaceous plants and relates these differences to soil and mineral nutrient conditions. REEs studied were yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), and lutetium (Lu). Leaf concentrations of sum REEs differed more than one order of magnitude between species, being highest in Anemone nemorosa (10.1 nmol/g dry mass) and lowest in Convallaria majalis (0.66 nmol/g) from the same site. Leaf concentrations of all REEs correlated positively (p<0.001), as did sum REE with calcium (Ca) and strontium (Sr) concentrations (p<0.001). A negative relationship (r=−0.83, (p<0.001) was measured between phosphorus (P) concentrations and sum REE concentrations in leaves. However, the proportions of the single REEs in the REE sum differed among species. In A. nemorosa, 57% of the molar REE sum was taken by Y+La, and only 21% by Ce. The other extreme was Maianthemum bifolium, with 37% La+Y and 41% Ce. These two species had 2.7–3.0% of the REE sum as heavier lanthanides, compared to 4.1–5.2% in the six other species. No clear relationship between soil properties or REE contents and leaf REE concentrations was detected. For La, however, an overrepresentation in leaves prevailed throughout all species compared to soils, whereas particularly Nd, Sm, and Tb had a lower proportion in the leaves of all species than in their soils. Possible uptake mechanisms of REEs in plants are discussed.     

Plant uptake of major and minor mineral elements as influenced by soil acidity and liming

This study reports effects on soil solution chemistry and plant uptake of 55 elements (Ag, Al, As, B, Ba, Be, Bi, Br, Ca, Cd, Ce, Co, Cr, Cs, Cu, Dy, Er, Eu, Fe, Gd, Ge, Hf, Hg, Ho, K, La, Li, Lu, Mg, Mn, Mo, Na, Nb, Nd, Ni, P, Pb, Pr, Rb, S, Sb, Sc, Se, Si, Sm, Sr, Tb, Th, Tl, U, V, W, Y, Yb, Zn, Zr) by raising the pH using addition of fine-grained precipitated calcium carbonate at 20 rates (yielding a soil solution pH range of 5.2 – 7.8) to A horizon samples of an acid Cambisol, cultivating a common grass (Agrostis capillaris L.) and determining the soil solution, root and shoot concentrations of these elements at the end of the experiment. For many of these elements, there is little or no previous information about concentrations in soil solutions, or in plant biomass, as related to soil pH/acidity or addition of calcium carbonate. Soil solutions were obtained by high speed centrifugation and ultrafiltration (0.2 m) of samples at 60% water-holding capacity. Concentrations of elements were determined by ICP-ES or (in most elements) ICP-MS, using isotopes specified. Soil solution pH, HCO₃ and organic C were also determined.Concentrations of elements in the biomass of A. capillaris were usually inversely related to soil solution pH. The most apparent (p<0.001) inverse, though often curvilinear, relationships between pH and concentrations in shoot biomass were measured for Ag, As, B, Ba, Eu, Ge, Li, Mn, Ni, P and Sr. Positive relationships (p<0.05) were only measured in Ca, Hg, Mg, Mo and S. For concentrations in root biomass, relationships were mostly, but not always, of the same sign and of a similar strength. Though soil solution pH and concentrations of elements were usually quite closely correlated, pH and/or HCO^– ₃ concentration more often accounted for a higher share of the variability in biomass concentration of elements than did soil solution concentration of the same element.     

Effects of Eu and Ca on yield and mineral nutrition of wheat (Triticum aestivum) seedlings

Although fertilisers enriched in rare earth elements (REE) are widely used in agricultural practice, little is known yet about behaviour of the REE in soil–plant system. Among REE, europium (Eu) may be of highest interest. Eu may serve as an indicator of biogeochemical processes due to a change of its valence state under different environmental conditions. Since chemical characteristics of Ca and REE are similar, Eu may compete with Ca for organic ligands. In the present work we studied the influence of Eu and Ca on the growth and mineral nutrition of wheat seedlings. An application of Eu favoured germination and root growth, whereas in combination with Ca it produced a more sustained leaf growth. Eu affected uptake and distribution of certain nutrients in different parts of a plant. The content of Eu in all parts of wheat seedlings at the end of germination significantly increased. Transfer of the seedlings germinated in the Eu-rich medium into soil resulted in the release of Eu from the plants. Nevertheless, 9 days after the sowing, Eu concentration in the seedlings was still much higher than in the control plants.     

Morphology and proliferation of B16 melanoma cells in the presence of lanthanoid and Al3+ ions

The effects of trivalent metal ions such as lanthanoid (La , Ce, Nd , Sm , Gd , Er , Yb , Lu ) and Al ions on the morphological change and proliferation of B16 melanoma cells in culture are discussed. These metal ions induced morphological transformations and decreased growth rates at doses of 1 mM. B16 melanoma cells treated with La , Ce , Nd , Sm , and Gd showed polyhedrical spreading. Elongation of axones was dependent on the metal ions. B16 melanoma cells treated with Er , Yb , Lu , and Al showed a long slender shape. Growth rates of melanoma cells in the presence of 1 mM of metal ions (La , Ce , Nd , Sm , Gd , Yb , Al ) were significantly lower than that of control cells. Measurements of cell cycle indicated that the metal ions arrested the transitions from G /G to S state. © Rapid Science 1998     

感耦等离子体发射光谱法研究土壤—铁芒萁系统中稀土元素的分布、累积和迁移特征

用感耦等离子体发射光谱法（ICP－AES）测定了东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La、Ce、Pr、Nd、Sm、Gd、Dy、Yb和Y的含量,并对其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,土训层的底土层含量最高,但表土层铈相对富集、稀土元素总量（∑REE）在铁芒萁植物体内的分布规律是叶＞根＞茎＞叶柄,单一稀土的分布规律各异,La、Ce、Pr、Nd的分布规律表现为：叶＞根＞茎＞叶柄;Sm和Gd在不同采样点表现为叶＞根＞茎＞叶柄或根＞叶＞茎＞叶柄;Dy、Yb和Y均有3种不同的分布模式：叶＞根＞茎＞叶柄、根＞叶＞茎＞叶柄及根＞茎＞叶＞叶柄,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。     

钙离子浓度对青檀生长和檀皮质量的影响

以Hoagland完全营养液为基质,利用5、10和15mmol·L^-13个Ca^2+浓度处理水平及一个无钙对照处理。对青檀苗木各生物组分积累的钙含量、生物量、密度、纤维长度、纤维宽度和纤维素含量进行测定分析．结果表明。对照处理下的青檀苗大部分死亡,且生长不良,其高生长量仅为有钙处理的50％左右;在有钙处理中,青檀一年苗的高生长和生物量差异不明显,但以10mmol·L^-1钙处理浓度的生长量和生物量最大;Ca^2+促进了根、叶和檀皮中钙的积累,并随着Ca^2+浓度的增加而提高,其分布为根>叶>檀皮;浓度钙处理对青檀木质部和檀皮密度、青檀木质部和檀皮的纤维形态影响不显著,其中10mmol·L^-1钙处理下木质部纤维长度和宽度最大,5mmol·L^-1钙处理下檀皮的纤维长度和长／宽比最大;不同钙处理间,檀皮(韧皮部)纤维均在2．0mm以上,檀皮的纤维长／宽比约为木质部长宽比值的4倍;浓度钙处理对青檀木质部和檀皮中纤维素含量有显著影响,且均以10mmol·L^-1。钙处理下纤维素含量最高．     

Trace elements in rock salt and their bioavailability estimated from solubility in acid

In this study, 18 partly commercially available samples of rock salt from Austria, Germany, Pakistan, Poland, Switzerland, and Ukraine were investigated with respect to their content of trace elements using instrumental neutron activation analysis. Elements detected were Al, Ba, Br, Ca, Ce, Cl, Co, Cr, Cs, Eu, Fe, Hf, La, Mn, Na, Rb, Sb, Sc, Sm, Sr, Ta, Tb, Th, and Zn, some of them only in individual cases. An estimation of the bioavailability of these trace elements was performed by dissolving an equivalent of the sodium chloride samples in diluted hydrochloric acid (simulating stomach acid), filtering off the insoluble components, and analyzing the evaporated filtrate. It could be shown that in most cases bioactive trace elements like Fe can be found in rock salt in the form of almost insoluble compounds and are therefore not significantly bioavailable, whereas thorium, for example, was partly bioavailable in two cases. A significant contribution to the recommended daily intake of metal trace elements by using rock salt for nutrition can be excluded.     

感耦等离子体发射光谱法研究土壤-铁芒萁系统中稀土元素的分布、累积和迁移特征

用感耦等离子体发射光谱法(ICP-AES)测定了江西赣南地区非稀土矿区和处不同稀土矿区内,土壤-铁芒萁系统中La、Ce、Pr、Nd、Sm、Gy、Db、Yb和Y的含量,并对其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,土壤剖面层的底土层含量最高,但表土层铈相对富集.稀土元素总量(∑REE)在铁芒萁植物体内的分布规律是叶＞根＞茎＞叶柄,单一稀土元素的分布规律各异,La、Ce、Pr、Nd的分布规律表现为:叶＞根＞茎＞叶柄;Sm和Gd在不同采样点表现为叶＞根＞茎＞叶柄或根＞叶＞茎＞叶柄;Dy、Yb和Y均有3种不同的分布模式:叶＞根＞茎＞叶柄、根＞叶＞茎＞叶柄及根＞茎＞叶＞叶柄.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 wheat: controlled by phosphate precipitation, cell wall absorption and solution complexation

Previous studies on rare earth element (REE) bioaccumulation have focused on their accumulation rate and fractionation, but the processes involved remain unclear. In this study, the accumulation and fractionation of REEs in wheat (Triticum aestivum L.) were investigated using solution culture with exogenous mixed REEs. A decrease in REE contents was observed from the roots to the tops of wheat. Significant fractionations of REEs were found in wheat organs as compared to the exogenous mixed REEs. Middle REE (MREE, the elements from Sm to Gd) enrichment and an M-type tetrad effect (an effect that can cause a split of REE patterns into four consecutive convex segments) were observed in the roots, which were probably caused by phosphate precipitation of REEs in/on the roots and absorption of REEs to root cell walls. Light REE (LREE, the elements from La to Eu) and heavy REE (HREE, the elements from Gd to Lu) enrichments were observed in the stems and leaves, respectively, accompanied by conspicuous W-type tetrad effects (an opposite effect to the M-type tetrad effect) in the REE patterns. HREE enrichment decreased from the older to the younger leaves and increased upwards within a single leaf. It is suggested that the solution complexation that occurred in the xylem vessels plays an important role in REE fractionations in the above-ground parts of wheat.     

Multivariate relationships and spatial distribution of geochemical features of soils in Jamaica

Abstract

Concentrations of 31 chemical elements in 165 soil samples from the tropical island of Jamaica were analyzed during the island-wide soil survey. Multivariate outliers were detected and remedied for quality control of the database. Multivariate analyses including principal component analysis (PCA), cluster analysis, and analysis of variance (ANOVA), and a geographic information system (GIS) were applied to study the geochemical features of element associations and sample clusters. The results show that rare earth elements, most of the heavy metals and trace elements (including As, Al, Cd, Ce, Co, Cr, Dy, Eu, Fe, Hf, Hg, La, Lu, Mn, Pb, Sb, Sc, Sm, Th, Ti, U, V, Yb, Zn) are enriched in the bauxitic soils relative to the non-bauxitic soils, and closely correlated with one another. Negative correlations between the bauxite-enriched elements and the mobile alkali and alkaline earth elements including Ca, Sr, Mg and Na are observed, showing the opposite tendencies of enrichment of the immobile elements and leaching of the mobile elements during the soil formation processes. The halogen elements of Br and I are also relatively enriched in the bauxitic soils, but they appear to be rather affected by sea-spray. Copper has poor correlations with all the other elements, which is likely to be related to mineralization. Significantly different concentrations of the bauxite-enriched elements are observed between the bauxitic and non-bauxitic soils.     

Comparative study of methods for determining lanthanide elements in biological materials by using NAA,HPLC postcolumn reaction,and ICP-MS

Biological Trace Element Research - Mice were injected intravenously with one of the following elements: Y, La, Ce, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, or Yb, at a dose of 25 mg/kg body wt. After 20 h,...     

Criticality of the Rare Earth Elements

Recent constraints on supplies of the rare earth elements (REEs) have led to concerns about their long‐term availability as well as the consequences that shortages would pose for modern technology. To assess this situation, we apply a comprehensive “criticality” methodology to the REE: lanthanum (La); cerium (Ce); praseodymium (Pr); neodymium (Nd); samarium (Sm); europium (Eu); gadolinium (Gd); terbium (Tb); dysprosium (Dy); holmium (Ho); erbium (Er); thulium (Tm); ytterbium (Yb); lutetium (Lu); and yttrium (Y). Assessments are made on national (U.S. and China) and global levels for the year 2008. Evaluations of each indicator are presented and the results plotted in “criticality space” on a 0 to 100 scale. Over the medium term (5 to 10 years), supply risk (SR) for all REEs is moderate with minimal variation (62.8 to 65.1). Over the long term (10 to 100 years), SR is low (42.1 to 49.2). Environmental implications scores, reflecting the economic allocation of environmental burdens, range from 4.2 for La to 34.4 for Lu. Eu, Er, and Dy have the highest vulnerability to supply restriction (VSR) at the global level (50.6, 49.2, and 47.4, respectively), whereas Sm has the lowest (15.1). This is mainly a reflection of their substitution potential. Similarly, at the national level for the United States and China, Eu and Sm have the highest and lowest VSR scores, respectively, although there are notable differences in scores among the REEs and between countries. Although China's export restrictions render REE supplies inadequate to meet demand at present, our analysis indicates a lower criticality for REEs over the longer term than for a number of other industrially used metals.     

Characterization of airborne particulates in bangkok urban area by neutron activation analysis

Samples of airborne particulates were collected in a residential area and in an area near a busy highway in Bangkok during the period from January 1997 to May 1998. A stacked filter system was used for the former site and a Partisol 2000 was used for the latter site. Both 2.5 Μm and 10-Μm particulates were collected every week. The total suspended particulate matters were also collected at the latter site. The samples were analyzed by neutron activation analysis utilizing neutron flux from a 2-MW TRIGA MARK III research reactor. The elements most frequently detected in the airborne particulates were Al, As, Br, Ca, Ce, Cl, Co, Cr, Cs, Fe, I, K, La, Mg, Mn, Na, Rb, Sb, Sc, Sm, Th, Ti, V, and Zn. The enrichment factor and factor analysis were used to investigate trends, sources, and origin of the atmospheric aerosols. Anthropogenic elements in road dust, construction dust, motor vehicles emission, and other combustion components were identified. A comparative study of data between both sites was performed and it was found that the mass concentration in the area close to the highway was about three times higher than in the residential area.     

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.     

The Effect of Age and Gender on 59 Trace-Element Contents in Human Rib Bone Investigated by Inductively Coupled Plasma Mass Spectrometry

The effect of age and gender on 59 trace-element contents in rib bone of 80 apparently healthy 15–55-year-old women (n?=?38) and men (n?=?42) was investigated by inductively coupled plasma mass spectrometry. Mean values (M?±?SΕΜ) for the mass fraction (milligrams per kilogram, on dry-weight basis) of Ba, Bi, Cd, Ce, Cu, Dy, Er, Gd, La, Li, Mn, Mo, Nd, Pb, Pr, Rb, Sm, Sr, Tb, Tl, U, Yb, and Zn for both female and male taken together were: Ba 2.5?±?0.2, Bi 0.015?±?0.002, Cd 0.044?±?0.005, Ce 0.029?±?0.002, Cu 1.05?±?0.06, Dy 0.0020?±?0.0003, Er 0.0011?±?0.0002, Gd 0.0015?±?0.0001, La 0.020?±?0.002, Li 0.040?±?0.002, Mn 0.354?±?0.004, Mo 0.052?±?0.006, Nd 0.011?±?0.001, Pb 2.24?±?0.14, Pr 0.0032?±?0.0004, Rb 1.51?±?0.06, Sm 0.0014?±?0.0001, Sr 291?±?20, Tb 0.00041?±?0.00005, Tl 0.00050?±?0.00003, U 0.0013?±?0.0001, Yb 0.00072?±?0.00007, and Zn 92.8?±?1.5, respectively. The upper limit of mean contents of Ag, Al, B, Be, Br, Cr, Cs, Hg, Ho, Lu, Ni, Sb, Te, Th, Ti, Tm, and Y were: Ag?≤?0.011, Al?≤?7.2, B?≤?0.65, Be?≤?0.0032, Br?≤?3.9, Cr?≤?0.25, Cs?≤?0.0077, Hg?≤?0.018, Ho?≤?0.00053, Lu?≤?0.00024, Ni?≤?1.05, Sb?≤?0.0096, Te?≤?0.0057, Th?≤?0.0030, Ti?≤?2.8, Tm?≤?0.00006, and Y?≤?0.0047, respectively. In all bone samples, the contents of As, Au, Co, Eu, Ga, Hf, Ir, Nb, Pd, Pt, Re, Rh, Sc, Se, Sn, Ta, V, W, and Zr were under detection limits. The Ce, Dy, Er, Gd, La, Nd, Pr, Sm, Tb, and Yb contents increase with age. Higher Sr mass fraction is typical of female rib as compared to those in male bone.     

Presence and possible origin of positive Eu anomaly in shoot samples of Juncus effusus L

BackgroundThe rare earth elements (REE) are non-essential elements for plants. They stimulate plant growth at low doses, but at high levels are phytotoxic. There are differences in concentrations of REE in various organs of the same plant species, but the normalized REE patterns can be very similar in samples of the same species collected in different locations. Here we compare normalized REE curves in above-ground samples of Juncus effusus L. (common rush, soft rush) collected from sites with different land-use types.MethodsThe concentrations of rare earth elements were measured in 55 shoot samples of J. effusus L. The samples were collected from 15 sampling sites located in the Holy Cross Mts., south-central Poland and analyzed with the use of inductively coupled plasma mass spectrometry (ICP-MS). The results were normalized to the North American Shale Composite and anomalies of different elements were calculated.ResultsTotal REE concentrations varied from 0.028 mg/kg to 2.7 mg/kg. The samples were enriched in the light REE (from La to Eu) with the highest concentrations of La and Ce. The North American Shale Composite (NASC)-normalized REE curves were roughly similar in all samples except for two samples collected in the acid mine drainageaffected areas.ConclusionAll samples showed positive europium anomalies in NASC-normalized REE concentration patterns. The most probable explanation of this is that the uptake and translocation of Eu in J. effusus (and possibly in other wetland plants) is caused by a short-term decrease of the redox potential in a rhizosphere favoring reduction of Eu³⁺ to Eu²⁺ and thus enhancing Eu mobility in the soil-plant environment.