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.     

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.     

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。     

Role of ligands in accumulation and fractionation of rare earth elements in plants

Few studies have been carried out on the effects of ligands on rare earth element (REE) bioaccumulation processes. In this study, the effects of phosphate (Pi, an inorganic ligand) and citrate (an organic ligand) on accumulation and fractionation of REEs in wheat were investigated using aqueous culture with extraneous mixed REEs (MRE). The results show that initial Pi solution culture at various levels followed by exposure to a fixed-MRE solution did not significantly change the total concentrations of REEs (SigmaREE) in roots, whereas the SigmaREE in leaves dramatically decreased with increasing levels of Pi applied. Simultaneous culture of wheat with mixture of MRE and citrate solutions caused obvious decreases of the SigmaREE in both roots and leaves. Compared with MRE, significant fractionations of REEs were found in wheat organs when no ligand was applied. Notable middle REE (MREE) enrichment and M-type tetrad effect were observed in the roots, and heavy REE (HREE) enrichment and W-type tetrad effect existed in the leaves. Pi treatments did not significantly affect the fractionations of REEs in the roots, but enrichment of HREEs in the leaves slightly increased at the highest level of Pi applied. Fractionations of REEs in both roots and leaves decreased with increasing levels of citrate applied; at higher levels of citrate (> or =150 microM), no above fractionation features were observed in wheat, but light REE (LREE) enrichment existed in the roots and leaves. The results indicate that ligands might play important roles in accumulation and fractionation of REEs during bioaccumulation processes.     

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.     

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.     

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.     

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.     

镧在草-菇-土系统中的循环与生物富集效应

利用稀土镧肥种植牧草南非马唐,采用含镧牧草栽培杏鲍菇和以菇渣作为有机肥种植牧草进行连续性试验,研究镧在草-菇-土系统中的分配与生物富集情况。结果表明：施镧处理的南非马唐和杏鲍菇各器官的镧元素含量均高于不施镧处理,其中镧在牧草南非马唐中的分布为根>叶>茎,镧在杏鲍菇中的分布为菌盖>菌柄;外源镧进入土壤以后,南非马唐不同器官的镧元素生物富集系数均随着镧施入量的增加而增大,其中以根的镧生物富集系数最大,介于0.443—0.580之间。除高剂量（M4）处理外,叶和茎的镧生物富集系数不同处理间无显著差异,但根出现明显变化;含镧牧草栽培杏鲍菇和菇渣种植南非马唐后,不同器官的镧含量无显著增加,说明镧残留在草-菇-土系统中迁移转化效率降低。     

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.     

Rare earth element, Al, and Sc partition between soil and Caatinger wood grown in north-east Brazil by instrumental neutron activation analysis

Seven representative wood species constituting Caatinger forest in north-east Brazil were chosen to analyze La, Ce, Sm, Eu, Yb, Sc, and Al by instrumental neutron activation analysis (INAA). Soil profiles were prepared where the trees were downed. Then soil and root samples from each horizontal soil layer, as well as the upper part of the wood, ground-level bark, and the bark at 1 m above were collected. In woods, the rare earth element (REE) was found to be mainly accumulated in root, which concentration was in the same order as that of soil. In all samples, concentration of La and Ce were found to be about ten times higher than those of the other REEs. The REE accumulation became higher, in both root and soil, in the order of La, Ce, and Sm. The partition rate of La and Eu was higher from soil to root, whereas Ce tended to be concentrated from root to bark. In the case of bark, there was no tendency of specific REE accumulating from ground level to the upper part. The correlation of La concentration to the other REE was higher in root than that of corresponding soil. Roots also showed higher correlation of REE to Al and Sc than that of soil or bark.     

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.     

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.     

茶园土壤类型对铁观音茶叶稀土元素分布和组成的影响

为探明铁观音茶的质量安全状况,追溯隐患来源,对福建安溪县不同土壤茶园的铁观音茶叶进行稀土元素的分布、组成、迁移和富集能力进行研究。结果表明,安溪县红壤、黄红壤、黄壤茶园稀土组成均以镧、铈、钕、钇为主,但具体组成特征各异。3种类型土壤茶园铁观音茶叶片、叶柄稀土元素组成均以钇、镧、铈、钕4种元素为主,且含量均以第3叶第2叶第1叶叶柄。同种土壤类型茶园铁观音茶树不同部位叶片的稀土元素组成特征类似,但叶与叶柄对稀土元素的吸收能力不同。土壤类型对茶叶稀土元素的累积有显著影响,黄红壤茶园的茶叶稀土元素含量要显著低于红壤、黄壤茶园的(P0.05)。土壤与茶叶中稀土元素组成的相关系数为0.886～0.985,P 0.001,表明二者稀土元素组成密切相关。因此,铁观音茶叶中稀土元素累积、分布与茶园土壤类型有显著相关性。     

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.     

Distribution of Rare Earth Elements and Structure Characterization of Chlorophyll-Lanthanum in a Natural Plant Fern Dicranopteris dichotoma

The distribution pattern of La, Ce, Nd, Th, Dy was in the order as leaf > root > stem, that of Pr, Sm, Eu, Cd, Ho, Y was as root > leaf > stem in fern Dicranopteris dichotoma Underw. Light and moderately heavy rare earth elements were easily selectively absorbed and then accumulated by the fern D. dichotoma. Many mainly light rare earth elements are bound to chlorophyll in D. dichotoma. Among the 15 detectable rare earth elements binding to chlorophyll, lanthanum content (50.08 % ) was the highest, and cerium content (19.40%) is the second of all. FXAFS (Fluorescence X-ray absorption fine structure) spectral analysis revealed that lanthanum coordinated 2 porphyrin rings and La-chlorophyll-a may have bilayer structure in D.d/chotoma.     

干旱区湿地芦苇各器官生态化学计量对土壤因子的响应

了解植物养分浓度及其化学计量对土壤因子的响应,对预测脆弱而敏感生态系统对环境变化的响应至关重要.以敦煌阳关湿地优势种芦苇(Phragmites australis)为对象,通过野外调查与实验分析,研究芦苇不同器官生态化学计量特征及其影响因素.结果 表明:芦苇各器官C、P含量为叶＞根＞茎,N含量及N∶P为叶＞茎＞根,C∶...     

Investigation on liver function among population in high background of rare earth area in South China

The health effects of long-term ingestion of rare earth elements (REEs) on the villagers living in high-REE-background areas in South Jangxi Province, China were studied. Major health complaints from the REE area population included indigestion, diarrhea, abdominal distension, anorexia, weakness, and fatigue, especially after high-fat or high-protein intake. Liver function tests were conducted for adult villagers. Among them, 45 live in a heavy rare earth (HREE) area, 62 in a light rare earth (LREE) area, and 49 in the control area. Test results showed that serum total protein and globulin from both HREE and LREE areas, as well as albumin from the LREE area, were significantly lower (p<0.05–0.01) compared to the results from the control area, whereas albumin from the HREE area showed no significant variance (p>0.05). The chi-square test showed that Serum-glutamic pyruvic transaminase (SGPT) in both areas were not significant (p>0.05), whereas the IgM in the HREE area was significantly elevated. It is our conclusion that long-term ingestion of REE affected activities of some digestive enzymes, causing malabsorption and indigestion, and might further lead to a low-protein effect for the villagers in the LREE area. However, the damage to the liver was rather mild. The elevation of IgM was probably the result of stimulation induced by the formation of a large amount of granules as a result of direct binding of REEs to globulin or albumin (combination of REEs with globulin or albumin).     

土壤镉胁迫对田七体内镉分布及富集特性影响

田七(Panax notoginseng)是我国的一种传统珍贵的草本药用植物,其重金属污染问题已经引起广泛关注。为了分析田七不同部位对镉毒害的响应,明确不同浓度镉污染对田七体内镉分布的基本特征以及不同部位的富集特性,以揭示镉胁迫对田七不同部位的影响机制及富集转移特性。该研究在"田七之乡"广西靖西市田七园以3年生田七为材料,土培条件下以不施镉处理为空白对照,设置6个镉浓度(5、10、20、30、40、50 mg·kg~(-1))梯度,研究了在不同浓度镉胁迫下田七不同部位镉积累特征以及转移特性。结果表明:在不同器官(叶、茎、剪口、须根、主根)随着镉浓度的增加各器官镉的积累量均显著(P0.05)增加,呈现出正相关关系。田七不同部位镉含量的分布特征表现:空白对照下田七各器官镉累积分布表现为须根剪口主根茎叶;当镉浓度为5、10、20、30、40、50 mg·kg~(-1)时,田七镉分布表现为剪口主根须根茎叶;地下部的镉含量显著高于地上部的镉含量;随着镉浓度的增加,无论地下部生物富集系数还是地上部生物富集系数均表现为逐渐降低的趋势。