Earth Elements In Soils Research Articles

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

ABSTRACTEffects 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.

Environmental Defects And Economic Impact On Global Market Of Rare Earth Metals

Rare earth elements include the 14 lanthanides as well as lanthanium and often yttrium. Actually, most of them are not very rare and occur widely dispersed in a variety of rocks. Rare earth metals are vital to some of the world's faster growing industries: catalysts, Nd-magnets, ceramics, glass, metallurgy, battery alloys, electronics and phosphors. Worldwide, the main countries for distribution of rare earths deposits include China, USA, Russia, Brasil, India, Australia, Greenland and Malaysia. The mining and processing of rare earth metals usually result in significant environmental defects. Many deposits are associated with high concentrations of radioactive elements such as uranium and thorium, which requires separate treatment and disposal. The accumulation of rare earth elements in soils has occurred due to pollution caused by the exploitation of rare earth resources and the wide use of rare earths as fertilizers in agriculture. This accumulation has a toxic effect on the soil microfauna community. However, there are large differences in market prices due to the degree of purity determined by the specifications in the applications. The main focus of this article is to overview Rare Earth Metals’ overall impact on global economy and their environmental defects on soils during processing techniques and as they are used as fertilizers.

Spatial distribution, sources and risk assessment of potentially toxic trace elements and rare earth elements in soils of the Langtang Himalaya, Nepal

Soils in the fragile Himalayan region could be affected by the transport and deposition of potentially toxic trace metals (PTEs) from urban and industrialized areas of South Asia. The transported pollutants could pose a serious threat to the soil quality in the pristine regions at high elevations having minimal direct human influence. Therefore, it is important to understand the geochemical and physical characteristics of soils in this region and determine the extent of their chemical pollution. In order to achieve these objectives, soil samples were collected from different elevation transects of the Langtang Himalaya in Nepal. The samples were analyzed for PTEs and rare earth elements for the purpose of identifying their possible sources and to evaluate their environmental risk in the region. The PTEs and REEs concentrations were measured by ICP-MS (X-7; Thermo-elemental, USA) and total organic carbon (TOC) by TOC analyzer. The results of this study were comparable to those of the world average background soil as well as the Tibetan plateau surface soil. TOC revealed a decreasing trend with increasing elevation. Correlation analysis and principle component analysis (PCA) indicated that most of the elements were highly associated with major crustal elements, suggesting that their primary sources were of natural origin. Furthermore, the geo-accumulation index (I geo), enrichment factor (EF) and pollution index (PI) analyses indicated that the Himalayan soils represent minimal pollution and the data from this study may be used as background values for the Himalayan region in the future studies. REEs in the soil samples were found to be consistent with an order of average abundance of the Earth’s crust. In addition, the chondrite-normalized REE distribution of the light REE suggested enrichment of LREE and Eu depletion. Moreover, this study emphasized that soils of the Himalayan region could, in future, be under threat of elemental pollution from long-range transport via atmospheric circulation and deposition.

Optimization of capillary electrophoresis method for the determination of rare earth elements in soils and natural waters

Currently, rare earth elements (REEs) in the environmental objects are determined by neutron activation and ICP-MS methods. Capillary electrophoresis (CE) is not used for these purposes because the poor detection limits (LOD). This weakness can be overcome by multiple concentrating of the samples through the high effective sample stacking process of triply charged ions Ln3+. LOD for REEs were received ranged from 0.2 to 1.2μg/l. The following composition of background electrolyte for CE determination of lanthanides was proposed: 12mM benzimidazole, 8mM dipropylglycolic acid, 10mM glycolic acid, pH=3.0. Using this background electrolyte the completely separation of REEs (Y+La+Ln without Pm) is possible for 12min. The sample preparation procedure for CE determination of lanthanides in soil and natural water was improved and the analysis of these analytes was performed. The validity of experimental results was confirmed by AES and ICP-AES methods.

Distribution of rare earth elements in soil and grape berries of Vitis vinifera cv. "Glera".

The renowned Vitis vinifera L. cultivar "Glera" (Magnoliopsida Vitaceae) has been grown for hundreds of years in the Italian regions of Veneto and Friuli to produce the sparkling Prosecco wine, with controlled designation of origin (DOC). We evaluated the relationship among the concentrations of rare earth elements (REE) in soil and in "Glera" grape berries in vineyards belonging to five different localities in the Veneto alluvial plain, all included in the DOC area of Prosecco. The concentration of REE in samples of soil and juice or solid residues of grape berries was determined by inductively coupled plasma mass spectrometry (ICP-MS), and the index of bioaccumulation was calculated to define the specific assimilation of these elements from soil to grape berries. The concentration of REE in soil samples allowed an identification of each locality examined, and REE were mostly detected in solid grape berry residues in comparison to juice. These data may be useful to associate REE distribution in soil and grape berries to a specific geographical origin, in order to prevent fraudulent use of wine denomination labels.

Anomalous abundance and redistribution patterns of rare earth elements in soils of a mining area in Inner Mongolia, China.

The Bayan Obo Mine, the largest rare earth element (REE) deposit ever found in the world, has been mined for nearly 60years for iron and rare earth elements. To assess the influences of mining activities on geochemical behavior of REEs in soils, 27 surface soil samples and three soil profile samples were collected from different directions in the vicinity of the mine area. The total concentrations of REEs in surface soils varied from 149.75 to 18,891.81mgkg(-1) with an average value of 1906.12mgkg(-1), which was apparently higher than the average values in China (181mgkg(-1)). The order of the average concentrations of individual REEs in surface soils was similar to that in Bayan Obo ores, which confirmed that the concentration and distribution of REEs in the soils was influenced by the mining activities. The concentrations of single REE in the soil profiles showed a similar trend with depth with an increase at 0-25cm section, then decreased and remained relatively stable in the deep part. The normalized curves inclined to the right side, showing the conspicuous fractionation between the light and heavy REEs, which supported by the North American Shale Composite (NASC) and Post-Archean Australian Shale (PAAS) normalized concentration ratios calculated for selected elements (La N /Yb N , La N /Sm N , Gd N /Yb N ). Slight positive Ce anomaly and negative Eu anomaly were also observed.

A sequential extraction procedure to evaluate the mobilization behavior of rare earth elements in soils and tailings materials

A novel sequential extraction method for evaluation of the mobilization behavior of rare earth elements in soils and mine tailings materials is presented. The sequence consists of the following four steps: 0.05 mol L−1 calcium nitrate (easily soluble and ion exchange fraction), 0.1 mol L−1 citric acid (fraction mobilized by complexation and carbonate bound), 0.05 mol L−1 hydroxylamine hydrochloride (pH = 2) (reducible fraction), 1.4 mol L−1 nitric acid (acid soluble fraction). The procedure was optimized with a certified soil material and a mine tailings material and was applied to eight samples of a soil profile. The different results obtained by using either the developed method or the widespread used BCR-Method for comparison are discussed. There were clear advantages using the newly created sequential extraction procedure in getting more detailed information about the bioavailable fraction and a fraction addressing REE phosphates.

Geochemical fractions of rare earth elements in soil around a mine tailing in Baotou, China.

Rare earth mine tailing dumps are environmental hazards because tailing easily leaches and erodes by water and wind. To assess the influence of mine tailing on the geochemical behavior of rare earth elements (REEs) in soil, sixty-seven surface soil samples and three soil profile samples were collected from different locations near China’s largest rare earth mine tailing. The total concentration of REEs in surface soils ranged from 156 to 5.65 × 104 mg·kg−1 with an average value of 4.67 × 103 mg·kg−1, which was significantly higher than the average value in China (181 mg·kg−1). We found obvious fractionation of both light and heavy REEs, which was supported by the North American Shale Composite (NASC) and the Post-Archean Average Australian Shale (PAAS) normalized concentration ratios calculated for selected elements (LaN/YbN, LaN/SmN and GdN/YbN). A slightly positive Ce anomaly and a negative Eu anomaly were also found. For all 14 REEs in soils, enrichment was intensified by the mine tailing sources and influenced by the prevailing wind.

Distribution and fractionation of rare earth elements in soil–water system and human blood and hair from a mining area in southwest Fujian Province, China

Accumulations of rare earth elements (REEs) in human body through multiple pathways including food ingestion, air inhalation and dermal absorption have received considerable attention due to their chronic toxicity to human health. The distribution and fractionation of 14 REEs were conducted in soil, well water, human blood and hair in the vicinity of a large-scale mining site in southwest Fujian Province, China. The LREEs/HREEs ratios were 9.17 for soil, 2.18 for water, 36.93 for human blood and 7.24 for human hair, respectively. The distribution patterns of REEs in soil, human blood and hair samples were characterized by LREEs enrichment and HREEs depletion, but LREEs depletion and HREEs enrichment in water sample. LaN/YbN values of these samples ranged from 0.41 to 1.83, LaN/SmN values from 0.43 to 4.92, and GdN/YbN values from 0.81 to 4.71. Soil and human blood showed enrichments of Ce, Gd and Er, but water showed a depletion of Ce. In addition, the normalized patterns showed a weak negative anomaly of Eu in soil and a weak negative anomaly of Nd in human blood and hair. Consequently, enrichment and depletion of REEs differ significantly among soil, water and human blood and hair, thus the REEs after entering into human body can undergo fractionation effects.

Quantification of rare earth elements using cloud point extraction with diglycolamide and ICP-MS for environmental analysis

This article describes the development of a procedure for the bulk separation and determination of rare earth elements in soils by combining alkaline fusion, cloud point extraction, and inorganic mass spectrometry.

A human health risk assessment of rare earth elements in soil and vegetables from a mining area in Fujian Province, Southeast China

Contaminated food through dietary intake has become the main potential risk impacts on human health. This study investigated concentrations of rare earth elements (REEs) in soil, vegetables, human hair and blood, and assessed human health risk through vegetables consumption in the vicinity of a large-scale mining area located in Hetian Town of Changting County, Fujian Province, Southeast China. The results of the study included the following mean concentrations for total and bio-available REEs of 242.92±68.98 (135.85–327.56)μgg−1 and 118.59±38.49 (57.89–158.96)μgg−1 dry weight (dw) in agricultural soil, respectively, and total REEs of 3.58±5.28 (0.07–64.42)μgg−1 dw in vegetable samples. Concentrations of total REEs in blood and hair collected from the local residents ranged from 424.76 to 1274.80μgL−1 with an average of 689.74±254.25μgL−1 and from 0.06 to 1.59μgg−1 with an average of 0.48±0.59μgg−1 of the study, respectively. In addition, a significant correlation was observed between REEs in blood and corresponding soil samples (R2=0.6556, p<0.05), however there was no correlation between REEs in hair and corresponding soils (p>0.05). Mean concentrations of REEs of 2.85 (0.59–10.24)μgL−1 in well water from the local households was 53-fold than that in the drinking water of Fuzhou city (0.054μgL−1). The health risk assessment indicated that vegetable consumption would not result in exceeding the safe values of estimate daily intake (EDI) REEs (100−110μgkg−1d−1) for adults and children, but attention should be paid to monitoring human beings health in such rare earth mining areas due to long-term exposure to high dose REEs from food consumptions.

Antioxidant response of soybean seedlings to joint stress of lanthanum and acid rain

Excess of rare earth elements in soil can be a serious environmental stress on plants, in particular when acid rain coexists. To understand how such a stress affects plants, we studied antioxidant response of soybean leaves and roots exposed to lanthanum (0.06, 0.18, and 0.85 mmol L(-1)) under acid rain conditions (pH 4.5 and 3.0). We found that low concentration of La3+ (0.06 mmol L(-1)) did not affect the activity of antioxidant enzymes (catalase and peroxidase) whereas high concentration of La3+ (≥0.18 mmol L(-1)) did. Compared to treatment with acid rain (pH 4.5 and pH 3.0) or La3+ alone, joint stress of La3+ and acid rain affected more severely the activity of catalase and peroxidase, and induced more H2O2 accumulation and lipid peroxidation. When treated with high level of La3+ (0.85 mmol L(-1)) alone or with acid rain (pH 4.5 and 3.0), roots were more affected than leaves regarding the inhibition of antioxidant enzymes, physiological function, and growth. The severity of oxidative damage and inhibition of growth caused by the joint stress associated positively with La3+ concentration and soil acidity. These results will help us understand plant response to joint stress, recognize the adverse environmental impact of rare earth elements in acidic soil, and develop measures to eliminate damage caused by such joint stress.

稀土元素对农田生态系统的影响研究进展

Rare earth ore mining and smelting,application of rare earth elements in farm lead to accumulation of rare earth elements in soil,and affect the structure and function stability of farmland ecosystem.This article reviews the main source,distribution and output of rare earth elements in farmland,the determination method of rare earth elements in soils and plants,and the effect of rare earth elements on crops,microorganisms,animal and human health in farmland ecosystem.Rare earth element toxicity evaluation and rare earth contaminated soil remediation of farmland ecosystem are discussed in the paper.Finally some problems will be pay attention to studying of rare earth elements on farmland ecosystem in the future.

Solos desenvolvidos sobre diferentes rochas vulcânicas da ilha de Fernando de Noronha: padrão de elementos terras raras e composição isotópica do chumbo

This study examines the influence of pedogenesis on the distribution of rare earth elements in soils derived from different rock types and formed under tropical humid climate, as well as the possible contribution of airborne Pb to these soils. We studied 5 soil profiles developed from different volcanic rocks cropping out in the Fernando de Noronha island. Results show that in the course of weathering, the soils were enriched in REE. The REE patterns of the soils are similar to those of the parent material, except for a slight HREE enrichment. Lead-isotope data indicate the presence of a nonradiogenic anthropogenic component in the upper horizons of the soil profiles.

Rare Earth Elements in Soils of Jharia Coal Field

There are many sources trough which the soil get enriched and contaminated with REEs. The determination of REEs in environmental samples has been limited because of the lack of sensitive analytical techniques. Soil samples were collected from four sites including open cast coal mine, natural coal burning, coal washery and control in the coal field located in Dhanbad, India. Total concentrations of rare earth elements (REEs) were determined using the inductively coupled plasma atomic absorption spectrometry in order to assess enrichment status in the coal field. Results showed that the mean concentrations of La, Pr, Eu, Tb, Ho, and Tm in open cast mine and natural coal burning sites were elevated compared to the reference concentrations, while Ce, Nd, Sm, and Gd were elevated in coal washery site. When compared to reference soil, heavy REEs (HREEs) were enriched in open cast mines and natural coal burning affected soils, however, the HREEs were depleted in the coal washery sites. But, the Chondrite-normalization diagram showed significant enrichment for light REEs (LREEs) in all the soils. High concentration of Pr, Eu, Tb, Ho, Tm, and Lu in coal mining and coal burning sites may pose human health risks. Factor analysis showed that distribution and relative abundance of REEs of the coal washery site is comparable with the control. Eventually washing or cleaning of coal could significantly decrease the emission of REEs from coal into the environment.

Environmental biogeochemical characteristics of rare earth elements in soil and soil-grown plants of the Hetai goldfield, Guangdong Province, China

Very few studies deal with the biogeochemical behaviors of rare earth elements (REEs) in goldfields. This paper presents the geochemical and biogeochemical characteristics of REEs within the soil–plant system in the Hetai goldfield, Guangdong, China. The samples from the goldfield region show anomalies in distribution patterns and behavioral characteristics of REES as compared with those from the background areas. The REEs in rocks, soils, and plants prove to be much higher than those in the surrounding regions. The distribution patterns of REEs are characterized by LREE-enrichment and HREE-depletion, with the REE concentrations in Layer A being the highest. Differentiations between LREEs and HREEs may lead to some extent of negative Eu anomaly in the soils. Research results demonstrate that the REEs in a soil profile can be transferred and accumulated during the mineral formation and supergenic geochemical processes, and the anomalies are obviously related to the geological settings for the REE-bearing ore-forming processes and to the geochemical characteristics of the habitats for the REE-bearing plants. For Dicranopteris dichotoma, the total amount of REEs in the tissues shows an order of leaf > root > stem, while for Pinus massoniana the order becomes root > leaf > stem. The distribution patterns of REEs in Pinus massoniana leaves are similar to those in soils where the plants grow up in the mineralization area. However, in the background areas the REE distribution patterns for Pinus massoniana stems are similar to those for soils where the plants grow up. Parameters such as biological absorption coefficients and biological transfer coefficients show the differences in REE absorption features among plants and indicate that REEs can be transferred among plant organs. The two coefficients can reveal the different survival mechanisms for the two plant species, which are subject to long-term REE-affected stress conditions in the gold mineralization zone.

Water–granite interaction: Clues from strontium, neodymium and rare earth elements in soil and waters

Strontium-, Nd-, and rare-earth-element-isotope data are presented from rock, weathered rock (arene) and saprolite, sediment and soil, shallow and deep groundwater (e.g. mineral-water springs), and surface waters in the Margeride massif, located in the French Massif Central. Granitoid rock and gneiss are the main lithologies encountered in the Margeride, which corresponds to a large and 5-km-deep laccolith. Compared to bedrock, the Sr isotopes in arene, regolith, sediment and soil strongly diverge with a linear increase in the 87Sr/ 86Sr and Rb/Sr ratios. Neodymium isotopes fluctuate least between bedrock and the weathering products. In order to characterise the theoretical Sr isotopic signature IRf(Sr) of water interacting with granite, a dissolution model was applied, based on the hypothesis that most of the Sr comes from the dissolution of plagioclase, K-feldspar and biotite. Similar to the Sr model, an approach was developed for modelling the theoretical Nd isotopic signature IRf(Nd) of water interacting with a granite, assuming that most Nd originates from dissolution of the same minerals as those that yield Sr, plus apatite. The IRf(Sr) ratio of water after equilibration with the Sr derived from minerals was calculated for the Margeride granite and compared to values measured in surface- and groundwaters. Comparison of the results shows agreement between the calculated IRf(Sr) and the observed 87Sr/ 86Sr ratios. When calculating the IRf(Nd) ratio of water after equilibration with the Nd derived from minerals of the Margeride granite, the results indicated good agreement with surface-water values, whereas mineralised waters analysed within the Margeride hydrosystem could not be directly linked to weathering of the granite alone. Because the recharge area of deep groundwater is located on the Margeride massif, very deep circulation involving interaction with other rocks (e.g. shales) at depths of >5 km must be considered.

Environmental biogeochemical behaviors of rare earth elements in soil–plant systems

With the continual increase in the utilization of rare earth elements (REEs) for industrial and agricultural purposes in China, the research into the environmental biogeochemical behavior of REEs has become a pressing issue. The REEs' content in soil and various parts of wheat under different conditions in soil-plant systems were measured by INAA and ICP-MS. The results showed four aspects. (1) The mean value of total REEs in soil of China was 176.8 mg kg(-1). The mean ratio of SigmaLREE/SigmaHREE in soils was 8.0 and cerium accounts for 42% of the total REEs. The content of REEs in wheat seed ranged between 10(-11) and 10(-8) g g(-1), 3-4 orders of magnitude lower than that in soil. (2) The REEs contents in ryegrass, especially in roots, were significantly related to that of soil. The bioavailability of REEs in soil mainly depended on the exchangeable fraction of REEs, which was strongly affected by the physico-chemical properties of the soil. (3) Long-term foliage-dressing with Changle microfertilizer of REEs did not affect the contents and distribution patterns of REEs in soil. At the maturing stage of spring wheat, the REEs content was in the order of root > leaf >stem and crust. Compared with the control, foliage-dressing has a higher accumulation of REEs in root and leaf. However, no significant difference was found in stem and crust between the two treatments. (4) There was no significant accumulation with the soil-dressing method. When comparing controls in both foliage- and soil-dressing methods, no distinct residue of REEs in grains was found.

Rare earth elements in soil and plant systems - A review

The rare earth elements (REEs) form a chemically uniform group and include yttrium (Y), lanthanum (La) and the lanthanides cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), and lutetium (Lu). Their average abundance in the Earth’s crust range from 66µg g−1 in Ce to 0.5µg g−1 in Tm and «0.1µg g−1 in Pm. Recent great improvements in more routine analytical technique, the use of REEs as fertilisers, at least in East Asian agriculture, and the importance of these elements as indicators in both pedological and physiological processes and reactions have contributed to an increased interest in these previously less considered elements in environmental sciences. This review of recent and current literature deals with REEs in primary and secondary soil minerals, concentrations in surface soils, factors influencing adsorption, solubility and transport in soils, including weathering and transformations of REE minerals, and vertical distribution in soil profiles. Reviewed and discussed are also concentrations, distribution and localisation of REEs in plants and plant organs, soil-plant relationships and interactions, effects on plant growth and crop production and their importance in plant physiology and biochemistry. The REEs are found, usually several elements together, as phosphates, carbonates and silicate minerals finely dispersed especially in magmatic and metamorphic rocks. REE concentrations in surface soils of humid climates, such as the A(E)-horizons of Podzols and Laterites, are usually lower than in the parent material, due to higher weathering and leaching rates than of the average soil constituents. Some fractionation may occur due to the formation of more element-specific secondary minerals. Transfer from soil to plant is usually low, but extreme accumulators are found, e.g., among several species of ferns. Roots have generally higher concentrations than shoots. Possible uptakemechanisms of REEs are discussed. Uptake is positively, though often weakly, correlated with soil acidity and easily soluble concentrations of the elements, but rarely well related to their total concentrations in the soil. Under certain conditions, low concentrations of at least some REEs seem to favour plant growth and productivity, but the physiological mechanisms are still not well understood. Some considerations concerning the boundary between essential and non-essential micro nutrients are discussed.

Application of microwave extraction for the evaluation of bioavailability of rare earth elements in soils

A single microwave extraction procedure was conducted to investigate the bioavailability of rare earth elements (REEs) by using different extractants of 0.05 M EDTA, 0.10 M CH 3COOH, 0.10 M HCl, and 0.05 M CaCl 2. The experimental conditions of heating time and microwave power were optimized. A microwave power of 60% and extraction time of 30 min were adopted. Compared to the conventional single extraction schemes reported in the literature, the recommended technique shortened the operational time, simplified the experimental task, improved the precision, and obtained consistent results with those obtained by using the conventional methods. In addition, the suggested microwave extraction method has been successfully used to evaluate the bioavailability of REEs in soils. Soil samples collected from 15 sites in China were extracted by four different extractants with microwave ancillary. Extractable REEs from soils were well correlated with REEs contents in shoots of wheat ( Troticum aestivum L.) under the greenhouse conditions. The correlation coefficients were 0.6514–0.8996, 0.4522–0.7783, 0.6506–0.8671, 0.4869–0.7014 between the extractable REEs in soils and their concentrations in wheat shoots for the extractants of CaCl 2, EDTA, CH 3COOH and HCl, respectively.