Distribution of rare earth elements in an alluvial aquifer affected by acid mine drainage: the Guadiamar aquifer (SW Spain)

This work analyses the spatial distribution, the origin, and the shale-normalised fractionation patterns of the rare earth elements (REE) in the alluvial aquifer of the Guadiamar River (south-western Spain). This river received notoriety in April 1998 for a spill that spread a great amount of slurry (mainly pyrites) and acid waters in a narrow strip along the river course. Groundwaters and surface waters were sampled to analyse, among other elements, the REEs. Their spatial distribution shows a peak close to the mining region, in an area with low values of pH and high concentrations of sulphates and other metals such as Zn, Cu, Co, Ni, Pb, and Cd. The patterns of shale-normalised fractionation at the most-contaminated points show an enrichment in the middle rare earth elements (MREE) with respect to the light (LREE) and heavy (HREE) ones, typical of acid waters. The Ce-anomaly becomes more negative as pH increases, due to the preferential fractionation of Ce in oxyhydroxides of Fe.     

Scandium,yttrium, and lanthanide contents in soil from Serbia and their accumulation in the mushroom Macrolepiota procera (Scop.) Singer

The mobility (fractionation) of rare earth elements (REEs) and their possible impacts on ecosystems are still relatively unknown. Soil samples were collected from two sites in central Serbia, an unpolluted mountain region (site 1) and a forest near a city (site 2). In order to investigate REE fractions (acid-soluble/exchangeable, reducible, oxidizable, and residual) in soils, BCR sequential extraction was performed. Additionally, the content of REEs was also determined in stipes and caps of the mushroom Macrolepiota procera, growing in the observed sites. Sc, Y, and lanthanide contents were determined by inductively coupled plasma mass spectrometry (ICP-MS), and results were subjected to multivariate data analysis. Application of pattern recognition technique revealed the existence of two distinguished clusters belonging to different geographical sites and determined by greater levels of Sc, Y, and lanthanides in Go? soil compared to Trstenik soil. Additionally, PCA analysis showed that REEs in soil were concentrated in two groups: the first consisted of elements belonging to light REEs and the second contained heavy REEs. These results suggest that the distribution of REEs in soils could indicate the geographical origin and type of soil. The bioconcentration factors and translocation factors for each REE were also calculated. This study provides baseline data on the rare earth element levels in the wild edible mushroom M. procera, growing in Serbia. In terms of bioconcentration and bioexclusion concept, Sc, Y, and REEs were bioexcluded in M. procera for both studied sites.

     

Rare earth elements in naturally grown fern Dicranopteris linearis in relation to their variation in soils in south-Jiangxi region (southern China)

Ferns (Dicranopteris linearis) and soils, sampled from four rare earth mining areas and one non-mining area locating in South-Jiangxi region, were chosen for analysis of 15 rare earth elements (REEs) by inductively coupled plasma-mass spectrometry (ICP-MS). The fern samples were divided into 4 parts: root, stem, petiole, and lamina. The soils of the same sites were also sampled, and 4 soil layers were observed at the profile: A (0-20 cm depth), B (20-150 cm depth), C (150-400 cm depth), and D (rock). The distribution patterns and transportation characteristics of REEs of different soil layers and of different parts of D. linearis were studied. The results showed that in the soil layers, the sigma REE (the sum of the concentrations of 15 REEs) of A layer, as well as B layer were lower than that of C layer, but Ce was relatively concentrated in A layer. The sigma REE of different parts of D. linearis were lamina, root > stem > petiole. The REE distribution patterns of D. linearis root were similar to the total REE distribution patterns of the A layer of their host soils, especially to the soluble REE distribution patterns of the A layer of their host soils. The REEs were fractionated in their transportation in D. linearis. The abundances of heavy rare earth elements (HREEs, Gd to Lu and Y) in the stem, petiole, lamina are lower than those in the root.     

Rare earth elements (REEs) in naturally grown plants in relation to their variation in soils

The concentrations of rare earth elements (REEs) in plant leaves, soils in which they grow, and mother rocks were determined using Inductively Coupled Plasma-Atomic Emission Spectrometry (ICP-AES). Concentration levels of REEs in most plants were low. However, one of the herb species, pokeweed (Phytolacca americana) and two species of ferns (Dicranopteris dichotoma and Athyrium yokoscence) revealed relatively high concentrations of REEs. In the case of pokeweed, the REE distribution pattern reflected well that of its soils. On the whole, high concentrations of REEs in plants were related to REE concentrations in the soils in which they grow. These observations are promising to evaluate the possible contamination of environment by REEs resulting from their increased usage in modern industry.     

Speciation of rare earth elements in soil and accumulation by wheat with rare earth fertilizer application

A greenhouse study was conducted to investigate the accumulation of rare earth elements (REEs), La, Ce, Pr and Nd, in winter wheat (Triticum aestivum L.), and the speciation of these elements in soil following the application of REE-based fertilizers. Improved crop yield was confirmed by the experiment. The accumulation behavior of La, Ce, Pr and Nd in wheat varied depending on the concentration of REE fertilizer application, i.e. increased with increasing REE concentration at low fertilization application, constant over the medium REE range, and decreased with increasing REE concentration at high fertilizer application. Significant negative correlation was obtained between REE contents in roots and soil pH (r = -0.5787 to -0.8442 for La). REEs in both the fertilized and unfertilized soils were fractionated by a three-stage sequential extraction procedure into three chemically distinct fractions: water soluble, exchangeable and carbonate bound (B1), Fe-Mn oxide bound (B2), and organic and sulfide bound (B3). REEs in fertilized soils were found mainly in the B2 and B3 fractions, with only a small amount in the B1 fraction. REEs in B1 and B2 fractions were negatively correlated with soil pH (r = -0.6892 to -0.8927 and -0.7462 to -0.9482). Significant correlation was obtained between REEs in B1 fraction and REE contents in root. The correlation coefficients ranged from 0.6159 to 0.7410 when fertilizer application was lower than 20.0 mg/kg soil. No acceptable relationship was observed between REE contents in shoot and any of the extractable fractions in soils.     

Bioaccumulation of the rare earth elements lanthanum, gadolinium and yttrium in carp (Cyprinus carpio)

Widespread use of the rare earth elements (REEs) in China for agricultural purposes, together with many other applications, has resulted in a remarkable increase of REE concentrations in the environment. The comparative bioaccumulations of representative light, medium and heavy REEs in a variety of tissues of carp (Cyprinus carpio L.) were investigated for an evaluation of their impacts on aquatic animals. The fish were exposed continuously to solutions containing 0.50 mg litre(-1) of each element for 45 days at pH 6.0 and sacrificed at time intervals. Skeleton, muscle, gills and internal organs were analysed for REE contents. A method using cation-exchange resin separation and ICP-AES determination was developed for the quatification of individual REEs. The results show that carp has low ability to take up the REEs under the experimental conditions. The order of REEs under the experimental conditions. The order of maximum bioconcentration factors was mostly internal organs > gills > skeleton > muscle. Neither synergistic nor antagonistic effects of the mixed REE solutions for carp were observed. The relative distributions of different REEs in the investigated tissues exhibited similar patterns. Among the selected tissues studied, the concentration of a heavy REE (Y) was the smallest, while concentrations of a medium (Gd) and a light REE (La) showed only a slight difference.     

Effect of earthworms (Eisenia fetida) on the fractionation and bioavailability of rare earth elements in nine Chinese soils

The effect of earthworm (Eisenia fetida) activity on soil pH, dissolved organic carbon (DOC), fraction distribution pattern and bioavailability of rare earth elements (REEs) Y, La, Ce, Pr and Nd in nine Chinese soils were investigated using pot experiments. A three-step extraction procedure recommended by the European Community (Standards, Measurements and Testing Programme) was used to fractionate REEs in soils into water soluble, exchangeable and carbonate bound (B1), Fe- and Mn-oxides bound (B2) and organic matter and sulfide bound (B3). Inoculated with earthworms, the soil pH, DOC and water-soluble rare earth elements fraction increased. A significant correlation was obtained between the increased DOC and the increased water-soluble REEs. REEs in fraction B1 increased after earthworm inoculation, while those in fraction B3 decreased. No significant differences were observed for REEs in fraction B2. The biomass and the concentrations of REEs in wheat shoots and roots increased after the treatment with earthworms. The results demonstrated that earthworm activity increased the mobility and bioavailability of REEs in soils.     

The fractionation and geochemical characteristics of rare earth elements measured in ambient size-resolved PM in an integrated iron and steelmaking industry zone

Environmental Science and Pollution Research - Improved understanding of the fractionation and geochemical characteristic of rare earth elements (REEs) from steel plant emissions is important due...     

稀土元素分馏作用研究进展

本文综述了环境中稀土元素的分馏过程以及分馏作用对其在岩石、土壤、植物、水环境中分布、迁移规律的影响,探讨了引起稀土分馏的机理,为稀土的环境化学研究提供了详实的材料。     

Effects of organic ligands on fractionation of rare earth elements (REEs) in hydroponic plants: an application to the determination of binding capacities by humic acid for modeling

Previous studies have revealed the fractionation processes of rare earth elements (REEs) in hydroponic plants, with a heavy REE (HREE, the elements from Gd to Lu) enrichment in leaves. In this study, effects on the HREE enrichment in soybean leaves with additions of carboxylic acids (acetate, malate, citrate, NTA, EDTA and DTPA) and two soil humic acids (HAs) were investigated. REE speciation in carboxylic acid and HA solutions was simulated using Visual MINTEQ and Model V, respectively. The results showed that the effects caused by carboxylic acids were strongly dependent on the differences between their binding strengths for light REEs (LREEs, the elements from La to Eu) and those for HREEs. A good correlation existed between these effects and the changes of free REE ions in solutions. This relationship was also observed for the HA treatments, provided that the intrinsic equilibrium constants of REEs for cation–proton exchange with HA (i.e., pK_MHA) in Model V were estimated using a free-energy relationship with the stability constants for REE complexation with lactic acid. It is suggested that this set of pK_MHA values is more suitable for use in Model V for the simulation of REE complexation with HA.     

Uptake and distribution of rare earth elements in rice seeds cultured in fertilizer solution of rare earth elements

The uptake behavior of rare earth elements (REEs) under pot conditions using deionized water and a REE fertilizer solution as the culture media as well as the distribution of REEs in rice proteins were studied. The uptake of REEs in rice seeds increased dramatically after a lag period of approximately three days. Roots can accumulate a much higher content of REEs than germs and the resting seeds. The REE content in each water-soluble (albumin) and salt-soluble (globulin) component of the rice seeds accounted for 5-8% and 4-6% of the total REEs, respectively. However, there are less than 1.5% of the total REEs were found in the alcohol-soluble (prolamin) and acetic acid-soluble (glutelin) components. The high performance liquid chromatography (HPLC) in the gel permeation and the reserved-phase were used to monitor changes in the molecular weight distribution changes of the soluble proteins of rice seeds during germination after having been cultured in the same solution for seven days. No changes occurred in the prolamin, while a slight change occurred in the albumin, globulin and glutelin. Fractionation of the albumin of rice seeds cultured in a REE fertilizer solution on the Sephadex G-100 column indicated that REEs, especially Ce, La, Pr and Nd, were associated mainly with biological compounds of a molecular weight between 10,000 and 12,000.     

Geochemical characteristics of dissolved rare earth elements in acid mine drainage from abandoned high-As coal mining area,southwestern China

Acid mine drainage (AMD) represents a major source of water pollution in the small watershed of Xingren coalfield in southwestern Guizhou Province. A detailed geochemical study was performed to investigate the origin, distribution, and migration of REEs by determining the concentrations of REEs and major solutes in AMD samples, concentrations of REEs in coal, bedrocks, and sediment samples, and modeling REEs aqueous species. The results highlighted that all water samples collected in the mining area are identified as low pH, high concentrations of Fe, Al, SO₄ ^2? and distinctive As and REEs. The spatial distributions of REEs showed a peak in where it is nearby the location of discharging of AMD, and then decrease significantly with distance away from the mining areas. Lots of labile REEs have an origin of coal and bedrocks, whereas the acid produced by the oxidation of pyrite is a prerequisite to cause the dissolution of coal and bedrocks, and then promoting REEs release in AMD. The North American Shale Composite (NASC)-normalized REE patterns of coal and bedrocks are enriched in light REEs (LREEs) and middle REEs (MREEs) relative to heavy REEs (HREEs). Contrary to these solid samples, AMD samples showed slightly enrichment of MREEs compared with LREEs and HREEs. This behavior implied that REEs probably fractionate during acid leaching, dissolution of bedrocks, and subsequent transport, so that the MREEs is primarily enriched in AMD samples. Calculation of REEs inorganic species for AMD demonstrated that sulfate complexes (Ln(SO₄)⁺and Ln(SO₄)₂ ^?) predominate in these species, accounting for most of proportions for the total REEs species. The high concentrations of dissolved SO₄ ^2? and low pH play a decisive role in controlling the presence of REEs in AMD, as these conditions are necessary for formation of stable REEs-sulfate complexes in current study. The migration and transportation of REEs in AMD are more likely constrained by adsorption and co-precipitation of Fe-Al hydroxides/hydroxysulfate. In addition, the MREEs is preferentially captured by poorly crystalline Fe-Al hydroxides/hydroxysulfate, which favors that sediments also preserve NASC-normalized patterns with MREEs enrichment in the stream.

     

Phytoextraction of rare earth elements in herbaceous plant species growing close to roads

The aim of study was to determine the phytoextraction of rare earth elements (REEs) to roots, stems and leaves of five herbaceous plant species (Achillea millefolium L., Artemisia vulgaris L., Papaver rhoeas L., Taraxacum officinale and Tripleurospermum inodorum), growing in four areas located in close proximity to a road with varied traffic intensity. Additionally, the relationship between road traffic intensity, REE concentration in soil and the content of these elements in plant organs was estimated. A. vulgaris and P. rhoeas were able to effectively transport REEs in their leaves, independently of area collection. The highest content of REEs was observed in P. rhoeas leaves and T. inodorum roots. Generally, HREEs were accumulated in P. rhoeas roots and leaves and also in the stems of T. inodorum and T. officinale, whereas LREEs were accumulated in T. inodorum roots and T. officinale stems. It is worth underlining that there was a clear relationship between road traffic intensity and REE, HREE and LREE concentration in soil. No positive correlation was found between the concentration of these elements in soil and their content in plants, with the exception of T. officinale. An effective transport of REEs from the root system to leaves was observed, what points to the possible ability of some of the tested plant species to remove REEs from soils near roads.     

Assessment of the bioavailability of rare earth elements in soils by chemical fractionation and multiple regression analysis

The bioavailability of rare earth elements (REEs) in soils was evaluated, based on the combination of chemical fractionation and multiple regression analysis. REEs in soils were partitioned by a sequential extraction procedure into water soluble (F(ws)), exchangeable (F(ec)), bound to carbonates (F(cb)), bound to organic matter (F(om)), bound to Fe-Mn oxides (F(fm)) and residual (F(rd)) fractions. Alfalfa (Medicago Staiva Linn.) had been grown on the soils in a pot-culture experiment under greenhouse conditions for 35 days. The concentrations of REEs in fractions and plant were determined by inductively coupled plasma-mass spectrometry (ICP-MS). Chemical fractionation showed that (F(ws)) fraction of REEs was less than 0.1% and residual (F(rd)) was the dominant form, more than 60% in soils. Bioaccumulation of REEs was observed in Alfalfa. REE availability to the plant was evaluated by multiple regression analysis. F(ws), F(ec), F(cb) and F(om) fractions were significantly correlated with REE uptake by alfalfa. But the exchangeable Pr(F(ec)) was significantly correlated with Pr concentration in alfalfa. F(ec), F(cb) and F(om) greatly contributed to La and Nd bioavailability; F(ec) and F(om) to Ce, Gd and Dy; F(ec) and F(cb) to Yb; and F(ws), F(ec) and F(om) to total REEs. This meant that the bioavailability of different species of REEs varied with individual REE. The results of this study indicated that the sequential extraction procedure, in conjunction with multiple regression analysis, may be useful for the prediction of plant uptake of REEs from soils.     

Chemical speciation and bioavailability of rare earth elements (REEs) in the ecosystem: a review

Rare earths (RE), chemically uniform group of elements due to similar physicochemical behavior, are termed as lanthanides. Natural occurrence depends on the geological circumstances and has been of long interest for geologist as tools for further scientific research into the region of ores, rocks, and oceanic water. The review paper mainly focuses to provide scientific literature about rare earth elements (REEs) with potential environmental and health effects in understanding the research. This is the initial review of RE speciation and bioavailability with current initiative toward development needs and research perceptive. In this paper, we have also discussed mineralogy, extraction, geochemistry, analytical methods of rare earth elements. In this study, REEs with their transformation and vertical distribution in different environments such as fresh and seawater, sediments, soil, weathering, transport, and solubility have been reported with most recent literature along key methods of findings. Speciation and bioavailability have been discussed in detail with special emphasis on soil, plant, and aquatic ecosystems and their impacts on the environment. This review shows that REE gained more importance in last few years due to their detrimental effects on living organisms, so their speciation, bioavailability, and composition are much more important to evaluate their health risks and are discussed thoroughly as well.     

Distribution of selected heavy metals and rare earth elements in surficial sediments from the polish sector of the Vistula Lagoon

The concentrations of 22 trace elements plus the rare earth elements (REE) were determined in the <63 μm fraction of surficial sediments from the Polish sector of the Vistula Lagoon by ICP-MS. For the anthropogenically-enriched elements, the mean element enrichment factors (EF's) decrease in the sequence Ag (9.9) > Sb (7.5) >As (5.8) ≥ Cd (5.2) > Pb (3.7), albeit with large variability in concentration in the sediments from one station to another. These observations demonstrate that sediments from the Vistula Lagoon are locally polluted by these anthropogenically-derived elements. Plots of NASC-normalized REE data show that the REE patterns of the sediments have not been significantly modified during transport from their source with only a minor depletion of the heavy rare earth elements (HUE) compare to the light rare earth elements (LREE). The lack of any significant anomalies for Ce and Eu indicates that redox processes have not played a major role in modifying the distribution of the REE. Factor ananalysis of the compositional data shows that sediments from the Polish sector of the Vistula Lagoon can be divided into three main groups depending on the geographical location and the degree of contamination by heavy metals.     

Effect of organic acids on adsorption and desorption of rare earth elements

Effect of citric, malic, tartaric and acetic acids on adsorption of La, Ce, Pr and Nd by and desorption from four typical Chinese soils was studied. Generally, adsorption capacities of rare earth elements (REEs) were significantly correlated with the cation exchange capacity (CEC) of soils. In the presence of acetic acids adsorption of REEs was similar to that in the presence of Ca(NO3)2. However, in the presence of citric, malic and tartaric acids adsorption of REEs by Heilongjiang, Zhejiang and Guangdong soils decreased to varying extents if compared with that in the presence of nitrate and acetic acid. The significance of suppression followed the order of citric acid > malic acid > tartaric acid > acetic acid, which was consistent with the order of stability of complexes of REEs with these organic acids. However, the adsorption increased with increasing equilibrium solution pH. For Jiangxi soil with low soil pH, CEC and organic matter these organic acids exerted an even more serious suppression effect on the adsorption of REEs. Another feature of the relationship between the adsorption of REEs and equilibrium solution pH was that the adsorption of REEs decreased with increase of pH from 2 to 4.5 and then slightly increased with further increase of pH. Desorption of REEs varied with soils and with organic acids as well. REEs were released easily from Heilongjiang, Zhejiang and Guangdong soils in the presence of organic acid. Generally, desorption of REEs decreased with increasing equilibrium solution pH. Effect of organic acids on desorption of REEs from Jiangxi soil was more complicated. In the presence of citric and malic acids no decrement and/or slight increase in desorption of REEs were observed over the equilibrium solution pH from 3 to 6.5. The reasons for this were ascribed to the strong complexing capacity of citric and malic acids and low soil pH, CEC and organic matter of Jiangxi soil.     

Effect of substrate properties and phosphorus supply on facilitating the uptake of rare earth elements (REE) in mixed culture cropping systems of Hordeum vulgare,Lupinus albus and Lupinus angustifolius

Environmental Science and Pollution Research - This study presents how phosphate (P) availability and intercropping may influence the migration of rare earth elements (REEs) in legume–grass...     

Geochemical behaviour of dissolved trace elements in a monsoon-dominated tropical river basin,Southwestern India

The study presents a 3-year time series data on dissolved trace elements and rare earth elements (REEs) in a monsoon-dominated river basin, the Nethravati River in tropical Southwestern India. The river basin lies on the metamorphic transition boundary which separates the Peninsular Gneiss and Southern Granulitic province belonging to Archean and Tertiary–Quaternary period (Western Dharwar Craton). The basin lithology is mainly composed of granite gneiss, charnockite and metasediment. This study highlights the importance of time series data for better estimation of metal fluxes and to understand the geochemical behaviour of metals in a river basin. The dissolved trace elements show seasonality in the river water metal concentrations forming two distinct groups of metals. First group is composed of heavy metals and minor elements that show higher concentrations during dry season and lesser concentrations during the monsoon season. Second group is composed of metals belonging to lanthanides and actinides with higher concentration in the monsoon and lower concentrations during the dry season. Although the metal concentration of both the groups appears to be controlled by the discharge, there are important biogeochemical processes affecting their concentration. This includes redox reactions (for Fe, Mn, As, Mo, Ba and Ce) and pH-mediated adsorption/desorption reactions (for Ni, Co, Cr, Cu and REEs). The abundance of Fe and Mn oxyhydroxides as a result of redox processes could be driving the geochemical redistribution of metals in the river water. There is a Ce anomaly (Ce/Ce*) at different time periods, both negative and positive, in case of dissolved phase, whereas there is positive anomaly in the particulate and bed sediments. The Ce anomaly correlates with the variations in the dissolved oxygen indicating the redistribution of Ce between particulate and dissolved phase under acidic to neutral pH and lower concentrations of dissolved organic carbon. Unlike other tropical and major world rivers, the effect of organic complexation on metal variability is negligible in the Nethravati River water.     

Effects of fulvic acid on the bioavailability of rare earth elements and GOT enzyme activity in wheat (Triticum aestivum)

Fulvic acid (FA) was extracted and purified from natural soil and the effects of such FA on the bioaccumulation of rare earth elements (REEs, La3+, Gd3+ and Y3+) in wheat seedling were investigated. The results indicated that low concentration of FA (<0.4 mg C/l to root, <0.7 mg C/l to tops (stem and leaves)) could increase the bioaccumulation values of REEs in wheat, but when the concentration of FA was high (>0.4 mg C/l to root, >1.5 mg C/l to tops) the bioaccumulation values were decreased. Kinetic experimental results suggested that bioaccumulation values of REEs in roots for 30 days were correlated with the kinetic linear growth equation, and correlation coefficients were higher than 0.861. The kinetic bioaccumulation pattern of REEs in tops was different from that in root. The bioaccumulation values of REEs in wheat root were much higher than in wheat tops. Variations of glutamic oxaloacetic transaminase (GOT) enzyme activities in wheat root and tops were determined. A good correlation existed between the bioaccumulation values of REEs and GOT enzyme activities, and the correlation coefficients were higher than 0.922. GOT is an important parameter influencing the bioavailability of REEs.