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Bioavailability of Lanthanides to Freshwater Organisms: Speciation, Accumulation and Toxicity

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Abstract

The lanthanides consist of a group of fifteen homologous metals and together with scandium (Sc) and yttrium (Y) they are known as the rare earth elements (REE). Contrasting to what this name suggests they are not rare at all and lanthanides can be found in most soils and sediments in quantities comparable to those of Pb and Cd. However, their soluble concentrations are strongly limited by the low solubility products of lanthanides with carbonate and phosphate. The increasing industrial uses of lanthanides are accompanied by increasing emissions, which mainly end up in the aquatic environment. Therefore, it should be investigated if these emissions cause adverse effects on aquatic biota. This is the background of the research described here.
... Stauber and Binet, 2000;Lürling and Tolman, 2010;Bogers 1995c). Dissolved concentrations of La are mainly responsible for adverse effects (Weltje 2002). When EC50s are calculated from total concentrations, the toxicity is underestimated. ...
... e Effect concentration recalculated as mg lanthanum per liter, if necessary. f According to Weltje (2002) the applied medium reflects freshwater speciation conditions with an ionic strength between freshwater and seawater. g Estimated from graph. ...
... In contrast to the number of freshwater studies, very few tests were conducted with marine organisms and none were found for sediment or chronic studies. Weltje (2002) tested the sensitivity of the marine bacterium Aliivibrio fischeri (formerly: Vibrio fischeri) on lanthanum in a medium which reflects freshwater conditions (details in Table 5). Inhibition only occurred at high concentrations with an EC50 of 5.56 mg La L À 1 . ...
Article
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Rare earth elements (REE) used to be taken as tracers of geological origin for fluvial transport. Nowadays their increased applications in innovative environmental-friendly technology (e.g. in catalysts, superconductors, lasers, batteries) and medical applications (e.g. MRI contrast agent) lead to man-made, elevated levels in the environment. So far, no regulatory thresholds for REE concentrations and emissions to the environment have been set because information on risks from REE is scarce. However, evidence gathers that REE have to be acknowledged as new, emerging contaminants with manifold ways of entry into the environment, e.g. through waste water from hospitals or through industrial effluents. This paper reviews existing information on bioaccumulation and ecotoxicity of lanthanum in the aquatic environment. Lanthanum is of specific interest as one of the major lanthanides in industrial effluents. This review focuses on the freshwater and the marine environment, and tackles the water column and sediments. From these data, methods to derive quality criteria for sediment and water are discussed and preliminary suggestions are made.
... This behavior remains for LC 50 based on total nominal, total measured and calculated free ion concentrations ( Fig. 1b). Another experimental demonstration about lanthanide's ecotoxicity shows an increase in toxicity when increasing atomic numbers (Weltje, 2002;Weltje et al., 2004). In this study, phosphates were not present in the exposure medium and speciation calculation was taken into account to set the highest lanthanide concentration to avoid precipitation of lanthanide as carbonates and hydroxides. ...
... Stanley and Byrne (1990) found that gadolinium uptake by marine algae in carbonate-manipulated media was related to Gd 3+ but could not completely explain their observation based on Gd 3+ alone. Weltje (2002) concluded that effects of the free ion cannot be separated easily from those of its nitrate and carbonate complexes, and that total dissolved concentration may be used to express toxicity. However, we should note these conclusions derived from a study with a specific organism (V. ...
... Similar toxicity values were obtained when phosphates were present in exposure medium and endpoint was based on nominal concentration (Den Dooren de Jong, 1965;Tai et al., 2010). The data obtained by Weltje (2002), without presence of phosphate in the exposure medium and results based on measured concentration, show a strong increase in toxicity when increasing atomic number. It seems that, in the absence of ligands inducing Ln precipitation, ecotoxicity of lanthanide increases with an increasing atomic number. ...
... Also refers to US EPA 2012Lacour et al., 2005;Hutchison et al., 2004Monafo et al., 1976Pang et al., 2001). Unpolluted site vs polluted site Weltje et al., (2002) La, Ce, Eu Blue mussel Mytilus edulis Unpolluted site vs polluted site Riget et al., (1996) ...
... c BCF is calculated from total or nominal REE concentrations in the water and expressed in wet weight, except otherwise described. d BCF is dynamic i.e., accumulation not in equilibrium yet, is calculated as described inWeltje et al (2002) and expressed based on fresh weight of plant. e Values are calculated from dry weight of tissue. ...
Technical Report
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This report by the Danish Centre for Environment and Energy (DCE) and Greenland Institute of Natural Resources (GINR) aims to gather worldwide information on excitotoxicity data on fluoride (F), rare earth elements (REEs), and naturally occurring radionuclides (NORs) that can potentially be used in Greenland. The report is not explicitly focused on Kvanefjeld and Tanbreeze mineral exploration projects in south Greenland but on the mining and milling of minerals containing REEs, NORs, and F in general in Greenland. The report provides relevant information to be used as a basis for environmental regulation and monitoring of mining projects and establish guidelines on concentrations threshold values for the REEs, NORs, and F in water, soil, dust, vegetation, berries, birds, and fish both in the mining area but also for the surrounding environment. This report can also be used for teaching or as guide for the general public, politicians, authorities, education, industry, and other Greenland stakeholders.
... Due to coexistence with other minerals, natural concentrations of lanthanides are similar to essential elements such as iodine, cobalt and selenium (Palasz and Czekaj 2000). Compared to the nonessential metals, concentrations of La, Ce and Nd tend to be higher than Pb and even concentrations of the less abundant REEs, (e.g., Tm and Lu), are typically higher than Cd in the earth crust (Weltje 2002). Cerium, at 60 mg kg -1 , is the most abundant lanthanide found in the Earth's crust, while the least plentiful are Tm and Lu (0.5 mg kg -1 ), which are still more abundant than gold (0.001 mg kg -1 ) (Kifle et al. 2013; Lewis and Jiménez-Villacorta 2013). ...
... REEs have low solubility and dissolved Ce and Lu (passing B0.45 lm filter) only ranged from 0.003 to 0.71 ng L -1 and 0.00004-0.007 ng L -1 , respectively, in pristine freshwater environments (Weltje 2002). Dissolved concentrations of other REEs are between these ranges. ...
... Due to coexistence with other minerals, natural concentrations of lanthanides are similar to essential elements such as iodine, cobalt and selenium (Palasz and Czekaj 2000). Compared to the nonessential metals, concentrations of La, Ce and Nd tend to be higher than Pb and even concentrations of the less abundant REEs, (e.g., Tm and Lu), are typically higher than Cd in the earth crust (Weltje 2002). Cerium, at 60 mg kg -1 , is the most abundant lanthanide found in the Earth's crust, while the least plentiful are Tm and Lu (0.5 mg kg -1 ), which are still more abundant than gold (0.001 mg kg -1 ) (Kifle et al. 2013; Lewis and Jiménez-Villacorta 2013). ...
... REEs have low solubility and dissolved Ce and Lu (passing B0.45 lm filter) only ranged from 0.003 to 0.71 ng L -1 and 0.00004-0.007 ng L -1 , respectively, in pristine freshwater environments (Weltje 2002). Dissolved concentrations of other REEs are between these ranges. ...
Article
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The distribution of 14 rare earth elements, Th and U was studied in streams of the study area at 21 sites. Aquatic mosses are known to accumulate even metabolically nonessential or toxic metals in concentrations much higher than their aqueous environment due to their unique morphology and physiology. Thus, the capacity of metal amplification in four aquatic mosses (Fontinalis squamosa, Brachythecium rivulare, Platyhypnidium riparioides and Thamnobryum alopecurum) was also evaluated as a potential bioindicator/biomonitoring tool. Thirteen REEs (0.001–2.81 μg L−1) and U were detected in the stream water. Mean content of lighter rare earth elements (LREEs) was higher than that of heavier rare earth elements (HREEs). Fourteen REEs and two actinides were detected in moss samples, including Yb and Th which were below detection level in water samples. LREE uptake (0.17–12.2 mg kg−1) was greater than HREE uptake (0.02–0.78 mg kg−1) in all mosses. Uptake of LREEs was observed in the order: B. rivulare >T. alopecurum >F. squamosa >P. riparioides and that of HREEs in the order: T. alopecurum >B. rivulare >F. squamosa >P. riparioides. Mean U content (0.68–1.62 mg kg−1) in the mosses was found in the order: B. rivulare >F. squamosa >T. alopecurum >P. riparioides. Th content ranged from 0.4 to 2.36 mg kg−1 in the order: B. rivulare >T. alopecurum >P. riparioides >F. squamosa. One-way ANOVA indicated a statistically significant difference (P ≤ 0.01) in mean concentrations of all elements (individually) in moss samples except for U. Highest bioconcentration factors of six REEs each were observed in B. rivulare (La, Ce, Sm, Eu, Tb and Dy) and T. alopecurum (Nd, Gd, Ho, Er, Tm and Lu). The highest BCFs for Pr and U were obtained in F. squamosa and P. riparioides, respectively. These species hold promise for biomonitoring studies in the future.
... Lanthanides are often used as analogs to actinides in biochemical and environmental studies, due the dangers inherent in working with radioactive materials [44]. Lanthanides are introduced into the waste cycle from medical waste associated with imaging technologies. ...
... Lanthanides are introduced into the waste cycle from medical waste associated with imaging technologies. They are relatively abundant in natural sources, as well, and in the earth's crust, concentrations of lanthanum (La), cesium (Ce) and neodymium (Nd), exceed those of lead, so these rare elements are often more prevalent than more common metals [44]. ...
Article
The structural characteristics associated with the binding of beneficial metals (i.e. - Mg2+, Zn2+ and Ca2+) to natural proteins has typically received more attention than competitive binding by toxic metals (e.g. – Pb2+, Hg2+, Cd2+, La3+, etc.). In this thesis, a statistical analysis of Pb2+-binding in crystallized protein structures indicates that Pb2+ does not bind preferentially with nitrogen, as generally assumed, but binds predominantly with oxygen, and to a lesser degree, sulfur. A comparison of Ca2+ and Pb2+ indicates that Pb2+ binds with a wider range of coordination numbers, with less formal change, and with less defined structure than Ca2+. The Pb2+ ion also appears to displace Ca2+ with little conformational stress in calcium binding proteins (CaBP’s). Experimental data from the binding of metals with engineered fluorescent proteins indicate that both Pb2+ and Gd3+ will occupy grafted calcium-binding sites with greater affinity than Ca2+, and strong evidence is presented to support the hypothesis that Pb2+ and Gd3+ will bind non-specifically on the protein surface. These results suggest that toxicity is associated with two binding mechanisms: displacement of the metal cofactor which disrupts protein function, and non-specific binding which maintains higher solubility of the metal.
... Correlations of air pollution and medical statistics confirm the results of investigations39404142434445. Recently, in connection with the development of analytical methh ods, rare earth elements (lanthanides, Sc, Y), which were earlier beyond the reach of analytical techniques, have been extensively studied in environmental objects from the point of view of their toxicity [46, 47]. Production waste and discharge of factories, gasoo line and other fuel combustion products, household garbage in towns, fertilizers, pesticides, and many other things are sources of environmental pollution. ...
... On the other hand, being a living organism, it accumulates elements in particular amounts depending on their concentration in the nutritional medium where S. platensis cells grow. Recently, particular attention has been given to the study of the role played by trace elements in the human organism41424344454647. Trace elements are important for acid metabolism. ...
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Development of methods for instrumental neutron activation analysis (INAA) and their applica� tions in the life sciences are reviewed. Emphasis is placed on epithermal activation with reactor neutrons (ENAA), and the advantages of this technique in analysis of environmental objects are shown. The results of applied INAA studies in the field of the life sciences carried out at the world’s leading nuclear centers are reported. Experience in employing a radioanalytical complex at the IBR�2 reactor (Frank Laboratory of Neutron Physics, Joint Institute for Nuclear Research, Dubna) for such studies is summarized.
... One of the measures is bioaccumulation concentration factor (BCF), which includes different contaminants' level in the organisms with respect to the medium. BCF values are based on the ratio between plant concentrations against surface water, and it was observed that it's similar for most of the REEs throughout the year in all of the studied areas in Lemna minor, while BCF values of Potamogeton pectinatus were moreover similar for all REEs but differed between study areas, and for some other species, BCF varied in both spatial and temporal scales (Weltje 2003). A reduction in BCF with the atomic number was reported when the concentration ratio in the biota to pore water was measured. ...
Chapter
Lanthanides (e.g. La, Gd, Nd, Ce) are being used increasingly due to their versatile applications in medical diagnosis, electronics, agriculture, industries, and research; hence, their global utility had been increased drastically in the last few decades. Lanthanide enrichment in agricultural fields due to repetitive use of fertilizer application and REE (rare-earth element)-based fertilizers leads to lanthanide-concentrated agricultural runoff to the water bodies consequently. Through biomagnification in the food chain, there is a risk of enrichment of these REEs in humans. Aquatic macrophytes are one of the important constituents of the food chain along with being a significant primary producer widely studied for metal accumulation and stress physiology. However, very limited knowledge on transfer processes, bioaccumulation, and distribution pattern of REEs is available. Chemical-assisted remediation and omics-guided phytoremediation using hyperaccumulator macrophytes are found to be the most popular methods, but macrophyte-based phytoremediation is preferable as it is eco-friendly and does not create any secondary pollutants. This chapter will cover the significant sources of REE contamination especially lanthanides, ecotoxicological effects on macrophytes, their stress physiology, and bioremediation strategies.
... The concomitant decrease of dissolved and increase of particulate REE in the test medium should be a consequence of REE precipitation as observed in numerous studies (Blinova et al., 2018;González et al., 2015;Romero-Freire et al., 2019). The difference between nominal and measured concentrations is probably related to REE precipitation but also to REE adsorption on glass walls (Crémazy et al., 2014;Weltje, 2002) despite the flask preconditioning (Lachaux et al., 2022a). These observations highlight the relevance to consider measured concentrations to characterize REE exposure and to avoid misinterpretation of observed biological effects (Lachaux et al., 2022b). ...
... Hence, environmental emissions of REE need to be monitored. This demands development of adequate monitoring approaches , selection of biomonitors and adequate analytic techniques [14]. Instrumental neutron activation analysis (INAA) is a powerful tool giving an opportunity to determine the contents of a number of chemical elements in a small single sample. ...
Chapter
Experiments in physics, Astro-particle physics and cosmology that require careful shielding against cosmic rays include dark matter searches, studies of radioactive decays, and neutrino detection experiments. The need for such shielding has motivated the construction of laboratory caverns in mines and adjacent to tunnels under mountains. There are currently about a dozen such laboratories, in existence or under construction, all in the Northern Hemisphere. A motivation has been made for the establishment of a Southern Hemisphere facility. In this paper a feasibility study of measurements of radon in air (using electret ion chambers and alpha spectroscopy), background gamma ray measurements (inside/outside) the tunnel using scintillator (inorganic) detectors, cosmic ray measurements using organic scintillators and radiometric analyses of representative rock samples for the establishment of such a facility in the South Africa is presented.
... Hence, environmental emissions of REE need to be monitored. This demands development of adequate monitoring approaches , selection of biomonitors and adequate analytic techniques [14]. Instrumental neutron activation analysis (INAA) is a powerful tool giving an opportunity to determine the contents of a number of chemical elements in a small single sample. ...
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The contents of 23 trace elements (Sc, V, Cr, Mn, Fe, Co, Zn, As, Se, Br, Rb, Sr, Mo, Ag, Sb, I, Ba, La, Ce, Sm, Eu, Hf, Ta) were quantitatively determined in soft tissues and shells of mass non-indigenous bivalve mussels—farmed Pacific oysters (Crassostrea gigas) and farmed and wild invasive Mediterranean mussels (Mytilus galloprovincialis) at the Atlantic coast of South Africa. The study revealed that the contents of the majority of elements in the soft tissues of both species were higher than those in the shells. The tissues of wild invasive Mediterranean mussels contain higher levels of a range of trace elements comparing to farmed mussels. The tissues of Pacific oysters contain much higher levels of almost all elements studied compared to the tissues of Mediterranean mussels. Higher content of zinc in the mussels and oysters from Saldanha Bay may evidence anthropogenic pollution of the bay’s ecosystem by this metal, which necessitates continued monitoring of levels of potentially toxic metals. Both alien species, and especially Pacific oysters, may serve as reliable biomonitors for trace elements in marine ecosystems. Both species are rich in essential elements and provide nutritionally-valuable seafoods.
... In the aquatic and soil environments, REEs can be found especially in the polluted regions [18] [19], possibly affecting the biota within [20] [21]. REEs are emitted to both aerial and aquatic environments from semiconductor industries mostly in East Asian countries [22] and hospitals in developed countries (REEs used for medical imaging) [23], respectively. ...
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Chapter
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Toxicity studies with lanthanides and Vibrio fischeri -importance of the free ion and QSAR development
  • L Weltje
  • J J M De Goeij
Weltje, L., de Goeij, J. J. M.: Toxicity studies with lanthanides and Vibrio fischeri -importance of the free ion and QSAR development. In: Abstracts of the 13 th Annual Meeting of SETAC-Europe. Hamburg, Germany, 2003, p. 107.