Assessment of the hazard of nine (doped) lanthanides-based ceramic oxides to four aquatic species.

The risk of environmental pollution with rare earth oxides rises in line with increasing application of these compounds in different sectors. However, data on potential environmental hazard of lanthanides is scarce and concerns mostly Ce and Gd. In this work, the aquatic toxicity of eight doped lanthanide-based ceramic oxides (Ce0.9Gd0.1O2, LaFeO3, Gd0.97CoO3, LaCoO3, (La0.5Sr0.5)0.99MnO3, Ce0.8Pr0.2O2, (La0.6Sr0.4)0.95CoO3, LaNiO4) and one non-doped oxide (CeO2) with primary size from 23 to 590nm were evaluated in four short-term laboratory assays with freshwater crustaceans and duckweeds. Results showed no acute toxicity (EC50>100mg/L) or very low acute toxicity for most studied oxides. Observed toxicity was probably due to bioavailable fraction of dopant metals (Ni and Co) but in the case of aquatic plants, decrease of nutrient availability (complexing of phosphorus by lanthanides) was also presumed. Studied oxides/metals accumulated in the aquatic plant tissue and in the gut of crustaceans and thus may be further transferred via the aquatic food chain. Accumulation of metals in the duckweed Lemna minor may be recommended as a cost-effective screening bioassay for assessment of potential hazard of poorly soluble oxides to aquatic ecosystems.

Toxicity of Nine (Doped) Rare Earth Metal Oxides and Respective Individual Metals to Aquatic Microorganisms Vibrio fischeri and Tetrahymena thermophila.

Despite the increasing use of rare earth elements (REEs) and oxides (REOs) in various technologies, the information on their ecotoxicological hazard is scarce. Here, the effects of La3+, Ce3+, Pr3+, Nd3+, Gd3+, CeO2, and eight doped REOs to marine bacteria Vibrio fischeri and freshwater protozoa Tetrahymena thermophila were studied in parallel with REO dopant metals (Co2+, Fe3+, Mn2+, Ni2+, Sr2+). The highest concentrations of REOs tested were 100 mg/L with protozoa in deionized water and 500 mg/L with bacteria in 2% NaCl. Although (i) most REOs produced reactive oxygen species; (ii) all studied soluble REEs were toxic to bacteria (half-effective concentration, EC50 3.5-21 mg metal/L; minimal bactericidal concentration, MBC 6.3-63 mg/L) and to protozoa (EC50 28-42 mg/L); and (iii) also some dopant metals (Ni2+, Fe3+) proved toxic (EC50 ≤ 3 mg/L), no toxicity of REOs to protozoa (EC50 > 100 mg/L) and bacteria (EC50 > 500 mg/L; MBC > 500 mg/L) was observed except for La2NiO4 (MBC 25 mg/L). According to kinetics of V. fischeri bioluminescence, the toxicity of REEs was triggered by disturbing cellular membrane integrity. Fortunately, as REEs and REOs are currently produced in moderate amounts and form in the environment insoluble salts and/or oxides, they apparently present no harm to aquatic bacteria and protozoa.

Potency of (doped) rare earth oxide particles and their constituent metals to inhibit algal growth and induce direct toxic effects.

Use of rare earth elements (REEs) has increased rapidly in recent decades due to technological advances. It has been accompanied by recurring rare earth element anomalies in water bodies. In this work we (i) studied the effects of eight novel doped and one non-doped rare earth oxide (REO) particles (aimed to be used in solid oxide fuel cells and gas separation membranes) on algae, (ii) quantified the individual adverse effects of the elements that constitute the (doped) REO particles and (iii) attempted to find a discernible pattern to relate REO particle physicochemical characteristics to algal growth inhibitory properties. Green algae Raphidocelis subcapitata (formerly Pseudokirchneriella subcapitata) were used as a test species in two different formats: a standard OECD201 algal growth inhibition assay and the algal viability assay (a 'spot test') that avoids nutrient removal effects. In the 24h 'spot' test that demonstrated direct toxicity, algae were not viable at REE concentrations above 1mgmetal/L. 72-hour algal growth inhibition EC50 values for four REE salts (Ce, Gd, La, Pr) were between 1.2 and 1.4mg/L, whereas the EC50 for REO particles ranged from 1 to 98mg/L. The growth inhibition of REEs was presumably the result of nutrient sequestration from the algal growth medium. The adverse effects of REO particles were at least in part due to the entrapment of algae within particle agglomerates. Adverse effects due to the dissolution of constituent elements from (doped) REO particles and the size or specific surface area of particles were excluded, except for La2NiO4. However, the structure of the particles and/or the varying effects of oxide composition might have played a role in the observed effects. As the production rates of these REO particles are negligible compared to other forms of REEs, there is presumably no acute risk for aquatic unicellular algae.