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.

[1]  Motohide Aoki,et al.  Evaluation of Metal Toxicity in Chlorella kessleri from the Perspective of the Periodic Table , 2008 .

[2]  F. Stagnitti,et al.  Biological toxicity of lanthanide elements on algae. , 2010, Chemosphere.

[3]  H. Gibb,et al.  Cobalt and inorganic cobalt compounds , 2006 .

[4]  A. Kahru,et al.  From ecotoxicology to nanoecotoxicology. , 2010, Toxicology.

[5]  Grant Douglas,et al.  Eutrophication management in surface waters using lanthanum modified bentonite: A review. , 2016, Water research.

[6]  S. Pokhrel,et al.  Toxicity of 12 metal-based nanoparticles to algae, bacteria and protozoa , 2015 .

[7]  S. Heise,et al.  Aquatic ecotoxicity of lanthanum - A review and an attempt to derive water and sediment quality criteria. , 2016, Ecotoxicology and environmental safety.

[8]  K. Boltes,et al.  Physicochemical characterization and ecotoxicological assessment of CeO2 nanoparticles using two aquatic microorganisms. , 2011, Toxicological sciences : an official journal of the Society of Toxicology.

[9]  Tom Van Gerven,et al.  Recycling of rare earths: a critical review , 2013 .

[10]  A. Ivask,et al.  A novel method for comparison of biocidal properties of nanomaterials to bacteria, yeasts and algae. , 2015, Journal of hazardous materials.

[11]  R. J. P. Williams,et al.  637. The stability of transition-metal complexes , 1953 .

[12]  Archana Sharma,et al.  Effects of lanthanum in cellular systems , 1988, Biological Trace Element Research.

[13]  L. Sigg,et al.  Influence of agglomeration of cerium oxide nanoparticles and speciation of cerium(III) on short term effects to the green algae Chlamydomonas reinhardtii. , 2014, Aquatic toxicology.

[14]  Gary L. Messing,et al.  Ceramic Powder Synthesis by Spray Pyrolysis , 1993 .

[15]  G. Klaver,et al.  Anthropogenic Rare Earth Element in rivers: Gadolinium and lanthanum. Partitioning between the dissolved and particulate phases in the Rhine River and spatial propagation through the Rhine-Meuse Delta (the Netherlands) , 2014 .

[16]  Brad M. Angel,et al.  On the mechanism of nanoparticulate CeO2 toxicity to freshwater algae. , 2015, Aquatic toxicology.

[17]  Colin R. Janssen,et al.  Aggregation and ecotoxicity of CeO₂ nanoparticles in synthetic and natural waters with variable pH, organic matter concentration and ionic strength. , 2011, Environmental pollution.

[18]  M. Pons,et al.  Lanthanide ecotoxicity: first attempt to measure environmental risk for aquatic organisms. , 2015, Environmental pollution.

[19]  M. Bau,et al.  Rare earth elements in the Rhine River, Germany: first case of anthropogenic lanthanum as a dissolved microcontaminant in the hydrosphere. , 2011, Environment international.

[20]  Colin R. Janssen,et al.  Comparison of the Effect of Different pH Buffering Techniques on the Toxicity of Copper and Zinc to Daphnia Magna and Pseudokirchneriella Subcapitata , 2004, Ecotoxicology.

[21]  Ilmari Pyykkö,et al.  Multilaboratory evaluation of 15 bioassays for (eco)toxicity screening and hazard ranking of engineered nanomaterials: FP7 project NANOVALID , 2016, Nanotoxicology.

[22]  F. Figueroa,et al.  Use of lanthanides to alleviate the effects of metal ion-deficiency in Desmodesmus quadricauda (Sphaeropleales, Chlorophyta) , 2015, Front. Microbiol..

[23]  Richard Roth,et al.  Evaluating rare earth element availability: a case with revolutionary demand from clean technologies. , 2012, Environmental science & technology.

[24]  Blahoslav Maršálek,et al.  Evaluation of alternative and standard toxicity assays for screening of environmental samples: Selection of an optimal test battery , 1998 .

[25]  M. Kumke,et al.  Combining spectroscopic and potentiometric approaches to characterize competitive binding to humic substances. , 2008, Environmental science & technology.

[26]  P. Dulski,et al.  Anthropogenic origin of positive gadolinium anomalies in river waters , 1996 .

[27]  Jamie R. Lead,et al.  Physico-chemical behaviour and algal toxicity of nanoparticulate CeO2 in freshwater , 2010 .

[28]  K. Bruland,et al.  Increases in Anthropogenic Gadolinium Anomalies and Rare Earth Element Concentrations in San Francisco Bay over a 20 Year Record. , 2016, Environmental science & technology.

[29]  C. Jeffrey Brinker,et al.  Surface Interactions with Compartmentalized Cellular Phosphates Explain Rare Earth Oxide Nanoparticle Hazard and Provide Opportunities for Safer Design , 2014, ACS nano.

[30]  K. Bišová,et al.  The effect of lanthanides on photosynthesis, growth, and chlorophyll profile of the green alga Desmodesmus quadricauda , 2016, Photosynthesis Research.

[31]  K. Kasemets,et al.  Toxicity of nanoparticles of CuO, ZnO and TiO2 to microalgae Pseudokirchneriella subcapitata. , 2009, The Science of the total environment.

[32]  S. Fricker The therapeutic application of lanthanides. , 2006, Chemical Society reviews.

[33]  C. Evans Biochemistry of the Lanthanides , 1990, Biochemistry of the Elements.

[34]  R. Rosal,et al.  An insight into the mechanisms of nanoceria toxicity in aquatic photosynthetic organisms. , 2012, Aquatic toxicology.

[35]  K. Wiik,et al.  High‐Temperature Proton‐Conducting LaNbO4‐Based Materials: Powder Synthesis by Spray Pyrolysis , 2007 .

[36]  N. Düzgüneş,et al.  La3+-induced fusion of phosphatidylserine liposomes. Close approach, intermembrane intermediates, and the electrostatic surface potential. , 1988, Biophysical journal.

[37]  Jamie R. Lead,et al.  Molecular toxicity of cerium oxide nanoparticles to the freshwater alga Chlamydomonas reinhardtii is associated with supra-environmental exposure concentrations , 2015, Nanotoxicology.

[38]  P. Pandard,et al.  Ecotoxicity of non-aged and aged CeO2 nanomaterials towards freshwater microalgae. , 2013, Environmental pollution.

[39]  M. Bau,et al.  Anthropogenic dissolved and colloid/nanoparticle-bound samarium, lanthanum and gadolinium in the Rhine River and the impending destruction of the natural rare earth element distribution in rivers , 2013 .

[40]  C. Leyval,et al.  Environmental fate and ecotoxicity of lanthanides: are they a uniform group beyond chemistry? , 2014, Environment international.

[41]  W. Roman,et al.  Tolerance ofChlorella vulgaris for metallic and non-metallic ions , 2005, Antonie van Leeuwenhoek.