The Metal Oxidation State in Cu, CuO, and Cu2O Nanoparticles Plays a Key Role in Toxicity to Sea Urchin Arbacia lixula, Paracentrotus lividus, and Sphaerechinus granularis Embryos.

Copper-based nanoparticles (as Cu₂O) are a key component in marine antifouling paints and, as coatings degrade, release nanoparticles that can affect a wide range of non-target organisms. This study investigates the impact of Cu₂O nanoparticles on the early development of urchins Arbacia lixula, Paracentrotus lividus and Sphaerechinus granularis, and benchmarks their toxicity against similarly sized Cu and CuO nanoparticles and ionic copper. Concentration-dependent toxicity was noted for all forms of copper at concentrations in the 1 to 5000 µg L^-1 range. EC₅₀ values after Cu₂O exposure indicated that A. lixula (99 µg L^-1) was generally more sensitive than the other two species, with EC₅₀ values of 371 µg L^-1 and 606 µg L^-1 noted for S. granularis and P. lividus, respectively. The same trend across species was noted for both Cu and CuO, although these nanoparticles generally showed higher EC₅₀ values, indicating lower toxicity compared to Cu₂O. LC₅₀ values qualitatively parallel the corresponding EC₅₀ values, with Cu₂O consistently the most toxic, while Cu was less harmful, and CuO did not reach LC₅₀ at any concentration. Again, greatest lethality was noted in A. lixula. While copper ion release from Cu was much greater than from CuO and Cu₂O, the latter showed similar or greater toxicity to developing embryos compared to Cu. This indicates that copper ions are not the sole driver of toxicity of Cu₂O, but there may also be a contribution derived from Cu₂O redox activity within cells or at membranes that negatively impact oxidative stress defence mechanisms and metabolic pathways.