The Metal Oxidation State in Cu, CuO, and Cu<sub>2</sub>O Nanoparticles Plays a Key Role in Toxicity to Sea Urchin <i>Arbacia lixula</i>, <i>Paracentrotus lividus,</i> and <i>Sphaerechinus granularis</i> Embryos

Copper-based nanoparticles (as Cu<sub>2</sub>O) 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 Cu<sub>2</sub>O nanoparticles on the ea...

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Main Authors: Ivana Čarapar, Lara Jurković, Dijana Pavičić-Hamer, Andrej Jaklin, Maja Dutour Sikirić, Bojan Hamer, Daniel Mark Lyons
Format: Article
Language:English
Published: MDPI AG 2025-06-01
Series:Toxics
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Online Access:https://www.mdpi.com/2305-6304/13/6/469
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author Ivana Čarapar
Lara Jurković
Dijana Pavičić-Hamer
Andrej Jaklin
Maja Dutour Sikirić
Bojan Hamer
Daniel Mark Lyons
author_facet Ivana Čarapar
Lara Jurković
Dijana Pavičić-Hamer
Andrej Jaklin
Maja Dutour Sikirić
Bojan Hamer
Daniel Mark Lyons
author_sort Ivana Čarapar
collection DOAJ
description Copper-based nanoparticles (as Cu<sub>2</sub>O) 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 Cu<sub>2</sub>O nanoparticles on the early development of urchins <i>Arbacia lixula</i>, <i>Paracentrotus lividus</i> and <i>Sphaerechinus granularis</i>, 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<sup>−1</sup> range. EC<sub>50</sub> values after Cu<sub>2</sub>O exposure indicated that <i>A. lixula</i> (99 µg L<sup>−1</sup>) was generally more sensitive than the other two species, with EC<sub>50</sub> values of 371 µg L<sup>−1</sup> and 606 µg L<sup>−1</sup> noted for <i>S. granularis</i> and <i>P. lividus</i>, respectively. The same trend across species was noted for both Cu and CuO, although these nanoparticles generally showed higher EC<sub>50</sub> values, indicating lower toxicity compared to Cu<sub>2</sub>O. LC<sub>50</sub> values qualitatively parallel the corresponding EC<sub>50</sub> values, with Cu<sub>2</sub>O consistently the most toxic, while Cu was less harmful, and CuO did not reach LC<sub>50</sub> at any concentration. Again, greatest lethality was noted in <i>A. lixula</i>. While copper ion release from Cu was much greater than from CuO and Cu<sub>2</sub>O, 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 Cu<sub>2</sub>O, but there may also be a contribution derived from Cu<sub>2</sub>O redox activity within cells or at membranes that negatively impact oxidative stress defence mechanisms and metabolic pathways.
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series Toxics
spelling doaj-art-e0e47bcf92d44f98a2fbecc670b5d7842025-08-20T03:26:52ZengMDPI AGToxics2305-63042025-06-0113646910.3390/toxics13060469The Metal Oxidation State in Cu, CuO, and Cu<sub>2</sub>O Nanoparticles Plays a Key Role in Toxicity to Sea Urchin <i>Arbacia lixula</i>, <i>Paracentrotus lividus,</i> and <i>Sphaerechinus granularis</i> EmbryosIvana Čarapar0Lara Jurković1Dijana Pavičić-Hamer2Andrej Jaklin3Maja Dutour Sikirić4Bojan Hamer5Daniel Mark Lyons6Center for Marine Research, Ruđer Bošković Institute, G. Paliaga 5, 52210 Rovinj, CroatiaCenter for Marine Research, Ruđer Bošković Institute, G. Paliaga 5, 52210 Rovinj, CroatiaCenter for Marine Research, Ruđer Bošković Institute, G. Paliaga 5, 52210 Rovinj, CroatiaCenter for Marine Research, Ruđer Bošković Institute, G. Paliaga 5, 52210 Rovinj, CroatiaDivision of Physical Chemistry, Ruđer Bošković Institute, Bijenička cesta 54, 10000 Zagreb, CroatiaCenter for Marine Research, Ruđer Bošković Institute, G. Paliaga 5, 52210 Rovinj, CroatiaCenter for Marine Research, Ruđer Bošković Institute, G. Paliaga 5, 52210 Rovinj, CroatiaCopper-based nanoparticles (as Cu<sub>2</sub>O) 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 Cu<sub>2</sub>O nanoparticles on the early development of urchins <i>Arbacia lixula</i>, <i>Paracentrotus lividus</i> and <i>Sphaerechinus granularis</i>, 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<sup>−1</sup> range. EC<sub>50</sub> values after Cu<sub>2</sub>O exposure indicated that <i>A. lixula</i> (99 µg L<sup>−1</sup>) was generally more sensitive than the other two species, with EC<sub>50</sub> values of 371 µg L<sup>−1</sup> and 606 µg L<sup>−1</sup> noted for <i>S. granularis</i> and <i>P. lividus</i>, respectively. The same trend across species was noted for both Cu and CuO, although these nanoparticles generally showed higher EC<sub>50</sub> values, indicating lower toxicity compared to Cu<sub>2</sub>O. LC<sub>50</sub> values qualitatively parallel the corresponding EC<sub>50</sub> values, with Cu<sub>2</sub>O consistently the most toxic, while Cu was less harmful, and CuO did not reach LC<sub>50</sub> at any concentration. Again, greatest lethality was noted in <i>A. lixula</i>. While copper ion release from Cu was much greater than from CuO and Cu<sub>2</sub>O, 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 Cu<sub>2</sub>O, but there may also be a contribution derived from Cu<sub>2</sub>O redox activity within cells or at membranes that negatively impact oxidative stress defence mechanisms and metabolic pathways.https://www.mdpi.com/2305-6304/13/6/469antifoulingcopperdevelopmental defectembryogenesismarinepaint
spellingShingle Ivana Čarapar
Lara Jurković
Dijana Pavičić-Hamer
Andrej Jaklin
Maja Dutour Sikirić
Bojan Hamer
Daniel Mark Lyons
The Metal Oxidation State in Cu, CuO, and Cu<sub>2</sub>O Nanoparticles Plays a Key Role in Toxicity to Sea Urchin <i>Arbacia lixula</i>, <i>Paracentrotus lividus,</i> and <i>Sphaerechinus granularis</i> Embryos
Toxics
antifouling
copper
developmental defect
embryogenesis
marine
paint
title The Metal Oxidation State in Cu, CuO, and Cu<sub>2</sub>O Nanoparticles Plays a Key Role in Toxicity to Sea Urchin <i>Arbacia lixula</i>, <i>Paracentrotus lividus,</i> and <i>Sphaerechinus granularis</i> Embryos
title_full The Metal Oxidation State in Cu, CuO, and Cu<sub>2</sub>O Nanoparticles Plays a Key Role in Toxicity to Sea Urchin <i>Arbacia lixula</i>, <i>Paracentrotus lividus,</i> and <i>Sphaerechinus granularis</i> Embryos
title_fullStr The Metal Oxidation State in Cu, CuO, and Cu<sub>2</sub>O Nanoparticles Plays a Key Role in Toxicity to Sea Urchin <i>Arbacia lixula</i>, <i>Paracentrotus lividus,</i> and <i>Sphaerechinus granularis</i> Embryos
title_full_unstemmed The Metal Oxidation State in Cu, CuO, and Cu<sub>2</sub>O Nanoparticles Plays a Key Role in Toxicity to Sea Urchin <i>Arbacia lixula</i>, <i>Paracentrotus lividus,</i> and <i>Sphaerechinus granularis</i> Embryos
title_short The Metal Oxidation State in Cu, CuO, and Cu<sub>2</sub>O Nanoparticles Plays a Key Role in Toxicity to Sea Urchin <i>Arbacia lixula</i>, <i>Paracentrotus lividus,</i> and <i>Sphaerechinus granularis</i> Embryos
title_sort metal oxidation state in cu cuo and cu sub 2 sub o nanoparticles plays a key role in toxicity to sea urchin i arbacia lixula i i paracentrotus lividus i and i sphaerechinus granularis i embryos
topic antifouling
copper
developmental defect
embryogenesis
marine
paint
url https://www.mdpi.com/2305-6304/13/6/469
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