Copper uptake kinetics and toxicological effects of ionic Cu and CuO nanoparticles on the seaweed Ulva rigida

Copper ion (Cu²⁺) and copper oxide (CuO) nanoparticle (NP) ecotoxicity are of increasing concern as they are considered to be a potential risk to marine systems. This study represents the first attempt to evaluate CuO NP impacts on the seaweeds and Cu²⁺ on the chlorophyte Ulva rigida. Effects on oxidative stress, antioxidant defence markers, photosystem II function, thalli growth, and cell viability in U. rigida exposed for 4 up 72 h to1 and 5 mg L^-1 Cu²⁺ and CuO NPs were examined. Hydrogen peroxide (H₂O₂) generation, superoxide dismutase (SOD) activity, malondialdehyde (MDA) content, and growth inhibition seemed to be reliable and early warning markers of toxicity. The most important variables of the principal component analysis (PCA): H₂O₂ generation, antioxidant stress markers, and growth-based toxicity index, were higher at 1 mg L^-1 CuO NPs compared to CuSO₄ and at 5 mg L^-1 CuSO₄ compared to CuO NPs. Intracellular uptake kinetics fit well to the Michaelis-Menten equation. The higher toxicity at 5 mg L^-1 CuSO₄ compared to 1 mg L^-1 was due to the higher Cu uptake with increasing concentration, suggesting and higher accumulation ability. On the contrary, 1 mg L^-1 CuO NPs induced more strongly toxicity effects than 5 mg L^-1. The relatively stronger effect of CuO NPs at 1 mg L^-1 than the respective CuSO₄ concentration could be attributed to the higher rate of initial uptake (V_c) and the mean rate of Cu uptake [C_max/(2 × K_m)] at CuO NP treatment. The intracellular seaweed experimental threshold of Cu, which coincided with the onset of oxidative stress, was within the Cu concentration range recorded in Mediterranean Ulva spp., indicating that it may pose a substantial risk to marine environments.