This study presents the behavior of novel anti-fouling nanomaterials in seawater and their toxicity towards target and non-target marine species.

Biofouling is a global problem that affects virtually all the immersed structures. Currently, several novel environmentally friendly approaches are being tested worldwide to decrease the toxicity of biocides in non-fouling species, such as the encapsulation/immobilization of commercially available biocides, in order to achieve control over the leaching rate. The present study addresses the toxicity of two widely used booster biocides, zinc pyrithione (ZnPT) and copper pyrithione (CuPT), in its free and incorporated forms in order to assess their toxicity and anti-fouling efficacy in target and non-target species. To achieve this goal, the following marine organisms were tested; the green microalgae Tetraselmis chuii (non-target species) and both target species, the diatom Phaeodactylum tricornutum and the mussel Mytilus edulis. Organisms were exposed to both biocides, two unloaded nanostructured materials and nanomaterials loaded with biocides, from 10 μg/L to 100 mg/L total weight, following standard protocols. The most eco-friendly and simultaneously efficient anti-fouling solution against the two photosynthetic species (nanoclays loaded with ZnPT) was then tested on mussels to assess its lethal efficacy (LC = 123 μg/L) and compared with free biocide (LC = 211 μg/L) and unloaded material (LC > 1000 μg/L). A second exposure test with sub-lethal concentrations (lower than 100 μg/L), using mussels, was carried out to assess biochemical changes caused by the tested compounds. Oxidative stress, detoxification and neurotransmission markers were not responsive; however, different antioxidant patterns were found with free ZnPT and loaded nanoclay exposures. Thus, the immobilization of the biocide ZnPT into nanoclays proved to be a promising efficient and eco-friendly anti-fouling strategy.

Abstract:The application of nano-structured compounds has been increasing rapidly in recent years, in several fields. The use of engineered nano-materials as carriers of antifouling compounds is just beginning and already reveals clear advantages compared to bulk active compounds, such as slowed and controlled release, novel functionality, and high loading capacity. This present study assesses the antifouling efficacy of two nanostructured materials, spherical mesoporous silica nanocapsules (SiNC) and Zn-Al layered double hydroxides (LDH), loaded with two commercial biocides, zinc prithione (ZnPT) and copper pyrithione (CuPT). The study used adult mussels from three geographical regions, the Atlantic Ocean, Mediterranean Sea, and the Red Sea, to examine the efficacy of the innovative compounds. The efficacy of these compounds on larvae of the bryozoan Bugula neritina from the Mediterranean Sea and the Red Sea was also examined. The results of this study demonstrated the environmentally friendly properties of unloaded LDH against the two-model systems, adult mussels or bryozoan larvae. ZnPT entrapped in LDH demonstrated the most effective antifouling compound against the two model systems. A comparison of the impact of the two compounds on macrofouling organisms from the different marine habitats examined in this study indicates a distinction associated with the organisms' different ecosystems. The Red Sea mussels and bryozoans, representing a tropical marine ecosystem, yielded the highest efficacy values among tested Atlantic Ocean and Mediterranean Sea mussels and bryozoans.

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