Abstract

Because of wide applications of surface-modified zinc oxide nanoparticles (ZnO-NPs) in commercial sunscreens and their easiness of being released into water, concerns have been raised over their potential effects on aquatic organisms. This study compared physicochemical properties of silane-coated and uncoated ZnO-NPs to elucidate their toxic potencies toward three freshwater and three marine microalgae. Surfaces of ZnO-NPs (20 nm) were modified by coating with 3-aminopropyltrimethoxysilane (A-ZnO-NPs) that provides the particles with a more hydrophilic surface, or dodecyltrichlorosilane (D-ZnO-NPs) that turns the particles to hydrophobic. Uncoated ZnO-NPs formed larger aggregates and released more Zn2+ than did either of the two coated ZnO-NPs. The three nanoparticles formed larger aggregates but released less Zn2+ at pH 8 than at pH 7. Although sensitivities varied among algal species, A-ZnO-NPs and uncoated ZnO-NPs were more potent at inhibiting growth of algal cells than were D-ZnO-NPs after 96-h exposure to ZnO, uncoated ZnO-NPs, each of the coated ZnO-NPs or ZnSO4 at 10 concentrations ranging from 0.1 to 100 mg/L. The marine diatom Thalassiosira pseudonana exposed to ZnO-NPs, A-ZnO-NPs or D-ZnO-NPs resulted in differential expressions of genes, suggesting that each of the coatings resulted in ZnO-NPs acting through different mechanisms of toxic action.

Highlights

  • Due to their wide band gap of 3.37 eV at room temperature, zinc oxide nanoparticles (ZnO-NPs), with at least one dimension between 1 and 100 nm, are excellent absorbers of ultraviolet radiation of solar light[1] and are widely used in sunscreens[2] and photocatalysts[3,4,5]

  • Because the coating serves as a barrier between nanoparticles and the environment, and hinders generation of reactive oxygen species (ROS), Zinc oxide (ZnO)-NPs coated with HP1, a coating agent commonly used in sunscreens have lesser photocatalytic activities than do uncoated ZnO-NPs21

  • Seawater-based f/2 medium at higher pH facilitated aggregation of ZnO, ZnO-NPs and the two coated ZnO-NPs; whereas the freshwater-based BG-11 medium at lower pH enhanced dissolution of the four test zinc compounds after seven days of exposure

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Summary

Introduction

Due to their wide band gap of 3.37 eV at room temperature, zinc oxide nanoparticles (ZnO-NPs), with at least one dimension between 1 and 100 nm, are excellent absorbers of ultraviolet radiation of solar light[1] and are widely used in sunscreens[2] and photocatalysts[3,4,5]. Because the coating serves as a barrier between nanoparticles and the environment, and hinders generation of ROS, ZnO-NPs coated with HP1 (triethoxycaprylylsilane), a coating agent commonly used in sunscreens have lesser photocatalytic activities than do uncoated ZnO-NPs21. Treatment with two coated ZnO-NPs (HP1 and MAX; dimethoxydiphenylsilane and triethoxycaprylylsilane crosspolymer) or Zn2+ from ZnSO4 had little effect on these cells Such differences in toxic potencies among Zn2+, coated and uncoated ZnO-NPs were supported by differentially-expressed genes in hepatic stellate cells[22]. Dodecyltrichlorosilane, which shares a similar chemical structure with HP1, provides a hydrophobic surface to ZnO-NPs. The present study had three primary goals to: (1) compare the physicochemical characteristics of coated and uncoated ZnO-NPs among several culture media; (2) investigate their acute toxicities to selected freshwater and marine microalgae species, and (3) determine molecular mechanisms of toxic action in a marine diatom species

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