Toxicity, bioaccumulation and biotransformation of glucose-capped silver nanoparticles in green microalgae chlorella vulgaris

Silver nanoparticles (AgNPs) are one of the most widely used nanomaterials in consumer products. When discharged into the aquatic environment AgNPs can cause toxicity to aquatic biota, through mechanisms that are still under debate, thus rendering the nanoparticles (NPs) effects evaluation a necessary step. Different aquatic organism models, i.e., microalgae, mussels, Daphnia magna, sea urchins and Danio rerio, etc. have been largely exploited for NPs toxicity assessment. On the other hand, alternative biological microorganisms abundantly present in nature, i.e., microalgae, are nowadays exploited as a potential sink for removal of toxic substances from the environment. Indeed, the green microalgae Chlorella vulgaris is one of the most used microorganisms for waste treatment. With the aim to verify the possible involvement of C. vulgaris not only as a model microorganism of NPs toxicity but also for the protection toward NPs pollution, we used these microalgae to measure the AgNPs biotoxicity and bioaccumulation. In particular, to exclude any toxicity derived by Ag+ ions release, green chemistry-synthesised and glucose-coated AgNPs (AgNPs-G) were used. C. vulgaris actively internalised AgNPs-G whose amount increases in a time- and dose-dependent manner. The internalised NPs, found inside large vacuoles, were not released back into the medium, even after 1 week, and did not undergo biotransformation since AgNPs-G maintained their crystalline nature. Biotoxicity of AgNPs-G causes an exposure time and AgNPs-G dose-dependent growth reduction and a decrease in chlorophyll-a amount. These results confirm C. vulgaris as a bioaccumulating microalgae for possible use in environmental protection

Nanoscale chemical imaging of nanoparticles under real-world wastewater treatment conditions

Understanding nanomaterial transformations within wastewater treatment plants is an important step to better predict their potential impact on the environment. Here, spatially resolved, in situ nano-X-ray fluorescence microscopy is applied to directly observe nanometer-scale dissolution, morphological, and chemical evolution of individual and aggregated ZnO nanorods in complex “real-world” conditions: influent water and primary sludge collected from a municipal wastewater system. A complete transformation of isolated ZnO nanorods into ZnS occurs after only 1 hour in influent water, but larger aggregates of the ZnO nanorods transform only partially, with small contributions of ZnS and Zn-phosphate (Zn3(PO4)2) species, after 3 hours. Transformation of aggregates of the ZnO nanorods toward mixed ZnS, Zn adsorbed to Fe-oxyhydroxides, and a large contribution of Zn3(PO4)2 phases are observed during their incubation in primary sludge for 3 hours. Discrete, isolated ZnO regions are imaged with unprecedented spatial resolution, revealing their incipient transformation toward Zn3(PO4)2. Passivation by transformation(s) into mixtures of less soluble phases may influence the subsequent bioreactivity of these nanomaterials. This work emphasizes the importance of imaging the nanoscale chemistry of mixtures of nanoparticles in highly complex, heterogeneous semi-solid matrices for improved prediction of their impacts on treatment processes, and potential environmental toxicity following release