Aging of nanosized titanium dioxide modulates the effects of dietary copper exposure on Daphnia magna - an assessment over two generations.

Nanosized titanium dioxide (nTiO2) is widely used in products, warranting its discharge from various sources into surface water bodies. However, nTiO2 co-occurs in surface waters with other contaminants, such as metals. Studies with nTiO2 and metals have indicated that the presence of natural organic matter (NOM) can mitigate their toxicity to aquatic organisms. In addition, "aging" of nTiO2 can affect toxicity. However, it is a research challenge, particularly when addressing sublethal responses from dietary exposure over multiple generations. We, therefore exposed the alga Desmodesmus subspicatus to nTiO2 (at concentrations of 0.0, 0.6 and 3.0 mg nTiO2/L) in nutrient medium aged for 0 or 3 days with copper (Cu) at concentrations of 0 and 116 µg Cu/L and with NOM at concentrations equivalent to 0 and 8 mg total organic carbon (TOC) per litre. Subsequently, the exposed alga was fed to Daphnia magna for 23 days over two generations and survival, reproduction and body length were assessed as endpoints of toxicity. In parallel, Cu accumulation and depuration from D. magna were measured. The results indicate that the reproduction of D. magna was the most sensitive parameter in this study, being reduced by 30% (at both parental (F0) and filial (F1) generations) and 50% (at F0 but not F1) due to the dietary Cu exposure in combination with nTiO2 for 0 and 3 days aging, respectively. There was no relationship between the effects observed on reproduction and Cu body burden in D. magna. Moreover, D. magna from the F1 generation showed an adaptive response to Cu in the treatment with 3.0 mg nTiO2/L aged for 3 days, potentially due to epigenetic inheritance. Unexpectedly, the presence of NOM hardly changed the observed effects, pointing towards the function of algal exopolymeric substances or intracellular organic matter, rendering the NOM irrelevant. Ultimately, the results indicate that the transferability of the impacts observed during the F0 to the responses in the F1 generation is challenging due to opposite effect directions. Additional mechanistic studies are needed to unravel this inconsistency in the responses between generations and to support the development of reliable effect models.

Nanosized titanium dioxide elevates toxicity of cationic metals species for Daphnia - have aging and natural organic matter an unexpected impact?

In aquatic ecosystems, nanosized titanium dioxide particles (nTiO2) likely interact with natural organic matter (NOM) and may alter the ecotoxicity of co-occurring metals. The magnitude of changes in toxicity may be modulated by the duration of interactions (i.e. aging) between these factors. As those interactions are hardly addressed in literature, the present study aimed at assessing the impact of aging durations (0, 1, 3 and 6 days) on metals with mainly cationic (silver (Ag), cadmium (Cd)) or anionic (arsenic (As)) toxic ions in combination with three nTiO2 levels (0.0, 0.6 and 3.0 mg/L) and two NOM levels (0 versus 8 mg TOC/L). The interaction of these factors was additionally investigated for two aging scenarios: in one scenario nTiO2 were aged together with one of the metals, while in other scenario metals were added to aged nTiO2. Subsequently, their combined acute effects on Daphnia magna were assessed. The results uncovered that nTiO2 elevate the toxicity of metals with mainly cationic species (i.e. Ag+ and Cd2+) with the effect size depending on their valence electron. Contrary, nTiO2 have no impact on the metal with mainly anionic species (i.e. HAsO42-). Furthermore, NOM reduced metal toxicity only for Ag and aging duration had a limited impact on the test outcome suggesting that relevant interactions between metal and nTiO2 occur rather quick (below 24 h). These findings suggest that the charge of metals' most toxic species is the determining factor for its interaction with nanoparticles and the resulting ecotoxicological effect assessment.