Incidental zinc sulfide nanoparticles (nano-ZnS) are spread on soils through organic waste (OW) recycling. Here we performed soil incubations with synthetic nano-ZnS (3 nm crystallite size), representative of the form found in OW. We used an original set of techniques to reveal the fate of nano-ZnS in two soils with different properties. 68Zn tracing and nano-DGT were combined during soil incubation to discriminate the available natural Zn from the soil, and the available Zn from the dissolved nano-68ZnS. This combination was crucial to highlight the dissolution of nano-68ZnS as of the third day of incubation. Based on the extended X-ray absorption fine structure, we revealed faster dissolution of nano-ZnS in clayey soil (82% within 1 month) than in sandy soil (2% within 1 month). However, the nano-DGT results showed limited availability of Zn released by nano-ZnS dissolution after 1 month in the clayey soil compared with the sandy soil. These results highlighted: (i) the key role of soil properties for nano-ZnS fate, and (ii) fast dissolution of nano-ZnS in clayey soil. Finally, the higher availability of Zn in the sandy soil despite the lower nano-ZnS dissolution rate is counterintuitive. This study demonstrated that, in addition to nanoparticle dissolution, it is also essential to take the availability of released ions into account when studying the fate of nanoparticles in soil.

Partie B | International audience | Incidental zinc sulfide nanoparticles (nano-ZnS) are spread on soils through organic waste (OW) recycling. Here we performed soil incubations with synthetic nano-ZnS (3 nm crystallite size), representative of the form found in OW. We used an original set of techniques to reveal the fate of nano-ZnS in two soils with different properties. 68 Zn tracing and nano-DGT were combined during soil incubation to discriminate the available natural Zn from the soil, and the available Zn from the dissolved nano-68 ZnS. This combination was crucial to highlight the dissolution of nano-68 ZnS as of the third day of incubation. Based on the extended X-ray absorption fine structure, we revealed faster dissolution of nano-ZnS in clayey soil (82% within 1 month) than in sandy soil (2% within 1 month). However, the nano-DGT results showed limited availability of Zn released by nano-ZnS dissolution after 1 month in the clayey soil compared with the sandy soil. These results highlighted: (i) the key role of soil properties for nano-ZnS fate, and (ii) fast dissolution of nano-ZnS in clayey soil. Finally, the higher availability of Zn in the sandy soil despite the lower nano-ZnS dissolution rate is counterintuitive. This study demonstrated that, in addition to nanoparticle dissolution, it is also essential to take the availability of released ions into account when studying the fate of nanoparticles in soil.

A full-factorial test design was applied to systematically investigate the contribution and significance of water chemistry parameters (pH, divalent cations and dissolved organic carbon (DOC) concentration) and their interactions on the behavior and fate of copper nanoparticles (CuNPs). The total amount of Cu remaining in the water column after 48 h of incubation was mostly influenced by divalent cation content, DOC concentration and the interaction of divalent cations and DOC. DOC concentration was the predominant factor influencing the dissolution of CuNPs, which was far more important than the effect of pH in the range from 6 to 9 on the dissolution of the CuNPs. The addition of DOC at concentrations ranging from 5 to 50 mg C/L resulted in a 3–5 fold reduction of dissolution of CuNPs after 48 h of incubation, as compared to the case without addition of DOC. Divalent cation content was found to be the most influential factor regarding aggregation behavior of the particles, followed by DOC concentration and the interaction of divalent cations and DOC. In addition, the aggregation behavior of CuNPs rather than particulate dissolution explained most of the variance in the sedimentation profiles of CuNPs. These results are meaningful for improved understanding and prediction of the behavior and fate of metallic NPs in aqueous environments.

Understanding how engineered nanoparticles (ENPs) interact with natural organic acids is important to ecological risk assessment of ENPs, but this interaction remains poorly studied. Here, we investigate the dispersion stability, ion release, and toxicity of yttrium oxide nanoparticles (nY2O3) suspensions after exposure to two low molecular weight natural organic acids (LOAs), namely benzoic acid and gallic acid. We find that in the presence of LOAs the nY2O3 suspensions become more stable with surface zeta potential more positive or negative, accompanied by small agglomerated size. LOA interaction with nY2O3 is shown to promote the release of dissolved yttrium from the nanoparticles, depending on the concentrations of LOAs. Toxic effects of the nY2O3 suspensions incubated with LOAs on Scenedesmus obliquus as a function of their mixture levels show three types of signs: stimulation, inhibition, and alleviation. The mechanism of the effects of LOAs on the nY2O3 toxicity may be mainly associated with the degree of agglomeration, particle-induced oxidative stress, and dissolved yttrium. Our results stressed the importance of LOA impacts on the fate and toxicity of ENPs in the aquatic environment.

We investigated the effects of different bioavailability scenarios on the rhamnolipid-enhanced biodegradation of pyrene by the representative polycyclic aromatic hydrocarbon degrader Mycobacterium gilvum VM552. This biosurfactant enhanced biodegradation when pyrene was provided in the form of solid crystals; no effect was observed when the same amount of the chemical was preloaded on polydimethylsiloxane (PDMS). An enhanced effect was observed when pyrene was sorbed into soil but not with the dissolved compound. Synchronous fluorescence spectrophotometry and liquid scintillation were used to determine the phase exchange of pyrene. We also investigated the phase distribution of bacteria. Our results suggest that the rhamnolipid can enhance the biodegradation of pyrene by micellar solubilization and increase diffusive uptake. These mechanisms increase substrate acquisition by bacterial cells at exposure concentrations well above the half-saturation constant for active uptake. The moderate solubilization of pyrene from PDMS by the rhamnolipid and the prevention of cell attachment may explain the lack of enhancement for pyrene-preloaded PDMS.

Dissolution of silver nanoparticles (AgNP with carbonate or citrate coating, total Ag 1–5 μM) was examined in the presence of the ligands cysteine, chloride and fulvic acids and of the oxidant hydrogen peroxide (H2O2) at low concentrations at pH 7.5. Dissolved Ag was separated from AgNP by ultrafiltration. Cysteine in the concentration range 0.2–5 μM resulted in an initial increase of dissolved Ag within few hours. Chloride (up to 0.1 mM) and fulvic acids (up to 15 mg L−1) had little effect on the dissolution of AgNP within hours to days. In contrast, very rapid dissolution within 1–2 h of both carbonate and citrate coated AgNP was observed in the presence of H2O2 in the concentration range 0.1–10 μM, under dark or light conditions. The high efficiency of H2O2 in dissolving AgNP is likely to be of importance in toxic effects of AgNP to algae, as H2O2 is produced and released into solution by algae.

To assess the effect of long-term dissolution on bioavailability and toxicity, triethoxyoctylsilane coated and uncoated zinc oxide nanoparticles (ZnO-NP), non-nano ZnO and ZnCl2 were equilibrated in natural soil for up to twelve months. Zn concentrations in pore water increased with time for all ZnO forms but peaked at intermediate concentrations of ZnO-NP and non-nano ZnO, while for coated ZnO-NP such a clear peak only was seen after 12 months. Dose-related increases in soil pH may explain decreased soluble Zn levels due to fixation of Zn released from ZnO at higher soil concentrations. At T = 0 uncoated ZnO-NP and non-nano ZnO were equally toxic to the springtail Folsomia candida, but not as toxic as coated ZnO-NP, and ZnCl2 being most toxic. After three months equilibration toxicity to F. candida was already reduced for all Zn forms, except for coated ZnO-NP which showed reduced toxicity only after 12 months equilibration.

Various parameters can influence the toxic response to silver nanoparticles (Ag NPs), including the size and surface properties, as well as the exposure environment and the biological site of action. Herein, we assess the intestinal toxicity of three different sizes (10, 40, and 100 nm) of Ag NPs in embryonic zebrafish, and describe the relationship between the properties and behavior of Ag NPs in the exposure medium, and induction of lethal and sublethal effects. We find that the composition of the medium and the size contribute to differential NPs agglomeration, release of Ag ions, and subsequent effects during exposure. The exposure medium causes dramatic reduction in silver dissolution due to the presence of salts and divalent cations, which limits the lethal potential of silver ions. Lethality is observed primarily for embryos exposed to medium sized Ag NPs (40 nm), but not to the supernatant originated from particles, which suggests that the exposure to particulate silver is the main cause of mortality. On the other hand, the exposure to 10 nm and 100 nm NPs, as well as Ag ions, only causes sublethal developmental defects in skeletal muscles and intestine, and induces a nitric oxide imbalance.

In this study, the phototoxicity of cadmium sulfide (CdS), molybdenum disulfide (MoS2), and tungsten disulfide (WS2) nanoparticles (NPs) toward Escherichia coli (E. coli) under UV irradiation (365 nm) was investigated. At the same mass concentration of NPs, the toxicity of three NPs decreased in the order of CdS > MoS2 > WS2. For example, the death rates of E. coli exposed to 50 mg/L CdS, MoS2, and WS2 were 96.7%, 38.5%, and 31.2%, respectively. Transmission electron microscope and laser scanning confocal microscope images of E. coli exposed to three NPs showed the damage of cell walls and release of intracellular components. The CdS-treated cell wall was more extensively damaged than those of MoS2-treated and WS2-treated bacteria. WS2 and MoS2 generated superoxide radical (O2⁻), singlet oxygen (¹O2), and hydroxyl radical under UV irradiation, CdS produced only O2⁻ and ¹O2. CdS and WS2 released ions under UV irradiation, while MoS2 did not. Reactive oxygen species (ROS) generation and toxic ion release jointly resulted in the antibacterial activities of CdS and WS2. ROS generation was the dominant toxic mechanism of MoS2 toward the bacteria. This study highlighted the importance of considering the hazardous effect of sulfide NPs after their release into natural waters under light irradiation condition.