Release of indium from In2O3 nanoparticles in model solutions and synthetic seawater.

Indium oxide (In2O3) nanoparticles (NPs) are used in electronic devices, from which indium (as its nanoparticulate form or as other generated chemical species) can be released to natural waters. To assess for the impacts of such releases (e.g. toxic effects), information on the kinetics and thermodynamics of the In2O3 dissolution processes is key. In this work, the evolution with time of the dissolution process was followed with the technique AGNES (Absence of Gradients and Nernstian Equilibrium Stripping) by measuring the free indium concentration ([In3+]). AGNES can determine the free ion concentration in the presence of nanoparticles without a prior separation step, as shown in the case of ZnO nanoparticles, a procedure that is more accurate than the typical sequence of centrifugation+filtration+elemental analysis. Excess of indium oxide NPs were dispersed in 0.1 mol L-1 KNO3 at various pH values ranging from 2 to 8. Additional dispersions with bulk In2O3 at pH 3 or NPs in synthetic seawater at pH 8 were also prepared. The temperature was carefully fixed at 25 °C. The dispersions were continuously stirred and samples were taken from time to time to measure free indium concentration with AGNES. 180-day contact of In2O3 to solutions at pH 2 and 3 was not enough to reach equilibrium. The dissolution of the NPs at pH 3 was faster than that of the bulk (i.e. non nanoparticulate) material. Equilibrium of the NPs with the solution was reached at pH 4 and 5 in KNO3 and at pH 8 in seawater, in shorter times for higher pH values, with free indium concentrations decreasing by a factor of 1000 for each increase in one pH unit. The solubility products of In(OH)3 and In2O3 were compared. Equilibration of NPs with synthetic seawater took <18 days, with an average free [In3+] (up to 196 days) of 1.03 amol L-1.

In Situ Tracking of Crystal-Surface-Dependent Cu2O Nanoparticle Dissolution in an Aqueous Environment.

Metal-oxide-based nanoparticles (MONPs) such as Cu2O NPs have attracted growing attention, but the potential discharges of MONPs have raised considerable concern of their environmental fate including their dissolution behavior. The impacts of morphology on MONP dissolution are largely uncertain due to the lack of in situ tracking techniques. In this study, we combined a series of in situ technologies including liquid-cell transmission electron microscopy and fluorescence probes to reveal the in situ dissolution process of Cu2O NPs in freshwater. Our results suggest that cubic Cu2O NPs exhibit a higher dissolution quantity compared with spherical NPs of the same surface area. The difference was mainly related to the crystal surface, while other factors such as particle size or aggregation status showed minor effects. Importantly, we demonstrated the simultaneous growth of new small NPs and the dissolution of pristine Cu2O NPs during the dissolution of Cu2O NPs. Cubic Cu2O NPs became much less soluble under O2-limited conditions, suggesting that O2 concentration largely affected the dependence of dissolution on the NP morphology. Our findings highlight the potential application of in situ techniques to track the environmental fates of MONPs, which would provide important information for assessing the ecological risks of engineered NPs.

Single-Particle Electrochemical Imaging Provides Insights into Silver Nanoparticle Dissolution at the Solution-Solid Interface.

Dissolution of nanoparticles is an environmental interfacial process that affects the transformation of nanoparticles. Understanding the dissolution processes of nanoparticles is important to predict their fate in the aquatic environment. However, studying nanoparticle dissolution kinetics is still challenging since dissolution is usually coupled with nanoparticle aggregation. Here, we probed the dissolution process of Ag nanoparticles at the single-particle level by surface plasmon resonance microscopy. The single-particle imaging capability enabled us to classify Ag nanoparticles, measure the dissolution dynamics of single nanoparticles, and correlate the aggregation size with oxidation activity. Moreover, we studied the dual effect of natural organic matter on the dissolution of Ag nanoparticles and validated this result with real natural freshwater. Our study provides new insights into the dissolution of Ag nanoparticles, and this technique can be extended for other nanomaterials to evaluate their fate in aquatic environments.

Fate and transformation of silver nanoparticles in different biological conditions.

The exploitation of silver nanoparticles (AgNPs) in biomedicine represents more than one third of their overall application. Despite their wide use and significant amount of scientific data on their effects on biological systems, detailed insight into their in vivo fate is still lacking. This study aimed to elucidate the biotransformation patterns of AgNPs following oral administration. Colloidal stability, biochemical transformation, dissolution, and degradation behaviour of different types of AgNPs were evaluated in systems modelled to represent biological environments relevant for oral administration, as well as in cell culture media and tissue compartments obtained from animal models. A multimethod approach was employed by implementing light scattering (dynamic and electrophoretic) techniques, spectroscopy (UV-vis, atomic absorption, nuclear magnetic resonance) and transmission electron microscopy. The obtained results demonstrated that AgNPs may transform very quickly during their journey through different biological conditions. They are able to degrade to an ionic form and again reconstruct to a nanoparticulate form, depending on the biological environment determined by specific body compartments. As suggested for other inorganic nanoparticles by other research groups, AgNPs fail to preserve their specific integrity in in vivo settings.

Fungus Aspergillus niger Processes Exogenous Zinc Nanoparticles into a Biogenic Oxalate Mineral.

Zinc oxide nanoparticles (ZnO NPs) belong to the most widely used nanoparticles in both commercial products and industrial applications. Hence, they are frequently released into the environment. Soil fungi can affect the mobilization of zinc from ZnO NPs in soils, and thus they can heavily influence the mobility and bioavailability of zinc there. Therefore, ubiquitous soil fungus Aspergillus niger was selected as a test organism to evaluate the fungal interaction with ZnO NPs. As anticipated, the A. niger strain significantly affected the stability of particulate forms of ZnO due to the acidification of its environment. The influence of ZnO NPs on fungus was compared to the aqueous Zn cations and to bulk ZnO as well. Bulk ZnO had the least effect on fungal growth, while the response of A. niger to ZnO NPs was comparable with ionic zinc. Our results have shown that soil fungus can efficiently bioaccumulate Zn that was bioextracted from ZnO. Furthermore, it influences Zn bioavailability to plants by ZnO NPs transformation to stable biogenic minerals. Hence, a newly formed biogenic mineral phase of zinc oxalate was identified after the experiment with A. niger strain's extracellular metabolites highlighting the fungal significance in zinc biogeochemistry.

Impact of lithiated cobalt oxide and phosphate nanoparticles on rainbow trout gill epithelial cells.

Metal oxide and phosphate nanoparticles (NPs) are ubiquitous in emerging applications, ranging from energy storage to catalysis. Cobalt-containing NPs are particularly important, where their widespread use raises questions about the relationship between composition, structure, and potential for environmental impacts. To address this gap, we investigated the effects of lithiated metal oxide and phosphate NPs on rainbow trout gill epithelial cells, a model for environmental exposure. Lithium cobalt oxide (LCO) NPs significantly reduced cell viability at10 µg/mL, while a 10-fold higher concentration of lithiated cobalt hydroxyphosphate (LCP) NPs was required to significantly reduce viability. Exposure to Li+ and Co2+ alone, at concentrations relevant to ion released from the NPs, did not reduce cell viability and minimally impacted reactive oxygen species (ROS) levels. Both LCO- and LCP-NPs were found within membrane-bound organelles. However, only LCP-NPs underwent rapid and complete dissolution in artificial lysosomal fluid. Unlike LCP-NPs, LCO-NPs significantly increased intracellular ROS, could be found within abnormal multilamellar bodies, and induced formation of intracellular vacuoles. Increased p53 gene expression, measured in individual cells, was observed at sub-toxic concentrations of both LCO- and LCP-NPs, implicating both in inductions of cellular damage and stress at concentrations approaching predicted environmental levels. Our results implicate the intact NP, not the dissolved ions, in the observed adverse effects and show that LCO-NPs significantly impact cell viability accompanied by increase in intracellular ROS and formation of organelles indicative of cell stress, while LCP-NPs have minimal adverse effects, possibly due to their rapid dissolution in acidic organelles.

In vivo comparisons of silver nanoparticle and silver ion transport after intranasal delivery in mice.

Silver nanoparticles (AgNPs) are widely available as consumer goods, and over-the-counter or nutraceutical products used for alleged therapeutic and antibacterial properties. Among these products, AgNP topical therapy is proposed for treating patients with upper airway bacterial rhinosinusitis. While silver ion release from AgNPs in biological systems is well known, limited investigations actually characterize this silver ion release and their subsequent biological effects distinct from delivered particulate metallic silver. This is in part due to the analytical complexity and difficulty involved in distinguishing silver ion release from metallic AgNPs in biological media. Therefore, this study compared intranasal administration of AgNPs versus soluble silver ion (AgNO3) control to examine their transport and biological differences in tissues. First, we compared bactericidal activities of AgNPs and AgNO3 in those bacteria commonly associated with clinical rhinosinusitis in vitro. Next, we evaluated silver residence time in the sinus cavity after intranasal delivery of AgNPs and AgNO3 to mice, and characterized tissue distribution of silver in the sinonasal mucosal epithelium. We found that AgNPs show reduced bactericidal activity compared to AgNO3 (i.e., MBC of 15ppm compared to 5ppm), and significantly lower residence times in the sinus cavity (AgNP concentrations of 3.76ppm after 3h compared to 9ppm for AgNO3). AgNPs were not readily taken up into or through respiratory epithelium, with very low silver levels found in blood and no detectable silver measured in the olfactory bulb and brain. Results indicate that limited tissue distribution of silver detected from AgNPs is due to AgNP dissolution to silver ion. AgNPs therefore demonstrate adequate safety through limited penetration and absorption, but limited potential therapeutic efficacy as antimicrobials in nasal applications, as concentrations of silver in the sinus cavity drop below the minimum bactericidal concentration within 3h.

Influence of daylight on the fate of silver and zinc oxide nanoparticles in natural aquatic environments.

Nanoparticles, such as silver (Ag-NP) and zinc oxide (ZnO-NP), are increasingly used in many consumer products. These nanoparticles (NPs) will likely be exposed to the aquatic environment (rain, river, lake water) and to light (visible and UV) in the products where they are applied, or after those products are discharged. Dissolution of Ag-NP and ZnO-NP is an important process because the dissolved Ag+ and Zn2+ are readily available and toxic for aquatic organisms. The objective of this study was to investigate the role of daylight (UV and visible) for the fate of engineered Ag-NP and ZnO-NPs in different types of natural waters. Ag-NP and ZnO-NP were exposed to rainwater, river Rhine, and lake waters (Greifen, Lucerne, Cristallina, Gruère) under different light conditions (no light, UV 300-400 nm and visible light 400-700 nm) for up to 8 days. Stronger agglomeration of Ag-NP was observed in the waters with higher ionic strength in comparison to those with lower ionic strength. Visible light tended to increase the dissolution of Ag-NP under most natural water conditions in comparison to dark conditions, whereas UV-light led to decreased dissolved Ag+ after longer exposure time. These effects illustrate the dynamic interactions of Ag-NP with light, which may lead both to increased oxidation and to increased reduction of Ag+ by organic compounds under UV-light. In the case of ZnO-NP, agglomeration occurred at higher ionic strength, but the effects of pH were predominant for dissolution, which occurred up to concentrations close to the solubility limit of ZnO(s) at pH around 8.2 and to nearly complete dissolution of ZnO-NP at lower pH (pH 4.8-6.5), with both visible and UV-light facilitating dissolution. This study thus shows that light conditions play an important role in the dissolution processes of nanoparticles.

Comparative in vitro genotoxicity study of ZnO nanoparticles, ZnO macroparticles and ZnCl2 to MDCK kidney cells: Size matters.

In the present study, we evaluated the roles that ZnO particle size and Zn ion release have on cyto- and genotoxicity in vitro. The Madin-Darby canine kidney (MDCK) cells were treated with ZnO nanoparticles (NPs), ZnO macroparticles (MPs), and ZnCl2 as a source of free Zn ions. We first tested cytotoxicity to define sub-cytotoxic exposure concentrations and afterwards we performed alkaline comet and cytokinesis-block micronucleus assays. Additionally, the activities of both catalase (CAT) and glutathione S-transferase (GST) were evaluated in order to examine the potential impairment of cellular stress-defence capacity. The amount of dissolved Zn ions from ZnO NPs in the cell culture medium was evaluated by an optimized voltammetric method. The results showed that all the tested zinc compounds induced similar concentration-dependent cytotoxicity, but only ZnO NPs significantly elevated DNA and chromosomal damage, which was accompanied by a reduction of GST and CAT activity. Although Zn ion release from ZnO NPs in cell culture medium was significant, our results show that this reason alone cannot explain the ZnO genotoxicity seen in this experiment. We discuss that genotoxicity of ZnO NPs depends on the particle size, which determines the physical principles of their dissolution and cellular internalisation.

Oxidative dissolution of silver nanoparticles: A new theoretical approach.

A general model of an oxidative dissolution of silver particle suspensions was developed that rigorously considers the bulk and surface solute transport. A two-step surface reaction scheme was proposed that comprises the formation of the silver oxide phase by direct oxidation and the acidic dissolution of this phase leading to silver ion release. By considering this, a complete set of equations is formulated describing oxygen and silver ion transport to and from particles' surfaces. These equations are solved in some limiting cases of nanoparticle dissolution in dilute suspensions. The obtained kinetic equations were used for the interpretation of experimental data pertinent to the dissolution kinetics of citrate-stabilized silver nanoparticles. In these kinetic measurements the role of pH and bulk suspension concentration was quantitatively evaluated by using the atomic absorption spectrometry (AAS). It was shown that the theoretical model adequately reflects the main features of the experimental results, especially the significant increase in the dissolution rate for lower pH. Also the presence of two kinetic regimes was quantitatively explained in terms of the decrease in the coverage of the fast dissolving oxide layer. The overall silver dissolution rate constants characterizing these two regimes were determined.

Developmental effects of two different copper oxide nanomaterials in sea urchin (Lytechinus pictus) embryos.

Copper oxide nanomaterials (nano-CuOs) are widely used and can be inadvertently introduced into estuarine and marine environments. We analyzed the effects of different nano-CuOs (a synthesized and a less-pure commercial form), as well as ionic copper (CuSO4) on embryo development in the white sea urchin, a well-known marine model. After 96 h of development with both nano-CuO exposures, we did not detect significant oxidative damage to proteins but did detect decreases in total antioxidant capacity. We show that the physicochemical characteristics of the two nano-CuOs play an essential role in their toxicities. Both nano-CuOs were internalized by embryos and their differential dissolution was the most important toxicological parameter. The synthesized nano-CuO showed greater toxicity (EC50 = 450 ppb of copper) and had increased dissolution (2.5% by weight over 96 h) as compared with the less-pure commercial nano-CuO (EC50 = 5395 ppb of copper, 0.73% dissolution by weight over 96 h). Copper caused specific developmental abnormalities in sea urchin embryos including disruption of the aboral-oral axis as a result in changes to the redox environment caused by dissolution of internalized nano-CuO. Abnormal skeleton formation also occurred.

Programmed iron oxide nanoparticles disintegration in anaerobic digesters boosts biogas production.

A novel concept of dosing iron ions using Fe3O4 engineered nanoparticles is used to improve biogas production in anaerobic digestion processes. Since small nanoparticles are unstable, they can be designed to provide ions in a controlled manner, and the highest ever reported improvement of biogas production is obtained. The nanoparticles evolution during operation is followed by an array of spectroscopic techniques.