Aggregation and Dissolution of 4 nm ZnO Nanoparticles in Aqueous Environments: Influence of pH, Ionic Strength, Size, and Adsorption of Humic Acid
TL;DR: Measurements of nanoparticle aggregation due to attractive particle-particle interactions show that ionic strength, pH, and adsorption of humic acid affect the aggregation of ZnO nanoparticles in aqueous solutions, which are consistent with the trends expected from Derjaguin-Landau-Verwey-Overbeek (DLVO) theory.
Abstract: Metal oxide nanoparticles are used in a wide range of commercial products, leading to an increased interest in the behavior of these materials in the aquatic environment. The current study focuses on the stability of some of the smallest ZnO nanomaterials, 4 ± 1 nm in diameter nanoparticles, in aqueous solutions as a function of pH and ionic strength as well as upon the adsorption of humic acid. Measurements of nanoparticle aggregation due to attractive particle−particle interactions show that ionic strength, pH, and adsorption of humic acid affect the aggregation of ZnO nanoparticles in aqueous solutions, which are consistent with the trends expected from Derjaguin−Landau−Verwey−Overbeek (DLVO) theory. Measurements of nanoparticle dissolution at both low and high pH show that zinc ions can be released into the aqueous phase and that humic acid under certain, but not all, conditions can increase Zn2+(aq) concentrations. Comparison of the dissolution of ZnO nanoparticles of different nanoparticle diameters...
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TL;DR: The nature and extent of the transformations that occur in nanomaterials must be understood before significant progress can be made toward understanding the environmental risks posed by these materials.
Abstract: Increasing use of engineered nanomaterials with novel properties relative to their bulk counterparts has generated a need to define their behaviors and impacts in the environment. The high surface ...
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TL;DR: These studies suggest relative high acute toxicity of ZnO NPs (in the low mg/l levels) to environmental species, although this toxicity is highly dependent on test species, physico-chemical properties of the material, and test methods.
766 citations
Cites background from "Aggregation and Dissolution of 4 nm..."
...Significant increase in solubility with decreasing particle size of ZnO have been reported (Bian et al., 2011; Meulenkamp, 1998; Mudunkotuwa et al., 2012; Reed et al., 2012) and increased surface area is one important reason for increased kinetic rates of dissolution (Mudunkotuwa et al., 2012)....
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TL;DR: Investigation of the toxicity of silver nanoparticles in A549 lung cells concluded that at high silver ion fractions the AgNPs did not add measurable additional toxicity to the AgNP suspension, whereas at low silver ion fraction AgNP suspensions are more toxic than their supernatant.
663 citations
TL;DR: If traditional approaches based on the DLVO-theory can be useful in specific cases, quantitative aggregation models taking into account DOM dynamics, bridging, and disaggregation are needed for a comprehensive modeling of colloids stability in natural media.
Abstract: This contribution critically reviews the state of knowledge on interactions of natural colloids and engineered nanoparticles with natural dissolved organic materials (DOM). These interactions determine the behavior and impact of colloids in natural system. Humic substances, polysaccharides, and proteins present in natural waters adsorb onto the surface of most colloids. We outline major adsorption mechanisms and structures of adsorption layers reported in the literature and discuss their generality on the basis of particle type, DOM type, and media composition. Advanced characterization methods of both DOM and colloids are needed to address insufficiently understood aspects as DOM fractionation upon adsorption, adsorption reversibility, and effect of capping agent. Precise knowledge on adsorption layer helps in predicting the colloidal stability of the sorbent. While humic substances tend to decrease aggregation and deposition through electrostatic and steric effects, bridging-flocculation can occur in th...
562 citations
TL;DR: A review of available dissolution data on NPs demonstrates there is a range of potential outcomes depending on the NPs and the exposure media, and it is imperative that toxicological studies are conducted in conjunction with dissolution of NPs to establish the true biological effect ofNPs and hence, assist in their regulation.
431 citations
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TL;DR: The results demonstrate that metal oxide nanoparticles induce a range of biological responses that vary from cytotoxic to cytoprotective and can only be properly understood by using a tiered test strategy such as that developed for oxidative stress and adapted to study other aspects of nanoparticle toxicity.
Abstract: Nanomaterials (NM) exhibit novel physicochemical properties that determine their interaction with biological substrates and processes. Three metal oxide nanoparticles that are currently being produced in high tonnage, TiO2, ZnO, and CeO2, were synthesized by flame spray pyrolysis process and compared in a mechanistic study to elucidate the physicochemical characteristics that determine cellular uptake, subcellular localization, and toxic effects based on a test paradigm that was originally developed for oxidative stress and cytotoxicity in RAW 264.7 and BEAS-2B cell lines. ZnO induced toxicity in both cells, leading to the generation of reactive oxygen species (ROS), oxidant injury, excitation of inflammation, and cell death. Using ICP-MS and fluorescent-labeled ZnO, it is found that ZnO dissolution could happen in culture medium and endosomes. Nondissolved ZnO nanoparticles enter caveolae in BEAS-2B but enter lysosomes in RAW 264.7 cells in which smaller particle remnants dissolve. In contrast, fluoresce...
2,206 citations
TL;DR: The results of this study make it possible for the first time to carry out a quantitative risk assessment of nanoparticles in the environment and suggest further detailed studies of nano-TiO2.
Abstract: The aim of this study was to use a life-cycle perspective to model the quantities of engineered nanoparticles released into the environment. Three types of nanoparticles were studied: nano silver (nano-Ag), nano TiO2 (nano-TiO2), and carbon nanotubes (CNT). The quantification was based on a substance flow analysis from products to air, soil, and water in Switzerland. The following parameters were used as model inputs: estimated worldwide production volume, allocation of the production volume to product categories, particle release from products, and flow coefficients within the environmental compartments. The predicted environmental concentrations (PEC) were then compared to the predicted no effect concentrations (PNEC) derived from the literature to estimate a possible risk. The expected concentrations of the three nanoparticles in the different environmental compartments vary widely, caused by the different life cycles of the nanoparticle-containing products. The PEC values for nano-TiO2 in water are 0....
1,776 citations
TL;DR: Spanhel et al. as mentioned in this paper showed that the aging of ZnO nanoparticles was governed by temperature, the water content, and the presence of reaction products, and they presented a better defined and more versatile procedure for production of clean ZnOs of readily adjustable particle size.
Abstract: ZnO nanoparticles in the size range from 2 to 7 nm were prepared by addition of LiOH to an ethanolic zinc acetate solution. This method [Spanhel, L.; Anderson, M. A. J. Am. Chem. Soc. 1991, 113, 2826] was modified and extended at several points. The synthesis of very small ZnO nuclei was simplified. It was found that aging of particles was governed by temperature, the water content, and the presence of reaction products. Water and acetate induced considerably accelerated particle growth. Growth could almost be stopped by removal of these species (“washing”). Washing consisted of repeated precipitation of ZnO by addition of alkanes such as heptane, removal of the supernatant, and redispersion in ethanol. The aging characteristics are interpreted in terms of the concentration of dissolved ZnII species and reactions well-known in sol−gel chemistry. These findings present a better-defined and more versatile procedure for production of clean ZnO sols of readily adjustable particle size. Such sols are of partic...
1,227 citations
TL;DR: The electrophoretic mobility of the particles in a given aqueous media was dominated by the presence of natural organic matter (NOM) and ionic strength, and independent of pH.
Abstract: There is a pressing need for information on the mobility of nanoparticles in the complex aqueous matrices found in realistic environmental conditions. We dispersed three different metal oxide nanoparticles (TiO(2), ZnO and CeO(2)) in samples taken from eight different aqueous media associated with seawater, lagoon, river, and groundwater, and measured their electrophoretic mobility, state of aggregation, and rate of sedimentation. The electrophoretic mobility of the particles in a given aqueous media was dominated by the presence of natural organic matter (NOM) and ionic strength, and independent of pH. NOM adsorbed onto these nanoparticles significantly reduces their aggregation, stabilizing them under many conditions. The transition from reaction to diffusion limited aggregation occurs at an electrophoretic mobility from around -2 to -0.8 microm s(-1) V(-1) cm. These results are key for designing and interpreting nanoparticle ecotoxicity studies in various environmental conditions.
1,165 citations
TL;DR: In this review, colloidal forces governing nanoparticle deposition and aggregation are outlined, and essential equations used to assess particle-particle and particle-surface interactions, along with Hamaker constants for specific nanoparticles and the attributes exclusive to nanoscale particle interactions, are described.
Abstract: The ever-increasing use of engineered nanomaterials will lead to heightened levels of these materials in the environment. The present review aims to provide a comprehensive overview of current knowledge regarding nanoparticle transport and aggregation in aquatic environments. Nanoparticle aggregation and deposition behavior will dictate particle transport potential and thus the environmental fate and potential ecotoxicological impacts of these materials. In this review, colloidal forces governing nanoparticle deposition and aggregation are outlined. Essential equations used to assess particle−particle and particle−surface interactions, along with Hamaker constants for specific nanoparticles and the attributes exclusive to nanoscale particle interactions, are described. Theoretical and experimental approaches for evaluating nanoparticle aggregation and deposition are presented, and the major findings of laboratory studies examining these processes are also summarized. Finally, we describe some of the chall...
1,028 citations