Solubility and batch retention of CeO2 nanoparticles in soils

There is a paucity of information on the environmental fate of cerium oxide nanoparticles (CeO2 NPs) for terrestrial systems that may be exposed to CeO2 NPs by the application of biosolids derived from wastewater treatment systems. Using ultrafiltration (UF), dissolution, and nonequilibrium retention (Kr) values of citrate-coated (8 nm diameter) CeO2 NPs and partitioning (Kd) values of dissolved Ce(III) and Ce(IV) were obtained in suspensions of 16 soils with a diversity of physicochemical properties. Dissolution of CeO2 NPs studied in solutions was only significant at pH 4 and was less than 3.1%, whereas no dissolved Ce was detected in soils spiked with CeO2 NPs. Kr values of CeO2 NP were low (median Kr=9.6 L kg(-1)) relative to Kd values of dissolved CeIII and CeIV (median Kd=3763 and 1808 L kg(-1), respectively), suggesting low CeO2 NP retention in soils. Surface adsorption of phosphate to CeO2 NP caused a negative zeta potential, which may explain the negative correlation of log Kr values with dissolved phosphate concentrations and the significant reduction of Kr values upon addition of phosphate to soils. The positive correlation of Kr values with clay content suggested heterocoagulation of CeO2 NPs with natural colloids in soils. Co-addition of CeO2 NPs with biosolids, on the other hand, did not affect retention.     

Size effects on adsorption of hematite nanoparticles on E. coli cells

Adsorption of engineered nanoparticles (NPs) onto bacterial cells is critical for quantifying nanobio interactions as well as toxicokinetic properties of NPs. The purpose of this work was to study adsorption of hematite (α-Fe(2)O(3)) NPs onto Escherichia coli cells and to determine the particle size effects on the adsorption kinetics. Adsorption of large NPs (76 and 98 nm) on cells reached equilibrium faster (within 30-40 min) than small NPs (approximately 60-90 min). The adsorption rates in mg Fe/(L · s) decreased in the order of 98 nm > 76 nm > 53 nm > 26 nm. However, adsorption rates expressed as the number of adsorbed hematite NPs per unit cell surface area in #/(m2 · s) were faster for small NPs than those for large NPs. To interpret the size effects on adsorption kinetics, the Extended Derjaguin-Landau-Verwey-Overbeek (EDLVO) theory was combined with interfacial force boundary layer (IFBL) theory. The computed adsorption rates for different sizes had excellent agreement with the experimental data, and they explained that that faster kinetics for smaller NPs could be attributed to faster particle mobility and lower energy barriers in the total interaction energy. This study lays the groundwork for quantifying the kinetic behavior of NPs interacting with microbial cells, and the results provide insight into adsorption processes at the nanoscale.     

Distribution of functionalized gold nanoparticles between water and lipid bilayers as model cell membranes

Lipid bilayers are biomembranes common to cellular life and constitute a continuous barrier between cells and their environment. Understanding the interaction of nanoparticles with lipid bilayers is an important step toward predicting subsequent biological effects. In this study, we assessed the affinity of functionalized gold nanoparticles (Au NPs) with sizes from 5 to 100 nm to lipid bilayers by determining the Au NP distribution between aqueous electrolytes and lipid bilayers. The Au NP distribution to lipid bilayers reached an apparent steady state in 24 h with smaller Au NPs distributing onto lipid bilayers more rapidly than larger ones. Au NPs distributed to lipid bilayers to a larger extent at lower pH. Tannic acid-functionalized Au NPs exhibited greater distribution to lipid bilayers than polyvinylpyrrolidone-functionalized Au NPs of the same size. Across the various Au NP sizes, we measure the lipid bilayer-water distribution coefficient (K(lipw) = C(lip)/C(w)) as 450 L/kg lipid, which is independent of dosimetric units. This work suggests that the nanoparticle-cell membrane interaction is dependent on solution chemistry and nanoparticle surface functionality. The K(lipw) value may be used to predict the affinity of spherical Au NPs across a certain size range toward lipid membranes.     

Impact of whey protein isolates and concentrates on the formation of protein nanoparticles‐stabilised Pickering emulsions

Whey protein nanoparticles (NPs) were prepared by heat‐induced method. The influences of whey protein isolates (WPIs) and concentrates (WPCs) on the formation of NPs were first investigated. Then Pickering emulsions were produced by protein NPs and their properties were evaluated. After heat treatment, WPC NPs showed larger particle size, higher stability against NaCl, lower negative charge and contact angle between air and water. Dispersions of WPC NPs appeared as higher turbidity and viscosity than those of WPI NPs. The interfacial tension of WPC NPs (~7.9 mN/m at 3 wt% NPs) was greatly lower than that of WPI NPs (~12.1 mN/m at 3 wt% NPs). WPC NPs‐stabilised emulsions had smaller particle size and were more homogeneous than WPI NPs‐stabilised emulsions. WPC NPs‐stabilised emulsions had higher stability against NaCl, pH and coalescence during storage.     

Influence of collector surface composition and water chemistry on the deposition of cerium dioxide nanoparticles: QCM-D and column experiment approaches

The deposition behavior of cerium dioxide (CeO(2)) nanoparticles (NPs) in dilute NaCl solutions was investigated as a function of collector surface composition, pH, ionic strength, and organic matter (OM). Sensors coated separately with silica, iron oxide, and alumina were applied in quartz crystal microbalance with dissipation (QCM-D) to examine the effect of these mineral phases on CeO(2) deposition in NaCl solution (1-200 mM). Frequency and dissipation shift followed the order: silica > iron oxide > alumina in 10 mM NaCl at pH 4.0. No significant deposition was observed at pH 6.0 and 8.5 on any of the tested sensors. However, ≥ 94.3% of CeO(2) NPs deposited onto Ottawa sand in columns in 10 mM NaCl at pH 6.0 and 8.5. The inconsistency in the different experimental approaches can be mainly attributed to NP aggregation, surface heterogeneity of Ottawa sand, and flow geometry. In QCM-D experiments, the deposition kinetics was found to be qualitatively consistent with the predictions based on the classical colloidal stability theory. The presence of low levels (1-6 mg/L) of Suwannee River humic acid, fulvic acid, alginate, citric acid, and carboxymethyl cellulose greatly enhanced the stability and mobility of CeO(2) NPs in 1 mM NaCl at pH 6.5. The poor correlation between the transport behavior and electrophoretic mobility of CeO(2) NPs implies that the electrosteric effect of OM was involved.     

Physical,mechanical, and antibacterial characteristics of bio-nanocomposite films loaded with Ag-modified SiO2 and TiO2 nanoparticles

In this study, starch-based films incorporating metal oxide (MO₂) nanoparticles (NPs) of TiO₂ and SiO₂ (at a concentration of 1 to 4 wt. %) were produced by solution casting method. In order to exhibit antimicrobial properties, MO₂ NPs were modified by synthesizing silver (Ag) ions over the NPs using cationic adsorption method. Ag ions were then reduced to metallic Ag by sodium borohydride solution. Scanning electron microscopy showed a smooth surface for the pure starch film. Incorporating MO₂@Ag NPs in the films increased surface roughness with agglomerated NPs within starch matrix. Energy dispersive X-ray analysis exhibited a uniform dispersion of Ag-loaded MO₂ NPs, which increases surface contact between these NPs and the biopolymer matrix leading to improved physical and mechanical properties of the resulting films. With increasing in the NPs concentrations, the tensile strength and elongation at break % of the films increased and decreased, respectively. Incorporating MO₂@Ag NPs into starch matrix decreased solubility in water and water vapor permeability of the obtained films, and significantly inhibited the growth of Escherichia coli and Staphylococcus aureus. The most antibacterial effect was obtained for the films containing higher weight concentrations of Ag-loaded SiO₂-NPs.     

In-situ synthesis of CuO nanoparticles on cotton fabrics using spark discharge method to fabricate antibacterial textile

In this research, the spark discharge method (SDM) was used for in-situ synthesis of copper and copper oxide nanoparticles (NPs) on cotton fabrics for producing antibacterial textile. Varieties of analytical techniques were applied for the characterization of both NPs and synthesized CuO NPs on cotton fabrics. The structural characterization of the particles was carried out by the X-ray powder diffraction method. Also, the morphological properties of treated cotton samples were investigated using scanning electron microscope. Particle size and size distribution were measured by dynamic light scattering apparatus. The results show that concentration of 100 ppm is enough for killing 10⁶ CFU/mL of bacteria. It is indicated that the synthesized CuO NPs are very strong against both Staphylococcus aureus and Escherichia coli. Also, the durability of antibacterial efficiency after 15 times of washing was tested. The results confirm that the antibacterial fastness properties are significant and no colonies spread over agar plate after 15 cycles of washing. It was concluded that SDM for in-situ synthesize of nano-CuO on cotton fabrics in batch systems is very promising method.     

Effects of copper nanoparticles exposure in the mussel Mytilus galloprovincialis

CuO NPs are widely used in various industrial and commercial applications. However, little is known about their potential toxicity or fate in the environment. In this study the effects of copper nanoparticles were investigated in the gills of mussels Mytilus galloprovincialis, comparative to Cu(2+). Mussels were exposed to 10 μg Cu·L(-1) of CuO NPs and Cu(2+) for 15 days, and biomarkers of oxidative stress, metal exposure and neurotoxicity evaluated. Results show that mussels accumulated copper in gills and responded differently to CuO NPs and Cu(2+), suggesting distinct modes of action. CuO NPs induced oxidative stress in mussels by overwhelming gills antioxidant defense system, while for Cu(2+) enzymatic activities remained unchanged or increased. CuO NPs and Cu(2+) originated lipid peroxidation in mussels despite different antioxidant efficiency. Moreover, an induction of MT was detected throughout the exposure in mussels exposed to nano and ionic Cu, more evident in CuO NPs exposure. Neurotoxic effects reflected as AChE inhibition were only detected at the end of the exposure period for both forms of copper. In overall, these findings show that filter-feeding organisms are significant targets for nanoparticle exposure and need to be included when evaluating the overall toxicological impact of nanoparticles in the aquatic environment.     

Attachment efficiency of nanoparticle aggregation in aqueous dispersions: modeling and experimental validation

To describe the aggregation kinetics of nanoparticles (NPs) in aqueous dispersions, a new equation for predicting the attachment efficiency is presented. The rationale is that at nanoscale, random kinetic motion may supersede the role of interaction energy in governing the aggregation kinetics of NPs, and aggregation could occur exclusively among the fraction of NPs with the minimum kinetic energy that exceeds the interaction energy barrier (E(b)). To justify this rationale, we examined the evolution of particle size distribution (PSD) and frequency distribution during aggregation, and further derived the new equation of attachment efficiency on the basis of the Maxwell-Boltzmann distribution and Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. The new equation was evaluated through aggregation experiments with CeO(2) NPs using time-resolved-dynamic light scattering (TR-DLS). Our results show that the prediction of the attachment efficiencies agreed remarkably well with experimental data and also correctly described the effects of ionic strength, natural organic matter (NOM), and temperature on attachment efficiency. Furthermore, the new equation was used to describe the attachment efficiencies of different types of engineered NPs selected from the literature and most of the fits showed good agreement with the inverse stability ratios (1/W) and experimentally derived results, although some minor discrepancies were present. Overall, the new equation provides an alternative theoretical approach in addition to 1/W for predicting attachment efficiency.     

Human exposure to nanoparticles through trophic transfer and the biosafety concerns that nanoparticle-contaminated foods pose to consumers

Nanotechnology is comprised of a wide range of technologies dealing with nano-sized structures (at least one dimension from 1 to 100 nm). Nanomaterials are classified as naturally occurring, incidentally synthesized, and intentionally manufactured. Potential benefits of manufactured nanoparticles (NPs) with different chemical compositions have been welcomed in various parts of the food industry such as food packaging and food security. Oral administration is the main way of introducing NPs into the human body. It has been demonstrated by the researchers that NPs have the potential to pose a greater threat to microbiota than bulk materials due to their particle size, surface chemistry, shape, internal structure, and intermediate stability. Even though nanotechnology is now widely applied in many areas of the food industry, the potential risks their extensive use could pose to the consumers and manufactured products are not yet fully understood. The literature shows that there is a knowledge gap about the presence or amounts of different NPs that could enter human body through different foodstuffs. This article is a review of the ways that the most widely found NPs enter human body, animals, plants and the environment. It focuses on the potential biosafety problems NPs might cause upon entering the human body. It also discusses the factors involved in the toxicity of NPs.     

Stability of citrate, PVP, and PEG coated silver nanoparticles in ecotoxicology media

Silver nanoparticles (AgNPs) are present in the environment and a number of ecotoxicology studies have shown that AgNPs might be highly toxic. Nevertheless, there are little data on their stability in toxicology media. This is an important issue as such dynamic changes affect exposure dose and the nature of the toxicant studied and have a direct impact on all (eco)toxicology data. In this study, monodisperse citrate, PVP, and PEG coated AgNPs with a core size of approximately 10 nm were synthesized and characterized; their behavior was examined in standard OECD media used for Daphnia sp. acute and chronic tests (in the absence of Daphnia). Surface plasmon resonance, size, aggregation, and shape were monitored over 21 days, comparable to a chronic exposure period. Charge stabilized particles (citrate) were more unstable than sterically stabilized particles. Replacement of chloride in the media (due to concerns over chloride-silver interactions) with either nitrate or sulfate resulted in increased shape and dissolution changes. PVP-stabilized NPs in a 10-fold diluted OECD media (chloride present) were found to be the most stable, with only small losses in total concentration over 21 days, and no shape, aggregation, or dissolution changes observed and are recommended for exposure studies.     

Mechanism of silver nanoparticle toxicity is dependent on dissolved silver and surface coating in Caenorhabditis elegans

The rapidly increasing use of silver nanoparticles (Ag NPs) in consumer products and medical applications has raised ecological and human health concerns. A key question for addressing these concerns is whether Ag NP toxicity is mechanistically unique to nanoparticulate silver, or if it is a result of the release of silver ions. Furthermore, since Ag NPs are produced in a large variety of monomer sizes and coatings, and since their physicochemical behavior depends on the media composition, it is important to understand how these variables modulate toxicity. We found that a lower ionic strength medium resulted in greater toxicity (measured as growth inhibition) of all tested Ag NPs to Caenorhabditis elegans and that both dissolved silver and coating influenced Ag NP toxicity. We found a linear correlation between Ag NP toxicity and dissolved silver, but no correlation between size and toxicity. We used three independent and complementary approaches to investigate the mechanisms of toxicity of differentially coated and sized Ag NPs: pharmacological (rescue with trolox and N-acetylcysteine), genetic (analysis of metal-sensitive and oxidative stress-sensitive mutants), and physicochemical (including analysis of dissolution of Ag NPs). Oxidative dissolution was limited in our experimental conditions (maximally 15% in 24 h) yet was key to the toxicity of most Ag NPs, highlighting a critical role for dissolved silver complexed with thiols in the toxicity of all tested Ag NPs. Some Ag NPs (typically less soluble due to size or coating) also acted via oxidative stress, an effect specific to nanoparticulate silver. However, in no case studied here was the toxicity of a Ag NP greater than would be predicted by complete dissolution of the same mass of silver as silver ions.     

Recent advances in biobased and biodegradable polymer nanocomposites,nanoparticles, and natural antioxidants for antibacterial and antioxidant food packaging applications

Inorganic nanoparticles (NPs) and natural antioxidant compounds are an emerging trend in the food industry. Incorporating these substances in biobased and biodegradable matrices as polysaccharides (e.g., starch, cellulose, and chitosan) and proteins has highlighted the potential in active food packaging applications due to more significant antimicrobial, antioxidant, UV blocking, oxygen scavenging, water vapor permeability effects, and low environmental impact. In recent years, the migration of metal NPs and metal oxides in food contact packaging and their toxicological potential have raised concerns about the safety of the nanomaterials. In this review, we provide a comprehensive overview of the main biobased and biodegradable polymer nanocomposites, inorganic NPs, natural antioxidants, and their potential use in active food packaging. The intrinsic properties of NPs and natural antioxidant actives in packaging materials are evaluated to extend shelf-life, safety, and food quality. Toxicological and safety aspects of inorganic NPs are highlighted to understand the current controversy on applying some nanomaterials in food packaging. The synergism of inorganic NPs and plant-derived natural antioxidant actives (e.g., vitamins, polyphenols, and carotenoids) and essential oils (EOs) potentiated the antibacterial and antioxidant properties of biodegradable nanocomposite films. Biodegradable packaging films based on green NPs—this is biosynthesized from plant extracts–showed suitable mechanical and barrier properties and had a lower environmental impact and offered efficient food protection. Furthermore, AgNPs and TiO₂ NPs released metal ions from packaging into contents insufficiently to cause harm to human cells, which could be helpful to understanding critical gaps and provide progress in the packaging field.     

Some new findings on the potential use of biocompatible silver nanoparticles in winemaking

There is currently an increasing commercial demand for silver nanoparticles (Ag NPs) due to their wide applicability in various markets. Because of their powerful antimicrobial properties, these nanoparticles are frequently used for food-associated consumer products. In this paper, the effect of two Ag NPs coated with biocompatible materials – PEG-Ag NPs 20 (polyethylene glycol) and GSH-Ag NPs (reduced glutathione) – to control microbial growth in wines was assessed. Both Ag NPs were subjected to an in vitro three-step digestion, and changes in their morphology and an assessment of their cytotoxicity against Caco-2 cells were determined. Both Ag NPs were effective against the different microbial population present in tested wines. Regarding their in vitro digestion, the size and shape of the nanoparticles were almost unaltered in the case of GSH-Ag NPs, while in PEG-Ag NPs 20 some particle agglomeration was observed. Overall, these results suggest that Ag NPs may reach the intestine in a nano-scaled form. Finally, Caco-2 cell experiments seemed to exclude toxicity of Ag NPs at the intestinal epithelium.Industrial relevanceTraditionally, sulphur dioxide (SO₂) has been used by oenologists to control the microbial population in wine. As a result of increasing evidence of possible health risks associated with this additive in wine, there has been growing interest in finding new alternatives to replace it. Silver nanoparticles display a broad spectrum of antimicrobial activity, so they could constitute a very promising approach to reducing SO₂ in winemaking.     

Evidence for bioavailability of Au nanoparticles from soil and biodistribution within earthworms (Eisenia fetida)

Because Au nanoparticles (NPs) are resistant to oxidative dissolution and are easily detected, they have been used as stable probes for the behavior of nanomaterials within biological systems. Previous studies provide somewhat limited evidence for bioavailability of Au NPs in food webs, because the spatial distribution within tissues and the speciation of Au was not determined. In this study, we provide multiple lines of evidence, including orthogonal microspectroscopic techniques, as well as evidence from biological responses, that Au NPs are bioavailable from soil to a model detritivore (Eisenia fetida). We also present limited evidence that Au NPs may cause adverse effects on earthworm reproduction. This is perhaps the first study to demonstrate that Au NPs can be taken up by detritivores from soil and distributed among tissues. We found that primary particle size (20 or 55 nm) did not consistently influence accumulated concentrations on a mass concentration basis; however, on a particle number basis the 20 nm particles were more bioavailable. Differences in bioavailability between the treatments may have been explained by aggregation behavior in pore water. The results suggest that nanoparticles present in soil from activities such as biosolids application have the potential to enter terrestrial food webs.     

Size-controlled dissolution of organic-coated silver nanoparticles

The solubility of Ag NPs can affect their toxicity and persistence in the environment. We measured the solubility of organic-coated silver nanoparticles (Ag NPs) having particle diameters ranging from 5 to 80 nm that were synthesized using various methods, and with different organic polymer coatings including poly(vinylpyrrolidone) and gum arabic. The size and morphology of Ag NPs were characterized by transmission electron microscopy (TEM). X-ray absorption fine structure (XAFS) spectroscopy and synchrotron-based total X-ray scattering and pair distribution function (PDF) analysis were used to determine the local structure around Ag and evaluate changes in crystal lattice parameters and structure as a function of NP size. Ag NP solubility dispersed in 1 mM NaHCO(3) at pH 8 was found to be well correlated with particle size based on the distribution of measured TEM sizes as predicted by the modified Kelvin equation. Solubility of Ag NPs was not affected by the synthesis method and coating as much as by their size. Based on the modified Kelvin equation, the surface tension of Ag NPs was found to be ～1 J/m(2), which is expected for bulk fcc (face centered cubic) silver. Analysis of XAFS, X-ray scattering, and PDFs confirm that the lattice parameter, a, of the fcc crystal structure of Ag NPs did not change with particle size for Ag NPs as small as 6 nm, indicating the absence of lattice strain. These results are consistent with the finding that Ag NP solubility can be estimated based on TEM-derived particle size using the modified Kelvin equation for particles in the size range of 5-40 nm in diameter.     

Dissolution and microstructural transformation of ZnO nanoparticles under the influence of phosphate

The toxicity and fate of nanoparticles (NPs) have been reported to be highly dependent on the chemistry of the medium, and the effects of phosphate have tended to be ignored despite the wide existence of phosphate contamination in aqueous environments. In the present study the influence of phosphate on the dissolution and microstructural transformation of ZnO NPs was investigated. Phosphate at a low concentration rapidly and substantially reduced the release of Zn(2+) into aqueous solution. Synchrotron X-ray absorption spectroscopy and X-ray diffraction analysis reveal that interaction between ZnO NPs and phosphate induced the transformation of ZnO into zinc phosphate. Transmission electronic microscopy observation shows that the morphology of the particles changed from structurally uniform nanosized spherical to anomalous and porous material containing mixed amorphous and crystalline phases of ZnO and zinc phosphate in the presence of phosphate. To our knowledge, this is the first study in which the detailed process of phosphate-induced speciation and microstructural transformation of ZnO NPs has been analyzed. In view of the wide existence of phosphate contamination in water and its strong metal-complexation capability, phosphate-induced transformations may play an important role in the behaviors, fate, and toxicity of many other metal-based nanomaterials in the environment.     

Bioaccumulation dynamics and modeling in an estuarine invertebrate following aqueous exposure to nanosized and dissolved silver

Predicting the environmental impact of engineered nanomaterials (ENMs) is increasingly important owing to the prevalence of emerging nanotechnologies. We derived waterborne uptake and efflux rate constants for the estuarine snail, Peringia ulvae, exposed to dissolved Ag (AgNO(3)) and silver nanoparticles (Ag NPs), using biodynamic modeling. Uptake rates demonstrated that dissolved Ag is twice as bioavailable as Ag in nanoparticle form. Biphasic loss dynamics revealed the faster elimination of Ag from Ag NPs at the start of depuration, but similar slow efflux rate constants. The integration of biodynamic parameters into our model accurately predicted Ag tissue burdens during chronic exposure with 85% of predicted values within a factor of 2 of observed values. Zeta potentials for the Ag NPs were lower in estuarine waters than in waters of less salinity; and uptake rates in P. ulvae were slower than reported for the freshwater snail Lymnaea stagnalis in similar experiments. This suggests aggregation of Ag NPs occurs in estuarine waters and reduces, but does not eliminate, bioavailability of Ag from the Ag NPs. Biodynamic modeling provides an effective methodology to determine bioavailable metal concentrations (originating from metal and metal-oxide nanoparticles) in the environment and may aid future ENM risk assessment.     

Sequestration of zinc from zinc oxide nanoparticles and life cycle effects in the sediment dweller amphipod Corophium volutator

We studied the effects of ZnO nanoparticles [ZnO NPs, primary particle size 35 ± 10 nm (circular diameter, TEM)], bulk [160 ± 81 nm (circular diameter, TEM)], and Zn ions (from ZnCl(2)) on mortality, growth, and reproductive endpoints in the sediment dwelling marine amphipod Corophium volutator over a complete lifecycle (100 days). ZnO NPs were characterized by size, aggregation, morphology, dissolution, and surface properties. ZnO NPs underwent aggregation and partial dissolution in the seawater exposure medium, resulting in a size distribution that ranged in size from discrete nanoparticles to the largest aggregate of several micrometers. Exposure via water to all forms of zinc in the range of 0.2-1.0 mg L(-1) delayed growth and affected the reproductive outcome of the exposed populations. STEM-EDX analysis was used to characterize insoluble zinc precipitates (sphaerites) of high sulfur content, which accumulated in the hepatopancreas following exposures. The elemental composition of the sphaerites did not differ for ZnO NP, Zn(2+), and bulk ZnO exposed organisms. These results provide an illustration of the comparable toxicity of Zn in bulk, soluble, and nanoscale forms on critical lifecycle parameters in a sediment dwelling organism.