Julián Alberto Gallego-Urrea

Potential Scenarios for Nanomaterial Release and Subsequent alteration in the Environment

The risks associated with exposure to engineered nanomaterials (ENM) will be determined in part by the processes that control their environmental fate and transformation. These processes act not only on ENM that might be released directly into the environment, but more importantly also on ENM in consumer products and those that have been released from the product. The environmental fate and transformation are likely to differ significantly for each of these cases. The ENM released from actual direct use or from nanomaterial-containing products are much more relevant for ecotoxicological studies and risk assessment than pristine ENM. Released ENM may have a greater or lesser environmental impact than the starting materials, depending on the transformation reactions and the material. Almost nothing is known about the environmental behavior and the effects of released and transformed ENM, although these are the materials that are actually present in the environment. Further research is needed to determine whether the release and transformation processes result in a similar or more diverse set of ENM and ultimately how this affects environmental behavior. This article addresses these questions, using four hypothetical case studies that cover a wide range of ENM, their direct use or product applications, and their likely fate in the environment. Furthermore, a more definitive classification scheme for ENM should be adopted that reflects their surface condition, which is a result of both industrial and environmental processes acting on the ENM. The authors conclude that it is not possible to assess the risks associated with the use of ENM by investigating only the pristine form of the ENM, without considering alterations and transformation processes.

Uptake and effects of manufactured silver nanoparticles in rainbow trout (Oncorhynchus mykiss) gill cells.

Nanoparticles are already widely used in technology, medicine and consumer products, but there are limited data on their effects on the aquatic environment. In this study the uptake and effect of citrate (AgNP(CIT)) and polyvinylpyrrolidone (AgNP(PVP)) coated manufactured silver nanoparticles, as well as AgNO(3) (Ag(+)) were tested using primary gill cells of rainbow trout (Oncorhynchus mykiss). Prior to use, the nanoparticles were characterized for size, surface charge and aggregation behavior. Gill cells were cultured either as monolayers on solid support, or as multilayers on a permeable support cell culturing system, enabling transport studies. The uptake of silver nanoparticles and Ag(+) after exposure to 10 mg L(-1) was determined with microscopical methods and inductively coupled plasma mass spectrometry (ICP-MS). Cytotoxicity, in terms of membrane integrity, as well as oxidative stress (depletion of reduced glutathione) was tested at silver concentrations ranging from 0.1 mg L(-1) to 10 mg L(-1). Results show that AgNP(CIT) nanoparticles are readily taken up into gill cell monolayers while uptake was less for AgNP(PVP). In contrast, it appears that the slightly smaller AgNP(PVP) were transported through cultured multilayers to a higher extent, with transport rates generally being in the ng cm(-2) range for 48 h exposures. Transport rates for all exposures were dependent on the epithelial tightness. Moderate cytotoxic effects were seen for all silver treatments. Levels of reduced glutathione were elevated in contrast to control groups, pointing on a possible overcompensation reaction. Taken together silver nanoparticles were taken up into cells and did cause silver transport over cultured epithelial layers with uptake and transport rates being different for the two nanoparticle species. All silver treatments had measurable effects on cell viability.

Silver nanoparticles and silver nitrate induce high toxicity to Pseudokirchneriella subcapitata, Daphnia magna and Danio rerio

Silver nanoparticles (AgNP) have gained attention over the years due to the antimicrobial function of silver, which has been exploited industrially to produce consumer goods that vary in type and application. Undoubtedly the increase of production and consumption of these silver-containing products will lead to the entry of silver compounds into the environment. In this study we have used Pseudokirchneriella subcapitata, Daphnia magna and Danio rerio as model organisms to investigate the toxicity of AgNP and AgNO₃ by assessing different biological endpoints and exposure periods. Organisms were exposed following specific and standardized protocols for each species/endpoints, with modifications when necessary. AgNP were characterized in each test-media by Transmission Electron Microscopy (TEM) and experiments were performed by Dynamic Light Scattering (DLS) to investigate the aggregation and agglomeration behavior of AgNP under different media chemical composition and test-period. TEM images of AgNP in the different test-media showed dissimilar patterns of agglomeration, with some agglomerates inside an organic layer, some loosely associated particles and also the presence of some individual particles. The toxicity of both AgNO₃ and AgNP differ significantly based on the test species: we found no differences in toxicity for algae, a small difference for zebrafish and a major difference in toxicity for Daphnia magna.

Measurements of nanoparticle number concentrations and size distributions in contrasting aquatic environments using nanoparticle tracking analysis

Environmental context. Manufactured and unintentionally produced nanoparticles have been of environmental concern owing to potential harm to humans and ecosystems, but very little is known of the actual concentrations of these owing to limitations of available methods. In order to understand both the potential adverse effects and the underlying natural processes, improved measurement techniques are needed. Here, we explore the feasibility of a novel minimum perturbation method that relates the diffusive movement of nanoparticles in a light field to their size distributions. Abstract. A feasibility study of nanoparticle tracking analysis (NTA) for aquatic environmental samples is presented here. The method has certain virtues such as minimum perturbation of the samples, high sensitivity in terms of particle concentration, and provision of number-based size distributions for aquatic samples. NTA gave linear calibration curves in terms of number concentration and accurately reproduced size measurements of certified reference material nanoparticles. However, the accuracy of the size distributions obtained with this method exhibited a high dependence on set-up parameters and the concentrations were shown to be strongly correlated with the refractive index of the material under examination. Different detection cameras and different data acquisition modes were compared and evaluated. Also, the effect of filtration of the samples was assessed. The size distributions for the contrasting environmental samples were fairly reasonable compared with other studies but an underestimation of small sizes was observed, which can be explained by a material-dependent lower detection limit in terms of size. The number concentrations obtained for the natural nanoparticles ranged from 0.5 to 20 × 108 particles mL–1 and correlated well with conventional turbidity measurements.

Geographically distributed classification of surface water chemical parameters influencing fate and behavior of nanoparticles and colloid facilitated contaminant transport.

The current production and use of nanomaterials in consumer products have increased the concern about the possibility that these enter the rivers during their entire life cycle. Further, many aquatic contaminants undergo partitioning to the ubiquitous aquatic colloids. Here is presented the development of a set of European water types for environmental risk assessment of chemicals transported as nanovectors as is the case of environmental fate of manufactured nanoparticles and colloid-bound contaminants. A compilation of river quality geochemical data with information about multi-element composition for near 800 rivers in Europe was used to perform a principal component analysis (PCA) and define 6 contrasting water classes. With the aid of geographical information system algorithms, it was possible to analyse how the different sampling locations were predominantly represented within each European water framework directive drainage basin. These water classes and their associated Debye-Hückel parameter are determining factors to evaluate the large scale fate and behaviour of nanomaterials and other colloid-transported pollutants in the European aquatic environment.

Influence of different types of natural organic matter on titania nanoparticle stability: effects of counter ion concentration and pH

The effects of biopolymeric (alginate) and refractory macromolecules (humic and fulvic acids) on the aggregation kinetics of anatase titanium dioxide (titania) nanoparticles were evaluated. The particles were synthesized using a wet-chemical method based on the hydrolysis of TiCl4. Stable suspensions of positively-charged titania were obtained at pH 2.5. One batch of this product was shifted above the point of zero charge to pH 12. These dispersions were mixed with three different types of well characterized environmental macromolecules: sodium alginate, fulvic acid and humic acid, and evaluated in terms of the stability. Changes in the particle size were measured using time-resolved dynamic light scattering (TR-DLS) at different concentrations of three electrolytes: NaCl, CaCl2 and Na2SO4, and at different solution pH values. Results were in agreement with DLVO calculations. The use of TR-DLS for determining aggregation rates is critically discussed.

Intermethod comparison of the particle size distributions of colloidal silica nanoparticles

Abstract There can be a large variation in the measured diameter of nanoparticles depending on which method is used. In this work, we have strived to accurately determine the mean particle diameter of 30–40 nm colloidal silica particles by using six different techniques. A quantitative agreement between the particle size distributions was obtained by scanning electron microscopy (SEM), and electrospray-scanning mobility particle sizer (ES-SMPS). However, transmission electron microscopy gave a distribution shifted to smaller sizes. After confirming that the magnification calibration was consistent, this was attributed to sample preparation artifacts. The hydrodynamic diameter, d h , was determined by dynamic light scattering (DLS) both in batch mode, and hyphenated with sedimentation field flow fractionation. Surprisingly the d h were smaller than the SEM, and ES-SMPS diameters. A plausible explanation for the smaller sizes found with DLS is that a permeable gel layer forms on the particle surface. Results from nanoparticle tracking analysis were strongly biased towards larger diameters, most likely because the silica particles provide low refractive index contrast. Calculations confirmed that the sensitivity is, depending on the shape of the laser beam, strongly size dependent for particles with diameters close to the visualization limit.

Uptake and elimination kinetics of silver nanoparticles and silver nitrate by Raphidocelis subcapitata: The influence of silver behaviour in solution

Abstract Raphidocelis subcapitata is a freshwater algae species that constitutes the basis of many aquatic trophic chains. In this study, R. subcapitata was used as a model species to investigate the kinetics of uptake and elimination of silver nanoparticles (AgNP) in comparison to silver nitrate (AgNO3) with particular focus on the Ag sized-fractions in solution. AgNP used in this study were provided in a suspension of 1 mg Ag/l, with an initial size of 3–8 nm and coated with an alkane material. Algae was exposed for 48 h to both AgNP and AgNO3 and sampled at different time points to determine their internal Ag concentration over time. Samples were collected and separated into different sized fractions: total (Agtot), water column Ag (Agwater), small particulate Ag (Agsmall.part.) and dissolved Ag (Agdis). At AgNO3 exposures algae reached higher bioconcentration factor (BCF) and lower elimination rate constants than at AgNP exposures, meaning that Ag is more readily taken up by algae in its dissolved form than in its small particulate form, however slowly eliminated. When modelling the kinetics based on the Agdis fraction, a higher BCF was found. This supports our hypothesis that Ag would be internalised by algae only in its dissolved form. In addition, algae images obtained by Coherent Anti-stokes Raman Scattering (CARS) microscopy demonstrated large aggregates of nanoparticles external to the algae cells with no evidence of its internalisation, thus providing a strong suggestion that these AgNP were not able to penetrate the cells and Ag accumulation happens through the uptake of Ag ions.

Multimethod 3D characterization of natural plate-like nanoparticles: shape effects on equivalent size measurements

The fundamental properties and processes that govern nanoparticle behavior in colloidal dispersions are critical to predict their performance in applications and also their environmental and health implications. Illite is a platy clay mineral that is present in large amounts in aquatic environments and can be used as a model natural particle for environmental risk assessment. However, the high-aspect ratio of illite makes conventional analysis, usually assuming a spherical size, insufficient for the assessment of shape-dependent properties. In the current paper, a multimethod characterization of a suspension of illite particles was done using atomic force microscopy, scanning electron microscopy, dynamic light scattering (DLS), nanoparticle tracking analysis, differential centrifugal sedimentation, and centrifugal-field flow fractionation coupled to multiangle light scattering and DLS. The relation between the different measurands was investigated, and the effect of the shape on the equivalent particle size was reported. While some of the used techniques are capable of assessing the aspect ratio of illite, the results confirm the need for multiple techniques and analysis of different types of measurands especially for high-aspect-ratio particles.

Characterizing the behavior, uptake, and toxicity of NM300K silver nanoparticles in Caenorhabditis elegans

Using Caenorhabditis elegans as a model organism, we addressed the potential linkage among toxicity of NM300K Ag nanoparticles (AgNPs), their particle size distribution, and the presence of dissolved Ag in the test media. Of the 3 endpoints assessed (growth, fertility, and reproduction), reproduction was the most sensitive, with the 50% effect concentration (EC50) ranging from 0.26 to 0.84 mg Ag L-1 and 0.08 to 0.11 mg Ag L-1 for NM300K and AgNO3 , respectively. Silver uptake by C. elegans was similar for both forms of Ag, whereas bioaccumulation was higher in AgNO3 exposure. The observed differences in toxicity between NM300K and AgNO3 did not correlate with bioaccumulated Ag, which suggests that toxicity is a function of the type of exposing agent (AgNPs vs AgNO3 ) and its mode of action. Before addition of the food source (Escherichia coli), size fractionation revealed that dissolved Ag comprised 13 to 90% and 4 to 8% of total Ag in the AgNO3 and NM300K treatments, respectively. No dissolved Ag was detectable in the actual test media due to immediate Ag adsorption to bacteria. The results of the present study indicate that information on behavior and characterization of exposure conditions is essential for nanotoxicity studies. Environ Toxicol Chem 2018;37:1799-1810.