Allan Philippe

Interactions of Dissolved Organic Matter with Natural and Engineered Inorganic Colloids: A Review

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 the presence of multivalent cations. In the presence of DOM, aggregation may become reversible and aggregate structure dynamic. Nonetheless, the role of shear forces is still poorly understood. 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.

Disaggregation of silver nanoparticle homoaggregates in a river water matrix.

Silver nanoparticles (Ag NPs) could be found in aquatic systems in the near future. Although the interplay between aggregate formation and disaggregation is an important factor for mobility, bioavailability and toxicity of Ag NPs in surface waters, the factors controlling disaggregation of Ag NP homoaggregates are still unknown. In this study, we investigated the reversibility of homoaggregation of citrate coated Ag NPs in a Rhine River water matrix. We characterized the disaggregation of Ag NP homoaggregates by ionic strength reduction and addition of Suwannee River humic acid (SRHA) in the presence of strong and weak shear forces. In order to understand the disaggregation processes, we also studied the nature of homoaggregates and their formation dynamics under the influence of SRHA, Ca(2+) concentration and nanoparticle concentration. Even in the presence of SRHA and at low particle concentrations (10 μg L(-1)), aggregates formed rapidly in filtered Rhine water. The critical coagulation concentration (CCC) of Ca(2+) in reconstituted Rhine water was 1.5 mmol L(-1) and was shifted towards higher values in the presence of SRHA. Analysis of the attachment efficiency as a function of Ca(2+) concentration showed that SRHA induces electrosteric stabilization at low Ca(2+) concentrations and cation-bridging flocculation at high Ca(2+) concentrations. Shear forces in the form of mechanical shaking or ultrasound were necessary for breaking the aggregates. Without ultrasound, SRHA also induced disaggregation, but it required several days to reach a stable size of dense aggregates still larger than the primary particles. Citrate stabilized Ag NPs may be in the form of reaction limited aggregates in aquatic systems similar to the Rhine River. The size and the structure of these aggregates will be dynamic and be determined by the solution conditions. Seasonal variations in the chemical composition of natural waters can result in a sedimentation-release cycle of engineered nanoparticles.

Evaluation of hydrodynamic chromatography coupled with UV-visible, fluorescence and inductively coupled plasma mass spectrometry detectors for sizing and quantifying colloids in environmental media.

In this study, we evaluated hydrodynamic chromatography (HDC) coupled with inductively coupled plasma mass spectrometry (ICP-MS) for the analysis of nanoparticles in environmental samples. Using two commercially available columns (Polymer Labs-PDSA type 1 and 2), a set of well characterised calibrants and a new external time marking method, we showed that flow rate and eluent composition have few influence on the size resolution and, therefore, can be adapted to the sample particularity. Monitoring the agglomeration of polystyrene nanoparticles over time succeeded without observable disagglomeration suggesting that even weak agglomerates can be measured using HDC. Simultaneous determination of gold colloid concentration and size using ICP-MS detection was validated for elemental concentrations in the ppb range. HDC-ICP-MS was successfully applied to samples containing a high organic and ionic background. Indeed, online combination of UV-visible, fluorescence and ICP-MS detectors allowed distinguishing between organic molecules and inorganic colloids during the analysis of Ag nanoparticles in synthetic surface waters and TiO2 and ZnO nanoparticles in commercial sunscreens. Taken together, our results demonstrate that HDC-ICP-MS is a flexible, sensitive and reliable method to measure the size and the concentration of inorganic colloids in complex media and suggest that there may be a promising future for the application of HDC in environmental science. Nonetheless the rigorous measurements of agglomerates and of matrices containing natural colloids still need to be studied in detail.

Hydrodynamic Chromatography Coupled with Single Particle-Inductively Coupled Plasma Mass Spectrometry for Investigating Nanoparticles Agglomerates

Studying the environmental fate of engineered or natural colloids requires efficient methods for measuring their size and quantifying them in the environment. For example, an ideal method should maintain its correctness, accuracy, reproducibility, and robustness when applied to samples contained in complex matrixes and distinguish the target particles from the natural colloidal background signals. Since it is expected that a large portion of nanoparticles will form homo- or heteroagglomerates when released into environmental media, it is necessary to differentiate agglomerates from primary particles. At present, most sizing techniques do not fulfill these requirements. In this study, we used online coupling of two promising complementary sizing techniques: hydrodynamic chromatography (HDC) and single-particle ICPMS analysis to analyze gold nanoparticles agglomerated under controlled conditions. We used the single-particle mode of the ICPMS detector to detect single particles eluted from an HDC-column and determine a mass and an effective diameter for each particle using a double calibration approach. The average agglomerate relative density and fractal dimension were calculated using these data and used to follow the morphological evolution of agglomerates over time during the agglomeration process. The results demonstrate the ability of HDC coupled to single-particle analysis to identify and characterize nanoparticle homoagglomerates and is a very promising technique for the analysis of colloids in complex media.

Evaluation of hydrodynamic chromatography coupled with inductively coupled plasma mass spectrometry detector for analysis of colloids in environmental media – effects of colloid composition, coating and shape

In this study, we evaluated hydrodynamic chromatography (HDC) coupled with inductively coupled plasma mass spectrometry (ICP-MS) for the analysis of nanoparticles with different coating and shapes. Using two commercially available HDC columns (Polymer Labs-PDSA type 1 and 2) and a set of well characterised calibrants of different materials (Au(0), Ag(0), SiO2, polystyrene), coatings (citric acid and tannic acid), and shapes (spheres, rod-like prisms, and hexagonal plates) we demonstrated that temperature does not influence the size resolution and, therefore, can be adapted to the sample particularity. Retention behaviour was not influenced by the particle material. However, a minor influence of the particle coating was observed for tannic acid coated silver nanoparticles. Particle shape noticeably affects the retention behaviour and can lead to erroneous size estimation if spherical calibrants are used to determine their effective diameter. Using the ICP-MS detector in the single-particle modus made possible to discriminate between spherical and rod-like particles despite some limitations. However, the development of a comprehensive physical model for the elution behaviour of particles with complex shapes in HDC is needed for obtaining quantitative information about the shape using HDC. Our findings demonstrate that HDC-ICP-MS is a promising method for measuring the size and the concentration of spherical inorganic colloids in complex media and suggest that HDC may be increasingly implemented in environmental science.

Extraction and characterization methods for titanium dioxide nanoparticles from commercialized sunscreens

Sunscreens are an important source of TiO2 nanoparticles in surface waters. The fate and toxicity of these particles have not been fully addressed due to the gap between model nanoparticles usually used in studies and the more complex particles found in commercial products. Therefore, mild extraction methods for TiO2 nanoparticles from sunscreens were evaluated for providing more realistic nanoparticle samples for future studies. We propose two methods based on ultrafiltration and ultracentrifugation, respectively, for extracting TiO2 nanoparticles from sunscreens using a surfactant solution as the solvent. These methods were tested on eleven commercial sunscreens with differing compositions. The ultracentrifugation variant allows extracting 250 mg from approximately 5 g of sunscreen in one day. Recoveries for ultrafiltration and ultracentrifugation were 52–96% and 78–98%, respectively. Purification efficiency was determined for the ultracentrifugation variant by determining the avobenzone concentration in sunscreen extracts using UV-spectrometry and was high for all tested sunscreens. Transmission electron microscopy and dynamic light scattering revealed a high diversity in particle shape, although size parameters were comparable (average hydrodynamic diameter: 19–34 nm). Isoelectric points were below 4.6 for all sunscreen extracts. Time-of-flight secondary ion mass spectrometry revealed that probably all TiO2 particles were coated; most of them with PDMS, some others with Al- and Si-based materials. Comparison of images of particles inside the sunscreens using cryogenic transmission electron microscopy and of extracted particles showed that while the shape of the primary nanoparticles was not affected by the extraction, they were agglomerated inside the sunscreens. These agglomerates could be completely disrupted using ultrasonication. Therefore, the particles extracted in the present study can be considered as more environmentally relevant in terms of size, shape, surface charge and coating than model TiO2 nanoparticles.

Retention and remobilization mechanisms of environmentally aged silver nanoparticles in an artificial riverbank filtration system

Riverbank filtration systems are important structures that ensure the cleaning of infiltrating surface water for drinking water production. In our study, we investigated the potential risk for a breakthrough of environmentally aged silver nanoparticles (Ag NP) through these systems. Additionally, we identified factors leading to the remobilization of Ag NP accumulated in surficial sediment layers in order to gain insights into remobilization mechanisms. We conducted column experiments with Ag NP in an outdoor pilot plant consisting of water-saturated sediment columns mimicking a riverbank filtration system. The NP had previously been aged in river water, soil extract, and ultrapure water, respectively. We investigated the depth-dependent breakthrough and retention of NP. In subsequent batch experiments, we studied the processes responsible for a remobilization of Ag NP retained in the upper 10 cm of the sediments, induced by ionic strength reduction, natural organic matter (NOM), and mechanical forces. We determined the amount of remobilized Ag by ICP-MS and differentiated between particulate and ionic Ag after remobilization using GFAAS. The presence of Ag-containing heteroaggregates was investigated by combining filtration with single-particle ICP-MS. Single and erratic Ag breakthrough events were mainly found in 30 cm depth and Ag NP were accumulated in the upper 20 cm of the columns. Soil-aged Ag NP showed the lowest retention of only 54%. Remobilization was induced by the reduction of ionic strength and the presence of NOM in combination with mechanical forces. The presence of calcium in the aging- as well as the remobilizing media reduced the remobilization potential. Silver NP were mainly remobilized as heteroaggregates with natural colloids, while dissolution played a minor role. Our study indicates that the breakthrough potential of Ag NP in riverbank filtration systems is generally low, but the aging in soil increases their mobility. Remobilization processes are associated to co-mobilization with natural colloids.