Single particle inductively coupled plasma-mass spectrometry: a performance evaluation and method comparison in the determination of nanoparticle size.

Sizing engineered nanoparticles in simple, laboratory systems is now a robust field of science; however, application of available techniques to more complex, natural systems is hindered by numerous challenges including low nanoparticle number concentrations, polydispersity from aggregation and/or dissolution, and interference from other incidental particulates. A new emerging technique, single particle inductively coupled plasma-mass spectrometry (spICPMS), has the potential to address many of these analytical challenges when sizing inorganic nanoparticles in environmental matrices. However, to date, there is little beyond the initial feasibility studies that investigates the performance characteristics and validation of spICPMS as a nanoparticle sizing technique. This study compares sizing of four silver nanoparticle dispersions (nominal diameters of 40, 60, 80, and 100 nm) by spICPMS to four established sizing techniques: dynamic light scattering, differential centrifugal sedimentation, nanoparticle tracking analysis, and TEM. Results show that spICPMS is able to size silver nanoparticles, across different sizes and particle number concentrations, with accuracy similar to the other commercially available techniques. Furthermore, a novel approach to evaluating particle coincidence is presented. In addition, spICPMS size measurements were successfully performed on nanoparticles suspended in algal growth media at low concentrations. Overall, while further development of the technique is needed, spICPMS yields important advantages over other techniques when sizing nanoparticles in environmentally relevant media.

Determining transport efficiency for the purpose of counting and sizing nanoparticles via single particle inductively coupled plasma mass spectrometry.

Currently there are few ideal methods for the characterization of nanoparticles in complex, environmental samples, leading to significant gaps in toxicity and exposure assessments of nanomaterials. Single particle-inductively coupled plasma-mass spectrometry (spICPMS) is an emerging technique that can both size and count metal-containing nanoparticles. A major benefit of the spICPMS method is its ability to characterize nanoparticles at concentrations relevant to the environment. This paper presents a practical guide on how to count and size nanoparticles using spICPMS. Different methods are investigated for measuring transport efficiency (i.e., nebulization efficiency), an important term in the spICPMS calculations. In addition, an alternative protocol is provided for determining particle size that broadens the applicability of the technique to all types of inorganic nanoparticles. Initial comparison, using well-characterized, monodisperse silver nanoparticles, showed the importance of having an accurate transport efficiency value when determining particle number concentration and, if using the newly presented protocol, particle size. Ultimately, the goal of this paper is to provide improvements to nanometrology by further developing this technique for the characterization of metal-containing nanoparticles.

Influence of stability on the acute toxicity of CdSe/ZnS nanocrystals to Daphnia magna.

The acute toxicity of polymer-coated CdSe/ZnS quantum dots (QDs) to Daphnia magna was investigated using 48-h exposure studies. The principal objective was to relate the toxicity of QDs to specific physical and chemical aspects of the QD. As such, two different CdSe core diameters, 2 nm QDs (green-emitting) and 5 nm QDs (red-emitting), and two different surface coatings, polyethylene oxide (PEO) and 11-mercaptoundecanoic acid (MUA) were studied. The QDs were characterized before and after the 48-h exposure using fluorescence, ultrafiltrations (3 kDa), and inductively coupled plasma-atomic emission spectrometry (ICP-AES) metal analysis. In addition, flow field flow fractionation-inductively coupled plasma-mass spectrometry (Fl FFF-ICP-MS) was used as a more extensive characterization technique to determine particle size and composition as well as identify other potential constituents in the QD solutions. The more stable QDs (PEO) were found to be less acutely toxic than the QDs with accelerated dissolution (MUA), suggesting QD stability has significant impact on the nanoparticles' short-term toxicity. The emergence of dissolved Cd(2+) in solution indicates that the toxicity of the MUA QDs is likely due to Cd poisoning, and a mass-based dose response occurred as a consequence of this mode of action. Alternatively, the PEO QDs caused acute toxicity without observed particle dissolution (i.e., no detectable metals were solubilized), suggesting an alternative mode of toxic action for these nanoparticles. Results of the present study suggest that using particle number, instead of mass, as a dose metric for the PEO QDs, produces markedly different conclusions, in that smaller core size does not equate to greater toxicity.

Synchrotron X-ray 2D and 3D elemental imaging of CdSe/ZnS quantum dot nanoparticles in Daphnia magna.

The potential toxicity of nanoparticles to aquatic organisms is of interest given that increased commercialization will inevitably lead to some instances of inadvertent environmental exposures. Cadmium selenide quantum dots (QDs) capped with zinc sulfide are used in the semiconductor industry and in cellular imaging. Their small size (<10 nm) suggests that they may be readily assimilated by exposed organisms. We exposed Daphnia magna to both red and green QDs and used synchrotron X-ray fluorescence to study the distribution of Zn and Se in the organism over a time period of 36 h. The QDs appeared to be confined to the gut, and there was no evidence of further assimilation into the organism. Zinc and Se fluorescence signals were highly correlated, suggesting that the QDs had not dissolved to any extent. There was no apparent difference between red or green QDs, i.e., there was no effect of QD size. 3D tomography confirmed that the QDs were exclusively in the gut area of the organism. It is possible that the QDs aggregated and were therefore too large to cross the gut wall.