Detection and Characterization of ZnO Nanoparticles in Surface and Waste Waters Using Single Particle ICPMS

The increasing production of ZnO nanoparticles (nZnO) makes their analysis and characterization extremely important from an ecological risk perspective, especially at the low concentrations at which they are expected to be found in natural waters. Single particle ICPMS (SP-ICPMS) is one of the few techniques available to detect and characterize nanoparticles at environmentally relevant concentrations. Unfortunately, at the very low particle concentrations where SP-ICPMS is performed, significant dissolution of the nZnO generally increases background levels of dissolved Zn to the point where measurements are not generally possible. By hyphenating SP-ICPMS with an ion-exchange resin, it was possible to characterize and quantify nZnO in order to gain insight into the nature of the nZnO in natural waters. Spiked and unspiked water samples were analyzed using a SP-ICPMS that was coupled to a column containing a strong metal binding resin (Chelex 100). In addition to the detection of ZnO nanoparticles and the determination of a size distribution in natural waters, it was possible to partition the dissolved Zn among free and/or labile and strongly bound Zn fractions. In two natural waters, a high proportion (ca. 93–100%) of dissolved Zn was measured, and the residual ZnO particles were mainly composed of small agglomerates (average sizes ranging from 133.6 to 172.4 nm in the surface water and from 167.6 to 216.4 nm in the wastewater effluent). Small numbers of small nanoparticles were also detected in nonspiked waters

Improvements to Single Particle ICPMS by the Online Coupling of Ion Exchange Resins

Single particle ICPMS (SP-ICPMS) is becoming a very promising technique for nanoparticle detection and characterization, especially at very low concentrations (∼10^–12–10^–10 M). Nonetheless, the ability of the technique to detect smaller nanoparticles is presently limited by the setting of threshold values for the discrimination of nanoparticles from the dissolved metal background. In this study, a new approach to attaining lower particle size detection limits has been developed by the online coupling of an ion exchange column (IEC) with SP-ICPMS (IEC-SP-ICPMS). The IEC effectively removes the continuous signal of dissolved metal, allowing for both lower detection limits and an improved resolution of solutions containing multiple particles. The feasibility and the efficiency of this coupling were investigated using silver nanoparticles in the presence of various concentrations of Ag⁺ and other major ions (Mg²⁺, Ca²⁺, Na⁺, K⁺, and Cl^–). The online elimination of the dissolved metal made data processing simpler and more accurate. Following the addition of 1 to 4 μg L^–1 of Ag⁺ spikes, symmetric particle size distributions were obtained using IEC-SP-ICPMS, whereas the use of SP-ICPMS alone led to asymmetric distributions, especially for nanoparticle sizes below 60 nm. Although this proof of principle study focused on nanosilver, the technique should be particularly useful for any of the metal based nanoparticles with high solubilities