Analysis of engineered nanomaterials in the environment

Abstract

With increasing incorporation of engineered nanoparticles (NPs) into consumer products, there is concern that these materials will be released to the environment with unknown ecological effects. Methods for detection and characterization of these materials at environmentally relevant concentrations are crucial to understanding this potential risk. A relatively new method, single particle inductively coupled plasma mass spectrometry (spICPMS), was applied to analysis of metal oxide NPs such as ZnO, CeO2, and TiO2, as well as silver nanowires and carbon nanotubes. A lack of nanoparticulate "pulses" in spICPMS analysis of nano-ZnO led to a study on ZnO NP solubility in a variety of matrices. Dissolution of nano-ZnO was observed in nanopure water (7.18 - 7.40 mg/L dissolved Zn, as measured by filtration) and Roswell Park Memorial Institute medium (RPMI-1640) (~5 mg/L), but much more dissolution was observed in Dulbecco's Modified Eagle's Medium (DMEM), where the dissolved Zn concentration exceeded 34 mg/L. These results suggest that solution chemistry exerts a strong influence on ZnO NP dissolution and can result in limits on zinc solubility due to precipitation of less soluble solid phases. Detection and sizing of metal-containing NPs was achieved at concentrations predicted for environmental samples (part-per trillion levels) using spICPMS. Sizing of silver nanowires, titanium dioxide and cerium oxide NPs was done by correlating ICP-MS response (pulses) from NPs entering the plasma to mass of metal in dissolved standards. The ratio of NP pulse detections to the total number of readings during analysis was optimized at 2.5% or less to minimize coincident pulses while still allowing definition of a size distribution. Detection of single walled carbon nanotubes (CNTs) was performed using spICPMS. This study focuses on using trace catalytic metal nanoparticles intercalated in the CNT structure as proxies for the nanotubes. The small, variable, amount of trace metal in each CNT makes separation from instrumental background challenging, and multiple approaches to this problem were attempted. To highlight the potential of spICPMS in environmental studies the release of CNTs from polymer nanocomposites into solution was monitored, showcasing the technique's ability to detect changes in released CNT concentrations as a function of CNT loading.