Past progress in environmental nanoanalysis and a future trajectory for atomic mass-spectrometry methods.

The development of engineered nanotechnology has necessitated a commensurate maturation of nanoanalysis capabilities. Building off a legacy established by electron microscopy and light-scattering, environmental nanoanalysis has now benefited from ongoing advancements in instrumentation and data analysis, which enable a deeper understanding of nanomaterial properties, behavior, and impacts. Where once environmental nanoparticles and colloids were grouped into broad 'dissolved or particulate' classes that are dependent on a filter size cut-off, now size distributions of submicron particles can be separated and characterized providing a more comprehensive examination of the nanoscale. Inductively coupled plasma-quadrupole mass spectrometry (ICP-QMS), directly coupled to field flow fractionation (FFF-ICP-QMS) or operated in single particle mode (spICP-MS) have spearheaded a revolution in nanoanalysis, enabling research into nanomaterial behavior in environmental and biological systems at expected release concentrations. However, the complexity of the nanoparticle population drives a need to characterize and quantify the multi-element composition of nanoparticles, which has begun to be realized through the application of time-of-flight MS (spICP-TOFMS). Despite its relative infancy, this technique has begun to make significant strides in more fully characterizing particulate systems and expanding our understanding of nanoparticle behavior. Though there is still more work to be done with regards to improving instrumentation and data processing, it is possible we are on the cusp of a new nanoanalysis revolution, capable of broadening our understanding of the size regime between dissolved and bulk particulate compartments of the environment.

Influence of dissolution on the uptake of bimetallic nanoparticles Au@Ag-NPs in soil organism Eisenia fetida.

A key aspect in the safety testing of metal nanoparticles (NPs) is the measurement of their dissolution and of the true particle uptake in organisms. Here, based on the tendency of Ag-NP to dissolve and Au-NP to be inert in the environment, we exposed the earthworm Eisenia fetida to Au core-Ag shell NPs (Au@Ag-NPs, Ag-NPs with a Au core) and to both single and combined exposures of non-coated Au-NPs, Ag-NPs, Ag+ and Au+ ions in natural soil. Our hypothesis was that the Ag shell would partially or completely dissolve from the Au@Ag-NPs and that the Au core would thereby behave as a tracer of particulate uptake. Au and Ag concentrations were quantified in all the soils, in soil extract and in organisms by inductively coupled plasma mass spectrometry (ICP-MS). The earthworm exposed to Au@Ag-NPs, and to all the combinations of Ag and Au, were analyzed by single particle inductively coupled plasma time-of-flight mass spectrometry (spICP-TOFMS) to allow the quantification of the metals that were truly part of a bimetallic particle. Results showed that only 5% of the total metal amounts in the earthworm were in the bimetallic particulate form and that the Ag shell increased in thickness, suggesting that biotransformation processes took place at the surface of the NPs. Additionally, the co-exposure to both metal ions led to a different uptake pattern compared to the single metal exposures. The study unequivocally confirmed that dissolution is the primary mechanism driving the uptake of (dissolving) metal NPs in earthworms. Therefore, the assessment of the uptake of metal nanoparticles is conservatively covered by the assessment of the uptake of their ionic counterpart.