Generation of Metal Nanoparticles from Silver and Copper Objects: Nanoparticle Dynamics on Surfaces and Potential Sources of Nanoparticles in the Environment

Abstract
The use of silver nanoparticles (AgNPs) in antimicrobial applications, including a wide range of consumer goods and apparel, has attracted attention because of the unknown health and environmental risks associated with these emerging materials. Of particular concern is whether there are new risks that are a direct consequence of their nanoscale size. Identifying those risks associated with nanoscale structure has been difficult due to the fundamental challenge of detecting and monitoring nanoparticles in products or the environment. Here, we introduce a new strategy to directly monitor nanoparticles and their transformations under a variety of environmental conditions. These studies reveal unprecedented dynamic behavior of AgNPs on surfaces. Most notably, under ambient conditions at relative humidities greater than 50%, new silver nanoparticles form in the vicinity of the parent particles. This humidity-dependent formation of new particles was broadly observed for a variety of AgNPs and substrate surface coatings. We hypothesize that nanoparticle production occurs through a process involving three stages: (i) oxidation and dissolution of silver from the surface of the particle, (ii) diffusion of silver ion across the surface in an adsorbed water layer, and (iii) formation of new, smaller particles by chemical and/or photoreduction. Guided by these findings, we investigated non-nanoscale sources of silver such as wire, jewelry, and eating utensils that are placed in contact with surfaces and found that they also formed new nanoparticles. Copper objects display similar reactivity, suggesting that this phenomenon may be more general. These findings challenge conventional thinking about nanoparticle reactivity and imply that the production of new nanoparticles is an intrinsic property of the material that is not strongly size dependent. The discovery that AgNPs and CuNPs are generated spontaneously from manmade objects implies that humans have long been in direct contact with these nanomaterials and that macroscale objects represent a potential source of incidental nanoparticles in the environment.