The widespread use of silver nanoparticles (Ag-NPs) in consumer and medical products provides strong motivation for a careful assessment of their environmental and human health risks. Recent studies have shown that Ag-NPs released to the natural environment undergo profound chemical transformations that can affect silver
bioavaila
bility, toxicity, and risk. Less is known a
bout Ag-NP chemical transformations in
biological systems, though the medical literature clearly reports that chronic silver ingestion produces argyrial deposits consisting of silver-, sulfur-, and selenium-containing particulate phases. Here we show that Ag-NPs undergo a rich set of
biochemical transformations, including accelerated oxidative dissolution in gastric acid, thiol
binding and exchange, photoreduction of thiol- or protein-
bound silver to secondary zerovalent Ag-NPs, and rapid reactions
between silver surfaces and reduced selenium species. Selenide is also o
bserved to rapidly exchange with sulfide in preformed Ag
b>2b>S solid phases. The com
bined results allow us to propose a conceptual model for Ag-NP transformation pathways in the human
body. In this model, argyrial silver deposits are not translocated engineered Ag-NPs,
but rather secondary particles formed
by partial dissolution in the GI tract followed
by ion uptake, systemic circulation as organo-Ag complexes, and immo
bilization as zerovalent Ag-NPs
by photoreduction in light-affected skin regions. The secondary Ag-NPs then undergo detoxifying transformations into sulfides and further into selenides or Se/S mixed phases through exchange reactions. The formation of secondary particles in
biological environments implies that Ag-NPs are not only a product of industrial nanotechnology
but also have long
been present in the human
body following exposure to more traditional chemical forms of silver.<
br>
Keywords:
bs.acs.org/action/doSearch?action=search&searchText=silver&qsSearchArea=searchText">silver; bs.acs.org/action/doSearch?action=search&searchText=selenium&qsSearchArea=searchText">selenium; bs.acs.org/action/doSearch?action=search&searchText=nanomaterial+transformation&qsSearchArea=searchText">nanomaterial transformation; bs.acs.org/action/doSearch?action=search&searchText=fate&qsSearchArea=searchText">fate; bs.acs.org/action/doSearch?action=search&searchText=health+risks&qsSearchArea=searchText">health risks; bs.acs.org/action/doSearch?action=search&searchText=photochemistry&qsSearchArea=searchText">photochemistry