New insights into the formation of silver-based nanoparticles under natural and semi-natural conditions.

For the first time, the natural formation of silver-based nanoparticles (Ag-b-NPs) was studied in field investigations of two pre-alpine lakes in Germany that contain geogenic silver traces in the sub-ng L-1 range. Light-sensitive microorganisms most likely accumulate and transport these silver traces from deeper water layers to the surface. At the surface of the eutrophic lake, approximately 40% of total silver (5.7 ng L-1 ) consisted of Ag-b-NPs, whereas in the oligotrophic lake with similar enrichment of silver species, no Ag-b-NPs were detected. Additional lab experiments with nature-related Ag(I) concentrations in the lower-ng L-1 range and natural organic matter with total organic carbon values of ≤5 mg L-1 revealed that, contrary to common interpretation in the literature, Ag-b-NPs are also or even preferably formed in the dark. Particle size increases gradually with increasing reaction time, showing that Ostwald ripening occurs even at such low particle concentrations. When sulfide ions are present, smaller Ag-b-NPs with a narrower size distribution are formed.