The increasingly widespread usage of silver (Ag) nanoparticles has raised concerns regarding their environmental risk. The behavior of Ag and its transfer risk to the food chain were investigated using a long-term field experiment that commenced in 1942 in which Ag-containing sewage sludge was repeatedly applied to the soil (25 applications during 20 years). The speciation of the Ag in both the sludge and the soils retrieved from the long-term experimental archive was examined using synchrotron-based X-ray absorption spectroscopy, and extractable Ag concentrations from soils were determined using 0.01 M Ca(NO3)2 and 0.005 M DTPA. The total Ag in the sludge during the time period of 1942-1961 ranged from 155 to 463 mg kg-1. These values are 1-2 orders of magnitude higher than those in currently produced sludge (ca. 0.5-20 mg kg-1). Long-term repeated applications of these sludges resulted in an increase of Ag in soils from 1.9 mg kg-1 in the control to up to 51 mg kg-1. The majority (>80%) of the Ag in both the sludge and the sludge-treated soils was present as insoluble Ag2S, thereby markedly reducing the bioavailability of this Ag. Concentrations of Ag in the archived crop samples were generally <0.70 mg kg-1 in edible tissues, much less than those in diets that may cause an adverse effects in animals and humans (>100 mg kg-1). These data indicate that the transfer of Ag (derived from both traditional Ag industry and current nano Ag industry) to the terrestrial food chain is limited.