Foliar exposure of the crop Lactuca sativa to silver nanoparticles: evidence for internalization and changes in Ag speciation.

The impact of engineered nanomaterials on plants, which act as a major point of entry of contaminants into trophic chains, is little documented. The foliar pathway is even less known than the soil-root pathway. However, significant inputs of nanoparticles (NPs) on plant foliage may be expected due to deposition of atmospheric particles or application of NP-containing pesticides. The uptake of Ag-NPs in the crop species Lactuca sativa after foliar exposure and their possible biotransformation and phytotoxic effects were studied. In addition to chemical analyses and ecotoxicological tests, micro X-ray fluorescence, micro X-ray absorption spectroscopy, time of flight secondary ion mass spectrometry and electron microscopy were used to localize and determine the speciation of Ag at sub-micrometer resolution. Although no sign of phytotoxicity was observed, Ag was effectively trapped on lettuce leaves and a thorough washing did not decrease Ag content significantly. We provide first evidence for the entrapment of Ag-NPs by the cuticle and penetration in the leaf tissue through stomata, for the diffusion of Ag in leaf tissues, and oxidation of Ag-NPs and complexation of Ag(+) by thiol-containing molecules. Such type of information is crucial for better assessing the risk associated to Ag-NP containing products.