Ion Mobility and Segregation in Seed Surfaces Subjected to Cold Plasma Treatments

Plasma treatment of seeds is an efficient procedure to accelerate germination, to improve initial stages of plant growth, and for protection against pathogen infection. Most studies relate these beneficial effects with biochemical modifications affecting the metabolism and genetic growth factors of seeds and young plants. Using barley seeds, in this work, we investigate the redistribution of ions in the seed surface upon their treatment with cold air plasmas. In addition, we investigate the effect of plasma in the lixiviation of ions through the seeds' hull when they are immersed in water. Ion redistribution in the outer layers of air plasma-treated seeds has been experimentally determined through X-ray photoelectron spectroscopy analysis in combination with in-depth chemical profiling with gas cluster ion beams. The results show that in the shallowest layers of the seed hull (at least up to a depth of ∼100 nm) there is an enrichment of K⁺ and Ca²⁺ ions, in addition to changes in the O/C and N/C atomic ratios. These data have been confirmed by the electron microscopy/fluorescence analysis of seed cuts. Observations have been accounted for by a Monte Carlo model, simulating the electrostatic interactions that develop between the negative charge accumulated at the seed surface due to the interaction with the plasma sheath and the positive ions existing in the interior. Furthermore, it is shown that upon water immersion of plasma-treated seeds mobilized ions tend to lixiviate more efficiently than in pristine seeds. The detection of a significant concentration of NO₃^- anions in the water has been attributed to a secondary reaction of nitrogen species incorporated into the seeds during plasma exposure with reactive oxygen species formed on their surface during this treatment. The implications of these findings for the improvement of the germination capacity of seeds are discussed.