Partitioning and stability of ionic, nano- and microsized zinc in natural soil suspensions

Batch experiments aimed at solid-liquid distribution of 40 nm engineered zinc oxide nanoparticles (ZnO-NP), microparticles (bulk ZnO), and ionic Zn in ZnSO₄ solution were conducted on eight field soil samples of different characteristics to identify how the form of Zn affects its distribution in soil. The concentration of Zn in different size fractions present in supernatant solutions obtained from centrifuged soil suspensions was also measured. The distribution between a liquid and a solid was different for the ionic Zn (ZnSO₄) and particulate Zn (ZnO-NP and bulk ZnO). In acidic soil solutions, the partitioning coefficient (K_dA) of the ionic Zn was in range of 14.7-15.9 compared to 133.4-194.1 for ZnO-NP and bulk ZnO. The situation was reversed under alkaline conditions resulting in a decreased retention of particulate forms of Zn by the solids, with ZnO-NP showing K_dA of 8.5-23.4 compared to 160.0-760.1 of ionic Zn. Soil pH thus appears to be the predominant factor influencing the solid-liquid distribution of Zn in different forms. Even the distribution of Zn in different size fractions is heavily affected by the soil pH, causing dissolution of ZnO-NP and bulk ZnO in acidic soils. In alkaline soils, applied ionic Zn (ZnSO₄) remained dissolved. This study shows that ZnO-NP are the most mobile of the three tested forms of Zn in alkaline soils. This may affect the spatial distribution of Zn in soil and potentially increase the effectivity of the application of Zn fertilizer when in nanoparticle form.