Effect of Initial Speciation of Copper- and Silver-Based Nanoparticles on Their Long-Term Fate and Phytoavailability in Freshwater Wetland Mesocosms

Ag-0- and CuO-engineered nanomaterials (ENMs) or their sulfidized forms are introduced into freshwater wetlands through wastewater effluent and agricultural runoff. Knowledge about the rates of transformations of these ENMs in realistic environments and the impact of the form of the incoming ENM (i.e., sulfidized or pristine) on bioavailability and fate is limited. Here, five freshwater wetland mesocosms were exposed to 3 g of total metal as CuO, CuS, Ag-0, or Ag2S ENMs or soluble CuNO3 added weekly for 1 month. Total metal and metal speciation was measured in sediment and plant samples collected 1, 3, 6, and 9 months after addition. The form of the added ENM did not affect the metal distribution, and ENMs distributed similarly to added ionic Cu or Ag. For the dosing condition used, similar to 50% of the added Ag or Cu metal mass was found in Egeria densa plant tissue, with the remainder primarily in the surficial sediment. Ag and CuO ENMs transformed quickly in sediment, with no evidence of CuO and only similar to 4% of silver present as Ag ENM 1 week after the last ENM addition. In contrast to sediment, Ag and CuO ENMs were persistent in E. densa tissues for up to 9 and 6 months, respectively. The persistence of ENMs in E. densa suggests that chronic exposures, or food web transfers, for both the transformed and the initially added ENMs are possible.