DOM affected behavior of manufactured nanoparticles in soil-plant system
Authors: Chefetz Benny , Xing Baoshan , Eshed-Williams Leor , Polubesova Tamara , Unrine Jason 
Published: January 2022

The overall goal of this project was to elucidate the role of dissolved organic matter (DOM) in soil retention, bioavailability and plant uptake of silver and cerium oxide NPs. The environmental risks of manufactured nanoparticles (NPs) are attracting increasing attention from both industrial and scientific communities. These NPs have shown to be taken-up, translocated and bio- accumulated in plant edible parts. However, very little is known about the behavior of NPs in soil-plant system as affected by dissolved organic matter (DOM). Thus DOM effect on NPs behavior is critical to assessing the environmental fate and risks related to NP exposure. Carbon-based nanomaterials embedded with metal NPs demonstrate a great potential to serve as catalyst and disinfectors. Hence, synthesis of novel carbon-based nanocomposites and testing them in the environmentally relevant conditions (particularly in the DOM presence) is important for their implementation in water purification. Sorption of DOM on Ag-Ag₂S NPs, CeO₂ NPs and synthesized Ag-Fe₃O₄-carbon nanotubebifunctional composite has been studied. High DOM concentration (50mg/L) decreased the adsorptive and catalytic efficiencies of all synthesized NPs. Recyclable Ag-Fe₃O₄-carbon nanotube composite exhibited excellent catalytic and anti-bacterial action, providing complete reduction of common pollutants and inactivating gram-negative and gram-positive bacteria at environmentally relevant DOM concentrations (5-10 mg/L). Our composite material may be suitable for water purification ranging from natural to the industrial waste effluents. We also examined the role of maize (Zeamays L.)-derived root exudates (a form of DOM) and their components on the aggregation and dissolution of CuONPs in the rhizosphere. Root exudates (RE) significantly inhibited the aggregation of CuONPs regardless of ionic strength and electrolyte type. With RE, the critical coagulation concentration of CuONPs in NaCl shifted from 30 to 125 mM and the value in CaCl₂ shifted from 4 to 20 mM. This inhibition was correlated with molecular weight (MW) of RE fractions. Higher MW fraction (> 10 kDa) reduced the aggregation most. RE also significantly promoted the dissolution of CuONPs and lower MW fraction (< 3 kDa) RE mainly contributed to this process. Also, Cu accumulation in plant root tissues was significantly enhanced by RE. This study provides useful insights into the interactions between RE and CuONPs, which is of significance for the safe use of CuONPs-based antimicrobial products in agricultural production. Wheat root exudates (RE) had high reducing ability to convert Ag+ to nAg under light exposure. Photo-induced reduction of Ag+ to nAg in pristine RE was mainly attributed to the 0-3 kDa fraction. Quantification of the silver species change over time suggested that Cl⁻ played an important role in photoconversion of Ag+ to nAg through the formation and redox cycling of photoreactiveAgCl. Potential electron donors for the photoreduction of Ag+ were identified to be reducing sugars and organic acids of low MW. Meanwhile, the stabilization of the formed particles was controlled by both low (0-3 kDa) and high (>3 kDa) MW molecules. This work provides new information for the formation mechanism of metal nanoparticles mediated by RE, which may further our understanding of the biogeochemical cycling and toxicity of heavy metal ions in agricultural and environmental systems. Copper sulfide nanoparticles (CuSNPs) at 1:1 and 1:4 ratios of Cu and S were synthesized, and their respective antifungal efficacy was evaluated against the pathogenic activity of Gibberellafujikuroi(Bakanae disease) in rice (Oryza sativa). In a 2-d in vitro study, CuS decreased G. fujikuroiColony- Forming Units (CFU) compared to controls. In a greenhouse study, treating with CuSNPs at 50 mg/L at the seed stage significantly decreased disease incidence on rice while the commercial Cu-based pesticide Kocide 3000 had no impact on disease. Foliar-applied CuONPs and CuS (1:1) NPs decreased disease incidence by 30.0 and 32.5%, respectively, which outperformed CuS (1:4) NPs (15%) and Kocide 3000 (12.5%). CuS (1:4) NPs also modulated the shoot salicylic acid (SA) and Jasmonic acid (JA) production to enhance the plant defense mechanisms against G. fujikuroiinfection. These results are useful for improving the delivery efficiency of agrichemicals via nano-enabled strategies while minimizing their environmental impact, and advance our understanding of the defense mechanisms triggered by the NPs presence in plants.