EDXRF for elemental determination of nanoparticle-related agricultural samples

The number of studies dealing with nanoparticles (NPs) and plants has increased. They subsidize the advances of agriculture in the 21st century; however, so far, beneficial as well as detrimental results have been reported. In this context, analytical tools for monitoring macronutrients and micronutrients in plants exposed to NPs, with adequate performance and low cost, are required. This work assesses the use of energy-dispersive X-ray fluorescence (EDXRF) spectrometry for elemental content evaluation in NP-containing agricultural samples. For Phaseolus vulgaris (common bean) seedlings treated with ZnO NP, CuO NP, and Fe₃O₄ NP, the limits of detection (LODs) were 0.4 mg kg⁻¹ for Zn and Cu and 0.6 mg kg⁻¹ for Fe after dry-ashing digestion, thus being suitable for NP oxide monitoring in seed priming. For submicron suspension fertilizers, Mn, Cu, and Zn were quantified as thin films after sample dilution. The LODs for Mn, Cu, and Zn were 0.09, 0.1, and 0.08 mg L⁻¹, respectively. Finally, for P. vulgaris plants exposed to 300-nm ZnO NP, we monitored P, S, K, Ca, and Zn directly in powdered leaves, whose LODs ranged from 1.3 to 27 mg kg⁻¹. No critical spectral interference was observed, and notable repeatability and suitable trueness were found in the cases of studies. EDXRF revealed itself a simple, fast, and reliable alternative to evaluate the elemental content in suspensions or the uptake of NP by plants.