Methanol-based extraction protocol for insoluble and moderately water-soluble nanoparticles in plants to enable characte

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Methanol-based extraction protocol for insoluble and moderately water-soluble nanoparticles in plants to enable characterization by single particle ICP-MS Stephanie Laughton 1,2 & Adam Laycock 3 & Garret Bland 1 & Frank von der Kammer 3 & Thilo Hofmann 3 & Elizabeth A. Casman 2,4 & Gregory V. Lowry 1,2 Received: 17 July 2020 / Revised: 7 October 2020 / Accepted: 15 October 2020 # Springer-Verlag GmbH Germany, part of Springer Nature 2020

Abstract The detection and characterization of soluble metal nanoparticles in plant tissues are an analytical challenge, though a scientific necessity for regulating nano-enabled agrichemicals. The efficacy of two extraction methods to prepare plant samples for analysis by single particle ICP-MS, an analytical method enabling both size determination and quantification of nanoparticles (NP), was assessed. A standard enzyme-based extraction was compared to a newly developed methanol-based approach. Au, CuO, and ZnO NPs were extracted from three different plant leaf materials (lettuce, corn, and kale) selected for their agricultural relevance and differing characteristics. The enzyme-based approach was found to be unsuitable because of changes in the recovered NP size distribution of CuO NP. The MeOH-based extraction allowed reproducible extraction of the particle size distribution (PSD) without major alteration caused by the extraction. The type of leaf tissue did not significantly affect the recovered PSD. Total metal losses during the extraction process were largely due to the filtration step prior to analysis by spICP-MS, though this did not significantly affect PSD recovery. The methanol extraction worked with the three different NPs and plants tested and is suitable for studying the fate of labile metal-based nano-enabled agrichemicals. Keywords Single particle ICP-MS . Metallic nanoparticle characterization . Agrichemical characterization

Introduction Nano-enabled agricultural pesticides and fertilizers utilizing metal nanoparticles (NPs) have been shown to offer benefits such as increased efficacy at lower application rates [1–3]. Supplementary Information The online version contains supplementary material available at https://doi.org/10.1007/s00216-02003014-8. * Gregory V. Lowry [email protected] 1

Department of Civil and Environmental Engineering, Carnegie Mellon University, Pittsburgh, PA 15213, USA

2

Center for Environmental Implications of NanoTechnology (CEINT), Carnegie Mellon University, Pittsburgh, PA 15213, USA

3

Department of Environmental Geosciences, University of Vienna, 1090 Vienna, Austria

4

Department of Engineering and Public Policy, Carnegie Mellon University, Pittsburgh, PA 15213, USA

Such agrichemicals have the potential to result in the intentional release of pristine metal NP directly into the environment and on to crops for human consumption. A clear understanding of the localization and transformations that these NPs undergo when interacting with crop plants is therefore essential to inform risk assessment and influence the s