Highly selective solid–liquid extraction of microplastic mixtures as a pre-preparation tool for quantitative nuclear magnetic resonance spectroscopy studies†

Despite various developments in the application of quantitative nuclear magnetic resonance (qNMR) spectroscopy toward microplastics in recent years, this method still lacks suitable sample preparation and fractionation procedures. As this poses a crucial obstacle for its utilisation on environmental samples, which contain various mixtures of polymers along with other matrix substances, this research aims to address this missing link by presenting an easy-to-apply procedure based on common laboratory equipment. The process selectively separates microplastics from inorganic constituents while performing the necessary fractionation of different types of microplastics prior to qNMR analysis. It allows subsequent quantification of polystyrene (PS), polybutadiene rubber (BR), polymethylmethacrylate (PMMA), polyvinylchloride (PVC), polyethylene terephthalate (PET) and polyamide (PA) from a single sample, establishing recovery rates greater than 88% for all tested polymer types. Additionally, we extended our previous qNMR protocol to include two common polymer types: polymethylmethacrylate (PMMA) and polyacrylonitrile (PAN), achieving limits of detection down to 1.76 μg ml⁻¹ and 12.53 μg ml⁻¹ as well as limits of quantification down to 5.88 μg ml⁻¹ and 41.78 μg ml⁻¹, respectively. Thus, the qNMR method presented herein is now applicable to eight abundant polymer types, allowing the quantification of up to three different types simultaneously.