Microplastics found in the environment are often covered with a biofilm, which makes their analysis difficult. Therefore, the biofilm is usually removed before analysis, which may affect the microplastic particles or lead to their loss during the procedure. In this work, we used laser-based analytical techniques and evaluated their performance in detecting, characterizing, and classifying pristine and aged microplastics with a developed biofilm. Five types of microplastics from different polymers were selected (polyamide, polyethylene, polyethylene terephthalate, polypropylene, and polyvinyl chloride) and aged under controlled conditions in freshwater and wastewater. The development of biofilm and the changes in the properties of the microplastic were evaluated. The pristine and aged microplastics were characterized by standard methods (e.g., optical and scanning electron microscopy, and Raman spectroscopy), and then laser-induced breakdown spectroscopy (LIBS) and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) were used. The results show that LIBS could identify different types of plastics regardless of the ageing and major biotic elements of the biofilm layer. LA-ICP-MS showed a high sensitivity to metals, which can be used as markers for various plastics. In addition, LA-ICP-MS can be employed in studies to monitor the adsorption and desorption (leaching) of metals during the ageing of microplastics. The use of these laser-based analytical techniques was found to be beneficial in the study of environmentally relevant microplastics.

Central European Institute of Technology Brno University of Technology Purkyňova 656 123 61200 Brno Czech Republic; Faculty of Mechanical Engineering Brno University of Technology Technická 2896 2 61669 Brno Czech Republic

Faculty of Chemistry and Chemical Technology University of Ljubljana Večna Pot 113 1000 Ljubljana Slovenia

Faculty of Mechanical Engineering Brno University of Technology Technická 2896 2 61669 Brno Czech Republic

Institute of Scientific Instruments Czech Academy of Sciences Královopolská 147 612 64 Brno Czech Republic

TU Wien Institute of Chemical Technologies and Analytics Getreidemarkt 9 164 1 AC 1060 Vienna Austria

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Raman microspectroscopy and laser-induced breakdown spectroscopy for the analysis of polyethylene microplastics in human soft tissues