There is a growing interest in monitoring microplastics in the environment, corresponding to increased public concerns regarding their potential adverse effects on ecosystems. Monitoring microplastics in the environment is difficult due to the complex matrices that can prevent reliable analysis if samples are not properly prepared first. Unfortunately, sample preparation methods are not yet standardized, and the various efforts to validate them overlook key aspects. The goal of this study was to develop a sample preparation method for wastewater samples, which removes natural organic matter without altering the properties of microplastics. Three protocols, based on KOH, H₂O₂, and Fenton reactions, were chosen out of ten protocols after a literature review and pre-experiments. In order to investigate the effects of these reagents on seven polymers (PS, PE, PET, PP, PA, PVC, and PLA), this study employed µFTIR, laser diffraction-based particle size analysis, as well as TD-Pyr-GC/MS. Furthermore, the study discussed issues and inconsistencies with the Fenton reactions reported in the literature in previous validation efforts. The findings of this study suggest that both H₂O₂ and Fenton reactions are most effective in terms of organic matter removal from microplastic samples while not affecting the tested polymers, whereas KOH dissolved most PLA and PET particles.

Micro-, submicro- and nanoplastic particles are increasingly regarded as vectors for trace organic chemicals. In order to determine adsorbed trace organic chemicals on polymers, it has usually been necessary to carry out complex extraction steps. With the help of a newly designed thermal desorption pyrolysis gas chromatography mass spectrometry (TD-Pyr-GC/MS) method, it is possible to identify adsorbed trace organic chemicals on micro-, submicro- and nanoparticles as well as the particle short chain polymers in one analytical setup without any transfers. This ensures a high sample throughput for the qualitative analysis of trace substances and polymer type. Since the measuring time per sample is only 2 h, a high sample throughput is possible. It is one of the few analytical methods which can be used also for the investigation of nanoplastic particles. Initially adsorbed substances are desorbed from the particle by thermal desorption (TD); subsequently, the polymer is fragmented by pyrolysis (PYR). Both particle treatment techniques are directly coupled with the same GC-MS system analyzing desorbed molecules and pyrolysis products, respectively. In this study, we developed a systematic and optimized method for this application. For method development, the trace organic chemicals phenanthrene, α-cypermethrin and triclosan were tested on reference polymers polystyrene (PS), polymethyl methacrylate (PMMA) and polyethylene (PE). Well-defined particle fractions were used, including polystyrene (sub)micro- (41 and 40 µm) and nanoparticles (78 nm) as well as 48-µm sized PE and PMMA particles, respectively. The sorption of phenanthrene (PMMA << PS 40 µm < 41 µm < PE < PS 78 nm) and α-cypermethrin (PS 41 µm < PS 40 µm < PE < PMMA < PS 78 nm) to the particles was strongly polymer-dependent. Triclosan adsorbed only on PE and on the nanoparticles of PS (PE < PS78).

Micro- and nanoplastic particles are increasingly seen not only as contaminants themselves, but also as potential vectors for trace organic chemicals (TOrCs) that might sorb onto these particles. An analysis of the sorbed TOrCs can either be performed directly from the particle or TOrCs can be extracted from the particle with a solvent. Another possibility is to analyze the remaining concentration in the aqueous phase by a differential approach. In this review, the focus is on analytical methods that are suitable for identifying and quantifying sorbed TOrCs on micro- and nano-plastics. Specific gas chromatography (GC), liquid chromatography (LC) and ultraviolet-visible spectroscopy (UV-VIS) methods are considered. The respective advantages of each method are explained in detail. In addition, influencing factors for sorption in the first place are being discussed including particle size and shape (especially micro and nanoparticles) and the type of polymer, as well as methods for determining sorption kinetics. Since the particles are not present in the environment in a virgin state, the influence of aging on sorption is also considered.

Assessing the sorption of trace organic compounds (TOrCs) into micro- and nanoplastic particles has traditionally been performed using an aqueous phase analysis or solvent extractions from the particle. Using thermal extraction/desorption–gas chromatography/mass spectrometry (TD-Pyr-GC/MS) offers a possibility to analyze the TOrCs directly from the particle without a long sample preparation. In this study, a combination of two analytical methods is demonstrated. First, the aqueous phase is quantified for TOrC concentrations using Gerstel Twister^® and TD-GC/MS. Subsequently, the TOrCs on the particles are analyzed. Different polymer types and sizes (polymethyl methacrylate (PMMA), 48 µm; polyethylene (PE), 48 µm; polystyrene (PS), 41 µm; and PS, 78 nm) were analyzed for three selected TOrCs (phenanthrene, triclosan, and α-cypermethrin). The results revealed that, over a period of 48 h, the highest and fastest sorption occurred for PS 78 nm particles. This was confirmed with a theoretical calculation of the particle surface area. It was also shown for the first time that direct quantification of TOrCs from PS 78 nm nanoparticles is possible. Furthermore, in a mixed solute solution, the three selected TOrCs were sorbed onto the particles simultaneously.