Using MALDI-TOF MS imaging and LC-HRMS for the investigation of the degradation of polycaprolactone diol exposed to different wastewater treatments.

Polymers are used in high amounts in a wide range of applications from biomedicine to industry. Because of the growing awareness of the increasing amounts of plastic wastes in the aquatic environment during recent years, the evaluation of their biodegradability deserves special attention. In the past, most efforts were dedicated to studying the biodegradation of polyesters in soil and compost, while very little research has been conducted on their fate in wastewater. Here, we assessed the ability of bacterial communities residing in the aerobic and denitrification tank from a wastewater treatment plant (WWTP) to degrade the polymeric ester polycaprolactone diol (PCLD; average molecular weight of 1250 Da). Following the incubation of the solid polymer in WWTP tanks, matrix-assisted laser desorption/ionization-mass spectrometry imaging (MALDI-MSI) was used to provide evidence for hydrolytic reactions and to study differences in the spatial degradation on the PCLD surface. It was demonstrated that regardless of the wastewater type, the chemical structure on the PCLD surface underwent modifications after 7 days of exposure. Apart from the parent PCLD peak series in MALDI-MSI mass spectra, the presence of a second oligomer series with mass peaks spaced by m/z 114 (as in PCLD) was observed. It was proposed to correspond to polycaprolactone (PCL) originating from the hydrolytic cleavage of the diethylene glycol from PCLD. Their ion masses were detected at m/z 104 below the PCLD peaks and their structures were proposed as PCL cyclized oligomers. Differences in the spatial distribution of low MW ions (<800) between the aerobic and denitrifying exposed samples in MALDI MSI were also noticeable. While the ions at m/z 221.1, 247.1 and 449.2 predominated in the aerobic exposed sample, those at m/z 475.5 and 677.4 were characteristic of the denitrifying one. The MALDI-MSI measurements in the low mass range were complemented with LC-HRMS analysis to determine plausible structures of the major degradation products. Ten transformation products (TPs) were detected in the denitrifying wastewater experiment, five of them were the result of ester hydrolysis forming caprolactone oligomers (TPs 220, 334, 448, 562, and 676) while the other series corresponded to formation of PCL chain with a terminal diethylene glycol, likewise formed by ester hydrolysis (TPs 246, 360, 474, 588, and 702). Graphical abstract Investigation of the polymer degradation in WWTPs by MALDI-MSI and LC-HRMS.