PMID- 38316252 OWN - NLM STAT- MEDLINE DCOM- 20240313 LR - 20240313 IS - 1873-6424 (Electronic) IS - 0269-7491 (Linking) VI - 345 DP - 2024 Mar 15 TI - Mechanistic interpretation of the sorption of terbuthylazine pesticide onto aged microplastics. PG - 123502 LID - S0269-7491(24)00216-1 [pii] LID - 10.1016/j.envpol.2024.123502 [doi] AB - Microplastics (MPs) pose a global concern due to their ubiquitous distribution. Once in the environment, they are subject to aging, which changes their chemical-physical properties and ability to interact with organic pollutants, such as pesticides. Therefore, this study investigated the interaction of the hydrophobic herbicide terbuthylazine (TBA), which is widely used in agriculture, with artificially aged polyethylene (PE) MP (PE-MP) to understand how aging affects its sorption. PE was aged by an accelerated weathering process including UV irradiation, hydrogen peroxide, and ultrasonic treatment, and aged particles were characterized in comparison to pristine particles. Sorption kinetics were performed for aged and pristine materials, while further sorption studies with aged PE-MP included determining environmental factors such as pH, temperature, and TBA concentration. Sorption of TBA was found to be significantly lower on aged PE-MP compared to pristine particles because aging led to the formation of oxygen-containing functional groups, resulting in a reduction in hydrophobicity and the formation of negatively charged sites on oxidized surfaces. For pristine PE-MP, sorption kinetics were best described by the pseudo-second-order model, while it was intra-particle diffusion for aged PE-MP as a result of crack and pore formation. Sorption followed a decreasing trend with increasing pH, while it became less favorable at higher temperatures. The isotherm data revealed a complex sorption process on altered, heterogeneous surfaces involving hydrophobic interactions, hydrogen bonding, and pi-pi interactions, and the process was best described by the Sips adsorption isotherm model. Desorption was found to be low, confirming a strong interaction. However, thermodynamic results imply that increased temperatures, such as those resulting from climate change, could promote the re-release of TBA from aged PE-MP into the environment. Time-of-flight secondary ion mass spectrometry (ToF-SIMS) confirmed TBA sorption onto PE. CI - Copyright (c) 2024 The Authors. Published by Elsevier Ltd.. All rights reserved. FAU - Junck, Johannes AU - Junck J AD - Institute of Soil Science and Soil Conservation, Research Center for Biosystems, Land Use and Nutrition, Justus Liebig University, Giessen, Germany. Electronic address: johannes.junck@en.uni-giessen.de. FAU - Diagboya, Paul N AU - Diagboya PN AD - Institute of Soil Science and Soil Conservation, Research Center for Biosystems, Land Use and Nutrition, Justus Liebig University, Giessen, Germany; Environmental Fate of Chemicals and Remediation (EnFaCRe) Laboratory, Department of Environmental Management and Toxicology, University of Delta, Agbor, Nigeria. FAU - Peqini, Aleksander AU - Peqini A AD - Institute of Soil Science and Soil Conservation, Research Center for Biosystems, Land Use and Nutrition, Justus Liebig University, Giessen, Germany; Faculty of Agriculture and Environment, Agricultural University of Tirana, Tirana, Albania. FAU - Rohnke, Marcus AU - Rohnke M AD - Institute of Physical Chemistry and Center for Materials Research, Justus Liebig University, Giessen, Germany. FAU - During, Rolf-Alexander AU - During RA AD - Institute of Soil Science and Soil Conservation, Research Center for Biosystems, Land Use and Nutrition, Justus Liebig University, Giessen, Germany. LA - eng PT - Journal Article DEP - 20240203 PL - England TA - Environ Pollut JT - Environmental pollution (Barking, Essex : 1987) JID - 8804476 RN - 0 (Microplastics) RN - 0 (Plastics) RN - M095B391J7 (terbutylazine) RN - 0 (Pesticides) RN - 0 (Triazines) RN - 9002-88-4 (Polyethylene) RN - 0 (Water Pollutants, Chemical) SB - IM MH - Microplastics/chemistry MH - Plastics/chemistry MH - *Pesticides/analysis MH - Triazines/analysis MH - Polyethylene/chemistry MH - Adsorption MH - *Water Pollutants, Chemical/analysis OTO - NOTNLM OT - Aged microplastics OT - Polyethylene OT - Surface chemistry OT - Thermodynamics OT - Time-of-flight secondary ion mass spectrometry (ToF-SIMS) OT - Triazines COIS- Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper. EDAT- 2024/02/06 00:42 MHDA- 2024/03/13 06:46 CRDT- 2024/02/05 19:23 PHST- 2023/11/25 00:00 [received] PHST- 2024/01/19 00:00 [revised] PHST- 2024/02/03 00:00 [accepted] PHST- 2024/03/13 06:46 [medline] PHST- 2024/02/06 00:42 [pubmed] PHST- 2024/02/05 19:23 [entrez] AID - S0269-7491(24)00216-1 [pii] AID - 10.1016/j.envpol.2024.123502 [doi] PST - ppublish SO - Environ Pollut. 2024 Mar 15;345:123502. doi: 10.1016/j.envpol.2024.123502. Epub 2024 Feb 3.