Sadam Hussain Tumrani, Bharat Prasad Sharma, Ali Raza Otho, Eman A. Ayob, Mohammed A. Amin, Mohamed Mohamed Soliman, Razium Ali Soomro, Selcan Karakuş
{"title":"Biodegradation of PLA in surface water and its behavior towards PFOA: interactional characteristics and computational insights","authors":"Sadam Hussain Tumrani, Bharat Prasad Sharma, Ali Raza Otho, Eman A. Ayob, Mohammed A. Amin, Mohamed Mohamed Soliman, Razium Ali Soomro, Selcan Karakuş","doi":"10.1007/s00396-025-05423-6","DOIUrl":null,"url":null,"abstract":"<div><p>The environmental impact of biodegradable microplastics (BMPs) is profoundly influenced by aging-induced surface transformations, yet their interactions with persistent organic pollutants, such as perfluorooctanoic acid (PFOA), remain poorly understood. This work investigates how aging polylactic acid (PLA), a common BMP, in simulated surface water for 80 days alters its physicochemical properties and behavior towards PFOA. Aging triggered oxidative and hydrolytic degradation, leading to pronounced morphological changes, including increased surface roughness, hydrophilicity, and oxygen-to-carbon (O/C) ratio from 0.82 to 1.28. These transformations introduced hydroxyl and carboxyl functional groups, shifting the PFOA adsorption mechanism from physisorption (in fresh PLA) to chemisorption (in aged PLA) via stronger electrostatic interactions and hydrogen bonding. Additionally, kinetic and isotherm analyses revealed a tenfold increase in PFOA monolayer adsorption capacity for aged PLA (PLA-80) compared to pristine PLA. Density functional theory (DFT) calculations corroborated these findings, demonstrating a reduced HOMO–LUMO energy gap upon PFOA adsorption, indicative of enhanced electronic reactivity and charge transfer. Topological analysis further identified multiple hydrogen-bonding sites, confirming the dominance of electrostatic forces in pollutant retention. These results underscore the critical role of aging in amplifying BMPs’ environmental reactivity, emphasizing the urgent need to incorporate aging processes into risk assessments for biodegradable plastics.</p></div>","PeriodicalId":520,"journal":{"name":"Colloid and Polymer Science","volume":"303 7","pages":"1397 - 1408"},"PeriodicalIF":2.3000,"publicationDate":"2025-05-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Colloid and Polymer Science","FirstCategoryId":"92","ListUrlMain":"https://link.springer.com/article/10.1007/s00396-025-05423-6","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0
Abstract
The environmental impact of biodegradable microplastics (BMPs) is profoundly influenced by aging-induced surface transformations, yet their interactions with persistent organic pollutants, such as perfluorooctanoic acid (PFOA), remain poorly understood. This work investigates how aging polylactic acid (PLA), a common BMP, in simulated surface water for 80 days alters its physicochemical properties and behavior towards PFOA. Aging triggered oxidative and hydrolytic degradation, leading to pronounced morphological changes, including increased surface roughness, hydrophilicity, and oxygen-to-carbon (O/C) ratio from 0.82 to 1.28. These transformations introduced hydroxyl and carboxyl functional groups, shifting the PFOA adsorption mechanism from physisorption (in fresh PLA) to chemisorption (in aged PLA) via stronger electrostatic interactions and hydrogen bonding. Additionally, kinetic and isotherm analyses revealed a tenfold increase in PFOA monolayer adsorption capacity for aged PLA (PLA-80) compared to pristine PLA. Density functional theory (DFT) calculations corroborated these findings, demonstrating a reduced HOMO–LUMO energy gap upon PFOA adsorption, indicative of enhanced electronic reactivity and charge transfer. Topological analysis further identified multiple hydrogen-bonding sites, confirming the dominance of electrostatic forces in pollutant retention. These results underscore the critical role of aging in amplifying BMPs’ environmental reactivity, emphasizing the urgent need to incorporate aging processes into risk assessments for biodegradable plastics.
期刊介绍:
Colloid and Polymer Science - a leading international journal of longstanding tradition - is devoted to colloid and polymer science and its interdisciplinary interactions. As such, it responds to a demand which has lost none of its actuality as revealed in the trends of contemporary materials science.