Title Sulfide induces physical damages and chemical transformation of microplastics via radical oxidation and sulfide addition
Authors Zhao, Mengting
Zhang, Tong
Yang, Xinlin
Liu, Xinlei
Zhu, Dongqiang
Chen, Wei
Affiliation Nankai Univ, Coll Environm Sci & Engn, Key Lab Pollut Proc & Environm Criteria, Minist Educ,Tianjin Key Lab Environm Remediat & P, Tianjin 300350, Peoples R China
Nankai Univ, Inst Polymer Chem, Minist Educ, Coll Chem,Key Lab Funct Polymer Mat, Tianjin 300071, Peoples R China
Peking Univ, Sch Urban & Environm Sci, Beijing 100871, Peoples R China
Keywords GRAPHENE OXIDE
WASTE-WATER
AQUEOUS SULFIDE
IDENTIFICATION
NANOPARTICLES
PRODUCTS
KINETICS
FATE
Issue Date 1-Jun-2021
Publisher WATER RESEARCH
Abstract Transformation of microplastics in aquatic environments and engineered systems (e.g., wastewater treatment plants) significantly affects their transport, fate and effects. Here, we present the counterintuitive finding that sulfide, a prevalent nucleophile and reductant, can result in oxidation of microplastics, in addition to sulfide addition. Treating four model microplastics (thermoplastic polyurethane, polystyrene, polyethylene terephthalate and polyethylene) with 0.1 mM sulfide in a Tris-buffer solution (pH 7.2, 25 degrees C) resulted in physical damages (embrittlement and cracking) and chemical transformation (increased O/C ratio and formation of C-S bonds) of the materials. Pre-aging of the microplastics with O-3 or UV treatment had varied effects on their reactivities toward sulfide, depending on the specific structural and surface chemistry properties of the polymers. Electron paramagnetic resonance and radical trapping/quenching experiments showed that sulfide underwent spontaneous oxidation to form center dot OH radicals, which acted as the primary oxidant to attack the carbon atoms in the polymer chains, leading to surface oxidation and chain scission. Notably, sulfide addition, verified with X-ray photoelectron spectroscopy and 13C-nuclear magnetic resonance spectroscopy analyses, likely contributed to the physicochemical transformation of microplastics together with radical oxidation in a synergistic manner. The findings unravel an important transformation route (and a potential source) of microplastics in the environment. (C) 2021 Elsevier Ltd. All rights reserved.
URI http://hdl.handle.net/20.500.11897/612603
ISSN 0043-1354
DOI 10.1016/j.watres.2021.117100
Indexed SCI(E)
Appears in Collections: 城市与环境学院

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