Microplastics (MPs) are presumed to be inert during aging under ambient conditions. In this study, four types of virgin MPs, including polystyrene (PS), phenolformaldehyde resin (PF), polyethylene (PE), and polyvinyl chloride (PVC), were aged under simulated solar light irradiation. Surprisingly, several environmentally persistent free radicals (EPFRs), which are considered to be a type of emerging contaminant, were detected on the irradiated PS and PF, rather than PE and PVC, by electron paramagnetic resonance (EPR) spectroscopy. Depending on the photoaging duration time, the characteristic g-factors of the EPFRs produced on PS and PF were 2.0044−2.0049 and 2.0043− 2.0044, respectively. The generated EPFRs on PS and PF decayed rapidly at the initial stage and then slowly disappeared with the elapsed aging time. Analyses by attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR), X-ray photoelectron spectroscopy (XPS), nuclear magnetic resonance (NMR), and gel permeation chromatography (GPC) suggested that MPs might experience chemical chain scission, O 2 /H 2 O addition, and EPFR formation under the light irradiation. Accompanying with the formation of EPFRs, reactive oxygen species, such as O 2•− and •OH, were also observed. The findings provide a novel insight to evaluate the potential hazards of MPs to organisms and ecosystems.

Nanoplastics (NPs) are becoming an emerging pollutant of global concern. A potential risk is that NPs may serve as carriers to increase the spreading of coexisting contaminants. In this study, we examined the effects of polystyrene nanoplastics (PSNPs, 100 nm), used as a model NP, on the transport of five organic contaminants of different polarity in saturated soil. The presence of low concentrations of PSNPs significantly enhanced the transport of nonpolar (pyrene) and weakly polar (2,2',4,4'-tetrabromodiphenyl ether) compounds, but had essentially no effects on the transport of three polar compounds (bisphenol A, bisphenol F, and 4-nonylphenol). The strikingly different effects of NPs on the transport of nonpolar/weakly polar versus polar contaminants could not be explained with different adsorption affinities, but was consistent with the polarity-dependent extents of desorption hysteresis. Notably, desorption hysteresis was only observed for nonpolar/weakly polar contaminants, likely because nonpolar compounds tended to adsorb in the inner matrices of glassy polymeric structure of polystyrene (resulting in physical entrapment of adsorbates), whereas polar compounds favored surface adsorption. This hypothesis was verified with supplemental adsorption and desorption experiments of pyrene and 4-nonylphenol using a dense, glassy polystyrene polymer and a flexible, rubbery polyethylene polymer. Overall, the findings of this study underscore the potentially significant environmental implication of NPs as contaminant carriers.

No abstract

We describe how the reduction of graphene oxide (GO) via environmentally relevant pathways affects its transport behavior in porous media. A pair of sulfide-reduced GOs (RGOs), prepared by reducing 10 mg/L GO with 0.1 mM Na2S for 3 and 5 days, respectively, exhibited lower mobility than did parent GO in saturated quartz sand. Interestingly, decreased mobility cannot simply be attributed to the increased hydrophobicity and aggregation upon GO reduction because the retention mechanisms of RGOs were highly cation-dependent. In the presence of Na(+) (a representative monovalent cation), the main retention mechanism was deposition in the secondary energy minimum. However, in the presence of Ca(2+) (a model divalent cation), cation bridging between RGO and sand grains became the most predominant retention mechanism; this was because sulfide reduction markedly increased the amount of hydroxyl groups (a strong metal-complexing moiety) on GO. When Na(+) was the background cation, increasing pH (which increased the accumulation of large hydrated Na(+) ions on grain surface) and the presence of Suwannee River humic acid (SRHA) significantly enhanced the transport of RGO, mainly due to steric hindrance. However, pH and SRHA had little effect when Ca(2+) was the background cation because neither affected the extent of cation bridging that controlled particle retention. These findings highlight the significance of abiotic transformations on the fate and transport of GO in aqueous systems.

Strong complexation between heavy metals and organic complexing agents makes the heavy metals difficult to be removed by classical chemical precipitation. In this study, a novel decomplexation method was developed using discharge plasma oxidation, which was followed by alkaline precipitation to treat water containing heavy metal-organic complex, that is, Cu-ethylenediaminetetraacetic acid (Cu-EDTA). The decomplexation efficiency of Cu complex reached up to nearly 100% after 60 min's oxidation by discharge plasma, which was accompanied by 82.1% of total organic carbon removal and energy efficiency of 0.62 g kWh. Presence of free Cu favored Cu-EDTA decomplexation, whereas the presence of excessive EDTA depressed this process. Cu-EDTA decomplexation was mainly driven by the produced O, O, O, and •OH by discharge plasma. Cu-EDTA decomplexation process was characterized by UV-vis, ATR-FTIR, total organic carbon, and three-dimensional fluorescence diagnosis. The main intermediates including Cu-EDDA, Cu-IDA, Cu-NTA, small organic acids, NH, and NO were identified, accompanied by Cu releasing. The followed precipitation process removed 78.1% of Cu, and Cu-associated precipitates included CuCO, CuCO(OH), CuO, and Cu(OH). A possible pathway of Cu complex decomplexation and Cu removal in such a system was proposed.