High-Resolution Mass Spectrometry Combined with Reactive Oxygen Species Reveals Differences in Photoreactivity of Dissolved Organic Matter from Microplastic Sources in Aqueous Environments.

Microplastics (MPs)-derived dissolved organic matter (MPs-DOM) is becoming a non-negligible source of DOM pools in aquatic systems, but there is limited understanding about the photoreactivity of different MPs-DOM. Herein, MPs-DOM from polystyrene (PS), polyethylene terephthalate (PET), poly(butylene adipate-co-terephthalate) (PBAT), PE, and polypropylene (PP), representing aromatic, biodegradable, and aliphatic plastics, were prepared to examine their photoreactivity. Spectral and high-resolution mass spectrometry analyses revealed that PS/PET/PBAT-DOM contained more unsaturated aromatic components, whereas PE/PP-DOM was richer in saturated aliphatic components. Photodegradation experiments observed that unsaturated aromatic molecules were prone to be degraded compared to saturated aliphatic molecules, leading to a higher degradation of PS/PET/PBAT-DOM than PE/PP-DOM. PS/PET/PBAT-DOM was mainly degraded by hydroxyl (•OH) via attacking unsaturated aromatic structures, whereas PE/PP-DOM by singlet oxygen (1O2) through oxidizing aliphatic side chains. The [•OH]ss was 1.21-1.60 × 10-4 M in PS/PET/PBAT-DOM and 0.97-1.14 × 10-4 M in PE/PP-DOM, while the [1O2]ss was 0.90-1.35 × 10-12 and 0.33-0.44 × 10-12 M, respectively. This contributes to the stronger photoreactivity of PS/PET/PBAT-DOM with a higher unsaturated aromatic degree than PE/PP-DOM. The photodegradation of MPs-DOM reflected a decreasing tendency from aromatic-unsaturated molecules to aliphatic-saturated molecules. Special attention should be paid to the photoreactivity and environmental impacts associated with MPs-DOM containing highly unsaturated aromatic compounds.

Molecular Weights of Dissolved Organic Matter Significantly Affect Photoaging of Microplastics.

The fate of ubiquitous microplastics (MPs) is largely influenced by dissolved organic matter (DOM) in aquatic environments, which has garnered significant attention. The reactivity of DOM is reported to be greatly regulated by molecular weights (MWs), yet little is known about the effects of different MW DOM on MP aging. Here, the aging behavior of polystyrene MPs (PSMPs) in the presence of different MW fulvic acids (FAs) and humic acids (HAs) was systematically investigated. Under ultraviolet (UV) illumination, O/C of PSMPs aged for 96 h surged from 0.008 to 0.146 in the lower MW FA (FA<1kDa) treatment, suggesting significant PSMP aging. However, FA exhibited a stronger effect on facilitating PSMP photoaging than HA, which can be attributed to the fact that FA<1kDa contains more quinone and phenolic moieties, demonstrating a higher redox capacity. Meanwhile, compared to other fractions, FA<1kDa was more actively involved in the increase of different reactive species yields by 50-290%, including •OH, which plays a key role in PSMP photoaging, and contributed to a 25% increase in electron-donating capacity (EDC). This study lays a theoretical foundation for a better understanding of the environmental fate of MPs.

Interactions between Iron Minerals and Dissolved Organic Matter Derived from Microplastics Inhibited the Ferrihydrite Transformation as Revealed at the Molecular Scale.

Microplastic-derived dissolved organic matter (MP-DOM) is an emerging carbon source in the environment. Interactions between MP-DOM and iron minerals alter the transformation of ferrihydrite (Fh) as well as the distribution and fate of MP-DOM. However, these interactions and their effects on both two components are not fully elucidated. In this study, we selected three types of MP-DOM as model substances and utilized Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) and extended X-ray absorption fine structure (EXAFS) spectroscopy to characterize the structural features of DOMs and DOM-mineral complexes at the molecular and atomic levels. Our results suggest that carboxyl and hydroxyl groups in MP-DOM increased the Fe-O bond length by 0.02-0.03 Å through interacting with Fe atoms in the first shell, thereby inhibiting the transformation of Fh to hematite (Hm). The most significant inhibition of Fh transformation was found in PS-DOM, followed by PBAT-DOM and PE-DOM. MP-DOM components, such as phenolic compounds and condensed polycyclic aromatics (MW > 360 Da) with high oxygen content and high unsaturation, exhibited stronger mineral adsorption affinity. These findings provide a profound theoretical basis for accurately predicting the behavior and fate of iron minerals as well as MP-DOM in complex natural environments.

Significant contribution of different sources of particulate organic matter to the photoaging of microplastics.

Particulate organic matter (POM), as an important component of organic matter, can act as a redox mediator and thus intervene in the environmental behavior of microplastics (MPs). However, quantitative information on the role of POM in the photoaging of MPs under ultraviolet (UV) light is still lacking. To raise the knowledge gap, through environmental simulation experiments and qualitative/quantitative experiments of active substances, we found that POM from peat soil has stronger oxidation capacity than POM from sediment, and the involvement of POM at high water content makes the aging of MPs more obvious. This is because the persistent radicals and electron-absorbing groups on the surface of POM indirectly generate reactive oxygen species (ROS) by promoting electron transfer, and the dissolved organic matter (DOM) released from POM under UV light (POM-DOM) is further excited to generate triplet-state photochemistry of DOM (3DOM*) to promote the aging of MPs. Theoretical calculations revealed that the benzene ring, mainly C = C, and C = O in the main chain in the plastic macromolecule structure are more susceptible to ROS attack, and the differences in the vulnerable sites contained in different plastic structures as well as the differences in the energy band gaps lead to differences in their aging processes. This study firstly elucidates the key role and intrinsic mechanism of POM in the photoaging of MPs, providing a theoretical basis for a comprehensive assessment of the effect of POM on MPs in the environment.

Metabolomics reveals how spinach plants reprogram metabolites to cope with intense stress responses induced by photoaged polystyrene nanoplastics (PSNPs).

While land-based sources have been recognized as significant long-term sinks for micro- and nanoplastics, there is limited knowledge about the uptake, translocation, and phytotoxicity of nanoplastics (NPs) in terrestrial environments, especially aged NPs. In this study, we investigated the impact of aged polystyrene nanoplastics (PSNPs) on the uptake, physiology, and metabolism of spinach. Our findings revealed that both pristine and aged PSNPs can accumulate in the roots and subsequently translocate to the aboveground tissues, thereby influencing numerous key growth indicators in spinach plants. A more pronounced impact was observed in the treatment of aged PSNPs, triggering more significant and extensive changes in metabolite levels. Furthermore, alterations in targeted pathways, specifically aminoacyl-tRNA biosynthesis and phenylpropanoid biosynthesis, were induced by aged PSNPs, while pristine PSNPs influenced pathways related to sulfur metabolism, biosynthesis of unsaturated fatty acids, and tryptophan metabolism. Additionally, tissue-specific responses were observed at the metabolomics level in both roots and leaves. These results highlight the existence of diverse and tissue-specific metabolic responses in spinach plants exposed to pristine and aged PSNPs, providing insights into the mechanisms of defense and detoxification against NP-induced stress.

Microbial metabolism influences microplastic perturbation of dissolved organic matter in agricultural soils.

An estimated 258 million tons of plastic enter the soil annually. Joining persistent types of microplastic (MP), there will be an increasing demand for biodegradable plastics. There are still many unknowns about plastic pollution by either type, and one large gap is the fate and composition of dissolved organic matter (DOM) released from MPs as well as how they interact with soil microbiomes in agricultural systems. In this study, polyethylene MPs, photoaged to different degrees, and virgin polylactic acid MPs were added to agricultural soil at different levels and incubated for 100 days to address this knowledge gap. We find that, upon MP addition, labile components of low aromaticity were degraded and transformed, resulting in increased aromaticity and oxidation degree, reduced molecular diversity, and changed nitrogen and sulfur contents of soil DOM. Terephthalate, acetate, oxalate, and L-lactate in DOM released by polylactic acid MPs and 4-nitrophenol, propanoate, and nitrate in DOM released by polyethylene MPs were the major molecules available to the soil microbiomes. The bacteria involved in the metabolism of DOM released by MPs are mainly concentrated in Proteobacteria, Actinobacteriota, and Bacteroidota, and fungi are mainly in Ascomycota and Basidiomycota. Our study provides an in-depth understanding of the microbial transformation of DOM released by MPs and its effects of DOM evolution in agricultural soils.