聚甲基丙烯酸甲酯(PMMA)是一種廣泛應用於日常生活中的塑膠，又稱為壓克力，常用於替代玻璃。目前已知PMMA 奈米塑膠[nanoplastics (NPs), <1 μm]存在於進流廢水、地表水和地下水中。儘管光降解是塑膠在環境中主要的降解途徑，但 PMMA 的高光學透明度和缺乏芳香環使其具有抗紫外線的特性。因此，PMMA NPs在太陽光下的光轉化機制仍不清楚。本研究對水中的PMMA NPs進行了為期兩個月(即1,506小時)的連續模擬太陽光照射實驗，這相當於346天的天然太陽光照射。
我們的結果顯示，光照導致PMMA NPs的濃度顯著轉化了12%。釋出於水中的溶解性有機碳(DOC)隨著照光時間逐漸增加至24.9 mg C/L，而溶解性無機碳(DIC)則無明顯釋出，代表沒有發生光礦化作用。碳質量平衡分析(包括固體PMMA NPs、DOC和DIC)顯示碳質量平衡接近100%，且PMMA NPs主要轉化為DOC。動力學分析顯示， PMMA NPs的轉化符合一階反應動力學，R2為0.92，在連續光照下的半衰期為14.64 ± 4.11個月。此外，與現有文獻全面比較發現，尺寸較小的塑膠顆粒在光照後通常具有較高的DOC生成速率與較短的半衰期，這表示顆粒尺寸對塑膠的光轉化具有重要作用。紫外可見光光譜(UV-visible)吸收度分析顯示，溶解性有機物質(DOM)在200-400 nm範圍內的吸光度隨著照光時間增加，這與DOC增加的趨勢一致。三維螢光激發發射光譜(F-EEM)分析則顯示DOM的螢光特徵與可溶性類微生物副產物及類蛋白質物質的特徵一致，且強度隨照光時間增加。此外，本研究開發了非目標分析方法，以深入了解生成的DOM結構。透過使用HILIC和反相C18管柱，我們鑑定出八種光轉化產物，其中四種被鑑定為信心等級3(暫定候選物)，包括酸類和酯類化合物。所有產物均為相對富含含氧官能基的親水性化合物。隨著光照時間增加，這些產物的存在呈現動態變化，但整體上持續生成。本研究為PMMA NPs的光化學宿命提供了重要的見解，強調了進一步了解轉化的PMMA NPs及溶解性產物可能對生態造成影響的重要性。

Polymethyl methacrylate (PMMA), commonly known as acrylic, is a widely used plastic in daily life, often serving as a substitute for glass. Currently, it is known that PMMA nanoplastics (NPs, <1 μm) exist in wastewater influent, surface water, and groundwater. While photodegradation is a key pathway for plastic degradation in the environment, PMMA’s high optical transparency and lack of aromatic rings make it UV-resistant. As a result, the phototransformation of PMMA NPs under sunlight remain unclear. This study conducted a two-month (i.e., 1,506 h) continuous simulated sunlight irradiation experiment on aqueous PMMA NPs, equivalent to 346 d of real sunlight irradiation.
Our result shows that sunlight irradiation resulted in a notable 12% transformation of PMMA NP concentration. The dissolved organic carbon (DOC) released into the water gradually increased to 24.9 mg C/L with prolonged irradiation, while there was no significant release of dissolved inorganic carbon (DIC), indicating no photo-mineralization. The carbon mass balance analysis (including solid PMMA NPs, DOC, and DIC) reveals a carbon mass balance of nearly 100%, and the predominant conversion of PMMA NPs into DOC. The kinetic analysis shows that the transformation of PMMA NPs can be adequately described by the first-order reaction kinetics with R2 = 0.92 with a half-life of 14.64 ± 4.11 months under continuous solar irradiation. Furthermore, a comprehensive comparison with existing literature reveals that irradiation of plastic particle with smaller sizes under environmentally relevant conditions tends to result in higher DOC formation rates with shorter half-lives, suggesting that the particle size plays a significant role in the phototransformation of plastics. The UV-visible absorbance analysis shows that the absorbance of dissolved organic matter (DOM) in the 200-400 nm range increased with irradiation time, consistent with the trend observed in the DOC increase. The fluorescence excitation-emission matrix (F-EEM) analysis reveals that the fluorescence characteristics of DOM were coincident to those of soluble microbial byproduct-like and protein-like substances, with the intensity increasing with irradiation time. Furthermore, this study developed a non-target analysis (NTA) method to gain insights into the structure of DOM formed. Using HILIC and reverse-phase C18 columns, we identified 8 phototransformation products, among which 4 were identified with a confidence level 3 (tentative candidates), including acids and ester compounds. All products were hydrophilic compounds relatively rich in oxygen-containing functional groups. With increased irradiation time, the presence of these products exhibited dynamic changes but continued to be produced overall. This study provides crucial insights into the photochemical fate of PMMA NP, highlighting the importance to further understanding of the possible ecological impact of transformed PMMA NPs and dissolved products.

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