Decomposability versus detectability: First validation of TED-GC/MS for microplastic detection in different environmental matrices

Maria Kittner, Paul Eisentraut, Daniel Dittmann, Ulrike Braun
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Abstract

A fast method for microplastic detection is thermal extraction desorption-gas chromatography/mass spectrometry (TED-GC/MS), which uses polymer-specific thermal decomposition products as marker compounds to determine polymer mass contents in environmental samples. So far, matrix impacts of different environmental matrices on TED-GC/MS performance had not yet been assessed systematically. Therefore, three solid freshwater matrices representing different aquatic bodies with varying organic matter contents were spiked with a total of eight polymers. Additionally, for the first time, the two biodegradable polymers polybutylene adipate terephthalate (PBAT) and polylactide (PLA) were analysed using TED-GC/MS. The methodological focus of this work was on detectability, quality of signal formation as well as realisation of quantification procedures and determination of the limit of detection (LOD) values. Overall, TED-GC/MS allowed the unambiguous detection of the environmentally most relevant polymers analysed, even at low mass contents: 0.02 wt% for polystyrene (PS), 0.04 wt% for the tyre component styrene butadiene rubber (SBR) and 0.2 wt% for polypropylene (PP), polyethylene (PE) and PBAT. Further, all obtained LOD values were increased in all matrices compared to the neat polymer without matrix. The LOD of the standard polymers were increased similarly (PS: 0.21–0.34 µg, SBR: 0.27–0.38 µg, PP: 0.32–0.36 µg, PMMA: 0.64–1.30 µg, PET: 0.90–1.37 µg, PE: 3.80–6.99 µg) and their decompositions by radical scission processes were not significantly influenced by the matrices. In contrast, matrix-specific LOD increases of both biodegradable polymers PBAT (LOD: 1.41–7.18 µg) and PLA (0.84–20.46 µg) were observed, probably due to their hetero-functional character and interactions with the matrices. In conclusion, the TED-GC/MS performance is not solely determined by the type of the polymers but also by the composition of the matrix.

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可分解性与可检测性:用于不同环境基质中微塑料检测的 TED-GC/MS 首次验证
热萃取解吸-气相色谱/质谱法(TED-GC/MS)是一种快速检测微塑料的方法,它利用聚合物特异性热分解产物作为标记化合物来确定环境样品中聚合物的质量含量。迄今为止,尚未系统评估过不同环境基质对 TED-GC/MS 性能的影响。因此,我们在代表不同有机物含量水体的三种固体淡水基质中添加了共八种聚合物。此外,还首次使用 TED-GC/MS 分析了聚对苯二甲酸丁二醇酯 (PBAT) 和聚乳酸 (PLA) 这两种可生物降解聚合物。这项工作在方法上的重点是可检测性、信号形成的质量以及定量程序的实现和检测限 (LOD) 值的确定。总体而言,TED-GC/MS 能够明确检测出所分析的与环境最相关的聚合物,即使质量含量很低:聚苯乙烯 (PS) 为 0.02 wt%,轮胎成分丁苯橡胶 (SBR) 为 0.04 wt%,聚丙烯 (PP)、聚乙烯 (PE) 和 PBAT 为 0.2 wt%。此外,与不含基质的纯聚合物相比,所有基质的 LOD 值都有所增加。标准聚合物的 LOD 值也有类似的增加(PS:0.21-0.34 µg;SBR:0.27-0.38 µg;PP:0.32-0.36 µg;PMMA:0.64-1.30 µg;PET:0.90-1.37 µg;PE:3.80-6.99 µg),它们在自由基裂解过程中的分解没有受到基质的显著影响。相反,生物可降解聚合物 PBAT(LOD:1.41-7.18 µg)和 PLA(0.84-20.46 µg)的 LOD 都出现了基质特异性增加,这可能是由于它们的杂官能特性以及与基质的相互作用。总之,TED-GC/MS 的性能不仅取决于聚合物的类型,还取决于基质的成分。
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