Combining respirometry and HPLC-HRMS to elucidate the biodegradation of polyethylene glycol and its derivatives

IF 7.4 2区化学 Q1 POLYMER SCIENCE

Polymer Degradation and Stability Pub Date : 2025-09-01 DOI:10.1016/j.polymdegradstab.2025.111639

Aaron Kintzi , Valentin Göldner , Soumya Daturpalli , Glauco Battagliarin , Andreas Künkel , Thilo Hofmann , Michael Zumstein

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引用次数: 0

Abstract

Water-soluble polymers (WSPs) fulfil essential functions in many applications, such as home and personal care, and are often released into wastewater systems after use. Biodegradable WSPs are therefore needed and standardized biodegradation testing is crucial for their development and regulation. In this study, we combined respirometry-based biodegradation testing with high-performance liquid chromatography coupled to high-resolution mass spectrometry (HPLC-HRMS) to obtain a process-level understanding of the biodegradation of polyethylene glycols (PEGs) by wastewater microbiomes. We used two derivatives with similar molecular weights: PEG and PEG-dimethyl ether (dmPEG). Both PEG and dmPEG exhibited substantial biodegradation, exceeding 80 % mineralization within 28 days. We demonstrate dmPEG biodegradation for the first time, while earlier reports claimed that dmPEG was non-biodegradable and that a terminal hydroxyl group is essential for PEG biodegradation. Our HPLC-HRMS analyses revealed significant shifts in the molecular weight (MW) distribution of PEG starting on day 3, implying that the initial lag phase primarily reflects microbial adaptation rather than PEG breakdown. Following this initial shift, the PEG MW distribution stabilized around 1.5 kDa and intermediates <1 kDa were not detected, which we ascribed to rapid microbial uptake and biodegradation of these low-MW species. The detection of carboxylated biodegradation intermediates in the cell-free supernatant provides evidence that certain steps in PEG biodegradation occur extracellularly. Together, our study highlights the potential of combining standardized biodegradation testing based on respirometry with HPLC-HRMS analysis to elucidate WSP biodegradation.

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结合呼吸测定法和高效液相色谱-质谱法研究聚乙二醇及其衍生物的生物降解

水溶性聚合物（WSPs）在许多应用中发挥重要作用，例如家庭和个人护理，并且经常在使用后释放到废水系统中。因此，需要可生物降解的wsp，标准化的生物降解测试对其开发和监管至关重要。在这项研究中，我们将基于呼吸法的生物降解测试与高效液相色谱-高分辨率质谱（HPLC-HRMS）相结合，以获得废水微生物群对聚乙二醇（peg）的生物降解过程水平的理解。我们使用了两种分子量相似的衍生物：PEG和PEG-二甲醚（dmPEG）。PEG和dmPEG均表现出明显的生物降解，28天内矿化率超过80%。我们首次证明了dmPEG的生物降解性，而之前的报道称dmPEG是不可生物降解的，并且末端羟基是PEG生物降解所必需的。我们的HPLC-HRMS分析显示，从第3天开始，PEG的分子量（MW）分布发生了显著变化，这意味着最初的滞后期主要反映了微生物的适应，而不是PEG的分解。在这一初始转变之后，PEG分子量分布稳定在1.5 kDa左右，中间产物<；1 kDa未被检测到，我们将其归因于这些低分子量物种的快速微生物吸收和生物降解。无细胞上清中羧基化生物降解中间体的检测提供了证据，证明PEG生物降解的某些步骤发生在细胞外。总之，我们的研究强调了将基于呼吸测量的标准化生物降解测试与HPLC-HRMS分析相结合的潜力，以阐明WSP的生物降解。

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来源期刊

Polymer Degradation and Stability 化学-高分子科学

CiteScore

10.10

自引率

10.20%

发文量

325

审稿时长

23 days

期刊介绍： Polymer Degradation and Stability deals with the degradation reactions and their control which are a major preoccupation of practitioners of the many and diverse aspects of modern polymer technology. Deteriorative reactions occur during processing, when polymers are subjected to heat, oxygen and mechanical stress, and during the useful life of the materials when oxygen and sunlight are the most important degradative agencies. In more specialised applications, degradation may be induced by high energy radiation, ozone, atmospheric pollutants, mechanical stress, biological action, hydrolysis and many other influences. The mechanisms of these reactions and stabilisation processes must be understood if the technology and application of polymers are to continue to advance. The reporting of investigations of this kind is therefore a major function of this journal. However there are also new developments in polymer technology in which degradation processes find positive applications. For example, photodegradable plastics are now available, the recycling of polymeric products will become increasingly important, degradation and combustion studies are involved in the definition of the fire hazards which are associated with polymeric materials and the microelectronics industry is vitally dependent upon polymer degradation in the manufacture of its circuitry. Polymer properties may also be improved by processes like curing and grafting, the chemistry of which can be closely related to that which causes physical deterioration in other circumstances.