Labad Francesc, Pérez Sandra
IDAEA-CSIC ONHEALTH Research Group Jordi Girona 18-26, Barcelona, 08034, Spain.
IDAEA-CSIC ONHEALTH Research Group Jordi Girona 18-26, Barcelona, 08034, Spain.
Anal Chim Acta. 2025 Oct 1;1369:344349. doi: 10.1016/j.aca.2025.344349. Epub 2025 Jun 20.
Highly polar substances have fallen from the scope of investigations due to this lack of accumulation into organic materials and the analytical difficulty they present using "traditional" techniques. This study presents an integrated analytical approach combining liquid chromatography (LC) and travelling-wave ion mobility spectrometry (TWIMS) coupled with high-resolution mass spectrometry (HRMS) for the separation, detection, and quantification of 45 challenging contaminants in urban water matrices. The targeted analytes, including 41 very mobile compounds and 37 highly polar substances (log D < 0), represent compounds that are often poorly retained under conventional reversed-phase and HILIC LC conditions.
TWIMS was used to determine the CCS of 33 small organic molecules (120-500 Da). A ΔCCS threshold of ≥0.5 % was identified as sufficient for proper separation on second-generation IMS instruments (resolving power >300 Rp). In cases where LC provided inadequate retention, TWIMS proved to be an effective complementary technique by exploiting differences in molecular size, shape, and charge to resolve compounds based on their collision cross-section (CCS) values. Surface water samples from the Chattahoochee River and tap water from Midtown Atlanta (USA) were analyzed, revealing that over 50 % of the targeted contaminants were detected in at least one matrix. Notably, compounds such as naphthalene-1-sulfonic acid, nicotine, and several per- and poly-fluoroalkyl substances (PFAS) were consistently observed, highlighting their ubiquitous occurrence in urban water impacted by industrial activities and heavy traffic.
The methodology employed not only improved the resolution and identification of small, highly polar molecules but also provided robust quantitative data essential for environmental monitoring and risk assessment. This approach underscores the potential of IMS as a valuable complementary tool to traditional LC-MS workflows in complex environmental analyses. Additionally, the data presented regarding the presence of highly polar substances in urban water matrices should inform stakeholders and implement preventive strategies.
由于缺乏在有机材料中的积累以及使用“传统”技术分析时存在困难，高极性物质已不在研究范围内。本研究提出了一种综合分析方法，将液相色谱（LC）与行波离子迁移谱（TWIMS）结合，并与高分辨率质谱（HRMS）联用，用于分离、检测和定量城市水基质中的45种具有挑战性的污染物。目标分析物包括41种极易迁移的化合物和37种高极性物质（log D < 0），这些化合物在传统反相和亲水作用液相色谱条件下通常保留性较差。
使用TWIMS测定了33种小分子有机化合物（120 - 500 Da）的碰撞截面（CCS）。确定≥0.5%的ΔCCS阈值足以在第二代离子迁移谱仪器上实现良好分离（分辨能力>300 Rp）。在液相色谱保留不足的情况下，TWIMS通过利用分子大小、形状和电荷的差异，基于化合物的碰撞截面（CCS）值来分离化合物，被证明是一种有效的补充技术。对查塔胡奇河的地表水样本和美国亚特兰大市中心的自来水进行了分析，结果显示至少在一种基质中检测到了超过50%的目标污染物。值得注意的是，萘 - 1 - 磺酸、尼古丁和几种全氟和多氟烷基物质（PFAS）等化合物一直被检测到，突出了它们在受工业活动和繁忙交通影响的城市水中普遍存在。
所采用的方法不仅提高了对小的、高极性分子的分辨率和鉴定能力，还提供了环境监测和风险评估所需的可靠定量数据。这种方法强调了离子迁移谱在复杂环境分析中作为传统液相色谱 - 质谱工作流程的宝贵补充工具的潜力。此外，关于城市水基质中高极性物质存在情况的数据应能为利益相关者提供信息，并实施预防策略。
