水体中短中链和新型全氟/多氟烷基化合物分析方法研究及前处理流程优化

Analytical Methods and Optimization of Pretreatment Processes for Short- and Medium-Chain and Novel Perfluoro/Polyfluoroalkyl Substances in Water

  • 摘要: 随着长链全氟和多氟烷基化合物(PFAS)的生产使用受限,短中链及新型替代品在水环境中广泛检出,其生态与健康风险亟待关注。然而,当前检测标准体系尚不完善,传统固相萃取(SPE)技术具有检出限低和抗干扰优势,但在实际应用中存在耗时长、成本高和易污染等不足。本文采用滤膜过滤后直接进样的方式,建立了超高效液相色谱-串联质谱法(UPLC-MS/MS)测定环境水体中18种痕量(ng/L级)短中链及新型PFAS包括7种全氟羧酸类(PFCA)、4种全氟磺酸类(PFSA)和7种新型替代品的分析方法。系统考察了样品保护剂、过滤膜、进样溶剂和进样瓶材质的影响,结果表明,添加10%甲醇可显著提升样品的保存稳定性;对5种过滤膜(再生纤维素、聚醚砜、聚四氟乙烯、混合纤维素和尼龙)在4种溶剂体系中的吸附行为研究发现,尼龙膜在纯水和10%甲醇-水溶液体系中吸附率最高(90%以上),而再生纤维素膜吸附最小,为本方法的最佳过滤膜;对于本方法的大体积进样而言(50μL),10%甲醇-水溶液是理想的进样溶剂,同时聚丙烯进样瓶储存效果最佳。本方法具有以下优势:①简便快捷,过滤后直接上机测试,无固相萃取和浓缩过程,单个样品前处理时间<5min,较传统SPE前处理方法效率提升10倍以上;②成本低,减少溶剂消耗与固相萃取柱等耗材的使用;③由于样品前处理仅涉及过滤操作,不仅减少了可能引起损失的环节,还显著降低了污染风险。本方法可应用于环境水体中痕量PFAS的快速监测,尤其适用于大规模环境靶向筛查与应急监测场景,但对浓度低于0.7ng/L的PFAS样品,受限于仪器灵敏度,定量准确性面临挑战。

     

    Abstract: With the production and use of long-chain per- and polyfluoroalkyl substances (PFAS) being restricted, short- and medium-chain as well as new alternative PFAS have been widely detected in water environments, and their ecological and health risks have drawn urgent attention. However, the current detection standard system is still not perfect. Traditional solid-phase extraction (SPE) technology has the advantages of a low detection limit and strong anti-interference ability, but it has disadvantages such as long-time consumption, high cost and easy contamination in practical application. Here, a method for the determination of 18 trace short- and medium-chain (ng/L level) and new PFAS in environmental water, including 7 perfluorocarboxylic acids, 4 perfluorosulfonic acids and 7 new alternatives, by ultra-high performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) was established by direct injection after filtration. The effects of sample protectants, filter membranes, injection solvents and injection bottle materials were systematically investigated. The results showed that the addition of 10% methanol could significantly improve the stability of the sample. The adsorption behavior of five filter membranes (regenerated cellulose, polyethersulfone, polytetrafluoroethylene, mixed cellulose and nylon) in 4 solvent systems was studied. It was found that the nylon membrane had the highest adsorption rate (above 90%) in pure water and 10% methanol-water solution system, while the regenerated cellulose membrane had the lowest adsorption rate, making it the best filter membrane for this method. For the large volume injection of this method (50μL), 10% methanol-water solution was the ideal injection solvent, and polypropylene injection bottles had the best storage effect. This method has the following advantages: (1) It is simple and fast, with direct injection after filtration, no solid-phase extraction and concentration process, and the sample pretreatment time for a single sample is less than 5min, which has more than 10 times the efficiency of the traditional SPE pretreatment method; (2) It is low-cost, reducing solvent consumption and the use of solid-phase extraction columns and other consumables; (3) Since the sample pretreatment only involves filtration, it not only reduces the possible loss links but also significantly reduces the risk of contamination. This method can be applied to the rapid monitoring of trace PFAS in environmental water, especially suitable for large-scale environmentally targeted screening and emergency monitoring scenarios. However, for PFAS samples with concentrations lower than 0.7ng/L, the quantitative accuracy is challenged due to the limitation of instrument sensitivity.

     

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