State Key Joint Laboratory of Environmental Simulation and Pollution Control (SKLESPC), Beijing Key Laboratory for Emerging Organic Contaminants Control (BKLEOC), Beijing Laboratory for Environmental Frontier Technologies (BLEFT), School of Environment, Tsinghua University, Beijing 100084, China.
Environ Sci Technol. 2022 May 17;56(10):6201-6211. doi: 10.1021/acs.est.1c03210. Epub 2022 Feb 2.
Sodium -perfluorous nonenoxybenzenesulfonate (OBS) is a novel fluorosurfactant used as the alternative to perfluorooctanesulfonic acid (PFOS) in several applications such as fire-fighting foams and chemical enhanced oil recovery ("EOR") in China, with the annual production capacity of about 3,500 t. Here, for the first time, we investigated the degradability of OBS under the conditions of UV/persulfate (UV/PS) and UV/sulfite (UV/SF) as typical redox processes. A higher reaction rate (1.05 min) and total organic carbon (TOC) reduction (46.9%) but a low defluorination rate (27.6%) along with the formation of a series of fluorinated intermediates were found in UV/PS, while a high defluorination rate (87.7%) was realized in UV/SF. In particular, a nontargeted workflow using high performance liquid chromatography-quadrupole time-of-flight mass spectrometry (HPLC/Q-TOF-MS) was established to detect fluorinated intermediates. Combined with the theoretical calculation, the distinctive degradation pathways in both oxidation and reduction processes were proposed. The degradation mechanism of OBS in UV/SF was proposed to be H/F exchange and subsequent HF elimination. Furthermore, the diluted OBS-based fluoroprotein (FP) foam was used to investigate the degradation of OBS, which confirms the treatability using the redox approach. This work provides insights into the degradability of OBS, fluorinated intermediate search, and proper treatment of related contamination.
过氟壬基苯磺酸钠(OBS)是一种新型氟表面活性剂,在中国的几种应用中被用作全氟辛烷磺酸(PFOS)的替代品,如消防泡沫和化学强化采油(“EOR”),其年产量约为 3500 吨。在这里,我们首次研究了 OBS 在紫外线/过硫酸盐(UV/PS)和紫外线/亚硫酸盐(UV/SF)作为典型氧化还原过程中的可降解性。在 UV/PS 中,发现了更高的反应速率(1.05 分钟)和总有机碳(TOC)去除率(46.9%),但脱氟率较低(27.6%),同时形成了一系列含氟中间体,而在 UV/SF 中实现了高脱氟率(87.7%)。特别是,建立了一种使用高效液相色谱-四极杆飞行时间质谱(HPLC/Q-TOF-MS)的非靶向工作流程来检测含氟中间体。结合理论计算,提出了两种氧化还原过程中独特的降解途径。提出了 UV/SF 中 OBS 的降解机制是 H/F 交换和随后的 HF 消除。此外,还使用稀释的基于 OBS 的氟蛋白(FP)泡沫来研究 OBS 的降解,这证实了氧化还原方法的处理能力。这项工作为 OBS 的可降解性、含氟中间体的搜索以及相关污染的适当处理提供了深入了解。