Nanosecond Transient Absorption of Hydrated Electrons and Reduction of Linear Perfluoroalkyl Acids and Sulfonates,Environmental Science & Technology Letters

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Nanosecond Transient Absorption of Hydrated Electrons and Reduction of Linear Perfluoroalkyl Acids and Sulfonates
Environmental Science & Technology Letters ( IF 8.9 ) Pub Date : 2021-06-08 , DOI: 10.1021/acs.estlett.1c00383
William A. Maza ₁ , Vanessa M. Breslin ₂ , Jeffrey C. Owrutsky ₁ , Bradford B. Pate ₁ , Albert Epshteyn ₁

Affiliation

We report the rate constants (k_q) and activation energies (E_a) associated with the initial reduction of linear perfluoroalkyl carboxylates (PFxA, x = the number of carbons present in the surfactant) and perfluoroalkyl sulfonates (PFxS) by the hydrated electron (e_aq^–) as measured using temperature-dependent transient absorption spectroscopy. The reduction of PFxA and PFxS by e_aq^– displays a negligible dependence on the number of carbons present in the surfactant and occurs with an apparent k_q on the order of 10⁸ to 10⁹ M^–1 s^–1 with the k_q corresponding to PFxA reduction being on average two times smaller than those for PFxS. There are no significant differences in the E_a associated with PFxA or PFxS reduction; the magnitude of E_a (∼11 kJ mol^–1) is consistent with the reduction of PFxA and PFxS being a diffusion controlled process. These results are discussed within the framework of recent theoretical and experimental work on the degradation of PFxA and PFxS.

中文翻译：

水合电子的纳秒瞬态吸收和线性全氟烷基酸和磺酸盐的还原

我们报告了与线性全氟烷基羧酸盐（PFxA，x = 表面活性剂中存在的碳数）和全氟烷基磺酸盐（PFxS）的初始还原相关的速率常数（k _q）和活化能（E _a）通过水合电子（ e _aq^– ) 使用温度相关瞬态吸收光谱法测量。PFxA和PFxS的通过e还原_水溶液^-存在于表面活性剂显示对碳原子数可忽略的依赖和与表观发生ķ _q 10的数量级上⁸到10 ⁹中号^-1小号^-1与k _q对应于 PFxA 的减少平均是 PFxS 减少的两倍。与 PFxA 或 PFxS 减少相关的E _a没有显着差异；的幅度Ë_一个（〜11千焦摩尔^-1）是具有PFxA和PFxS是扩散控制的过程的降低是一致的。这些结果在最近关于 PFxA 和 PFxS 降解的理论和实验工作的框架内进行了讨论。

更新日期：2021-07-13

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