Comparative Thermodynamic and Structural Analysis of Polyfluorinated Dodecylphosphonic Acid Adsorption to Distilled and River Water Interfaces
Comparative Thermodynamic and Structural Analysis of Polyfluorinated Dodecylphosphonic Acid Adsorption to Distilled and River Water Interfaces
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多氟十二烷基膦酸在蒸馏水和河水界面吸附的比较热力学和结构分析
DOI：
10.1021/acs.jpca.3c01487
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发表时间：
2023
期刊：
影响因子：
--
通讯作者：
Baio, Joe E.
中科院分区：
文献类型：
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作者：
Carpenter, Andrew P.;White, Jade N.;Hasbrook, Annemarie;Reierson, Makenna;Baio, Joe E.
随着人们对全氟烷基和多氟烷基物质（PFAS）在环境中构成的健康风险的关注日益增加，有必要了解这些污染物是如何在环境界面上积累的。解开分子吸附的细节，特别是当环境系统中存在与其他分子的潜在相互作用时，可能会模糊以分子特异性关注特定污染物的能力。通常环境界面的吸附研究需要简化的方法，实验室实验可能不完全适用于环境系统。在这项工作中，我们研究了蒸馏水（最还原的“环境”表面）和河水表面的多氟十二烷基膦酸（F21-DDPA），以探索使用振动和频率（VSF）光谱作为自然环境表面氟化污染物的实验探针。我们展示了在测量河流水面的PFAS吸附等温线时，VSF光谱如何比非特异性表面张力测量提供优势。C-F拉伸区的VSF光谱选择性地探测了F21-DDPA的存在，并可用于提取有意义的结构见解和计算表面浓度，即使在复杂的河流水面。这项研究强调了VSF光谱在自然环境界面上作为氟化污染物探针的潜力。
As concerns rise about the health risks posed by per- and polyfluoroalkyl substances (PFAS) in the environment, there is a need to understand how these pollutants accumulate at environmental interfaces. Untangling the details of molecular adsorption, particularly when there are potential interactions with other molecules in environmental systems, can obscure the ability to focus on a particular contaminant with molecular specificity. Often adsorption studies of environmental interfaces require a reductionist approach, where laboratory experiments may not be fully tractable to environmental systems. In this work, we study polyfluorinated dodecylphosphonic acid (F21-DDPA) at the aqueous surfaces of distilled water (the most reduced “environmental” surface) and river water to explore the use of vibrational sum-frequency (VSF) spectroscopy as an experimental probe of fluorinated contaminants at natural environmental surfaces. We demonstrate how VSF spectroscopy offers advantages over nonspecific surface tension measurements when measuring PFAS adsorption isotherms at river water surfaces. VSF spectra of the C–F stretching region selectively probe the presence of F21-DDPA and can be used to extract meaningful structural insights and calculate surface concentrations, even at the complex river water surface. This study highlights the potential for VSF spectroscopy to be developed as a probe of fluorinated contaminants at natural environmental interfaces.