Collaborative Research: Fundamental Studies on the Environmental Fate of Short-Chain and Emerging Fluorinated Alkyl Substances Using Mass-Spectrometry and Molecular Modelling

合作研究：利用质谱和分子模型对短链和新兴氟化烷基物质的环境归趋进行基础研究

• 批准号: 1904825
• 负责人: Scott Simpson
• 金额: $ 11.94万
• 依托单位: Saint Bonaventure University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2019
• 资助国家: 美国
• 起止时间: 2019-09-01 至 2023-09-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1904825&HistoricalAwards=false
• 关键词: Collaborative; Research; Fundamental; Studies; Environmental

The Environmental Chemical Science Program of the Chemistry Division funds Professor Diana Aga of the Chemistry Department at the University at Buffalo and Professor Scott Simpson of the Chemistry Department at St. Bonaventure University to identify per- and polyfluoroalkyl substances (PFASs) that contaminate the environment. These chemicals are widely used in a variety of industrial applications, including fire-fighting foams and paints, as well as in consumer products, such as food packaging and cleaning products. Residues of PFASs have emerged as significant environmental contaminants. The residues do not break down easily and accumulate in fish and wildlife over time. They are also found in drinking water sources. Exposure to these chemicals may lead to a wide range of adverse human health effects. Many important questions remain unanswered such as how PFASs are distributed in the environment, how they can be removed from drinking water sources, or how toxicities of individual components and mixtures can be measured. The research team is identifying PFASs in the environment and developing tools to predict their mobility (e.g. how they are dispersed) and persistence (how long they stay in the environment). This project will enable the development of more accurate PFASs risk assessment models and treatment technologies. This research provides opportunities for undergraduate students from a primarily undergraduate institution to directly collaborate with graduate students at the University at Buffalo. Additionally, graduate students are hosted by scientists at the Environmental Protection Agency to gain insight on how scientific and technical information are used for developing public policies. Summer camps for high school students from local "All-Girls" high schools are organized to promote careers in STEM.Over 5,000 different PFASs are potentially released from the multiple formulations produced throughout the U.S. The development of treatment strategies and complete understanding of their toxicity is hampered by the lack of standardized analytical methods and important parameters. These include the octanol-water partition coefficient for complex contaminant mixtures. Because of the varying degrees of environmental transformations, there are many unknown degradation products that have not yet been identified. Through concerted experimental and computational efforts, tools for the reliable quantification, identification, and characterization of emerging PFASs in the environment are being developed. The theoretical tools include pairing physiochemical data generated from Density Functional Theory (DFT) and Conductor like Screening Model for Real Solvents (COSMO-RS) calculations. In order to aid in the identification of unknown PFASs, the results are compared with experimentally determined liquid chromatography tandem mass spectrometry (LC-MS) retention times. In addition, different LC-MS instruments and LC columns are being evaluated to determine efficient separation of emerging PFASs, minimize the variability of results, improve the accuracy of the LC-MS analysis, and estimate soil mobility of PFASs. The data generated from these fundamental studies are essential for developing and testing practical methods for assessing risks associated with exposure to PFASs in the environment.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

化学系的环境化学科学计划资助布法罗大学化学系的戴安娜·阿加教授和圣博纳文图尔大学化学系的斯科特·辛普森教授来识别污染环境的全氟烷基物质和多氟烷基物质（PFAS）。这些化学品广泛用于各种工业应用，包括消防泡沫和油漆，以及食品包装和清洁产品等消费品。 PFAS 残留物已成为重要的环境污染物。这些残留物不易分解，并且随着时间的推移会在鱼类和野生动物体内积累。它们也存在于饮用水源中。接触这些化学物质可能会对人类健康造成广泛的不利影响。许多重要问题仍未得到解答，例如 PFAS 在环境中如何分布、如何从饮用水源中去除它们，或者如何测量单个成分和混合物的毒性。 研究团队正在识别环境中的 PFAS，并开发工具来预测它们的流动性（例如它们如何分散）和持久性（它们在环境中停留的时间）。该项目将有助于开发更准确的 PFAS 风险评估模型和处理技术。这项研究为来自主要本科院校的本科生提供了与布法罗大学研究生直接合作的机会。此外，研究生由环境保护局的科学家接待，以深入了解如何使用科学和技术信息来制定公共政策。 为当地“全女子”高中的高中生组织夏令营，以促进 STEM 职业发展。美国各地生产的多种配方中可能会释放出 5,000 多种不同的 PFAS。治疗策略的制定和对其毒性的全面了解是至关重要的由于缺乏标准化分析方法和重要参数而受到阻碍。其中包括复杂污染物混合物的辛醇-水分配系数。由于环境转变程度不同，有许多未知的降解产物尚未被鉴定。通过协调一致的实验和计算工作，正在开发对环境中新兴 PFAS 进行可靠量化、识别和表征的工具。理论工具包括由密度泛函理论 (DFT) 和类导体筛选模型 (COSMO-RS) 计算生成的配对物理化学数据。为了帮助识别未知的 PFAS，将结果与实验确定的液相色谱串联质谱 (LC-MS) 保留时间进行比较。 此外，正在评估不同的 LC-MS 仪器和 LC 色谱柱，以确定新兴 PFAS 的有效分离，最大限度地减少结果的可变性，提高 LC-MS 分析的准确性，并估计 PFAS 的土壤迁移率。这些基础研究生成的数据对于开发和测试评估与环境中接触 PFAS 相关的风险的实用方法至关重要。该奖项反映了 NSF 的法定使命，并通过使用基金会的智力价值和更广泛的影响进行评估，被认为值得支持审查标准。

项目成果

Applying Density Functional Theory to Common Organic Mechanisms: A Computational Exercise

将密度泛函理论应用于常见的有机机制：计算练习

• DOI: 10.1021/acs.jchemed.2c00935
• 发表时间: 2022-11-30
• 期刊: Journal of Chemical Education
• 影响因子: 3
• 作者: Jonathan P. Antle;Masashi W. Kimura;Stefano Racioppi;Corey Damon;Meredith Lang;Caitlyn M. Gatley;L. Sánchez B.;Daniel P. Miller;E. Zurek;Adam M. Brown;Kellie Gast;S. Simpson
• 通讯作者: S. Simpson

Increasing Confidence in Resolving Isomers of Emerging Per-And Polyfluoroalkyl Substances (PFASs) by Using DFT and Cosmo-Rs to Predict Chromatographic Retention Factors

使用 DFT 和 Cosmo-R 预测色谱保留因子，提高分离新兴全氟烷基物质和多氟烷基物质 (PFAS) 异构体的信心

• 发表时间: 2022-05
• 期刊: Annual meeting abstracts
• 作者: Antle, J.;Guardin, M.G.;Aga, D.;Simpson, S.
• 通讯作者: Simpson, S.

Resolving identities of emerging per and polyfluoroalkyl substances isomers based on COSMO-RS derived retention factor and mass fragmentation patterns

基于 COSMO-RS 导出的保留因子和质量碎片模式解析新出现的全氟烷基物质异构体和多氟烷基物质异构体的身份

• 发表时间: 2021-12
• 期刊: Pacifichem
• 作者: Simpson, Scott;Guardian, M.G.;Aga, D.S.
• 通讯作者: Aga, D.S.

Resolving unknown isomers of emerging per- and polyfluoroalkyl substances (PFASs) in environmental samples using COSMO-RS-derived retention factor and mass fragmentation patterns

使用 COSMO-RS 衍生的保留因子和质量碎片模式解析环境样品中新出现的全氟烷基物质和多氟烷基物质 (PFAS) 的未知异构体

• DOI: 10.1016/j.jhazmat.2020.123478
• 发表时间: 2021-01
• 期刊: Journal of Hazardous Materials
• 影响因子: 13.6
• 作者: Guardian, Mary Grace;Antle, Jonathan P.;Vexelman, Paul A.;Aga, Diana S.;Simpson, Scott M.
• 通讯作者: Simpson, Scott M.

Building Chemical Intuition about Physicochemical Properties of C8-Per-/Polyfluoroalkyl Carboxylic Acids through Computational Means.

通过计算手段建立关于 C8-全/多氟烷基羧酸的物理化学性质的化学直觉。

• DOI: 10.1021/acsestengg.3c00267
• 发表时间: 2023-12-04
• 期刊: ACS ES&T engineering
• 影响因子: 7.1
• 作者: Jonathan P. Antle;Michael A. LaRock;Zackary Falls;Carla A. Ng;G. E. Atilla‐Gokcumen;D. Aga;Scott M. Simpson
• 通讯作者: Scott M. Simpson