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.

化学部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特大学化学系的斯科特·辛普森教授，以确定污染环境的全氟烷基物质(PFAS)和多氟烷基物质(PFAS)。这些化学品广泛用于各种工业应用，包括防火泡沫和涂料，以及食品包装和清洁产品等消费品。全氟辛烷磺酸的残留已成为严重的环境污染物。这些残留物不容易分解，随着时间的推移在鱼类和野生动物中积累。它们也存在于饮用水水源中。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。许多重要的问题仍然没有得到回答，例如全氟辛烷磺酸如何在环境中分布，如何从饮用水水源中去除它们，或者如何衡量单个成分和混合物的毒性。研究小组正在确定环境中的全氟辛烷磺酸，并开发工具来预测它们的移动性(例如，它们是如何分散的)和持久性(它们在环境中停留的时间)。该项目将使开发更准确的全氟辛烷磺酸风险评估模型和处理技术成为可能。这项研究为主要是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主持，以深入了解如何将科学和技术信息用于制定公共政策。为当地“全女生”高中的高中生组织夏令营，以促进STEM的职业发展。美国各地生产的多种配方中可能释放出5000多种不同的全氟辛烷磺酸。由于缺乏标准化的分析方法和重要参数，治疗策略的制定和对其毒性的全面了解受到阻碍。其中包括复杂污染物混合物的辛醇-水分配系数。由于环境变化的程度不同，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努力，正在开发用于可靠地量化、识别和表征环境中新出现的全氟辛烷磺酸的工具。理论工具包括由密度泛函理论(DFT)和实溶剂类导体屏蔽模型(COSMO-RS)计算产生的物理化学数据配对。为了帮助鉴定未知的PFASs，将结果与实验测定的LC-MS保留时间进行了比较。此外，正在对不同的LC-MS仪器和LC柱进行评估，以确定新出现的PFASs的有效分离，最大限度地减少结果的变异性，提高LC-MS分析的准确性，并估计PFASs的土壤流动性。这些基础研究产生的数据对于开发和测试评估与环境中全氟辛烷磺酸暴露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优势和更广泛的影响审查标准进行评估，被认为值得支持。

项目成果

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
• 期刊: Pacifichem
• 作者: Simpson, Scott;Guardian, M.G.;Aga, D.S.
• 通讯作者: Aga, D.S.

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
• 期刊: Annual meeting abstracts
• 作者: Antle, J.;Guardin, M.G.;Aga, D.;Simpson, S.
• 通讯作者: Simpson, S.

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

• DOI: 10.1021/acsestengg.3c00267
• 发表时间: 2023-12
• 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

The Search for Molecular Corks Beyond Carbon Monoxide: A Quantum Mechanical Study of N-Heterocyclic Carbene Adsorption on Pd/Cu(111) and Pt/Cu(111) Single Atom Alloys

• DOI: 10.1016/j.jciso.2021.100013
• 发表时间: 2021-02
• 作者: S. Simpson

Quantum chemical exercise linking computational chemistry to general chemistry topics

将计算化学与一般化学主题联系起来的量子化学练习

• DOI: 10.1515/cti-2019-0014
• 发表时间: 2020
• 期刊: Chemistry Teacher International
• 作者: Simpson, Scott;Evanoski-Cole, Ashley;Gast, Kellie;Wedvik, Madeleine C.;Schneider, Patrick W.;Klingensmith, Isaac
• 通讯作者: Klingensmith, Isaac