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.

化学司的环境化学科学计划是布法罗大学化学系的戴安娜·阿加（Diana Aga）教授，圣邦纳旺特大学化学系的斯科特·辛普森（Scott Simpson）教授，以识别污染环境的污染和多氟烷基物质（PFASS）。这些化学物质广泛用于各种工业应用中，包括消防泡沫和油漆以及消费产品，例如食品包装和清洁产品。 PFAS的残留物已成为严重的环境污染物。随着时间的流逝，残留物不会轻易分解，并在鱼类和野生动植物中积聚。它们也在饮用水源中发现。接触这些化学物质可能会导致广泛的不良人类健康影响。许多重要的问题仍未得到解答，例如如何在环境中分布PFAS，如何从饮用水源中删除它们，或者如何测量单个成分和混合物的毒性。 研究小组正在确定环境中的PFAS，并开发工具以预测其移动性（例如，它们的分散方式）和持久性（它们在环境中停留多长时间）。该项目将使更准确的PFAS风险评估模型和治疗技术能够开发。这项研究为主要是本科机构的本科生提供了机会，可以直接与布法罗大学的研究生合作。此外，研究生由环境保护署的科学家主持，以了解如何使用科学和技术信息来制定公共政策。 来自当地“全女孩”高中的高中学生的夏令营是为了促进STEM的职业而组织的。5,000个不同的PFAS可能会从美国整个美国产生的多种配方中释放出治疗策略的发展和对其毒性的完全了解受到缺乏标准化的分析方法和重要参数的阻碍。其中包括用于复杂污染物混合物的辛醇 - 水分系数。由于环境转化的程度不同，尚未确定许多未知的降解产品。通过一致的实验和计算工作，正在开发可靠的量化，识别和表征的工具。理论工具包括由密度功能理论（DFT）生成的配对生理化学数据和实际溶剂（COSMO-RS）计算的筛选模型。为了帮助鉴定未知的PFAS，将结果与实验确定的液相色谱串联质谱法（LC-MS）保留时间进行了比较。 此外，正在评估不同的LC-MS仪器和LC色谱柱，以确定新兴PFASS的有效分离，最大程度地减少结果的可变性，提高LC-MS分析的准确性，并估计PFASS的土壤迁移率。这些基本研究产生的数据对于开发和测试与环境中暴露于PFASS相关的风险的实用方法至关重要。该奖项反映了NSF的法定任务，并被认为是值得通过基金会的智力优点和更广泛影响的审查标准通过评估来获得支持的。

项目成果

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

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.

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

Investigating bond dissociation energies in per- and polyfluorinated alkyl substances complexed with metal ions

研究与金属离子络合的全氟和多氟烷基物质的键解离能

• 发表时间: 2023
• 期刊: ACS Fall 2023
• 作者: Marciesky, M.;Ng, C.;Simpson, S.
• 通讯作者: Simpson, S.