A better understanding of environmental impact through ultrahigh resolution mass spectrometry and organic geochemistry

概述：人类活动对环境的影响日益受到关注。迫切需要改进环境监测方法，特别是在理解高度复杂样品的化学方面。以傅立叶变换离子回旋共振(FTICR)为代表的超高分辨质谱学是一种先进的分析方法，在复杂混合物的现代表征中发挥着主导作用。两个例子包括对石油和环境样品的分析，导致产生复杂的数据集，这些数据集随后充当有机成分的分子“概况”或“指纹”。这类样品的详细分子特征，通常包括数以万计的有机成分，可以使用各种方法进行处理和可视化。对所得到的样品概况进行比较，可以洞察样品的来源以及人为或环境过程的影响。与统计部的合作还大大改进了复杂数据集的处理和内部软件的制作，这些软件与商业数据分析软件一起使用。实际应用的例子包括加拿大阿尔伯塔省与环境和油砂行业相关的水的表征，以及最近与英国地质调查局合作对斯塔滕岛(美国纽约)的土壤岩心进行的研究，其中对不同深度的土壤进行分析，提供了该地区石油污染的化学史。这一合作项目(PHD)是基于与英国地质调查局共同开发的一个项目，将首次探索FTICR-MS的用途，以提高我们对以下方面的认识：1)英国石炭纪泥岩中的非常规碳氢化合物资源；2)UKGEOS Clyde和Thornton遗址土壤中的有机污染；3)泰晤士河(伦敦)和越南红河(河内)潮汐河段的河口和河流沉积物样本。方法：Vane博士和他在英国地质调查局(BGS)的团队将提供来自国际感兴趣地点的样本，而Barrow博士和他的研究团队将为12T FTICR质谱仪提供专业知识。超高分辨率质谱仪将为一系列环境样品提供新的信息，在这些样品中，较低分辨率的技术提供的细节较少，关键细节可能会丢失。将探索环境中的样品收集、实验室中的样品提取/制备方法、电离方法和碎裂方法，以更全面地了解复杂样品的组成。最先进的数据分析方法最初源于对石油分析的研究，将被用来分析和显示数据，然后可以对样本进行比较。还将探索数据处理方法，以优化样本比较。可能的时间表：第一年：FTICR质谱学入门，12T SolariX培训，数据分析方法入门，初始样品分析第二年：如何从关键岩心区间收集样品的培训，标准石油环境分析和数据查询工具(BGS)入门。使用FTICR MS对非常规碳氢化合物泥岩和环境(土壤)进行表征第3年利用FTICR MS对河口沉积物进行表征所有FTICR MS和传统的地球化学数据集整合以研究土壤、沉积物和岩石基质的化学指纹图谱，目的是了解受污染土壤和沉积物中的英国碳氢化合物资源和石油污染。

Overview:Anthropogenic impact upon the environment is of increasing concern. There is a strong need for improved methodologies for environmental monitoring, particularly with respect to understanding the chemistry of highly complex samples. Ultrahigh resolution mass spectrometry, such as Fourier transform ion cyclotron resonance (FTICR) mass spectrometry (MS), is a state-of-the-art analytical method which has been playing a leading role in the modern characterization of complex mixtures. Two examples include the analysis of petroleum and environmental samples, leading to complex data sets which subsequently serve as molecular "profiles" or "fingerprints" of the organic components. The detailed molecular characterization of such samples, typically including tens of thousands of organic compositions, can be processed and visualized using a variety of methods. Comparisons of the resulting sample profiles can provide insight into sample origins and the effects of anthropogenic or environmental processes. Collaboration with the Department of Statistics has also resulted in significantly improved processing of complex data sets and the production of in-house software, used in conjunction with commercial data analysis software. Examples of real-world applications include characterization of water associated with the environment and the oil sands industry in Alberta (Canada) and, in collaboration with the British Geological Survey, the recent study of soil cores from Staten Island (New York, USA), where analysis of soil from varying depths provides a chemical history of oil contamination in the region. This Collaborative Studentship (PhD) is based on a co-developed project with the British Geological Survey and will explore for the first time the utility of FTICR-MS to enhance our understanding of: 1) Unconventional hydrocarbon resources in Carboniferous mudstones of the UK; 2) Organic Pollution in soils from the UKGEOS Clyde and Thornton sites and; 3) Estuarine and river sediment samples from the Tidal reaches of the Thames (London) and the Red River (Hanoi) Vietnam. Methodology:Dr. Vane and his team at the British Geological Survey (BGS) will provide samples from international sites of interest, while Dr. Barrow and his research group will provide expertise for the 12 T FTICR mass spectrometer. Ultrahigh resolution mass spectrometry will offer new information for a range of environmental samples, where lower resolution techniques provide less detailed profiles and key details can be lost. Sample collection in the environment, sample extraction/preparation methods in the laboratory, ionization methods, and fragmentation methods will be explored to develop a fuller picture of the composition of complex samples. State-of-the-art data analysis methods, originally arising from research into petroleum analysis, will be used to analyze the visualize the data, where samples can then be compared. Data processing methods will also be explored to optimize the sample comparisons. Possible timeline:Year 1: Introduction to FTICR mass spectrometry, training on the 12 T solariX, introduction to data analysis methods, analysis of initial samples Year 2: Training in how to collect samples from key core intervals, introduction to standard petroleum environmental analyses and data interrogation tools (BGS). Characterization of unconventional hydrocarbon mudrocks and environmental (soils) using FTICR MS. Year 3 Characterization of estuarine sediments using FTICR MS. Integration of all FTICR MS and traditional geochemistry data sets to investigate chemical fingerprinting of soils, sediment and rock matrices with the aim understanding UK hydrocarbon resource and petroleum pollution in contaminated soils and sediments.