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的方法，特别是在了解高度复杂样品的化学方面。超高分辨率质谱，如傅里叶变换离子回旋共振（FTICR）质谱（MS），是一种最先进的分析方法，在复杂混合物的现代表征中起着主导作用。两个例子包括对石油和环境样本的分析，得出复杂的数据集，这些数据集随后作为有机成分的分子“剖面”或“指纹”。这些样品的详细分子特征，通常包括成千上万的有机成分，可以使用各种方法进行处理和可视化。对所得样品剖面的比较可以深入了解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与阿尔伯塔省（加拿大）的环境和油砂工业相关的水的特征，以及与英国地质调查局合作，最近对史坦顿岛（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历史。该合作奖学金（博士学位）基于与英国地质调查局共同开发的项目，将首次探索FTICR-MS的实用性，以增强我们对以下方面的理解：1)英国石炭系泥岩中的非常规油气资源；2) UKGEOS克莱德和桑顿遗址土壤的有机污染；3)来自泰晤士河（伦敦）和红河（河内）潮汐河段的河口和河流沉积物样本。方法:博士。Vane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博士和他的研究小组将为12 T FTICR质谱仪提供专业知识。超高分辨率质谱法将为一系列环境样品提供新的信息，而低分辨率技术提供的详细资料较少，关键细节可能会丢失。环境中的样品收集，实验室中的样品提取/制备方法，电离方法和破碎方法将被探索，以开发复杂样品组成的更全面的图景。最先进的数据分析方法最初源于石油分析研究，将用于分析可视化数据，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。可能的时间安排：第一年：介绍FTICR质谱，在12t solariX上进行培训，介绍数据分析方法，分析初始样品。第二年：培训如何从关键岩心段收集样品，介绍标准石油环境分析和数据询问工具（BGS）。利用FTICR MS表征非常规烃泥岩和环境（土壤）第三年利用FTICR MS表征河口沉积物整合所有FTICR MS和传统的地球化学数据集，研究土壤、沉积物和岩石基质的化学指纹图谱，目的是了解英国受污染土壤和沉积物中的碳氢化合物资源和石油污染情况。

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.