Reading the molecular fine print: Ultrahigh resolution mass spectrometry and the environmental impact of the Athabasca oil sands industry

概述：加拿大艾伯塔省的油砂行业代表着另一种石油来源，使加拿大成为美国最大的石油供应国。油砂材料由粘土、沙、水和沥青组成，其中的沥青可以使用碱性热水提取过程来提取。生产一桶石油大约需要三桶水，但由于联邦法规，这种水，油砂工艺受影响的水(OSPW)不能排放回环境中。因此，OSPW被储存在巨大的尾矿池中，目前估计尾矿池的水量约为1万亿升。大量的尾矿库水中含有已知对水环境有毒的物质。例如，最近的研究表明，许多经典的环烷酸以及重金属和盐类都是主要的毒物。因此，未来释放OSPW对水环境的人为影响日益受到关注。迫切需要改进用于环境监测的油砂环烷酸的表征方法，特别是在了解高度复杂的环境样品的化学方面。关于OSPW的有机部分在水环境中的去向和迁移的全面表征尚未确立。超高分辨率质谱学，特别是傅里叶变换离子回旋共振(FTICR)质谱学在环境样品的分子表征中发挥了关键作用，导致了复杂的数据集，这些数据集随后充当OSPW中有机成分的“轮廓”或“指纹”。这项拟议的工作将首次利用华威大学开发的专利软件工具的进展，来改进和扩展OSPW中主要有毒成分的分子表征，包括更深入地了解异构体结构。方法：这项研究将对从阿萨巴斯卡油砂地区收集的油砂处理水以及加拿大未开发页岩气和致密油藏上覆的地下水进行指纹识别。需要更好地了解环境过程对分子剖面的影响，因为它可以用来建立油砂组分环境命运的模型。为了解决这一问题，将在实验室对油砂组分在土壤中的传输及其随后的微生物降解进行实验研究。得到的样品将用超高分辨率质谱仪进行表征；通常在环烷酸混合物的质谱图中观察到的最小质量差异之一是3.4丙二醛，这是由富含Ox和SOx等压素的复杂混合物产生的。该项目还将完善对MS数据的解释和比较，以更好地表征水环境中的环烷酸。

Overview:The oil sands industry in Alberta, Canada, represents an alternative source of petroleum which has positioned Canada as the leading supplier of oil to the USA. The oil sands material consist of clay, sand, water, and bitumen, where the bitumen can be extracted using an alkaline hot water extractions process. Approximately three barrels of water are needed to produce one barrel of oil but this water, oil sands process affected water (OSPW), cannot be discharged back into the environment, due to federal regulations. As a result, the OSPW is stored in vast tailings ponds, currently estimated to hold approximately 1 trillion litres of water. The vast amounts of tailings pond waters contain substances that are known to be toxic to aquatic environments. For example, recent studies have implicated a wide range of classical naphthenic acids as principal toxicants, along with heavy metals and salts. The anthropogenic impact of future release of OSPW upon the aquatic environment is thus of increasing concern. There is a strong need for improved methodologies for characterization of the oil sands naphthenic acids for environmental monitoring, particularly with respect to understanding the chemistry of highly complex environmental samples. The comprehensive characterization of the organic fraction of OSPW with regards to fate and transport in aquatic environments is not yet established. Ultrahigh resolution mass spectrometry, particularly Fourier transform ion cyclotron resonance (FTICR) mass spectrometry (MS), has played a key role in the molecular characterization of environmental samples, leading to complex data sets which subsequently serve as "profiles" or "fingerprints" of the organic components in OSPW. The proposed work will, for the first time, utilize advances in proprietary software tools, developed at the University of Warwick, to improve and expand the molecular characterization of principal toxic components in OSPW, including providing greater insight into isomeric structures.Methodology:This study will fingerprint oil sands processed waters collected from the Athabasca oil sands region, along with groundwater overlying undeveloped shale gas and tight oil reservoirs in Canada. A better understanding of the influence of environmental processes upon the molecular profiles is required, as it can be used to build a model of the environmental fate of oil sands components. In order to address this, the transport of oil sands components through soil and their subsequent microbial degradation will be experimentally investigated in the laboratory. The resulting samples will be characterized using ultrahigh resolution mass spectrometry; one of the smallest mass differences commonly observed in the mass spectra of naphthenic acid mixtures is 3.4 mDa, resulting from the complex mixture rich in Ox and SOx isobars. The project will also refine the interpretation and comparison of MS data to better characterize naphthenic acids in aquatic environments.