Rates of depletion of lubricant and fuel contaminants from Antarctic regions during natural attenuation and remediation procedures - hydrocarbon degradation data

Metadata record for data expected from ASAC Project 2915See the link below for public details on this project.Petroleum contamination poses a major threat to Antarctic and subantarctic ecosystems because diesel and lubricants are persistent and, at poorly defined concentrations, are toxic in marine environments. This project will asses how quickly important components in these products are naturally depleted using a model field experiment. We will identify and quantify the non-degrading portions of the fuels, and assess the longevity and rate of removal of these. We will relate the chemical analysis data with biological data on organisms in the sea-bottom sediments, in order to assess which components of the fuels do most harm to the organisms.Project objectives:The overall objective is to better understand the long-term environmental impact of spilled petroleum products in Antarctic marine systems.Decades of Antarctic exploration have left a significant legacy of petroleum pollution on-land and in nearshore marine environments, particularly around human stations. The natural attenuation of spilled diesel and lubricants occurs slowly in cold climates, particularly once the pollutants have adsorbed onto marine sediments. Major programmes funded by the AAD have identified the location of spills, and the nature and fate of some of the pollutants. This project will address some of the significant uncertainties which still exist regarding the natural depletion and ecotoxicological impact of spilled diesel and lubricants in the marine environment. A new PhD student at Macquarie University will carry-out much of this work, in collaboration with the CI and investigators. The specific objectives are:1. To develop a quantitative method using cutting edge two-dimensional gas chromatography-mass spectrometry (GCxGC-TOFMS) to identify the components of spilled diesel and lubricants, especially the complex mixtures of recalcitrant residues and the secondary products of alteration.2. To calculate the rates of removal of pollutants in the marine environment by comprehensive statistical treatment of the chemical data-set, and to assess the processes by which this removal occurs (e.g. aerobic/anaerobic biodegradation, water-washing, etc).3. To assess the degradation rates and longevity of pollutant components against the biology of the disturbed communities of microbes and microfauna in the same experiments, so as to form a hypothesis of which components of the complex mixtures have the most important ecotoxicological response and environment impact.4. Using the most important single isolated or related groups of components, to test the specific ecotoxicological impact of each in the marine environment using a short-term field experiment and laboratory toxicity tests. Taken from the 2008-2009 Progress Report:Progress against objectives:1. A GCxGC-FID was installed at Macquarie University. No TOFMS has been purchased yet, due to non-funding of ARC Lief grant application. No further progress made towards this objective.2. We have a comprehensive dataset now of the rates of removal of hydrocarbon components of SAB from the SRE4 experiment. Detailed GC-MS has been carried out so as to track removal of components in much more detail than can be achieved by GC-FID alone. TPH data have been calculated. The data has been utilised in the draft of one paper by Shane Powell (Powell, Stark, Snape, Woolfenden, Bowman, Riddle; Effects of diesel and lubricant oils on Antarctic benthic microbial communities over five years) which has not been submitted yet, and in an early draft of a paper by PhD student Ellen Woolfenden (E. N. M. Woolfenden, G. Hince, S. Powell, S. Stark, J. Stark, I. Snape, S. George; Effects of diesel and lubricant oils on Antarctic benthic microbial communities over five years).3. This has partly been done, and is being written up by the Powell et al. paper referred to above. Detailed analysis of which are the most toxic compounds of SAB awaits further work-up of the data.4. The field season to carry out this test was postponed from 08/09 to 09/10. Taken from the 2009-2010 Progress Report:Progress against objectives:1. An ARC LIEF grant application was successful and a TOFMS will be purchased from the funds gained in mid 2010.2. So far the 0-1cm of 10cm cores of marine sediment spiked with Biodegradable lubricant, used lubricant, clean lubricant and Special Antarctic Blend (SAB) diesel have been analysed by gas chromatography coupled to a flame ionisation detector (GC-FID). Analyses by GC-FID allowed the Total Petroleum Hydrocarbon (TPH) concentration at each sample time to be calculated from statistical analysis. Further analyses were performed on the SAB sediments extractions by GC-MS (mass spectrometry). The chromatograms of the extractions were compared with chromatograms of standard mixtures of compounds and a compound identification library and thus, peaks were identified. From this peak identification, degradation patterns of compounds and groups of compounds could be seen; naphthalenes degrade less readily with increasing methyl groups but still degrade more readily than n-alkanes. From the analyses of the 0-1cm sediment extractions the most recalcitrant compounds were (adamantanes and diamantanes) and the most water soluble compounds were (naphthalenes and alkylnaphthalenes) in SAB diesel. The data has been written up in a draft paper by PhD student Ellen Woolfenden (E. N. M. Woolfenden, G. Hince, S. Powell, S. Stark, J. Stark, I. Snape, S. George; Effects of diesel and lubricant oils on Antarctic benthic microbial communities over five years). This paper will be submitted by May 2010.We also have started analysing the depth profiles for SAB in the SRE4 experiment. It is interesting to know as to whether any biodegradation patterns will be seen in the 1-10 cm depths of the sediment. Therefore the cores have been sectioned into 1 cm intervals and extracted at AAD. The extractions are awaiting analysis by GC-FID initially and GC-MS for further analysis.3. This has partly been done, and is being written up by a Shane Powell et al. paper, that has not been published yet. Detailed analysis of which are the most toxic compounds of SAB awaits further work-up of the data.4. The field season to carry out this test was carried out by Ellen Woolfenden in fieldseason 09/10. Samples have been collected and are stored at AAD. Marine sediment was collected and different portions were spiked with certain compounds from each of these groups as well as a selection of n-alkanes and SAB diesel as a comparison. These sediments have been extracted and are awaiting analysis by GC-MS to identify which of the compounds are depleted most readily within the experimental groups without the influence of other compounds present in SAB diesel. Ellen will be analysing them later in 2010. The dataset provided by Ellen Woolfenden contain a number of excel spreadsheets, as well as a word document providing further information about the data.

本数据集为ASAC项目2915的预期数据元记录，项目公开详情见下方链接。
石油污染对南极及亚极区生态系统构成严重威胁：柴油与润滑油具有持久性，且在浓度未明确界定的情况下会对海洋环境产生毒性。本项目将通过模拟野外实验，评估此类产品中的关键组分的自然降解速率。我们将识别并量化燃料中的难降解组分，评估其留存时长与去除速率。同时，我们会将化学分析数据与海底沉积物中生物的生物学数据相关联，以明确燃料中哪些组分对生物的危害最为显著。

项目目标：
总体目标：更深入地理解泄漏石油产品在南极海洋系统中的长期环境影响。
数十年的南极考察活动已在陆地及近岸海洋环境（尤其是人类科考站周边）留下了大量石油污染遗留问题。在寒冷气候下，泄漏柴油与润滑油的自然衰减过程十分缓慢，尤其是当污染物吸附至海洋沉积物后。由澳大利亚南极局（Australian Antarctic Division, AAD）资助的重大科研项目已探明了泄漏点位置以及部分污染物的性质与归趋。本项目将针对南极海洋环境中泄漏柴油与润滑油的自然降解及生态毒理影响尚存的重大不确定性展开研究。麦考瑞大学（Macquarie University）的一名新晋博士生将与首席研究员及其他研究人员合作，承担本项目的大部分工作。具体目标如下：
1. 开发基于前沿二维气相色谱-飞行时间质谱联用技术（two-dimensional gas chromatography-mass spectrometry, GCxGC-TOFMS）的定量分析方法，以识别泄漏柴油与润滑油的组分，尤其是复杂的难降解残留混合物以及次生转化产物。
2. 通过对化学数据集进行全面的统计学处理，计算海洋环境中污染物的去除速率，并评估污染物去除的相关过程（如好氧/厌氧生物降解、水洗作用等）。
3. 结合同一实验中受扰动的微生物与微小型底栖动物群落的生物学特征，评估污染物组分的降解速率与留存时长，从而形成关于复杂混合物中哪些组分可引发最为显著的生态毒理响应与环境影响的假说。
4. 选取最为关键的单一或相关组分组，通过短期野外实验与实验室毒性测试，评估其在海洋环境中的特定生态毒理影响。

摘录自2008-2009年度进展报告：
目标完成进展：
1. 麦考瑞大学已安装一台二维气相色谱-火焰离子化检测器（gas chromatography-flame ionization detector, GC-FID）。由于澳大利亚研究理事会（Australian Research Council, ARC）LIEF项目申请未获资助，尚未采购飞行时间质谱（TOFMS），本项目暂未在该目标上取得进一步进展。
2. 目前我们已获取SRE4实验中南极混合柴油（Special Antarctic Blend, SAB）烃类组分去除速率的完整数据集。我们已开展详细的气相色谱-质谱（gas chromatography-mass spectrometry, GC-MS）分析，相比单独使用GC-FID，该分析可更细致地追踪组分的去除过程。我们已计算得到总石油烃（Total Petroleum Hydrocarbon, TPH）数据。相关数据已被用于Shane Powell等人撰写的一篇待投稿论文草稿（《柴油与润滑油对南极底栖微生物群落的五年影响》，作者：Powell, Stark, Snape, Woolfenden, Bowman, Riddle），以及博士生Ellen Woolfenden撰写的一篇早期论文草稿（《柴油与润滑油对南极底栖微生物群落的五年影响》，作者：E. N. M. Woolfenden, G. Hince, S. Powell, S. Stark, J. Stark, I. Snape, S. George）。
3. 该目标已部分完成，相关内容已被写入上述Shane Powell等人的论文中。针对SAB中哪些组分毒性最强的详细分析，仍需进一步处理数据。
4. 原计划于2008/2009年度开展的该实验野外季被推迟至2009/2010年度。

摘录自2009-2010年度进展报告：
目标完成进展：
1. 澳大利亚研究理事会（ARC）LIEF项目申请已获批，将于2010年中期使用获批资金采购TOFMS。
2. 目前，我们已通过GC-FID对10cm海洋沉积物岩芯的0-1cm表层进行了分析，这些沉积物分别投加了可生物降解润滑油、废弃润滑油、纯净润滑油以及南极混合柴油（SAB）。通过GC-FID分析，我们可通过统计学计算得到每个采样时间点的总石油烃（TPH）浓度。我们还通过GC-MS对SAB沉积物提取物开展了进一步分析。将提取物的色谱图与标准化合物混合物以及化合物识别库的色谱图进行比对，从而完成峰识别。基于峰识别结果，我们可观察到化合物及化合物组的降解模式：随着甲基取代基增多，萘类化合物的降解难度略有提升，但仍比正构烷烃更易降解。通过对0-1cm沉积物提取物的分析，我们发现SAB柴油中最难降解的化合物为金刚烷类与双金刚烷类化合物，水溶性最强的化合物为萘类与烷基萘类化合物。相关数据已被博士生Ellen Woolfenden写入论文草稿（《柴油与润滑油对南极底栖微生物群落的五年影响》，作者：E. N. M. Woolfenden, G. Hince, S. Powell, S. Stark, J. Stark, I. Snape, S. George），该论文将于2010年5月前提交。
我们还启动了SRE4实验中SAB的深度剖面分析。了解沉积物1-10cm深度是否存在降解模式是一项有趣的研究内容。因此，我们已将岩芯按1cm间隔进行切片，并在澳大利亚南极局（AAD）完成了提取物制备。这些提取物将首先通过GC-FID进行分析，后续再通过GC-MS开展进一步分析。
3. 该目标已部分完成，相关内容已被Shane Powell等人撰写的一篇尚未发表的论文收录。针对SAB中哪些组分毒性最强的详细分析，仍需进一步处理数据。
4. 原计划开展该实验的野外季已于2009/2010年度由Ellen Woolfenden完成。样品已被采集并存储于澳大利亚南极局（AAD）。研究人员采集了海洋沉积物，并向不同沉积物组分中添加了选定的各类组分化合物，以及一系列正构烷烃与SAB柴油作为对照。这些沉积物已完成提取物制备，待通过GC-MS分析，以明确在不受SAB柴油中其他化合物干扰的情况下，实验各组中哪些化合物最易被降解。Ellen将于2010年下半年开展相关分析。
Ellen Woolfenden提供的数据集包含多个Excel电子表格，以及一份详细说明数据信息的Word文档。