Jagoš R. Radović

Resolution and Quantification of Complex Mixtures of Polycyclic Aromatic Hydrocarbons in Heavy Fuel Oil Sample by Means of GC × GC-TOFMS Combined to Multivariate Curve Resolution

Comprehensive two-dimensional gas chromatography time-of-flight mass spectrometry (GC × GC-TOFMS) combined to multivariate curve resolution-alternating least-squares (MCR-ALS) is proposed for the resolution and quantification of very complex mixtures of compounds such as polycyclic aromatic hydrocarbons (PAHs) in heavy fuel oil (HFO). Different GC × GC-TOFMS data slices acquired during the analysis of HFO samples and PAH standards were simultaneously analyzed using the MCR-ALS method to resolve the pure component elution profiles in the two chromatographic dimensions as well as their pure mass spectra. Outstandingly, retention time shifts within and between GC × GC runs were not affecting the results obtained using the proposed strategy and proper resolution of strongly coeluted compounds, baseline and background contributions was achieved. Calibration curves built up with standard samples of PAHs allowed the quantification of ten of them in HFO aromatic fractions. Relative errors in their estimated concentrations were in all cases below 6%. The obtained results were compared to those obtained by commercial software provided with GC × GC-TOFMS instruments and to Parallel Factor Analysis (PARAFAC). Inspection of these results showed improvement in terms of data fitting, elution process description, concentration relative errors and relative standard deviations.

Recalcitrance and degradation of petroleum biomarkers upon abiotic and biotic natural weathering of Deepwater Horizon oil.

Petroleum biomarkers such as hopanoids, steranes, and triaromatic steroids (TAS) are commonly used to investigate the source and fate of petroleum hydrocarbons in the environment based on the premise that these compounds are resistant to biotic and abiotic degradation. To test the validity of this premise in the context of the Deepwater Horizon disaster, we investigated changes to these biomarkers as induced by natural weathering of crude oil discharged from the Macondo Well (MW). For surface slicks collected from May to June in 2010, and other oiled samples collected on beaches in the northern Gulf of Mexico from July 2010 until August 2012, hopanoids with up to 31 carbons as well as steranes and diasteranes were not systematically affected by weathering processes. In contrast, TAS and C32- to C35-homohopanes were depleted in all samples relative to 17α(H),21β(H)-hopane (C30-hopane). Compared to MW oil, C35-homohopanes and TAS were depleted by 18 ± 10% and 36 ± 20%, respectively, in surface slicks collected from May to June 2010, and by 37 ± 9% and 67 ± 10%, respectively, in samples collected along beaches from April 2011 through August 2012. Based on patterns of relative losses of individual compounds, we hypothesize biodegradation and photooxidation as main degradation processes for homohopanes and TAS, respectively. This study highlights that (i) TAS and homohopanes can be degraded within several years following an oil spill, (ii) the use of homohopanes and TAS for oil spill forensics must account for degradation, and (iii) these compounds provide a window to parse biodegradation and photooxidation during advanced stages of oil weathering.

Assessment of photochemical processes in marine oil spill fingerprinting.

Understanding weathering processes plays a critical role in oil spill forensics, which is based on the comparison of the distributions of selected compounds assumed to be recalcitrant and/or have consistent weathering transformations. Yet, these assumptions are based on limited laboratory and oil-spill studies. With access to additional sites that have been oiled by different types of oils and exposures, there is a great opportunity to expand on our knowledge about these transformations. Here, we demonstrate the effects of photooxidation on the overall composition of spilled oils caused by natural and simulated sunlight, and particularly on the often used polycyclic aromatic hydrocarbons (PAHs) and the biomarker triaromatic steranes (TAS). Both laboratory and field data from oil released from the Macondo well oil following the Deepwater Horizon disaster (2010), and heavy fuel-oil from the Prestige tanker spill (2002) have been obtained to improve the data interpretation of the typical fingerprinting methodology.

Post incident monitoring to evaluate environmental damage from shipping incidents: Chemical and biological assessments

Oil and chemical spills in the marine environment are an issue of growing concern. Oil exploration and exploitation is moving from the continental shelf to deeper waters, and to northern latitudes where the risk of an oil spill is potentially greater and may affect pristine ecosystems. Moreover, a growing number of chemical products are transported by sea and maritime incidents of hazardous and noxious substances (HNS) are expected to increase. Consequently, it seems timely to review all of the experience gained from past spills to be able to cope with appropriate response and mitigation strategies to combat future incidents. Accordingly, this overview is focused on the dissemination of the most successful approaches to both detect and assess accidental releases using chemical as well as biological approaches for spills of either oil or HNS in the marine environment. Aerial surveillance, sampling techniques for water, suspended particles, sediments and biota are reviewed. Early warning bioassays and biomarkers to assess spills are also presented. Finally, research needs and gaps in knowledge are discussed.

Effects of simulated weathering on the toxicity of selected crude oils and their components to sea urchin embryos

Artificial weathering of Angolan crude and a Heavy Fuel Oil (HFO) was performed by evaporation and photooxidation. The aliphatic, aromatic, polar and asphaltene fractions of the fresh and weathered oils were isolated. The toxicity of the water accommodated fraction or an oil/fraction dissolved in DMSO was assessed using the sea urchin embryo test. Photooxidation was observed to decrease the aromatics content and increase polar compounds. A slight reduction in the toxicity of Angolan crude was observed following weathering for the water-accommodated fraction and the extract in DMSO, but no effect was seen for the Heavy Fuel Oil. For aliphatic compounds, the toxicity decreased in the order fresh>evaporated>photooxidated for both Angolan crude and HFO. Weathering slightly increased the toxicity of the aromatic and polar fractions of the oil. The aromatic fractions were responsible for most of the toxicity and the polar compounds were the second most important toxic components, despite having less or similar abundance than the aliphatic fraction. The toxic contribution of the aromatic compounds was higher for the HFO than for the Angolan crude. A decrease in the toxicity of Angolan crude following weathering correlated with a reduction in the toxicity of the aliphatic fraction.

Compositional properties characterizing commonly transported oils and controlling their fate in the marine environment

Oil spills relating to shipping incidents remain of substantial concern with respect to marine pollution. Whilst most frequently a reactive approach is adopted in post-incident monitoring (for the specific product involved), this paper reports important physical and compositional characteristics of commonly transported oils and oil products to afford pro-active assessments. These properties include specific gravity, viscosity, elemental composition and, of particular relevance, the relative class compositions between aliphatics, aromatics, resins and asphaltenes. The latter were determined experimentally using thin layer chromatography with flame ionization detection. Diagnostic ratios of specific compounds are reported, statistically analysed, and their significance in identification of different oil types and the weathering processes is discussed. The influence of the properties on fates under different environmental conditions (selected to represent contrasting European regional seas) are examined using the NOAA Automated Data Inquiry for Oil Spills (ADIOS2) model. Relative contributions of the different environmental conditions and properties to the fate of the oil at sea are discussed.

Environmental Assessment of Spills Related to Oil Exploitation in Canada’s Oil Sands Region

Abstract Canada’s oil sands region (COSR) is located in its western province of Alberta which contains one of the largest oil reserves in the world, in the form of biodegraded heavy oils and bitumens, but also has conventional oil containing reservoirs. In this chapter, we analyzed historical cases of oil releases related to oil production and transport in COSR, in order to determine long-term trends and the main causes of spills. Furthermore, we assessed the potential postspill environmental behavior, fate, and effects of nonhydrocarbon-rich COSR oil resources, in the context of their unique physicochemical properties. The long-term spill record shows a decreasing trend through time of released volumes relative to total oil output from COSR. Some of the largest oil releases occurred due to pipeline ruptures or leaks, often caused by corrosion. High oil viscosity and density reduce spill spreading, but can cause sinking of oil when spilled into water. The high concentrations of heteroatom-containing species in many COSR oils is a poorly understood risk factor affecting water solubility and environmental behavior in these polar compound-rich oil fractions. Advanced analytical tools and methods are needed to better understand the environmental impacts of spills of heteroatom-rich heavy oils and bitumens, and to improve spill response, monitoring, and remediation strategies.

Marine snow increases the adverse effects of oil on benthic invertebrates

After the Deepwater Horizon oil spill, a MOSSFA (Marine Oil Snow Sedimentation and Flocculent Accumulation) event took place, transporting an estimated 14% of total released oil to the sediment, and smothering parts of the benthic ecosystem. This microcosm study describes the effects of oiled artificial marine snow on benthic macroinvertebrates. Corophium volutator survival was reduced by 80% in oil-contaminated snow. Hydrobia ulvae survival was reduced by 40% in oil-contaminated snow, possibly due to consumption of oiled snow. Macoma balthica was sensitive to marine snow, addition of oil slightly decreased survival. This study reveals trait-dependent sensitivity to oil with or without marine snow. The main drivers for organismal response to marine snow and oil are motility, sensitivity to hypoxia and oil toxicity, and feeding habits. Adverse effects of MOSSFA events on benthos will have consequence for the benthic-pelagic habitat and food chain, and should receive more attention in oil spill management.

Rapid Screening of Glycerol Ether Lipid Biomarkers in Recent Marine Sediment Using Atmospheric Pressure Photoionization in Positive Mode Fourier Transform Ion Cyclotron Resonance Mass Spectrometry

Many of the molecular proxies commonly used for paleoenvironmental reconstruction are focused on a limited set of glycerol ether lipids, mainly due to the lack of more comprehensive analytical methods and instrumentation able to deal with a more diverse range of species. In this study, we describe an FTICR-MS-based method for rapid, nontargeted screening of ether lipid biomarkers in recent marine sediments. This method involves simplified sample preparation and enables rapid identification of known and novel ether lipid species. Using this method, we were able to identify complete series of core glycerol dialkyl glycerol tetraethers (GDGTs with 0 to 8 alicyclic rings), including the complete resolution of GDGT-4 and the unexpected detection of GDGTs with more than 5 rings, in sediments from mesophilic marine environments (sea surface temperature, SST, of 24-25 °C). Additionally, mono- and dihydroxy-GDGT analogs (including novel species with >2 rings), as well as glycerol dialkanol diethers, GDDs (including novel species with >5 rings) were detected. Finally, we putatively identified other, previously unreported groups of glycerol ether lipid species. Adequacy of the APPI-P FTICR-MS data for the determination of commonly used GDGT-based proxy indices was demonstrated. The results of this study show great potential for the use of FTICR-MS as both a rapid method for determining existing proxy indices and, perhaps more importantly, as a tool for the early detection of possible new biomarkers and proxies that may establish novel geochemical relationships between archaeal ether lipids and key environmental-, energy-, and climate-related system variables.

Photochemical effects on oil spill fingerprinting

Abstract Weathering processes play a critical role in oil spill forensics, which is based on the comparison of the distributions of selected oil components in source and spill samples, assumed to be recalcitrant and/or having consistent weathering transformations. Among these processes, photo-oxidation, which is not important in terms of the mass balance after a spill, is potentially significant in modifying the oil composition and hence challenging the source identification, particularly in areas with large sunlight incidence. Understanding these processes is essential for a correct interpretation of the fingerprinting results. The assessment of the effects of photo-oxidation on the chemical composition of oil has been carried out through a number of laboratory and oil spill studies. They have demonstrated that photo-oxidation primarily affects the aromatic compounds and modifies the values of the diagnostic ratios commonly used in oil spill fingerprinting. These studies provide the basis for the recognition of photochemical processes in the spilled oils and improve the data interpretation of the typical fingerprinting methodology.