Puspa L. Adhikari

Application of enhanced gas chromatography/triple quadrupole mass spectrometry for monitoring petroleum weathering and forensic source fingerprinting in samples impacted by the Deepwater Horizon oil spill

Accurate characterization of petroleum hydrocarbons in complex and weathered oil residues is analytically challenging. This is primarily due to chemical compositional complexity of both the oil residues and environmental matrices, and the lack of instrumental selectivity due to co-elution of interferences with the target analytes. To overcome these analytical selectivity issues, we used an enhanced resolution gas chromatography coupled with triple quadrupole mass spectrometry in Multiple Reaction Monitoring (MRM) mode (GC/MS/MS-MRM) to eliminate interferences within the ion chromatograms of target analytes found in environmental samples. This new GC/MS/MS-MRM method was developed and used for forensic fingerprinting of deep-water and marsh sediment samples containing oily residues from the Deepwater Horizon oil spill. The results showed that the GC/MS/MS-MRM method increases selectivity, eliminates interferences, and provides more accurate quantitation and characterization of trace levels of alkyl-PAHs and biomarker compounds, from weathered oil residues in complex sample matrices. The higher selectivity of the new method, even at low detection limits, provides greater insights on isomer and homolog compositional patterns and the extent of oil weathering under various environmental conditions. The method also provides flat chromatographic baselines for accurate and unambiguous calculation of petroleum forensic biomarker compound ratios. Thus, this GC/MS/MS-MRM method can be a reliable analytical strategy for more accurate and selective trace level analyses in petroleum forensic studies, and for tacking continuous weathering of oil residues.

Chapter 32 – Louisiana Coastal Marsh Environments and MC252 Oil Biomarker Chemistry

Abstract Gas chromatography/mass spectrometry analysis of over 700 near-surface sediments and sediments cores collected from Louisiana coastal salt marshes has provided an insight into the unique effects that these environments have on the Deepwater Horizon (DWH) oil residues deposited in them after the accidental release in April 2010. The weathering of oil residues was dependent on whether it was deposited on the surface, incorporated just below the sediment surface, or buried in the anoxic soil layer that can be typically found in these environments. One of the primary effects observed was a predictable weathering pattern of the biomarkers found in these oil residues, particularly changes in the diasterane and regular sterane biomarkers. Qualitative and quantitative oil source fingerprinting techniques were employed to determine if any oil residues detected were from the DWH oil spill (i.e., MC252 oil). The redistribution of buried oil residues in some of the impacted marshes by tropical weather events remains a concern 6 years after the DWH spill.

234)Th as a tracer of vertical transport of polycyclic aromatic hydrocarbons in the northern Gulf of Mexico.

Particle-mediated vertical flux of polycyclic aromatic hydrocarbons (PAHs) plays an important role in their removal from upper oceans and sets a limit on the amount delivered to the deep-sea sediments. In this study, we applied a one-dimensional steady-state (234)Th scavenging model to estimate vertical flux of PAHs in the northern Gulf of Mexico and compared them with sediment trap based flux estimates. The (234)Th-based ∑PAH43 fluxes were 6.7±1.0μgm(-2)d(-1) and 3.7±0.6μgm(-2)d(-1) while sediment trap-based fluxes were 4.0±0.6μgm(-2)d(-1) and 4.5±0.7μgm(-2)d(-1) at 150m and 250m, respectively. Alkylated homologues contributed to 80% of the total PAH fluxes which is in contrary to other regions where combustion derived parent PAHs dominate the fluxes. The results indicate that the (238)U-(234)Th disequilibria can be an effective tracer of particulate PAH fluxes in upper mesopelagic zones and can provide flux estimates with high spatial coverage needed to quantify their long term fate and transport in the marine systems.

Coupled effects of oil spill and hurricane on saltmarsh terrestrial arthropods

Terrestrial arthropods play an important role in saltmarsh ecosystems, mainly affecting the saltmarsh’s primary production as the main consumers of terrestrial primary production and decomposition. Some of these arthropods, including selected insects and spiders, can be used as ecological indicators of overall marsh environmental health, as they are differentially sensitive to ecological stressors, such as land loss, erosion, oil spills, and tropical storms. In the present study, we used terrestrial arthropods collected from seven (three lightly-oiled, four heavily-oiled) sites in Barataria Bay and from three unoiled reference sites in Delacroix, Louisiana, to determine the impacts of the distribution and re-distribution of Deepwater Horizon (DWH) oil on these saltmarsh ecosystems. A total of 9,476 and 12,256 insects were collected in 2013 and 2014, respectively. The results show that the terrestrial arthropods were negatively affected by the re-distribution of DWH oil by Hurricane Isaac in 2012, although the level of impacts varied among the arthropod groups. Moreover, the mean diversity index was higher (>1.5) in 2014 than in 2013 (<1.5) for all sites, suggesting a recovery trajectory of the saltmarsh arthropod population. The higher taxonomic richness observed in the reference sites compared to the oiled sites for both years also indicated long-term impacts of DWH oil to the saltmarsh arthropod community. Whereas a slow recovery of certain terrestrial arthropods was observed, long-term monitoring of arthropod communities would help better understand the recovery and succession of the marsh ecosystems.

Correction: Coupled effects of oil spill and hurricane on saltmarsh terrestrial arthropods

[This corrects the article DOI: 10.1371/journal.pone.0194941.].

How much oil is actually removed by evaporation, photo-oxidation and microbial weathering?

Crude oil is a complex mixture of thousands of organic compounds including alkanes, aromatics, asphaltenes, resins and waxes. A number of physical, chemical and biological weathering processes, as ...