Analyses of Water Samples From the Deepwater Horizon Oil Spill: Documentation of the Subsurface Plume

Surface and subsurface water samples were collected in the vicinity of the Deepwater Horizon (DWH) wellhead in the Gulf of Mexico. Samples were extracted with dichloromethane and analyzed for a toxic component, polycyclic aromatic hydrocarbons (PAHs), using total scanning fluorescence (TSF) and by gas chromatography/mass spectrometry (GC/MS). An aliquot of fresh, floating oil from a surface sample was used as a DWH oil reference standard. Twelve of 19 samples collected from 24 May 2010 to 6 June 2010 on the R/V Walton Smith cruise contained TSF maximum intensities above background (0.7 µg L À1 based on 1 L sample size). These 12 samples had total petroleum hydrocarbon (TPH) concentrations as measured by quantitative gas chromatography flame ionization detector (FID) ranging from 2 to 442 µg L À1 . Quantitative GC/MS analysis of these 12 samples resulted in total PAH concentrations ranging from 0.01 to 59 µg L À1 . Low molecular weight, more water-soluble naphthalene and alkylated naphthalene dominated the PAH composition patterns for 11 of the 12 water samples. Sample 12 exhibited substantially reduced concentrations of naphthalenes relative to other PAH compounds. The total PAH concentrations were positively correlated (R 2 = 0.80) with the TSF maximum intensity (MI). TSF is a simple, rapid technique providing an accurate prediction of the amount of PAH present in a sample. TSFderived estimates of the relative contribution of PAH present in the oil provided evidence that PAH represented~10% of the higher molecular weight TPH. The subsurface oil plume was confirmed by the analyses of discrete water samples for TSF, TPH, and PAH

Linking Ramped Pyrolysis Isotope Data To oil Content through PAH Analysis

Ramped pyrolysis isotope (13C and 14C) analysis coupled with polycyclic aromatic hydrocarbon (PAH) analysis demonstrates the utility of ramped pyrolysis in screening for oil content in sediments. Here, sediments from Barataria Bay, Louisiana, USA that were contaminated by oil from the 2010 BP Deepwater Horizon spill display relationships between oil contamination, pyrolysis profiles, and isotopic composition. Sediment samples with low PAH concentrations are thermochemically stable until higher temperatures, while samples containing high concentrations of PAHs pyrolyze at low temperatures. High PAH samples are also depleted in radiocarbon (14C), especially in the fractions that pyrolyze at low temperatures. This lack of radiocarbon in low temperature pyrolyzates is indicative of thermochemically unstable, 14C-free oil content. This study presents a proof of concept that oil contamination can be identified by changes in thermochemical stability in organic material and corroborated by isotope analysis of individual pyrolyzates, thereby providing a basis for application of ramped pyrolysis isotope analysis to samples deposited in different environments for different lengths of time

Differences in the induction of cyp1A and related genes in cultured rainbow trout Oncorhynchus mykiss. Additional considerations for the use of EROD activity as a biomarker

Two rainbow trout Oncorhynchus mykiss fish farms were repeatedly sampled in order to observe the variability of ethoxyresorufin-O-deethylase (EROD) activity and of related genes in the liver. Fish coming from fish farm A exhibited EROD levels that could be considered as basal according to the scientific literature, however, EROD activity in fish coming from fish farm B was significantly increased. This was accompanied by augmented aryl hydrocarbon receptor (ahr) and cytochrome P4501A (cyp1A) messenger RNA expression and reduced oestrogen receptor (er) and vitellogenin (vtg) transcription. Only sediment extracts from the entry channel of fish farm B induced EROD activity in O. mykiss cultured cells, however, this induction could not be explained by the levels of polyaromatic hydrocarbons (PAH) and polychlorinated biphenyls (PCB) measured in the sediments. The results of this study point out that O. mykiss cultured in fish farms could be used as sentinels for indication of pollution. In this particular work, however, no conclusive evidence has been found for a relationship between the presence of PAHs and PCBs and the observed EROD induction. © 2012 The Authors. Journal of Fish Biology © 2012 The Fisheries Society of the British Isles

Linking Ramped Pyrolysis Isotope Data To oil Content through PAH Analysis

Ramped pyrolysis isotope (13C and 14C) analysis coupled with polycyclic aromatic hydrocarbon (PAH) analysis demonstrates the utility of ramped pyrolysis in screening for oil content in sediments. Here, sediments from Barataria Bay, Louisiana, USA that were contaminated by oil from the 2010 BP Deepwater Horizon spill display relationships between oil contamination, pyrolysis profiles, and isotopic composition. Sediment samples with low PAH concentrations are thermochemically stable until higher temperatures, while samples containing high concentrations of PAHs pyrolyze at low temperatures. High PAH samples are also depleted in radiocarbon (14C), especially in the fractions that pyrolyze at low temperatures. This lack of radiocarbon in low temperature pyrolyzates is indicative of thermochemically unstable, 14C-free oil content. This study presents a proof of concept that oil contamination can be identified by changes in thermochemical stability in organic material and corroborated by isotope analysis of individual pyrolyzates, thereby providing a basis for application of ramped pyrolysis isotope analysis to samples deposited in different environments for different lengths of time

Employing Extant Stable Carbon Isotope Data in Gulf of Mexico Sedimentary Organic Matter for Oil Spill Studies

We have compiled and mapped available carbon isotope data from sedimentary organic material sampled from the Gulf of Mexico prior to 2010. These data provide a baseline to which any changes in the Gulf of Mexico after the 2010 Deepwater Horizon oil spill can be compared. The mean (±1σ) δ13C values, relative to PDB, are −21.4±1.9‰ (entire Gulf of Mexico), −21.7±1.2‰ (shelf sediments), −20.4±1.6‰ (deepwater sediments), and −25.2±4.1‰ (seep-affected sediments). We compare pre-spill mean δ13C values to carbon isotope measurements of sedimentary organic material from coretop samples collected after the 2010 Deepwater Horizon oil spill. The differences between the mean compiled δ13C values and the post-spill δ13C values are corroborated by qualitative relationships with the concentration of polycyclic aromatic hydrocarbons (PAHs), a proxy for oil contamination, in the sediment. The relationships between δ13C of the sedimentary organic material and PAH concentrations allow estimation of background levels of PAHs on the shelf and in the deep Gulf of Mexico. Higher background levels of PAH on the shelf likely relate to Mississippi River outflow and its deposition of petrogenic PAH in riverine sediments

Analyses of Water Samples From the Deepwater Horizon Oil Spill: Documentation of the Subsurface Plume

Surface and subsurface water samples were collected in the vicinity of the Deepwater Horizon (DWH) wellhead in the Gulf of Mexico. Samples were extracted with dichloromethane and analyzed for a toxic component, polycyclic aromatic hydrocarbons (PAHs), using total scanning fluorescence (TSF) and by gas chromatography/mass spectrometry (GC/MS). An aliquot of fresh, floating oil from a surface sample was used as a DWH oil reference standard. Twelve of 19 samples collected from 24 May 2010 to 6 June 2010 on the R/V Walton Smith cruise contained TSF maximum intensities above background (0.7 μg L-1 based on 1 L sample size). These 12 samples had total petroleum hydrocarbon (TPH) concentrations as measured by quantitative gas chromatography flame ionization detector (FID) ranging from 2 to 442 μg L-1. Quantitative GC/MS analysis of these 12 samples resulted in total PAH concentrations ranging from 0.01 to 59 μg L-1. Low molecular weight, more water-soluble naphthalene and alkylated naphthalene dominated the PAH composition patterns for 11 of the 12 water samples. Sample 12 exhibited substantially reduced concentrations of naphthalenes relative to other PAH compounds. The total PAH concentrations were positively correlated (R2 = 0.80) with the TSF maximum intensity (MI). TSF is a simple, rapid technique providing an accurate prediction of the amount of PAH present in a sample. TSFderived estimates of the relative contribution of PAH present in the oil provided evidence that PAH represented ~10% of the higher molecular weight TPH. The subsurface oil plume was confirmed by the analyses of discrete water samples for TSF, TPH, and PAH