Occurrence, source and ecological assessment of petroleum related hydrocarbons in intertidal marine sediments of the Bay of Fundy, New Brunswick, Canada.

Total petroleum hydrocarbons (TPH), n-alkanes, petroleum-related biomarkers of terpanes and steranes, and polycyclic aromatic hydrocarbons (PAHs) were analyzed in the intertidal sediments in the Bay of Fundy, Nova Scotia/New Brunswick, Canada. Sites close to the harbour and more densely populated areas had higher TPH levels than other pristine areas. n-Alkanes presented a typical single bell-shape in n-C16 to n-C35 range and an obvious odd to even carbon preference. Most sites had trace amounts of petroleum biomarkers. Abundant non-alkylated PAHs and lower amounts of alkylated PAHs represented the major input of the incomplete combustion of solid (e.g., coal, coke, biomass, and coal tar) and liquid fuels. The toxicity estimation for PAHs indicates that they did not have potential toxicity to benthic organisms at most sampling sites. However, possible to probable negative effects from the measured PAH concentrations were found for the two samples from Courtenay Bay and Saint Andrews.

Effect of evaporative weathering and oil-sediment interaction on the fate and behavior of diluted bitumen in marine environments. Part 2. The water accommodated and particle-laden hydrocarbon species and toxicity of the aqueous phase.

In this study, the water accommodated and particle-laden hydrocarbon species, and the toxicity of the aqueous phase after oil-sediment interactions by varying the weathering states of diluted bitumen (Cold Lake blend (CLB)), oil type from light to heavy, and sediment type. Compared to the original oils, the sediment-laden total petroleum hydrocarbons (TPH) contained fewer hydrocarbons in the carbon range C34 range. Sediment-laden oil amounts generally decreased with an increased viscosity and asphaltene content of the test oils, as well as with increased sediment particle size. The presence of sediments significantly decreased the oil accommodated in water due to the formation of oil particulate aggregates (OPA) after mixing and settling. Less water accommodated TPH and polycyclic aromatic hydrocarbons (PAHs) were observed for weathered CLB products. However, oil and sediment types did not clearly affect the water accommodated TPH and PAHs. Light molecular PAHs and their alkylated congeners accounted for most of the water accommodated PAH congeners. A microtoxicity test demonstrated that with or without sediment, and regardless of sediment type, the toxicity of the water phase did not change significantly. Light oil of Alberta sweet mixed blend (ASMB) had the highest toxicity, followed by fresh CLB, and then all other oils, suggesting that ASMB and fresh CLB had relatively higher levels of light toxic components dissolved in the water phase compared with the other tested oils.

Fate of oxygenated intermediates in solar irradiated diluted bitumen mixed with saltwater.

Two types of diluted bitumen (dilbit) and a light crude oil spiked onto the surface of saltwater were irradiated with natural solar light in Ottawa to assess the impact of sunlight to the fate of oxygenated intermediates. Oxygenated components, including carbonyl polycyclic aromatic hydrocarbons (PAHs) and acidic polar fractions (naphthenic acid fraction compounds, NAFCs), were identified after periods of solar exposure under both winter and summer conditions. Carbonyl PAHs and NAFCs were formed in both seasons; however, light crude and summer irradiation produced higher abundance of them than dilbits and winter exposure. The formed NAFCs were abundant with the congeners containing a heteroatom of oxygen only (Oo species), accompanied by the minor amounts of sulfur- and nitrogen-containing acids. The produced Oo species were predominant with the congeners with light molecular weight, high degree of saturation and heavy oxygen numbers. For both carbonyl PAHs and NAFCs, their abundance continually increased throughout the period of winter exposure. In the summer, some carbonyl PAHs and all Oo species increased during the early exposure period; then they decreased with continued exposure for most oils, illustrating their transitional nature. Oxygenated intermediates thus appear to have been created through the photo-oxidation of non-to medium-polar petroleum hydrocarbons or the intermediates of aldehydes or ketones (O1). Oil properties, the duration of exposure, exposure season and the chemical structure of these intermediates are critical factors controlling their fate through photo-oxidation. The observed chemical changes highlight the effects of sunlight on the potential behavior, fate and impact of spilled oil, with the creation of new resin group compounds and the reduction of aromatics and saturates. These results also imply that the ecological effects of spilled oil, after ageing in sunlight, depend on the specific oil involved and the environmental conditions.

Characterization of chemical fingerprints of unconventional Bakken crude oil.

The ability to characterize the composition of emerging unconventional Bakken tight oil is essential to better prepare for potential spills and to assess associated environmental concerns. The present work measured and compared the physical and chemical properties of Bakken crudes with conventional crude oils from various regions and different types of refined petroleum products. The physicochemical properties of Bakken crude are overall similar to those of conventional light crudes. The Bakken crude consists of high concentrations of monoaromatic hydrocarbons and alkylated PAHs with a clear dominance of the alkylated naphthalene homologues followed by the phenanthrene series. Its pyrogenic index (PI) values are considerably lower than typical conventional crude oils. The Bakken crude oils in this study exhibit a low abundance of petroleum biomarker such as terpanes, steranes and diamondoids and bicyclic sesquiterpanes. Since tight oil from the Bakken region is produced from low-permeability formations, variations in abundance and diagnostic ratios of common target petroleum hydrocarbons were found among these oils.

Occurrence, source and ecological assessment of baseline hydrocarbons in the intertidal marine sediments along the shoreline of Douglas Channel to Hecate Strait in British Columbia.

The occurrence, source and ecological assessment of baseline hydrocarbons in the intertidal zone along the northern British shoreline were evaluated based on analyzing total petroleum hydrocarbons (TPH), n-alkanes, petroleum related biomarkers such as terpanes and steranes, and polycyclic aromatic hydrocarbons (PAHs) including non-alkylated and alkylated homologues (APAHs). The TPH levels, n-alkanes, petroleum biomarkers and PAHs in all the sampling sites, except for Masset Harbor/York Point at Gil Island were low, without obvious unresolved complex mixture (UCM) and petroleum contamination input. Specifically, n-alkanes showed a major terrestrial plants input; PAHs with abundant non-alkylated PAHs but minor APAHs showed a major pyrogenic input. However, obvious petroleum-derived hydrocarbons have impacted Masset Harbor. A historical petroleum input was found in York Point at Gil Island, due to the presence of the low level of petroleum biomarkers. Ecological assessment of 13 non-alkylated PAHs in Masset Harbor indicated no potential toxicity to the benthic organisms.

Forensic identification of spilled biodiesel and its blends with petroleum oil based on fingerprinting information.

A case study is presented for the forensic identification of several spilled biodiesels and its blends with petroleum oil using integrated forensic oil fingerprinting techniques. The integrated fingerprinting techniques combined SPE with GC/MS for obtaining individual petroleum hydrocarbons (aliphatic hydrocarbons, polyaromatic hydrocarbons and their alkylated derivatives and biomarkers), and biodiesel hydrocarbons (fatty acid methyl esters, free fatty acids, glycerol, monoacylglycerides, and free sterols). HPLC equipped with evaporative scattering laser detector was also used for identifying the compounds that conventional GC/MS could not finish. The three environmental samples (E1, E2, and E3) and one suspected source sample (S2) were dominant with vegetable oil with high acid values and low concentration of fatty acid methyl ester. The suspected source sample S2 was responsible for the three spilled samples although E1 was slightly contaminated by petroleum oil with light hydrocarbons. The suspected source sample S1 exhibited with the high content of glycerol, low content of glycerides, and high polarity, indicating its difference from the other samples. These samples may be the separated byproducts in producing biodiesel. Canola oil source is the most possible feedstock for the three environmental samples and the suspected source sample S2.

Characteristics of bicyclic sesquiterpanes in crude oils and petroleum products.

This study presents a quantitative gas chromatography-mass spectrometry analysis of bicyclic sesquiterpanes (BSs) in numerous crude oils and refined petroleum products including light and mid-range distillate fuels, residual fuels, and lubricating oils collected from various sources. Ten commonly recognized bicyclic sesquiterpanes were determined in all the studied crude oils and diesel range fuels with principal dominance of BS3 (C(15)H(28)), BS5 (C(15)H(28)) and BS10 (C(16)H(30)), while they were generally not detected or in trace in light fuel oils like gasoline and kerosene and most lubricating oils. Laboratory distillation of crude oils demonstrated that sesquiterpanes were highly enriched in the medium distillation fractions of approximately 180 to 481 degrees C and were generally absent or very low in the light distillation fraction (boiling point to approximately 180 degrees C) and the heavy residual fraction (>481 degrees C). The effect of evaporative weathering on a series of diagnostic ratios of sesquiterpanes, n-alkanes, and biomarkers was evaluated with two suites of weathered oil samples. The change of abundance of sesquiterpanes was used to determine the extent of weathering of artificially evaporated crude oils and diesel. In addition to the pentacyclic biomarker C(29) and C(30) alphabeta-hopane, C(15) and C(16) sesquiterpanes might be alternative internal marker compounds to provide a direct way to estimate the depletion of oils, particularly diesels, in oil spill investigations. These findings may offer potential applications for both oil identification and oil-source correlation in cases where the tri- to pentacyclic biomarkers are absent due to refining or environmental weathering of oils.