Paleo-biodegradation and hydrocarbon mixing in a major hybrid petroleum reservoir.

Some of the parental material for hydrocarbons produced from low-permeability reservoirs in Western Canada corresponds to thermal products from biodegraded oil. This has been proved by the occurrence of framboidal pyrite, which is often formed during microbial sulfate reduction (MSR). In addition, the identified pyrite framboids are associated with the presence of phosphorus (P). Phosphorus (as phosphate) is a key nutrient and energy carrier for sulfate-reducing bacteria. The pyrite-P assemblage occurs embedded in solid bitumen (thermal residue), which confirms that migrated hydrocarbons provided the environment for microbial growth. Molecular products of severe biodegradation such as 17-nortricyclic terpanes were also detected. Biodegradation effects have been masked not only by thermal degradation of biodegraded oil during maximum burial, but also due to hydrocarbon mixing with late gas-condensate charges. Suitable conditions for biodegradation (< 80 °C, basin uplift) occurred during the Early Cretaceous. The confirmation of paleo-biodegradation means that there was a significant hydrocarbon loss that we have not accounted for. Likewise, MSR and Early Cretaceous seawater sulfate might have played an important role in the generation of the hydrogen sulfide (H2S) detected today.

Isotopic and microbial evidence for biodegradation of diluted bitumen in the unsaturated zone.

The oil sands region in Western Canada is one of the world's largest proven oil reserves. To facilitate pipeline transport, highly viscous oil sands bitumen is blended with lighter hydrocarbon fractions to produce diluted bitumen (dilbit). Anticipated increases in dilbit production and transport raise the risk of inland spills. To understand the behaviour of dilbit in the unsaturated or vadose zone following a surface spill, we ran parallel dilbit and conventional heavy crude exposures, along with an untreated control, using large soil-filled columns over 104 days. Phospholipid fatty acids (PLFAs), biomarkers for the active microbial population, were extracted from column soil cores. Stable carbon isotope contents (δ13C) of individual PLFAs and radiocarbon contents (Δ14C) of bulk PLFAs were characterized over the course of the experiment. The Δ14CPLFA values in soils impacted by dilbit (-221.1 to -54.7‰) and conventional heavy crude (-259.4 to -97.9‰) indicated similar levels of microbial uptake of fossil carbon. In contrast, Δ14CPLFA values in the control column (-46.1 to +53.7‰) reflected assimilation of more recently fixed organic carbon. Sequencing of 16S ribosomal RNA genes extracted from soil cores revealed a significant increase in the relative abundance of Polaromonas, a known hydrocarbon-degrader, following exposure to both types of oil. This study demonstrates that in the first several months following a surface spill, dilbit has a similar potential for biodegradation by a native shallow subsurface microbial community as conventional heavy crude oil.

Comparing simulated shallow subsurface spills of diluted bitumen and conventional crude oil.

Increased oil production in Canada has resulted in proposals to extend or develop new oil pipelines. Many of these proposals have been met by concerns from the public over potential environmental impacts related to construction and the potential for oil spills to negatively affect groundwater quality. Crude oil sourced from the Alberta oil sands represents a significant proportion of this increase in production. This crude oil is produced as bitumen, which is subsequently diluted with light hydrocarbons to lower viscosity to allow for pipeline transport producing diluted bitumen. In this study, we pumped water through tanks filled with sand to simulate groundwater flow. Tanks were injected with either conventional crude or diluted bitumen to simulate a crude oil spill from a pipeline rupture occurring below the water table representing a pipeline river crossing scenario. Water samples were collected from the downstream end of the tanks throughout the experiment period (∼two months). Compared to water quality guidelines, effluent waters from both conventional crude and diluted bitumen tanks contained elevated concentrations of dissolved organic compounds, particularly benzene, ethylbenzene, toluene and xylenes (BTEX). The effluent from each tank had similar concentrations of benzene, whereas discharge water from conventional crude tanks contained higher concentrations of ethylbenzene, toluene and xylenes. In both tanks, and as expected, the BTEX concentrations appeared to be proportional to those determined in their injected crude oils. The measured dissolved concentrations of benzene, ethylbenzene and toluene are lower than predicted which is attributed largely due to dilution along the flow path. In addition to organic constituents, effluent sampled from the diluted bitumen tank contained some metals (Co, Cr, Fe and V) which measured constituents of the oil.

Naphthenic acids in groundwater overlying undeveloped shale gas and tight oil reservoirs.

The acid extractable organics (AEOs) containing naphthenic acids (NAs) in groundwater overlying undeveloped shale gas (Saint-Édouard region) and tight oil (Haldimand sector, Gaspé) reservoirs in Québec, Canada, were analysed using high resolution Orbitrap mass spectrometry and thermal conversion/elemental analysis - isotope ratio mass spectrometry. As classically defined by CnH2n+ZO2, the most abundant NAs detected in the majority of groundwater samples were straight-chain (Z = 0) or monounsaturated (Z = -2) C16 and C18 fatty acids. Several groundwater samples from both study areas, however, contained significant proportions of presumably alicyclic bicyclic NAs (i.e., Z = -4) in the C10-C18 range. These compounds may have originated from migrated waters containing a different distribution of NAs, or are the product of in situ microbial alteration of shale organic matter and petroleum. In most groundwater samples, intramolecular carbon isotope values generated by pyrolysis (δ13Cpyr) of AEOs were on average around 2-3‰ heavier than those generated by bulk combustion (δ13C) of AEOs, providing further support for microbial reworking of subsurface organic carbon. Although concentrations of AEOs were very low (<2.0 mg/L), the detection of potentially toxic bicyclic acids in groundwater overlying unconventional hydrocarbon reservoirs points to a natural background source of organic contaminants prior to any large-scale commercial hydrocarbon development.

Isotopic Evidence for Oil Sands Petroleum Coke in the Peace-Athabasca Delta.

The continued growth of mining and upgrading activities in Canada's Athabasca oil sands (AOS) region has led to concerns about emissions of contaminants such as polycyclic aromatic hydrocarbons (PAHs). Whereas a recent increase in PAH emissions has been demonstrated within around 50 km of the main center of surface mining and upgrading operations, the exact nature of the predominant source(s) and the geographical extent of the deposition are still under debate. Here, we report a century-long source apportionment of PAHs using dual (δ(2)H, δ(13)C) compound-specific isotope analysis on phenanthrene deposited in a lake from the Athabasca sector of the Peace-Athabasca Delta situated ∼150 km downstream (north) of the main center of mining operations. The isotopic signatures in the core were compared to those of the main potential sources in this region (i.e., unprocessed AOS bitumen, upgrader residual coke, forest fires, coal, gasoline and diesel soot). A significant concurrent increase (∼55.0‰) in δ(2)H and decrease (∼1.5‰) in δ(13)C of phenanthrene over the last three decades pointed to an increasingly greater component of petcoke-derived PAHs. This study is the first to quantify long-range (i.e., >100 km) transport of a previously under-considered anthropogenic PAH source in the AOS region.

Assessing microbial uptake of petroleum hydrocarbons in groundwater systems using natural abundance radiocarbon.

Carbon sources utilized by the active microbial communities in shallow groundwater systems underlying three petroleum service stations were characterized using natural abundance radiocarbon ((14)C). Total organic carbon (TOC) Delta(14)C values ranged from -314 to -972 per thousand and petroleum-extracted residues (EXT-RES) ranged from -293 to -971 per thousand. Phospholipid fatty acids (PLFAs)-biomarkers for active microbial populations-ranged from -405 to -885 per thousand and a comparison of these values with potential carbon sources pointed to significant microbial assimilation of (14)C-free fossil carbon. The most (14)C-depleted PLFAs were found in the samples with the highest concentrations of total petroleum hydrocarbons (TPHs). A radiocarbon mass balance indicated up to 43% of the carbon in microbial PLFAs was derived from TPHs, providing direct evidence for biodegradation at two of three sites. At lower levels of TPHs Delta(14)C values of PLFAs were generally similar to or more enriched than all other carbon in the system indicating microbial utilization of a more (14)C-enriched carbon source and no resolvable evidence for microbial incorporation of petroleum-derived carbon. Results from this study suggest that it is possible to delineate petroleum biodegradation in groundwater systems using these techniques even in complex situations where there exists a wide range in the ages of natural organic matter (i.e., EXT-RES).