Long-Term Biocide Efficacy and Its Effect on a Souring Microbial Community.

Reservoir souring, which is the production of H2S mainly by sulfate-reducing microorganisms (SRM) in oil reservoirs, has been a long-standing issue for the oil industry. While biocides have been frequently applied to control biogenic souring, the effects of biocide treatment are usually temporary, and biocides eventually fail. The reasons for biocide failure and the long-term response of the microbial community remain poorly understood. In this study, one-time biocide treatments with glutaraldehyde (GA) and an aldehyde-releasing biocide (ARB) at low (100 ppm) and high (750 ppm) doses were individually applied to a complex SRM community, followed by 1 year of monitoring of the chemical responses and the microbial community succession. The chemical results showed that souring control failed after 7 days at a dose of 100 ppm regardless of the biocide type and lasting souring control for the entire 1-year period was achieved only with ARB at 750 ppm. Microbial community analyses suggested that the high-dose biocide treatments resulted in 1 order of magnitude lower average total microbial abundance and average SRM abundance, compared to the low-dose treatments. The recurrence of souring was associated with reduction of alpha diversity and with long-term microbial community structure changes; therefore, monitoring changes in microbial community metrics may provide early warnings of the failure of a biocide-based souring control program in the field. Furthermore, spore-forming sulfate reducers (Desulfotomaculum and Desulfurispora) were enriched and became dominant in both GA-treated groups, which could cause challenges for the design of long-lasting remedial souring control strategies. IMPORTANCE Reservoir souring is a problem for the oil and gas industry, because H2S corrodes the steel infrastructure, downgrades oil quality, and poses substantial risks to field personnel and the environment. Biocides have been widely applied to remedy souring, but the long-term performance of biocide treatments is hard to predict or to optimize due to limited understanding of the microbial ecology affected by biocide treatment. This study investigates the long-term biocide performance and associated changes in the abundance, diversity, and structure of the souring microbial community, thus advancing the knowledge toward a deeper understanding of the microbial ecology of biocide-treated systems and contributing to the improvement of current biocide-based souring control practices. The study showcases the potential application of incorporating microbial community analyses to forecast souring, and it highlights the long-term consequences of biocide treatment in the microbial communities, with relevance to both operators and regulators.

Shale oil production and groundwater: What can we learn from produced water data?

As oil production in the Permian Basin surges, the impact of shale production on groundwater resources has become a growing concern. Most existing studies focus on the impact of shale production on shallow freshwater aquifers. There is little understanding of the shale development's impact on other groundwater resources (e.g., deep carbonate aquifers and deep basin meteoric aquifers). The possible natural hydraulic connections between shallow aquifers and formation water suggest such an impact can be consequential. This study explores the relationship between shale production and groundwater using produced water (PW) samples from active unconventional oil wells. Focusing on the most productive portion of the Permian Basin-the four-county region in Southeast New Mexico between 2007 and 2016, a large produced water dataset allows us to analyze the conditional correlations between shale oil production and PW constituents. The results suggest that (1) expanding from primarily conventional wells to unconventional wells during the recent shale boom has led to dramatic increases of the TDS, chloride, sodium, and calcium levels in groundwater (i.e., producing formation). (2) Nearby oil well density positively correlates with the TDS, chloride, and sodium levels in the PW samples.

Genotoxicity detection of oil-containing drill cuttings by Comet assay based on a demersal marine fish Mugilogobius chulae.

An enormous amount of oil-containing drill cuttings have been produced by the marine oil and gas industry. The environmental impacts of discharged drilling waste have been extensively studied. However, there is still an urgent need to develop alternative methods to identify the genotoxicity of untreated and treated drill waste in a timely manner before it is discharged. In this study, we developed a relatively rapid, sensitive, and accurate genotoxicity-detection method using Comet assay and the marine benthic goby Mugilogobius chulae. This goby is sensitive to a standard toxicant mitomycin C (MMC). The optimal exposure period for genotoxicity detection using M. chulae was determined. Three genotoxic indices (tail length (TL), tail DNA content (TD), and tail moment (TM)) were used to assess the effectiveness of high-temperature treatment of oil-contaminated waste. Untreated oil-containing drill cuttings exhibited the highest genotoxicity to goby cells. Genotoxicity was dramatically reduced after thermal treatment of drill cuttings at 350 °C and 500 °C. TD and TM exhibited significant correlation with the concentration of total petroleum hydrocarbons (TPHs)/total polycyclic aromatic hydrocarbons (PAHs) according to Pearson and Mantel correlation analyses (P values were <0.05). Using redundancy analysis (RDA) and variation partition analysis (VPA), the genotoxic effects of the drill cuttings were ascribed to total alkanes and specific groups of PAHs. In conclusion, this newly established biological model has the potential to be widely used to detect the genetic damage of untreated or treated oil-containing drill cuttings discharged into the marine environment.

Hyperthermophilic Clostridium sp. N-4 produced a glycoprotein biosurfactant that enhanced recovery of residual oil at 96 °C in lab studies.

Biosurfactant producing hypethermophilic microorganisms are essentially required for Microbial Enhanced Oil Recovery (MEOR) from high temperature oil reservoirs (above 90 °C). In the present study, biosurfactant producing Clostridium sp. N-4, optimally growing at 96 °C was isolated from a high temperature oil reservoir. Effect of pH, temperature and salinity on production and activity of N-4 biosurfactant was investigated. Biosurfactant produced by N-4 was partially purified by acid precipitation, characterized using FT-IR spectroscopy; and evaluated for its ability to enhance oil recovery in sand pack studies. The strain N-4 produced biosurfactant over a wide range of pH (5.0-9.0) and salinity (0-13%) at high temperature (80-100 °C) and optimally at pH 7, 96 °C and 4% salinity. N-4 biosurfactant was active at 37-101 °C; pH, 5-10 and salinity of 0-12 % (w/v). N-4 biosurfactant, characterized as glycoprotein reduced the surface tension of water by 32 ± 0.4 mN/m at critical micelle concentration of 100 µg/ml. N-4 biosurfactant mobilized 17.15% of residual oil saturation in sand pack studies. Similarly, the strain N-4 also recovered 36.92% of the residual oil in sand pack studies under the conditions mimicking the environment of depleted high temperature oil reservoir. Thus, the biosurfactant producing Clostridium sp. N-4 was identified as a suitable agent for enhanced oil recovery from high temperature oil reservoirs.

Aqueous- and solid-phase molybdenum geochemistry of oil sands fluid petroleum coke deposits, Alberta, Canada.

Fluid petroleum coke generated at oil sands operations in the Athabasca Oil Sands Region of northern Alberta, Canada, contains elevated concentrations of molybdenum (Mo) and other metals including nickel (Ni) and vanadium (V). Solid-phase Mo concentrations in fluid petroleum coke are typically 10 to 100 times lower than V and Ni, yet dissolved Mo concentrations in associated pore waters are often comparable with these metals. We collected pore water and solids from fluid petroleum coke deposits in the AOSR to examine geochemical controls on Mo mobility. Dissolved Mo concentrations increased with depth below the water table, reaching maxima of 1.4-2.2 mg L-1, within a mixing zone between slightly acidic and oxic meteoric water and mildly alkaline and anoxic oil sands process-affected water (OSPW). Dissolved Mo concentrations decreased slightly with depth below the mixing zone. X-ray absorption spectroscopy revealed that Mo(VI) and Mo(IV) species were present in coke solids. The Mo(VI) occurred as tetrahedrally coordinated MoO42- adsorbed via inner- and outer-sphere complexation, and was coordinated in an environment similar to Fe-(hydr)oxide surface complexes. The OSPW likely promoted desorption of outer-sphere Mo(VI) complexes, resulting in higher dissolved Mo concentrations in the mixing zone. The principal Mo(IV) species was MoS2, which originated as a catalyst added upstream of the fluid coking process. Although MoS2 is likely stable under anoxic conditions below the mixing zone, oxidative weathering in the presence of meteoric water may promote long-term Mo release.

Microbial community composition of a hydrocarbon reservoir 40 years after a CO2 enhanced oil recovery flood.

Injecting CO2 into depleted oil reservoirs to extract additional crude oil is a common enhanced oil recovery (CO2-EOR) technique. However, little is known about how in situ microbial communities may be impacted by CO2 flooding, or if any permanent microbiological changes occur after flooding has ceased. Formation water was collected from an oil field that was flooded for CO2-EOR in the 1980s, including samples from areas affected by or outside of the flood region, to determine the impacts of CO2-EOR on reservoir microbial communities. Archaea, specifically methanogens, were more abundant than bacteria in all samples, while identified bacteria exhibited much greater diversity than the archaea. Microbial communities in CO2-impacted and non-impacted samples did not significantly differ (ANOSIM: Statistic R = -0.2597, significance = 0.769). However, several low abundance bacteria were found to be significantly associated with the CO2-affected group; very few of these species are known to metabolize CO2 or are associated with CO2-rich habitats. Although this study had limitations, on a broad scale, either the CO2 flood did not impact the microbial community composition of the target formation, or microbial communities in affected wells may have reverted back to pre-injection conditions over the ca. 40 years since the CO2-EOR.

Efficient big data assimilation through sparse representation: A 3D benchmark case study in petroleum engineering.

Data assimilation is an important discipline in geosciences that aims to combine the information contents from both prior geophysical models and observational data (observations) to obtain improved model estimates. Ensemble-based methods are among the state-of-the-art assimilation algorithms in the data assimilation community. When applying ensemble-based methods to assimilate big geophysical data, substantial computational resources are needed in order to compute and/or store certain quantities (e.g., the Kalman-gain-type matrix), given both big model and data sizes. In addition, uncertainty quantification of observational data, e.g., in terms of estimating the observation error covariance matrix, also becomes computationally challenging, if not infeasible. To tackle the aforementioned challenges in the presence of big data, in a previous study, the authors proposed a wavelet-based sparse representation procedure for 2D seismic data assimilation problems (also known as history matching problems in petroleum engineering). In the current study, we extend the sparse representation procedure to 3D problems, as this is an important step towards real field case studies. To demonstrate the efficiency of the extended sparse representation procedure, we apply an ensemble-based seismic history matching framework with the extended sparse representation procedure to a 3D benchmark case, the Brugge field. In this benchmark case study, the total number of seismic data is in the order of [Formula: see text]. We show that the wavelet-based sparse representation procedure is extremely efficient in reducing the size of seismic data, while preserving the salient features of seismic data. Moreover, even with a substantial data-size reduction through sparse representation, the ensemble-based seismic history matching framework can still achieve good estimation accuracy.

Comparative metagenomics reveals different hydrocarbon degradative abilities from enriched oil-drilling waste.

The oil drilling process generates large volumes of waste with inadequate treatments. Here, oil drilling waste (ODW) microbial communities demonstrate different hydrocarbon degradative abilities when exposed to distinct nutrient enrichments as revealed by comparative metagenomics. The ODW was enriched in Luria Broth (LBE) and Potato Dextrose (PDE) media to examine the structure and functional variations of microbial consortia. Two metagenomes were sequenced on Ion Torrent platform and analyzed using MG-RAST. The STAMP software was used to analyze statistically significant differences amongst different attributes of metagenomes. The microbial diversity presented in the different enrichments was distinct and heterogeneous. The metabolic pathways and enzymes were mainly related to the aerobic hydrocarbons degradation. Moreover, our results showed efficient biodegradation after 15 days of treatment for aliphatic hydrocarbons (C8-C33) and polycyclic aromatic hydrocarbons (PAHs), with a total of about 50.5% and 46.4% for LBE and 44.6% and 37.9% for PDE, respectively. The results obtained suggest the idea that the enzymatic apparatus have the potential to degrade petroleum compounds.

Application of ultrahigh-performance liquid chromatography-quadrupole time-of-flight mass spectrometry for the characterization of organic aerosol: Searching for naphthenic acids.

Naphthenic acids (NAs) are naturally occurring constituents of hydrocarbon deposits (petroleum, oil sands bitumen, and crude oils), and present in any facilities that extract, process or use crude oil or bitumen for manufacturing. In the Athabasca oil sands region (AOSR) of Alberta, Canada, this diverse group of saturated acyclic, monocyclic, and polycyclic carboxylic acids is present in bitumen and in tailing ponds. Little is known about the occurrence of residual oil sands derived organic material, including NAs, in atmospheric particulate matter (PM). This work describes the optimization of an ultrahigh-performance liquid chromatography-quadrupole time-of-flight mass spectrometry (UPLC/QTOF-MS) method to characterize and identify classical NAs in atmospheric PM. Under the optimum conditions, analysis of the Sigma-Aldrich technical NA STD Mix showed the absence of saturated fatty acids, while branched and cyclic NAs isomers with carbon number ranged between 10 and 30, and Z families between 0 and -12 were detected. Higher molecular weight NAs representing compounds with carbon number ranging between 30 and 40 were identified in the analyzed PM samples collected in AOSR. In contrast, isomeric branched acyclic NAs were not detected in the background (PM-R) samples collected far from AOSR. Except for fatty acids (Z=0), other Z homologues were also not detectable or present at very low concentration in the analysed PM-R samples. Preliminary examination of NA profiles showed that the composition of NAs in PM collected in close proximity to surface mining operations is predominantly "refractory" high molecular weight branched NAs, differing from that collected closer to upgraders and tailings ponds. It is suspected that dust released from the mine faces and dry tailings in the AOSR are sources of NAs to atmosphere. Further samples should be examined to confirm findings. This preliminary study presents, to our knowledge, the first direct identification of branched acyclic and cyclic NAs in atmospheric PM.

[Changes of microbial abundance and functional genes in oil and gas under gaseous hydrocarbon condition].

Objective: Hydrocarbon microseepage is a natural phenomenon that hydrocarbon gases of subsurface petroleum accumulations migrate upward by reservoir pressure. The detection of the activity and distribution of these highly specialized populations can be used to forecast the existence of oil and gas deposits. However, the hydrocarbon-oxidizing bacterial population are usually not predominant in soil samples above the typical onshore oil and gas reservoirs. It is hard to assess the abundance of hydrocarbon-oxidizing bacteria. Methods: In this study, changes of microbial abundance and functional genes were studied. Results: Under gaseous hydrocarbon condition, changes of methane and butane oxidizing bacteria were different. Furthermore, changes of functional genes indicated that genome analysis was more proper for microbial anomalies detection. Conclusion: The profiling data of this study provide a comprehensive insight into gene expression profiles and lay the foundation for optimizing the microbial prospecting technology.

Activation of CO2-reducing methanogens in oil reservoir after addition of nutrient.

Nutrient addition as part of microbial enhanced oil recovery (MEOR) operations have important implications for more energy recovery from oil reservoirs, but very little is known about the in situ response of microorganisms after intervention. An analysis of two genes as biomarkers, mcrA encoding the key enzyme in methanogenesis and fthfs encoding the key enzyme in acetogenesis, was conducted during nutrient addition in oil reservoir. Clone library data showed that dominant mcrA sequences changed from acetoclastic (Methanosaetaceae) to CO2-reducing methanogens (Methanomicrobiales and Methanobacteriales), and the authentic acetogens affiliated to Firmicutes decreased after the intervention. Principal coordinates analysis (PCoA) and Jackknife environment clusters revealed evidence on the shift of the microbial community structure among the samples. Quantitative analysis of methanogens via qPCR showed that Methanobacteriales and Methanomicrobiales increased after nutrient addition, while acetoclastic methanogens (Methanosaetaceae) changed slightly. Nutrient treatment activated native CO2-reducing methanogens in oil reservoir. The high frequency of Methanobacteriales and Methanomicrobiales (CO2-reducers) after nutrient addition in this petroleum system suggested that CO2-reducing methanogenesis was involved in methane production. The nutrient addition could promote the methane production. The results will likely improve strategies of utilizing microorganisms in subsurface environments.

Foam front propagation in anisotropic oil reservoirs.

The pressure-driven growth model is considered, describing the motion of a foam front through an oil reservoir during foam improved oil recovery, foam being formed as gas advances into an initially liquid-filled reservoir. In the model, the foam front is represented by a set of so-called "material points" that track the advance of gas into the liquid-filled region. According to the model, the shape of the foam front is prone to develop concave sharply curved concavities, where the orientation of the front changes rapidly over a small spatial distance: these are referred to as "concave corners". These concave corners need to be propagated differently from the material points on the foam front itself. Typically the corner must move faster than those material points, otherwise spurious numerical artifacts develop in the computed shape of the front. A propagation rule or "speed up" rule is derived for the concave corners, which is shown to be sensitive to the level of anisotropy in the permeability of the reservoir and also sensitive to the orientation of the corners themselves. In particular if a corner in an anisotropic reservoir were to be propagated according to an isotropic speed up rule, this might not be sufficient to suppress spurious numerical artifacts, at least for certain orientations of the corner. On the other hand, systems that are both heterogeneous and anisotropic tend to be well behaved numerically, regardless of whether one uses the isotropic or anisotropic speed up rule for corners. This comes about because, in the heterogeneous and anisotropic case, the orientation of the corner is such that the "correct" anisotropic speed is just very slightly less than the "incorrect" isotropic one. The anisotropic rule does however manage to keep the corner very slightly sharper than the isotropic rule does.

Volatile-organic molecular characterization of shale-oil produced water from the Permian Basin.

Growth in unconventional oil and gas has spurred concerns on environmental impact and interest in beneficial uses of produced water (PW), especially in arid regions such as the Permian Basin, the largest U.S. tight-oil producer. To evaluate environmental impact, treatment, and reuse potential, there is a need to characterize the compositional variability of PW. Although hydraulic fracturing has caused a significant increase in shale-oil production, there are no high-resolution organic composition data for the shale-oil PW from the Permian Basin or other shale-oil plays (Eagle Ford, Bakken, etc.). PW was collected from shale-oil wells in the Midland sub-basin of the Permian Basin. Molecular characterization was conducted using high-resolution solid phase micro extraction gas chromatography time-of-flight mass spectrometry. Approximately 1400 compounds were identified, and 327 compounds had a >70% library match. PW contained alkane, cyclohexane, cyclopentane, BTEX (benzene, toluene, ethylbenzene, and xylene), alkyl benzenes, propyl-benzene, and naphthalene. PW also contained heteroatomic compounds containing nitrogen, oxygen, and sulfur. 3D van Krevelen and double bond equivalence versus carbon number analyses were used to evaluate molecular variability. Source composition, as well as solubility, controlled the distribution of volatile compounds found in shale-oil PW. The salinity also increased with depth, ranging from 105 to 162 g/L total dissolved solids. These data fill a gap for shale-oil PW composition, the associated petroleomics plots provide a fingerprinting framework, and the results for the Permian shale-oil PW suggest that partial treatment of suspended solids and organics would support some beneficial uses such as onsite reuse and bio-energy production.

Comprehensive Chemical Characterization of Hydrocarbons in NIST Standard Reference Material 2779 Gulf of Mexico Crude Oil.

Comprehensive chemical information is needed to understand the environmental fate and impact of hydrocarbons released during oil spills. However, chemical information remains incomplete because of the limitations of current analytical techniques and the inherent chemical complexity of crude oils. In this work, gas chromatography (GC)-amenable C9-C33 hydrocarbons were comprehensively characterized from the National Institute of Standards and Technology Standard Reference Material (NIST SRM) 2779 Gulf of Mexico crude oil by GC coupled to vacuum ultraviolet photoionization mass spectrometry (GC/VUV-MS), with a mass balance of 68 ± 22%. This technique overcomes one important limitation faced by traditional GC and even comprehensive 2D gas chromatography (GC×GC): the necessity for individual compounds to be chromatographically resolved from one another in order to be characterized. VUV photoionization minimizes fragmentation of the molecular ions, facilitating the characterization of the observed hydrocarbons as a function of molecular weight (carbon number, NC), structure (number of double bond equivalents, NDBE), and mass fraction (mg kg(-1)), which represent important metrics for understanding their fate and environmental impacts. Linear alkanes (8 ± 1%), branched alkanes (11 ± 2%), and cycloalkanes (37 ± 12%) dominated the mass with the largest contribution from cycloalkanes containing one or two rings and one or more alkyl side chains (27 ± 9%). Linearity and good agreement with previous work for a subset of >100 components and for the sum of compound classes provided confidence in our measurements and represents the first independent assessment of our analytical approach and calibration methodology. Another crude oil collected from the Marlin platform (35 km northeast of the Macondo well) was shown to be chemically identical within experimental errors to NIST SRM 2779, demonstrating that Marlin crude is an appropriate surrogate oil for researchers conducting laboratory research into impacts of the DeepWater Horizon disaster.

Well-to-Wheels Greenhouse Gas Emissions of Canadian Oil Sands Products: Implications for U.S. Petroleum Fuels.

Greenhouse gas (GHG) regulations affecting U.S. transportation fuels require holistic examination of the life-cycle emissions of U.S. petroleum feedstocks. With an expanded system boundary that included land disturbance-induced GHG emissions, we estimated well-to-wheels (WTW) GHG emissions of U.S. production of gasoline and diesel sourced from Canadian oil sands. Our analysis was based on detailed characterization of the energy intensities of 27 oil sands projects, representing industrial practices and technological advances since 2008. Four major oil sands production pathways were examined, including bitumen and synthetic crude oil (SCO) from both surface mining and in situ projects. Pathway-average GHG emissions from oil sands extraction, separation, and upgrading ranged from ∼6.1 to ∼27.3 g CO2 equivalents per megajoule (in lower heating value, CO2e/MJ). This range can be compared to ∼4.4 g CO2e/MJ for U.S. conventional crude oil recovery. Depending on the extraction technology and product type output of oil sands projects, the WTW GHG emissions for gasoline and diesel produced from bitumen and SCO in U.S. refineries were in the range of 100-115 and 99-117 g CO2e/MJ, respectively, representing, on average, about 18% and 21% higher emissions than those derived from U.S. conventional crudes. WTW GHG emissions of gasoline and diesel derived from diluted bitumen ranged from 97 to 103 and 96 to 104 g CO2e/MJ, respectively, showing the effect of diluent use on fuel emissions.

Treatment of heavy oil wastewater by UASB-BAFs using the combination of yeast and bacteria.

A novel system integrating an upflow anaerobic sludge blanket (UASB) reactor and a two-stage biological aerated filter (BAF) system was investigated as advanced treatment of heavy oil wastewater with large amounts of dissolved recalcitrant organic substances and low levels of nitrogen and phosphorus nutrients. #1 BAF, inoculated with two yeast strains (Candida tropicalis and Rhodotorula dairenensis), was installed in the upper reaches of #2 BAF inoculated with activated sludge. During the 180-day study period, the chemical oxygen demand (COD), ammonia nitrogen (NH3-N), oil and polyaromatic hydrocarbons (PAHs) in the wastewater were removed by 90.2%, 90.8%, 86.5% and 89.4%, respectively. Although the wastewater qualities fluctuated and the hydraulic retention time continuously decreased, the effluent quality index met the national discharge standard steadily. The UASB process greatly improved the biodegradability of the wastewater, while #1 BAF played an important role not only in degrading COD but also in removing oil and high molecular weight PAHs. This work demonstrates that the hybrid UASB-BAFs system containing yeast-bacteria consortium has the potential to be used in bioremediation of high-strength oily wastewater.

Bicyclic naphthenic acids in oil sands process water: identification by comprehensive multidimensional gas chromatography-mass spectrometry.

Although bicyclic acids have been reported to be the major naphthenic acids in oil sands process-affected water (OSPW) and a well-accepted screening assay indicated that some bicyclics were the most acutely toxic acids tested, none have yet been identified. Here we show by comprehensive multidimensional gas chromatography-mass spectrometry (GC×GC-MS), that >100 C8-15 bicyclic acids are typically present in OSPW. Synthesis or purchase allowed us to establish the GC×GC retention times of methyl esters of numerous of these and the mass spectra and published spectra of some additional types, allowed us to identify bicyclo[2.2.1]heptane, bicyclo[3.2.1]octane, bicyclo[4.3.0]nonane, bicyclo[3.3.1]nonane and bicyclo[4.4.0]decane acids in OSPW and a bicyclo[2.2.2]octane acid in a commercial acid mixture. The retention positions of authentic bicyclo[3.3.0]octane and bicyclo[4.2.0]octane carboxylic acid methyl esters and published retention indices, showed these were also possibilities, as were bicyclo[3.1.1]heptane acids. Bicyclo[5.3.0]decane and cyclopentylcyclopentane carboxylic acids were ruled out in the samples analysed, on the basis that the corresponding alkanes eluted well after bicyclo[4.4.0]decane (latest eluting acids). Bicyclo[4.2.1]nonane, bicyclo[3.2.2]nonane, bicyclo[3.3.2]decane, bicyclo[4.2.2]decane and spiro[4.5]decane carboxylic acids could not be ruled out or in, as no authentic compounds or literature data were available. Mass spectra of the methyl esters of the higher bicyclic C12-15 acids suggested that many were simply analogues of the acids identified above, with longer alkanoate chains and/or alkyl substituents. Our hypothesis is that these acids represent the biotransformation products of the initially somewhat more bio-resistant bicyclanes of petroleum. Although remediation studies suggest that many bicyclic acids can be relatively quickly removed from suitably treated OSPW, examination by GC×GC-MS may show which isomers are affected most. Knowledge of the structures will allow the toxicity of any residual isomers to be calculated and measured.

Combined hydrolysis acidification and bio-contact oxidation system with air-lift tubes and activated carbon bioreactor for oilfield wastewater treatment.

This paper investigated the enhancement of the COD reduction of an oilfield wastewater treatment process by installing air-lift tubes and adding an activated carbon bioreactor (ACB) to form a combined hydrolysis acidification and bio-contact oxidation system with air-lift tubes (HA/air-lift BCO) and an ACB. Three heat-resistant bacterial strains were cultivated and subsequently applied in above pilot plant test. Installing air-lift tubes in aerobic tanks reduced the necessary air to water ratio from 20 to 5. Continuous operation of the HA/air-lift BCO system for 2 months with a hydraulic retention time of 36 h, a volumetric load of 0.14 kg COD/(m(3)d) (hydrolysis-acidification or anaerobic tank), and 0.06 kg COD/(m(3)d) (aerobic tanks) achieved an average reduction of COD by 60%, oil and grease by 62%, total suspended solids by 75%, and sulfides by 77%. With a COD load of 0.56 kg/(m(3)d), the average COD in the ACB effluent was 58 mg/L.

Strontium isotopes test long-term zonal isolation of injected and Marcellus formation water after hydraulic fracturing.

One concern regarding unconventional hydrocarbon production from organic-rich shale is that hydraulic fracture stimulation could create pathways that allow injected fluids and deep brines from the target formation or adjacent units to migrate upward into shallow drinking water aquifers. This study presents Sr isotope and geochemical data from a well-constrained site in Greene County, Pennsylvania, in which samples were collected before and after hydraulic fracturing of the Middle Devonian Marcellus Shale. Results spanning a 15-month period indicated no significant migration of Marcellus-derived fluids into Upper Devonian/Lower Mississippian units located 900-1200 m above the lateral Marcellus boreholes or into groundwater sampled at a spring near the site. Monitoring the Sr isotope ratio of water from legacy oil and gas wells or drinking water wells can provide a sensitive early warning of upward brine migration for many years after well stimulation.

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),21ß(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.