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1.
Environ Res ; 252(Pt 3): 118972, 2024 Jul 01.
Article in English | MEDLINE | ID: mdl-38657851

ABSTRACT

This study aims to provide a thorough characterization of dissolved organics in oil sands process water (OSPW) in field-based aquatic mesocosms at both molecular and bulk measurement levels using multiple analytical methods. In a 3-year outdoor mesocosm experiment, the analysis of naphthenic acid (NA) species was conducted using ultra-performance liquid chromatography time-of-flight mass spectrometry (UPLC-TOFMS). The results revealed the removal of both total NAs (38% and 35%) and classical NAs (O2-NAs, 58% and 49%) in undiluted and half-diluted OSPW, respectively. The increased ratios of oxidized NAs (O3-O6 NAs) to classical NAs suggested a transformation trend. The results also indicated that O2-NAs with higher carbon number and lower double bond equivalent (DBE) were more easily degraded in the mesocosm systems. Biomimetic extraction using solid-phase microextraction (BE-SPME) measurement displayed 26% (undiluted OSPW) and 30% (half-diluted OSPW) decrease in total bioavailable organics over 3 years. Naphthenic acids fraction compounds (NAFCs) obtained by liquid-liquid extraction (LLE) were also determined using Fourier transform infrared spectroscopy (FTIR). Reduction in acute toxicity for undiluted (43%) and half-diluted (26%) OSPW was observed over 3 years, which are well correlated with the decreases of NAs and BE-SPME concentrations. Moreover, BE-SPME values were found to be linearly correlated with total NAs concentrations (r = 0.96) and NAFCs (r = 0.96). Additionally, the linear relationships of individual O2-O6 NA species and BE-SPME concentrations unveiled the changes in the relative abundances of O2-O6 NA species in total bioavailable organics over time in the mesocosms. The present study has provided comprehensive insights by integrating various analytical methods, contributing valuable information for assessing the effectiveness of aquatic mesocosm systems in studying the temporal changes of organics in OSPW.


Subject(s)
Oil and Gas Fields , Water Pollutants, Chemical , Water Pollutants, Chemical/analysis , Oil and Gas Fields/chemistry , Carboxylic Acids/analysis , Solid Phase Microextraction/methods , Mass Spectrometry/methods
2.
Proc Natl Acad Sci U S A ; 117(7): 3670-3677, 2020 02 18.
Article in English | MEDLINE | ID: mdl-32015108

ABSTRACT

The number of horizontally drilled shale oil and gas wells in the United States has increased from nearly 28,000 in 2007 to nearly 127,000 in 2017, and research has suggested the potential for the development of shale resources to affect nearby stream ecosystems. However, the ability to generalize current studies is limited by the small geographic scope as well as limited breadth and integration of measured chemical and biological indicators parameters. This study tested the hypothesis that a quantifiable, significant relationship exists between the density of oil and gas (OG) development, increasing stream water concentrations of known geochemical tracers of OG extraction, and the composition of benthic macroinvertebrate and microbial communities. Twenty-five headwater streams that drain lands across a gradient of shale gas development intensity were sampled. Our strategy included comprehensive measurements across multiple seasons of sampling to account for temporal variability of geochemical parameters, including known shale OG geochemical tracers, and microbial and benthic macroinvertebrate communities. No significant relationships were found between the intensity of OG development, shale OG geochemical tracers, or benthic macroinvertebrate or microbial community composition, whereas significant seasonal differences in stream chemistry were observed. These results highlight the importance of considering spatial and temporal variability in stream chemistry and biota and not only the presence of anthropogenic activities in a watershed. This comprehensive, integrated study of geochemical and biological variability of headwater streams in watersheds undergoing OG development provides a robust framework for examining the effects of energy development at a regional scale.


Subject(s)
Ecosystem , Oil and Gas Fields/chemistry , Rivers/chemistry , Animals , Bacteria/classification , Bacteria/genetics , Bacteria/isolation & purification , Environmental Monitoring , Invertebrates/classification , Invertebrates/growth & development , Pennsylvania , Rivers/microbiology , Rivers/parasitology
3.
Int J Mol Sci ; 23(3)2022 Jan 30.
Article in English | MEDLINE | ID: mdl-35163528

ABSTRACT

During the fracture stimulation of oil and gas wells, fracturing fluids are used to create fractures and transport the proppant into the fractured reservoirs. The fracturing fluid viscosity is responsible for proppant suspension, the viscosity can be increased through the incorporation of guar polymer and cross-linkers. After the fracturing operation, the fluid viscosity is decreased by breakers for efficient oil and gas recovery. Different types of enzyme breakers have been engineered and employed to reduce the fracturing fluid's viscosity, but thermal stability remains the major constraint for the use of enzymes. The latest enzyme engineering approaches such as direct evolution and rational design, have great potential to increase the enzyme breakers' thermostability against high temperatures of reservoirs. In this review article, we have reviewed recently advanced enzyme molecular engineering technologies and how these strategies could be used to enhance the thermostability of enzyme breakers in the upstream oil and gas industry.


Subject(s)
Enzymes/chemistry , Enzymes/metabolism , Protein Engineering/methods , Enzyme Stability , Oil and Gas Fields/chemistry , Oil and Gas Industry , Thermodynamics
4.
Appl Environ Microbiol ; 87(17): e0084221, 2021 08 11.
Article in English | MEDLINE | ID: mdl-34160245

ABSTRACT

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.


Subject(s)
Bacteria/drug effects , Disinfectants/pharmacology , Microbiota/drug effects , Acids/analysis , Acids/metabolism , Bacteria/classification , Bacteria/isolation & purification , Bacteria/metabolism , Oil and Gas Fields/chemistry , Oil and Gas Fields/microbiology , Oxidation-Reduction , Sulfates/analysis , Sulfates/metabolism , Time Factors
5.
Ecotoxicol Environ Saf ; 208: 111655, 2021 Jan 15.
Article in English | MEDLINE | ID: mdl-33396169

ABSTRACT

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.


Subject(s)
DNA Damage , Environmental Monitoring/methods , Fishes/genetics , Petroleum/toxicity , Water Pollutants, Chemical/toxicity , Animals , Comet Assay , Fishes/physiology , Hot Temperature , Hydrocarbons/analysis , Hydrocarbons/toxicity , Oil and Gas Fields/chemistry , Petroleum/analysis , Polycyclic Aromatic Hydrocarbons/analysis , Polycyclic Aromatic Hydrocarbons/toxicity , Refuse Disposal , Water Pollutants, Chemical/analysis
6.
Article in English | MEDLINE | ID: mdl-32427053

ABSTRACT

Understanding the physicochemical characteristics of oil-based cuttings (OBCs) is an important foundation for subsequent treatment and management. The macro- and microscopic properties of white oil-based cuttings (WOBCs) and diesel-based cuttings (DBCs) after the different pretreatment steps have been assessed using scanning electron microscopy. The organic and inorganic compositions of OBCs have been analyzed using X-ray diffraction, Fourier-transform infrared spectrometry, and gas chromatography-mass spectrometry. Inorganic matter (SiO2, BaSO4, and CaCO3), alkanes, aromatic compounds, and water were the main components of OBCs. The organic content (26.14%) and alkane content of the WOBCs were higher than that of the DBCs, whereas for the inorganic content (70.87%), the reverse was true. The macro- and micromorphologies of OBCs were quite different because their oil and water contents were different. The oil contents of OBCs decreased in the order A1 (14.64%) > A3 (12.67%) > A2 (11.06%) and B1 (9.19%) > B3 (8.94%) > B2 (4.66%); the water contents decreased in the order A1 (2.99%) > A3 (2.19%) > A2 (1.09%) and B1 (2.30%) > B3 (1.87%) > B2 (1.09%). Moreover, a skid-mounted treatment technology for OBCs was proposed. The results can be a scientific guidance for the treatment and management of OBCs.


Subject(s)
Hazardous Substances/chemistry , Inorganic Chemicals/chemistry , Mineral Oil/chemistry , Oil and Gas Fields/chemistry , Polycyclic Aromatic Hydrocarbons/chemistry , Water Purification/methods , Chemical Phenomena , Gas Chromatography-Mass Spectrometry , Hazardous Substances/analysis , Inorganic Chemicals/analysis , Mineral Oil/analysis , Natural Gas/analysis , Polycyclic Aromatic Hydrocarbons/analysis , Wastewater/analysis , Wastewater/chemistry , Water Pollutants, Chemical/analysis , Water Pollutants, Chemical/chemistry
8.
Ecotoxicol Environ Saf ; 170: 62-67, 2019 Apr 15.
Article in English | MEDLINE | ID: mdl-30529621

ABSTRACT

Oil sands process-affected water (OSPW), a byproduct of the extraction of bitumen in the surface mining of oil sands, is currently stored in massive on-site tailings ponds. Determining the potential effects of OSPW on aquatic ecosystems is of main concern to oil sands companies and legislators concerned about the reclamation of mining sites. In the present study, the interaction of OSPW with the chemosensory system of rainbow trout was studied. Using an electro-olfactography (EOG) technique, a 24 h inhibition curve was established and concentrations that inhibit the olfactory system by 20% and 80% (IC20 and IC80) were estimated at 3% and 22% OSPW, respectively. To study the interaction of exposure time and concentration along with the mechanism of the toxic effects, rainbow trout were exposed to 3% and 22% OSPW for 2, 24, and 96 h. An EOG investigation of olfactory sensitivity demonstrated a positive interaction between exposure time and concentration of OSPW concentration, because an increase in either or both elevated the inhibitory effect. To investigate whether or not structural damage of the olfactory epithelium could account for the observed inhibitory effects of OSPW on fish olfaction, the ultrastructure of the olfactory epithelium of exposed fish was investigated using scanning electron microscopy (SEM) and light microscopy (LM). The SEM micrographs showed no changes in the structure of the olfactory epithelium. The light micrographs revealed an increase in the number of mucous cells in 22% OSPW. The results of the present study demonstrated that exposure to OSPW impairs the olfactory system of rainbow trout and its effects increase gradually with increasing exposure time. The present study demonstrated that structural epithelial damage did not contribute to the inhibitory effects of OSPW on the olfactory system.


Subject(s)
Hydrocarbons/chemistry , Oil and Gas Fields/chemistry , Olfactory Bulb/physiopathology , Oncorhynchus mykiss , Water Pollutants, Chemical/toxicity , Animals , Inhibitory Concentration 50 , Olfactory Bulb/drug effects , Toxicity Tests
9.
Environ Monit Assess ; 191(8): 479, 2019 Jul 02.
Article in English | MEDLINE | ID: mdl-31267345

ABSTRACT

Energy reserves have been exploited in the Atlantic Canadian provinces since the early 1600s, and many fossil fuel extraction sites have been abandoned over this long history of energy development. Oil, natural gas, and coal extraction sites are a source of greenhouse gas emissions, particularly for methane (CH4). In this study, we used multiple sampling methods to measure CH4 from abandoned coal mine openings in Nova Scotia and a legacy oilfield in New Brunswick. Atmospheric and shallow soil gases were sampled around legacy sites using flux rate chamber measurements (spatial and temporal) and plot-scale atmospheric gas surveys, in addition to regional gas screening surveys over larger populations of sites to confirm whether small-scale observations were reflected regionally. Only one oil and gas site (2.4 ± 3.1⋅ 102 mg m- 2 day- 1) and one abandoned coal mine opening (1.0 ± 1.1⋅ 102 mg m- 2 day- 1) were affected by soil CH4 migration, though rates of leakage were minimal and would rank as low severity on industrial scales. Plot-scale atmospheric gas screening showed super-ambient CH4 concentrations at 5 sites in total (n = 16), 2 coal adits and 3 abandoned oil and gas wells. Regional gas screening surveys suggest that 11% of legacy oil and gas sites have some emission impacts, compared with 1-2% of legacy coal sites. These frequencies are close, albeit lower than the 15% of legacy oil and gas sites and 10% of abandoned coal mine openings flagged from our aggregated small-scale observations. These sites may emit less than other developments studied to date either because more time has elapsed since extraction, or because differences in regional geology reduce the likelihood of sustained emissions. This study provides valuable information to help understand the methane emission risks associated with legacy energy sites.


Subject(s)
Coal , Environmental Monitoring , Environmental Pollution/analysis , Greenhouse Gases/analysis , Methane/analysis , Natural Gas , New Brunswick , Nova Scotia , Oil and Gas Fields/chemistry , Soil/chemistry
10.
Wei Sheng Wu Xue Bao ; 57(1): 43-53, 2017 Jan 04.
Article in Zh | MEDLINE | ID: mdl-29746222

ABSTRACT

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.


Subject(s)
Bacteria/metabolism , Bacterial Proteins/genetics , Biodiversity , Hydrocarbons/metabolism , Bacteria/classification , Bacteria/genetics , Bacteria/isolation & purification , Bacterial Proteins/metabolism , Biodegradation, Environmental , Butanes/metabolism , Hydrocarbons/chemistry , Methane/metabolism , Oil and Gas Fields/chemistry , Oil and Gas Fields/microbiology , Petroleum/metabolism , Soil Microbiology
11.
Eur Phys J E Soft Matter ; 39(4): 42, 2016 Apr.
Article in English | MEDLINE | ID: mdl-27090239

ABSTRACT

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.


Subject(s)
Models, Theoretical , Oil and Gas Fields , Anisotropy , Motion , Oil and Gas Fields/chemistry , Petroleum , Pressure
12.
Nature ; 517(7535): 411-2, 2015 Jan 22.
Article in English | MEDLINE | ID: mdl-25612014
13.
Proc Natl Acad Sci U S A ; 110(49): 19731-6, 2013 Dec 03.
Article in English | MEDLINE | ID: mdl-24248376

ABSTRACT

Natural gas from tight shale formations will provide the United States with a major source of energy over the next several decades. Estimates of gas production from these formations have mainly relied on formulas designed for wells with a different geometry. We consider the simplest model of gas production consistent with the basic physics and geometry of the extraction process. In principle, solutions of the model depend upon many parameters, but in practice and within a given gas field, all but two can be fixed at typical values, leading to a nonlinear diffusion problem we solve exactly with a scaling curve. The scaling curve production rate declines as 1 over the square root of time early on, and it later declines exponentially. This simple model provides a surprisingly accurate description of gas extraction from 8,294 wells in the United States' oldest shale play, the Barnett Shale. There is good agreement with the scaling theory for 2,057 horizontal wells in which production started to decline exponentially in less than 10 y. The remaining 6,237 horizontal wells in our analysis are too young for us to predict when exponential decline will set in, but the model can nevertheless be used to establish lower and upper bounds on well lifetime. Finally, we obtain upper and lower bounds on the gas that will be produced by the wells in our sample, individually and in total. The estimated ultimate recovery from our sample of 8,294 wells is between 10 and 20 trillion standard cubic feet.


Subject(s)
Extraction and Processing Industry/methods , Extraction and Processing Industry/statistics & numerical data , Models, Theoretical , Natural Gas/analysis , Oil and Gas Fields/chemistry , Computer Simulation , Conservation of Energy Resources/statistics & numerical data , Natural Gas/economics , Texas
14.
Ecotoxicol Environ Saf ; 133: 281-9, 2016 Nov.
Article in English | MEDLINE | ID: mdl-27479772

ABSTRACT

Surface soils from Borholla oilfield in the upper Brahmaputra Valley in India were studied for the USEPA's 16 priority Polycyclic Aromatic Hydrocarbons (PAHs). Analysis of PAHs was carried out by high performance liquid chromatography (HPLC) system equipped with an UV detector. Seasonality in PAHs concentrations was evident and the concentrations were found to be greater in post-monsoon season. There has been a dominance of low molecular weight PAHs (80-90% of total PAHs) indicating recent deposition from combustion sources. The concentration profiles appeared in the decreasing order of 3-ring >2-ring >4-ring >5-ring >6 ring PAHs. The sources of PAHs were identified using isomer pair ratios and Principal Component Analysis-Multiple Linear Regression (PCA-MLR) and Positive Matrix Factorisation (PMF). The ratios of diagnostic pairs indicated for both pyrogenic and petrogenic input of PAHs. The PCA-MLR modelling revealed that the <16% of contribution came from petrogenic origin and the rest 85% was found to be from pyrogenic sources. The PMF model also shown that <19% of PAHs source were petrogenic origin whereas rest from pyrogenic origin. The correlations of black carbon (BC) with PAHs also supported the pyrogenic contribution. The analysis of air mass back trajectories revealed that there has been contribution of both local and distant sources, through long range transport of pollutants, which were deposited to the site.


Subject(s)
Environmental Monitoring , Oil and Gas Fields/chemistry , Polycyclic Aromatic Hydrocarbons/chemistry , Soil Pollutants/chemistry , Soil/chemistry , India , Linear Models , Models, Theoretical , Principal Component Analysis , Seasons
15.
Article in English | MEDLINE | ID: mdl-27220373

ABSTRACT

The aging oily wastewater (AOW) from Tarim oilfield in China was treated by demulsification/flocculation. A novel sewage treatment agent (YL-7) was developed using a cationic surfactant (LY) and flocculants (polydimethyl diallyl ammonium chloride (PDMDAAC)/polyaluminum chloride (PAC)). At an YL-7 dosage of 320 mg L(-1) at 323 K for 90 min, the oil content of AOW was reduced from 728.8 mg L(-1) to 23.7 mg L(-1), and oil removal efficiency reached 96.7%. Microorganism flocs (extracted from AOW) with high negative zeta potential enhanced the stability of oil/water emulsion. LY and PDMDAAC neutralized the negative charge on the oil droplet surface. PDMDAAC and PAC mainly bridged and swept flocs during the flocculation process. YL-7 was found to be a suitable sewage treatment agent in removing oil from AOW.


Subject(s)
Aluminum Hydroxide/chemistry , Environmental Restoration and Remediation/methods , Oil and Gas Fields/chemistry , Wastewater/chemistry , Water Pollutants, Chemical/chemistry , China , Flocculation , Hydrogen-Ion Concentration
16.
Environ Monit Assess ; 188(9): 542, 2016 Sep.
Article in English | MEDLINE | ID: mdl-27581009

ABSTRACT

Atmospheric deposition of polycyclic aromatic compounds (PACs) via and onto snow, and their releasing during spring snowmelt has been a concern in the Athabasca Oil Sands Region of Alberta. This study was designed to evaluate the concentrations, loadings, and distribution of PACs in springtime snowpack and how they have changed since the first study in 2008. Snowpack samples were collected in late winters 2011-2014 at varying distances from the main developments. PAC concentration and deposition declined exponentially with distance, with pyrenes, chrysenes, and dibenzothiophenes dominating the distribution within the first 50 km. The distribution of PACs was different between sites located close to upgraders and others located close to mining facilities. Overall, PAC loadings were correlated with priority pollutant elements and water chemistry parameters, while wind direction and speed were not strong contributors to the variability observed. Total PAC mass deposition during winter months and within the first 50 km was initially estimated by integrating the exponential decay function fitted through the data using a limited number of sites from 2011 to 2014: 1236 kg (2011), 1800 kg (2012), 814 kg (2013), and 1367 (2014). Total loadings were estimated to have a twofold increase between 2008 and 2014, although the increase observed was not constant. Finally, kriging interpolation is presented as an alternative and more robust approach to estimate PAC mass deposition in the area. After a more intensive sampling campaign in 2014, the PAC mass deposition was estimated to be 1968 kg.


Subject(s)
Oil and Gas Fields/chemistry , Polycyclic Aromatic Hydrocarbons/analysis , Snow/chemistry , Alberta , Environmental Monitoring , Seasons
17.
Rapid Commun Mass Spectrom ; 29(8): 735-44, 2015 Apr 30.
Article in English | MEDLINE | ID: mdl-26406488

ABSTRACT

RATIONALE: Approximately 1 billion m(3) of oil sands process-affected water (OSPW) is currently stored in tailings ponds in Northern Alberta, Canada. The dissolved organic compounds in OSPW have been termed a supercomplex mixture of bitumen-derived substances and continuing efforts to understand its underlying chemical composition are important for evaluating its environmental hazards. METHODS: Packed column supercritical fluid chromatography (SFC) was applied to OSPW analysis for the first time. By combining four columns in series (each 25 cm × 4.6 mm I.D., 5.0 µm bare silica) approximately 80,000 plates were achieved on a 1 m column. Using a simple fixed restrictor, the SFC eluent was coupled directly to ultrahigh-resolution orbitrap mass spectrometry (SFC/Orbitrap-MS). RESULTS: SFC/Orbitrap-MS, with positive and negative atmospheric pressure chemical ionization (APCI +/-), revealed the partial or full chromatographic separation of isomers for a wide array of chemical species, including naphthenic acids (Cn H2n + Z O2 ) and unknown sulfur- and nitrogen-containing molecules. For smaller compounds (e.g. naphthenic acids where n ≤10), or for larger structurally constrained compounds (e.g. C16 naphthenic acid with 9 double-bond equivalents), apparent baseline resolution of many isomers was possible. Isomer-specific MS/MS experiments furthermore allowed characterization of functional groups in novel species. For example, in APCI+ mode, up to 16 isomers of C6 H11 ON were revealed to have amide and amino functionalities. CONCLUSIONS: This combination of high efficiency chromatography and ultra-high mass resolution detection resulted in a powerful method with capabilities for characterizing or 'fingerprinting' unknown species with little interference. The method has great promise for environmental monitoring and forensics in the oil sands region, as well as for further studies on the composition of dissolved organic compounds in OSPW.


Subject(s)
Carboxylic Acids/analysis , Nitrogen Compounds/analysis , Oil and Gas Fields/chemistry , Sulfur Compounds/analysis , Water Pollutants, Chemical/analysis , Water/analysis , Chromatography, Supercritical Fluid/methods , Environmental Monitoring/methods , Mass Spectrometry/methods
18.
Environ Sci Technol ; 49(5): 2991-8, 2015 Mar 03.
Article in English | MEDLINE | ID: mdl-25602941

ABSTRACT

Results are reported from an ongoing passive air monitoring study for polycyclic aromatic compounds (PACs) in the Athabasca oil sands region in Alberta, Canada. Polyurethane foam (PUF) disk passive air samplers were deployed for consecutive 2-month periods from November 2010 to June 2012 at 17 sites. Samples were analyzed for polycyclic aromatic hydrocarbons (PAHs), alkylated PAHs, dibenzothiophene and its alkylated derivatives (DBTs). Relative to parent PAHs, alkylated PAHs and DBTs are enriched in bitumen and therefore considered to be petrogenic markers. Concentrations in air were in the range 0.03-210 ng/m(3), 0.15-230 ng/m(3) and 0.01-61 ng/m(3) for ∑PAHs, ∑alkylated PAHs and ΣDBTs, respectively. An exponential decline of the PAC concentrations in air with distance from mining areas and related petrogenic sources was observed. The most significant exponential declines were for the alkylated PAHs and DBTs and attributed to their association with mining-related emissions and near-source deposition, due to their lower volatility and greater association with depositing particles. Seasonal trends in concentrations in air for PACs were not observed for any of the compound classes. However, a forest fire episode during April to July 2011 resulted in greatly elevated PAH levels at all passive sampling locations. Alkylated PAHs and DBTs were not elevated during the forest fire period, supporting their association with petrogenic sources. Based on the results of this study, an "Athabasca PAC profile" is proposed as a potential source marker for the oil sands region. The profile is characterized by ∑PAHs/∑Alkylated PAHs = ∼0.2 and ∑PAHs/∑DBTs = ∼5.


Subject(s)
Air Pollutants/analysis , Environmental Monitoring/methods , Oil and Gas Fields/chemistry , Polycyclic Aromatic Hydrocarbons/analysis , Alberta
19.
Environ Sci Technol ; 49(22): 13130-8, 2015 Nov 17.
Article in English | MEDLINE | ID: mdl-26460682

ABSTRACT

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.


Subject(s)
Hydrocarbons/chemistry , Petroleum/analysis , Chromatography, Gas , Gulf of Mexico , Isomerism , Mass Spectrometry , Molecular Weight , Oil and Gas Fields/chemistry , Petroleum Pollution/analysis , Reference Standards , Temperature
20.
Environ Sci Technol ; 49(15): 9222-9, 2015 Aug 04.
Article in English | MEDLINE | ID: mdl-26186496

ABSTRACT

Recent studies suggest the possibility of CO2 sequestration in depleted shale gas formations, motivated by large storage capacity estimates in these formations. Questions remain regarding the dynamic response and practicality of injection of large amounts of CO2 into shale gas wells. A two-component (CO2 and CH4) model of gas flow in a shale gas formation including adsorption effects provides the basis to investigate the dynamics of CO2 injection. History-matching of gas production data allows for formation parameter estimation. Application to three shale gas-producing regions shows that CO2 can only be injected at low rates into individual wells and that individual well capacity is relatively small, despite significant capacity variation between shale plays. The estimated total capacity of an average Marcellus Shale well in Pennsylvania is 0.5 million metric tonnes (Mt) of CO2, compared with 0.15 Mt in an average Barnett Shale well. Applying the individual well estimates to the total number of existing and permitted planned wells (as of March, 2015) in each play yields a current estimated capacity of 7200-9600 Mt in the Marcellus Shale in Pennsylvania and 2100-3100 Mt in the Barnett Shale.


Subject(s)
Carbon Dioxide/analysis , Geologic Sediments/chemistry , Models, Theoretical , Oil and Gas Fields/chemistry , Computer Simulation , Methane/analysis , Natural Gas/analysis , Pennsylvania , Pressure , Time Factors
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