Results for “OILS” — Page 27

DOE OSTI2014

Metagenomics reveals sediment microbial community response to Deepwater Horizon oil spill

The Deepwater Horizon (DWH) oil spill in the spring of 2010 resulted in an input of ~4.1 million barrels of oil to the Gulf of Mexico; >22% of this oil is unaccounted for, with unknown environmental consequences. Here we investigated the impact of oil deposition on microbial communities in surface sediments collected at 64 sites by targeted sequencing of 16S rRNA genes, shotgun metagenomic sequencing of 14 of these samples and mineralization experiments using 14C-labeled model substrates. The 16S rRNA gene data indicated that the most heavily oil-impacted sediments were enriched in an uncultured Gammaproteobacterium and a Colwellia species, both of which were highly similar to sequences in the DWH deep-sea hydrocarbon plume. The primary drivers in structuring the microbial community were nitrogen and hydrocarbons. Annotation of unassembled metagenomic data revealed the most abundant hydrocarbon degradation pathway encoded genes involved in degrading aliphatic and simple aromatics via butane monooxygenase. The activity of key hydrocarbon degradation pathways by sediment microbes was confirmed by determining the mineralization of 14C-labeled model substrates in the following order: propylene glycol, dodecane, toluene and phenanthrene. Further, analysis of metagenomic sequence data revealed an increase in abundance of genes involved in denitrification pathways in samples that exceeded the Environmental Protection Agency (EPA)’s benchmarks for polycyclic aromatic hydrocarbons (PAHs) compared with those that did not. Importantly, these data demonstrate that the indigenous sediment microbiota contributed an important ecosystem service for remediation of oil in the Gulf. However, PAHs were more recalcitrant to degradation, and their persistence could have deleterious impacts on the sediment ecosystem.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2025

Water structure and electric fields at the interface of oil droplets

Interfacial water exhibits rich and complex behaviour, playing an important part in chemistry, biology, geology and engineering. However, there is still much debate on the fundamental properties of water at hydrophobic interfaces, such as orientational ordering, the concentration of hydronium and hydroxide, improper hydrogen bonds and the presence of large electric fields. This controversy arises from the challenges in measuring interfacial systems, even with the most advanced experimental techniques and theoretical approaches available. Here we report on an in-solution, interface-selective Raman spectroscopy method using multivariate curve resolution to probe hexadecane-in-water emulsions, aided by a monomer-field theoretical model for Raman spectroscopy. Our results indicate that oil-water emulsion interfaces can exhibit reduced tetrahedral order and weaker hydrogen bonding, along with a substantial population of free hydroxyl groups that experience about 95 cm -1 redshift in their stretching mode compared with planar oil-water interfaces. Given the known electrostatic zeta potential characteristic of oil droplets, we propose the existence of a strong electric field (about 50-90 MV cm -1 ) emanating from the oil phase. This field is inferred indirectly but supported by control experiments and theoretical estimates. These observations are either absent or opposite in the molecular hydrophobic interface formed by small solutes or at planar oil-water interfaces. Instead, water structural disorder and enhanced electric fields emerge as unique features of the mesoscale interface in oil-water emulsions, potentially contributing to the accelerated chemical reactivity observed at hydrophobic-water interfaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2017

Mitigating oil spills in the water column

The scale and scope of uncontrolled oil spills can be devastating. Diverse marine environments and fragile ecologies are some of the most susceptible to the many ill effects, while the economic costs can be crippling. A notoriously difficult challenge with no known technological solution is the successful removal of oil dispersed in the water column. Here, we address this problem through cheap and reusable oil sorbents based on the chemical modification of polymer foams. Interfacial chemistry was optimized and subsequently tested in a simulated marine environment at the National Oil Spill Response Research & Renewable Energy Test Facility, Ohmsett. We find favorable performance for surface oil mitigation and, for the first time, demonstrate the advanced sorbent's efficiency and efficacy at pilot scale in extraction of crude oil and refined petroleum products dispersed in the water column. As a result, this is a potentially disruptive technology, opening a new field of environmental science focused on sub-surface pollutant sequestration.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2024

Cycloalkane-rich sustainable aviation fuel production via hydrotreating lignocellulosic biomass-derived catalytic fast pyrolysis oils

Sustainable aviation fuel (SAF) produced from lignocellulosic biomass is emerging as an ideal alternative to conventional jet fuel for aviation sector decarbonization. Catalytic fast pyrolysis (CFP) can convert lignocellulosic biomass into relatively stable bio-oil that can be selectively transformed to various transportation fuels through hydroprocessing under conditions of different severities. In this contribution, two CFP oils produced from pine-based feedstocks over different types of catalysts (i.e., ZSM-5 and Pt/TiO 2 catalysts) were hydrotreated at 125 bar in a non-isothermal process with a maximum temperature of 385 °C over a sulfided NiMo/Al 2 O 3 catalyst to produce SAF with high cycloalkane concentrations of 89–92 wt%. Cycloalkanes are an important component of jet fuel with advantageous fuel properties, such as high energy density, low sooting, and potential for replacing aromatic hydrocarbons to provide good seal swelling properties. The hydrotreating process successfully converted 91–92% of the biogenic carbon in the CFP oil intermediates to liquid-phase hydrotreated products. Through distillation, 39–40 wt% of the hydrotreated oils were collected in the jet-fuel range as SAF fractions. The rest of the hydrotreated product could be valorized as fuels (e.g., diesel) or chemicals. The SAF fractions with oxygen contents below the detection limit (<0.01 wt%) met ASTM D7566 finished fuel blend and D4054 Tier 1 specifications with respect to density, lower heating value (LHV), volatility, flash point, and freeze point. These results indicate hydrotreating lignocellulosic biomass-derived CFP oil as a promising pathway to produce high-quality SAF rich in cycloalkanes. Continued research is required to increase the SAF yield by process improvements, such as increased CFP oil yields, and an enhanced production of SAF-range molecules via e.g., cracking of high-molecular weight compounds either during CFP or hydrotreating, as well as evaluation of a broader range of jet fuel properties and performance requirements.

09 BIOMASS FUELS↗

DOE OSTI2015

Metabolic engineering of oilseed crops to produce high levels of novel acetyl glyceride oils with reduced viscosity, freezing point and calorific value

Summary Seed oils have proved recalcitrant to modification for the production of industrially useful lipids. Here, we demonstrate the successful metabolic engineering and subsequent field production of an oilseed crop with the highest accumulation of unusual oil achieved so far in transgenic plants. Previously, expression of the E uonymus alatus diacylglycerol acetyltransferase ( E a DA c T ) gene in wild‐type A rabidopsis seeds resulted in the accumulation of 45 mol% of unusual 3‐acetyl‐1,2‐diacyl‐ sn ‐glycerols (acetyl‐ TAG s) in the seed oil (Durrett et al ., 2010 PNAS 107:9464). Expression of E a DA c T in dgat1 mutants compromised in their ability to synthesize regular triacylglycerols increased acetyl‐ TAG s to 65 mol%. Camelina and soybean transformed with the E a DA c T gene accumulate acetyl‐triacylglycerols (acetyl‐ TAG s) at up to 70 mol% of seed oil. A similar strategy of coexpression of E a DA c T together with RNA i suppression of DGAT 1 increased acetyl‐ TAG levels to up to 85 mol% in field‐grown transgenic C amelina. Additionally, total moles of triacylglycerol ( TAG ) per seed increased 20%. Analysis of the acetyl‐ TAG fraction revealed a twofold reduction in very long chain fatty acids ( VLCFA ), consistent with their displacement from the sn ‐3 position by acetate. Seed germination remained high, and seedlings were able to metabolize the stored acetyl‐ TAG s as rapidly as regular triacylglycerols. Viscosity, freezing point and caloric content of the C amelina acetyl‐ TAG oils were reduced, enabling use of this oil in several nonfood and food applications.

Liu, Jinjie↗

DOE OSTI2024

Development of vegetative oil sorghum: From lab‐to‐field

Summary Biomass crops engineered to accumulate energy‐dense triacylglycerols (TAG or ‘vegetable oils’) in their vegetative tissues have emerged as potential feedstocks to meet the growing demand for renewable diesel and sustainable aviation fuel (SAF). Unlike oil palm and oilseed crops, the current commercial sources of TAG, vegetative tissues, such as leaves and stems, only transiently accumulate TAG. In this report, we used grain (Texas430 or TX430) and sugar‐accumulating ‘sweet’ (Ramada) genotypes of sorghum, a high‐yielding, environmentally resilient biomass crop, to accumulate TAG in leaves and stems. We initially tested several gene combinations for a ‘push‐pull‐protect’ strategy. The top TAG‐yielding constructs contained five oil transgenes for a sorghum WRINKLED1 transcription factor (‘push’), a Cuphea viscosissima diacylglycerol acyltransferase (DGAT; ‘pull’), a modified sesame oleosin (‘protect’) and two combinations of specialized Cuphea lysophosphatidic acid acyltransferases and medium‐chain acyl‐acyl carrier protein thioesterases. Though intended to generate oils with medium‐chain fatty acids, engineered lines accumulated oleic acid‐rich oil to amounts of up to 2.5% DW in leaves and 2.0% DW in stems in the greenhouse, 36‐fold and 49‐fold increases relative to wild‐type (WT) plants, respectively. Under field conditions, the top‐performing event accumulated TAG to amount to 5.5% DW in leaves and 3.5% DW in stems, 78‐fold and 58‐fold increases, respectively, relative to WT TX430. Transcriptomic and fluxomic analyses revealed potential bottlenecks for increased TAG accumulation. Overall, our studies highlight the utility of a lab‐to‐field pipeline coupled with systems biology studies to deliver high vegetative oil sorghum for SAF and renewable diesel production.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2022

Data for Coprocessing Corn Germ Meal for Oil Recovery and Ethanol Production, a Process Model for Lipid-Producing Energy Crops

Efforts to engineer high-productivity crops to accumulate oils in their vegetative tissue present the possibility of expanding biodiesel production. However, processing the new crops for lipid recovery and ethanol production from cell wall saccharides is challenging and expensive. In a previous study using corn germ meal as a model substrate, we reported that liquid hot water (LHW) pretreatment enriched the lipid concentration by 2.2 to 4.2 fold. This study investigated combining oil recovery with ethanol production by extracting oil following LHW and simultaneous saccharification and co-fermentation (SSCF) of the biomass. Corn germ meal was again used to model the oil-bearing energy crops. Pretreated germ meal hydrolysate or solids (160 °C and 180 °C for 10 minutes) were fermented, and lipids were extracted from both the spent fermentation whole broth and fermentation solids, which were recovered by centrifugation and convective drying. Lipid contents in spent fermentation solids increased 3.7 to 5.7 fold compared to the beginning germ meal. The highest lipid yield achieved after fermentation was 36.0 mg lipid g−1 raw biomass; the maximum relative amount of triacylglycerol (TAG) was 50.9% of extracted oil. Although the fermentation step increased the lipid concentration of the recovered solids, it did not improve the lipid yields of pretreated biomass and detrimentally affected oil compositions by increasing the relative concentrations of free fatty acids.

Conversion↗

DOE OSTI2013

Brine-in-crude-oil emulsions at the Strategic Petroleum Reserve

Metastable water-in-crude-oil emulsion formation could occur in a Strategic Petroleum Reserve (SPR) cavern if water were to flow into the crude-oil layer at a sufficient rate. Such a situation could arise during a drawdown from a cavern with a broken-hanging brine string. A high asphaltene content (> 1.5 wt %) of the crude oil provides the strongest predictor of whether a metastable water-in-crude-oil emulsion will form. However there are many crude oils with an asphaltene content > 1.5 wt % that don't form stable emulsions, but few with a low asphaltene content that do form stable emulsions. Most of the oils that form stable emulsions are "sour" by SPR standards indicating they contain total sulfur > 0.50 wt %.

02 PETROLEUM↗

DOE OSTI2014

Modeling CO 2 Sequestration in Saline Aquifer and Depleted Oil Reservoir To Evaluate Regional CO 2 Sequestration Potential of Ozark Plateau Aquifer System, South-Central Kansas

1. Drilled, cored, and logged three wells to the basement and collecting more than 2,700 ft of conventional core; obtained 20 m i2 of multicomponent 3D seismic imaging and merged and reprocessed more than 125 mi 2 of existing 3D seismic data for use in modeling CO 2 - EOR oil recovery and CO 2 storage in five oil fields in southern Kansas. 2. Determined the technical feasibility of injecting and sequestering CO 2 in a set of four depleted oil reservoirs in the Cutter, Pleasant Prairie South, Eubank, and Shuck fields in southwest Kansas; of concurrently recovering oil from those fields; and of quantifying the volumes of CO2 sequestered and oil recovered during the process. 3. Formed a consortium of six oil operating companies, five of which own and operate the four fields. The consortium became part of the Southwest Kansas CO 2 -EOR Initiative for the purpose of sharing data, knowledge, and interest in understanding the potential for CO 2 -EOR in Kansas. 4. Built a regional well database covering 30,000 mi 2 and containing stratigraphic tops from ~90,000 wells; correlated 30 major stratigraphic horizons; digitized key wells, including wireline logs and sample logs; and analyzed more than 3,000 drill stem tests to establish that fluid levels in deep aquifers below the Permian evaporites are not connected to the surface and therefore pressures are not hydrostatic. Connectivity with the surface aquifers is lacking because shale aquitards and impermeable evaporite layers consist of both halite and anhydrite. 5. Developed extensive web applications and an interactive mapping system that do the following: a. Facilitate access to a wide array of data obtained in the study, including core descriptions and analyses, sample logs, digital (LAS) well logs, seismic data, gravity and magnetics maps, structural and stratigraphic maps, inferred fault traces, earthquakes, Class I and II disposal wells, and surface lineaments. b. Provide real-time analysis of the project dataset, including automated integration and viewing of well logs, core, core analyses, brine chemistry, and stratigraphy using the Java Profile app. A cross-section app allows for the display of log data for up to four wells at a time. 6. Integrated interpretations from the project’s interactive web-based mapping system to gain insights to aid in assessing the efficacy of geologic CO 2 storage in Kansas and insights toward understanding recent seismicity to aid in evaluating induced vs. naturally occurring earthquakes. 7. Developed a digital type-log system, including web-based software to modify and refine stratigraphic nomenclature to provide stakeholders a common means for communication about the subsurface. 8. Contracted use of a nuclear magnetic resonance (NMR) log and ran it slowly to capture response and characterize larger pores common for carbonate reservoirs. Used NMR to extend core analyses to apply permeability, relative permeability to CO 2 , and capillary pressure to the major rock types, each uniquely expressed as a reservoir quality index (RQI), present in the Mississippian and Arbuckle rocks. 9. Characterized and evaluated the possible role of microbes in dense brines. Used microbes to compliment H/O stable isotopes to fingerprint brine systems. Used perforation/swabbing to obtain samples from multiple hydrostratigraphic units and confirmed equivalent results using less expensive drill stem tests (DST). 10. Used an integrated approach from whole core, logs, tests, and seismic to verify and quantify properties of vuggy, brecciated, and fractured carbonate intervals. 11. Used complex geocellular static and dynamic models to evaluate regional storage capacity using large parallel processing. 12. Carbonates are complex reservoirs and CO 2 -EOR needs to move to the next generation to increase effectiveness of CO 2 and efficiency and safety of the injection.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2014

Modeling CO 2 Sequestration in Saline Aquifer and Depleted Oil Reservoir To Evaluate Regional CO 2 Sequestration Potential of Ozark Plateau Aquifer System, South-Central Kansas

1. Drilled, cored, and logged three wells to the basement and collecting more than 2,700 ft of conventional core; obtained 20 m i2 of multicomponent 3D seismic imaging and merged and reprocessed more than 125 mi 2 of existing 3D seismic data for use in modeling CO 2 - EOR oil recovery and CO 2 storage in five oil fields in southern Kansas. 2. Determined the technical feasibility of injecting and sequestering CO 2 in a set of four depleted oil reservoirs in the Cutter, Pleasant Prairie South, Eubank, and Shuck fields in southwest Kansas; of concurrently recovering oil from those fields; and of quantifying the volumes of CO2 sequestered and oil recovered during the process. 3. Formed a consortium of six oil operating companies, five of which own and operate the four fields. The consortium became part of the Southwest Kansas CO 2 -EOR Initiative for the purpose of sharing data, knowledge, and interest in understanding the potential for CO 2 -EOR in Kansas. 4. Built a regional well database covering 30,000 mi 2 and containing stratigraphic tops from ~90,000 wells; correlated 30 major stratigraphic horizons; digitized key wells, including wireline logs and sample logs; and analyzed more than 3,000 drill stem tests to establish that fluid levels in deep aquifers below the Permian evaporites are not connected to the surface and therefore pressures are not hydrostatic. Connectivity with the surface aquifers is lacking because shale aquitards and impermeable evaporite layers consist of both halite and anhydrite. 5. Developed extensive web applications and an interactive mapping system that do the following: a. Facilitate access to a wide array of data obtained in the study, including core descriptions and analyses, sample logs, digital (LAS) well logs, seismic data, gravity and magnetics maps, structural and stratigraphic maps, inferred fault traces, earthquakes, Class I and II disposal wells, and surface lineaments. b. Provide real-time analysis of the project dataset, including automated integration and viewing of well logs, core, core analyses, brine chemistry, and stratigraphy using the Java Profile app. A cross-section app allows for the display of log data for up to four wells at a time. 6. Integrated interpretations from the project’s interactive web-based mapping system to gain insights to aid in assessing the efficacy of geologic CO 2 storage in Kansas and insights toward understanding recent seismicity to aid in evaluating induced vs. naturally occurring earthquakes. 7. Developed a digital type-log system, including web-based software to modify and refine stratigraphic nomenclature to provide stakeholders a common means for communication about the subsurface. 8. Contracted use of a nuclear magnetic resonance (NMR) log and ran it slowly to capture response and characterize larger pores common for carbonate reservoirs. Used NMR to extend core analyses to apply permeability, relative permeability to CO 2 , and capillary pressure to the major rock types, each uniquely expressed as a reservoir quality index (RQI), present in the Mississippian and Arbuckle rocks. 9. Characterized and evaluated the possible role of microbes in dense brines. Used microbes to compliment H/O stable isotopes to fingerprint brine systems. Used perforation/swabbing to obtain samples from multiple hydrostratigraphic units and confirmed equivalent results using less expensive drill stem tests (DST). 10. Used an integrated approach from whole core, logs, tests, and seismic to verify and quantify properties of vuggy, brecciated, and fractured carbonate intervals. 11. Used complex geocellular static and dynamic models to evaluate regional storage capacity using large parallel processing. 12. Carbonates are complex reservoirs and CO 2 -EOR needs to move to the next generation to increase effectiveness of CO 2 and efficiency and safety of the injection.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2014

Modeling CO 2 Sequestration in Saline Aquifer and Depleted Oil Reservoir To Evaluate Regional CO 2 Sequestration Potential of Ozark Plateau Aquifer System, South-Central Kansas

1. Drilled, cored, and logged three wells to the basement and collecting more than 2,700 ft of conventional core; obtained 20 m i2 of multicomponent 3D seismic imaging and merged and reprocessed more than 125 mi 2 of existing 3D seismic data for use in modeling CO 2 - EOR oil recovery and CO 2 storage in five oil fields in southern Kansas. 2. Determined the technical feasibility of injecting and sequestering CO 2 in a set of four depleted oil reservoirs in the Cutter, Pleasant Prairie South, Eubank, and Shuck fields in southwest Kansas; of concurrently recovering oil from those fields; and of quantifying the volumes of CO2 sequestered and oil recovered during the process. 3. Formed a consortium of six oil operating companies, five of which own and operate the four fields. The consortium became part of the Southwest Kansas CO 2 -EOR Initiative for the purpose of sharing data, knowledge, and interest in understanding the potential for CO 2 -EOR in Kansas. 4. Built a regional well database covering 30,000 mi 2 and containing stratigraphic tops from ~90,000 wells; correlated 30 major stratigraphic horizons; digitized key wells, including wireline logs and sample logs; and analyzed more than 3,000 drill stem tests to establish that fluid levels in deep aquifers below the Permian evaporites are not connected to the surface and therefore pressures are not hydrostatic. Connectivity with the surface aquifers is lacking because shale aquitards and impermeable evaporite layers consist of both halite and anhydrite. 5. Developed extensive web applications and an interactive mapping system that do the following: a. Facilitate access to a wide array of data obtained in the study, including core descriptions and analyses, sample logs, digital (LAS) well logs, seismic data, gravity and magnetics maps, structural and stratigraphic maps, inferred fault traces, earthquakes, Class I and II disposal wells, and surface lineaments. b. Provide real-time analysis of the project dataset, including automated integration and viewing of well logs, core, core analyses, brine chemistry, and stratigraphy using the Java Profile app. A cross-section app allows for the display of log data for up to four wells at a time. 6. Integrated interpretations from the project’s interactive web-based mapping system to gain insights to aid in assessing the efficacy of geologic CO 2 storage in Kansas and insights toward understanding recent seismicity to aid in evaluating induced vs. naturally occurring earthquakes. 7. Developed a digital type-log system, including web-based software to modify and refine stratigraphic nomenclature to provide stakeholders a common means for communication about the subsurface. 8. Contracted use of a nuclear magnetic resonance (NMR) log and ran it slowly to capture response and characterize larger pores common for carbonate reservoirs. Used NMR to extend core analyses to apply permeability, relative permeability to CO 2 , and capillary pressure to the major rock types, each uniquely expressed as a reservoir quality index (RQI), present in the Mississippian and Arbuckle rocks. 9. Characterized and evaluated the possible role of microbes in dense brines. Used microbes to compliment H/O stable isotopes to fingerprint brine systems. Used perforation/swabbing to obtain samples from multiple hydrostratigraphic units and confirmed equivalent results using less expensive drill stem tests (DST). 10. Used an integrated approach from whole core, logs, tests, and seismic to verify and quantify properties of vuggy, brecciated, and fractured carbonate intervals. 11. Used complex geocellular static and dynamic models to evaluate regional storage capacity using large parallel processing. 12. Carbonates are complex reservoirs and CO 2 -EOR needs to move to the next generation to increase effectiveness of CO 2 and efficiency and safety of the injection.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2014

Modeling CO 2 Sequestration in Saline Aquifer and Depleted Oil Reservoir To Evaluate Regional CO 2 Sequestration Potential of Ozark Plateau Aquifer System, South-Central Kansas

1. Drilled, cored, and logged three wells to the basement and collecting more than 2,700 ft of conventional core; obtained 20 m i2 of multicomponent 3D seismic imaging and merged and reprocessed more than 125 mi 2 of existing 3D seismic data for use in modeling CO 2 - EOR oil recovery and CO 2 storage in five oil fields in southern Kansas. 2. Determined the technical feasibility of injecting and sequestering CO 2 in a set of four depleted oil reservoirs in the Cutter, Pleasant Prairie South, Eubank, and Shuck fields in southwest Kansas; of concurrently recovering oil from those fields; and of quantifying the volumes of CO2 sequestered and oil recovered during the process. 3. Formed a consortium of six oil operating companies, five of which own and operate the four fields. The consortium became part of the Southwest Kansas CO 2 -EOR Initiative for the purpose of sharing data, knowledge, and interest in understanding the potential for CO 2 -EOR in Kansas. 4. Built a regional well database covering 30,000 mi 2 and containing stratigraphic tops from ~90,000 wells; correlated 30 major stratigraphic horizons; digitized key wells, including wireline logs and sample logs; and analyzed more than 3,000 drill stem tests to establish that fluid levels in deep aquifers below the Permian evaporites are not connected to the surface and therefore pressures are not hydrostatic. Connectivity with the surface aquifers is lacking because shale aquitards and impermeable evaporite layers consist of both halite and anhydrite. 5. Developed extensive web applications and an interactive mapping system that do the following: a. Facilitate access to a wide array of data obtained in the study, including core descriptions and analyses, sample logs, digital (LAS) well logs, seismic data, gravity and magnetics maps, structural and stratigraphic maps, inferred fault traces, earthquakes, Class I and II disposal wells, and surface lineaments. b. Provide real-time analysis of the project dataset, including automated integration and viewing of well logs, core, core analyses, brine chemistry, and stratigraphy using the Java Profile app. A cross-section app allows for the display of log data for up to four wells at a time. 6. Integrated interpretations from the project’s interactive web-based mapping system to gain insights to aid in assessing the efficacy of geologic CO 2 storage in Kansas and insights toward understanding recent seismicity to aid in evaluating induced vs. naturally occurring earthquakes. 7. Developed a digital type-log system, including web-based software to modify and refine stratigraphic nomenclature to provide stakeholders a common means for communication about the subsurface. 8. Contracted use of a nuclear magnetic resonance (NMR) log and ran it slowly to capture response and characterize larger pores common for carbonate reservoirs. Used NMR to extend core analyses to apply permeability, relative permeability to CO 2 , and capillary pressure to the major rock types, each uniquely expressed as a reservoir quality index (RQI), present in the Mississippian and Arbuckle rocks. 9. Characterized and evaluated the possible role of microbes in dense brines. Used microbes to compliment H/O stable isotopes to fingerprint brine systems. Used perforation/swabbing to obtain samples from multiple hydrostratigraphic units and confirmed equivalent results using less expensive drill stem tests (DST). 10. Used an integrated approach from whole core, logs, tests, and seismic to verify and quantify properties of vuggy, brecciated, and fractured carbonate intervals. 11. Used complex geocellular static and dynamic models to evaluate regional storage capacity using large parallel processing. 12. Carbonates are complex reservoirs and CO 2 -EOR needs to move to the next generation to increase effectiveness of CO 2 and efficiency and safety of the injection.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2018

Using Meta-Analysis to Estimate World Oil Demand Elasticity

Oil demand elasticities are important behavioral parameters for assessing the effectiveness of many energy policy proposals and the economic impact of oil market shocks. Most of the literature on petroleum demand computes elasticities for one particular petroleum product in a country or group of countries. There are fewer published values for world oil demand elasticity because the reduced-form single equation approach used in much of the petroleum product demand literature leads to endogeneity bias when applied to global demand. This study uses meta-analysis techniques to compute world oil demand elasticity. Metaregressions are first conducted to identify sources of variation in elasticity estimates for transportation and non-transportation sectors collected from 75 studies published from 2000 to 2015. The estimated coefficients from the metaregressions are then summarized into elasticity baseline values for several combinations of moderator variable values. Finally, a global oil demand elasticity is computed as the consumption-weighted average of the two sectoral elasticities. Resulting mean values for the short-run oil demand elasticities with respect to price range from -0.7 to -0.14 depending on the attributes selected for the price variable. The long-run range of mean values is much wider (-0.26, -0.83).

Uria Martinez, Rocio↗

DOE OSTI2020

2020 Annual Report of Available Drawdowns for Each Oil Storage Cavern in the Strategic Petroleum Reserve

The Department of Energy maintains an up-to-date documentation of the number of available full drawdowns of each of the caverns owned by the Strategic Petroleum Reserve (SPR). This information is important for assessing the SPR's ability to deliver oil to domestic oil companies expeditiously if national or world events dictate a rapid sale and deployment of the oil reserves. Sandia was directed to develop and implement a process to continuously assess and report the evolution of drawdown capacity, the subject of this report. A cavern has an available drawdown if after that drawdown, the long-term stability of the cavern, the cavern field, or the oil quality are not compromised. Thus, determining the number of available drawdowns requires the consideration of several factors regarding cavern and wellbore integrity and stability, including stress states caused by cavern geometry and operations, salt damage caused by dilatant and tensile stresses, the effect of enhanced creep on wellbore integrity, and the sympathetic stress effect of operations on neighboring caverns. A consensus has now been built regarding the assessment of drawdown capabilities and risks for the SPR caverns. The process involves an initial assessment of the pillar-to-diameter (P/D) ratio for each cavern with respect to neighboring caverns. A large pillar thickness between adjacent caverns should be strong enough to withstand the stresses induced by closure of the caverns due to salt creep. The first evaluation of P/D includes a calculation of the evolution of P/D after a number of full cavern drawdowns. The most common storage industry standard is to keep this value greater than 1.0, which should ensure a pillar thick enough to prevent loss of fluids to the surrounding rock mass. However, many of the SPR caverns currently have a P/D less than 1.0 or will likely have a low P/D after one or two full drawdowns. For these caverns, it is important to examine the structural integrity with more detail using geomechanical models. Finite-element geomechanical models have been used to determine the stress states in the pillars following successive drawdowns. By computing the tensile and dilatant stresses in the salt, areas of potential structural instability can be identified that may represent "red flags" for additional drawdowns. These analyses have found that many caverns will maintain structural integrity even when grown via drawdowns to dimensions resulting in a P/D of less than 1.0. The analyses have also confirmed that certain caverns should only be completely drawn down one time. As the SPR caverns are utilized and partial drawdowns are performed to remove oil from the caverns (e.g., for occasional oil sales authorized by the Congress or the President), the changes to the cavern caused by these procedures must be tracked and accounted for so that an ongoing assessment of the cavern's drawdown capacity may be continued. A proposed methodology for assessing and tracking the available drawdowns for each cavern was presented in Sobolik et al. (2018). This report includes an update to the baseline drawdowns for each cavern, and provides an initial assessment of the evolution of drawdown expenditure for several caverns

02 PETROLEUM↗

DOE OSTI2020

Development of Ionic Liquid-Additized, GF-5/6 Compatible Low-Viscosity Oils for Automotive Engine and Rear Axle Lubrication for 4% Improved Fuel Economy

This joint project among ORNL, GM, and DRO successfully developed ionic liquid-additized low viscosity lubricants, SAE 0W-12 and 70W-80, for both IC engine and rear axle lubrication, respectively, and demonstrated combined vehicle fuel economy improvement (FEI). Phosphonium-alkylphosphate ILs have been found to be the most effective among the candidates in protecting surface damage from both sliding wear and rolling contact fatigue, and optimal IL concentrations have been determined. The IL’s impact on three-way catalyst seems to be significantly less adverse than the conventional ZDDP. Oil formulations were optimized for both energy efficiency and wear protection. Tribological bench testing of the IL-additized low-viscosity oils showed at least 40% lower boundary friction, more than 60% lower elastohydrodynamic friction, and greater than 50% less wear compared with commercial baselines. IL-additized lubricants have demonstrated FEI by 9.9% in engine dynamometer tests under extreme conditions and 6.9% increased power output in gear rig tests. Prototype IL-additized engine oil and rear axle fluid exhibited combined FEI of 1.39% and 3.24% benchmarked against the state-of-the-art baselines in vehicle testing of fresh oils under the Federal Test Procedure (FTP) city cycle and Highway Fuel Economy Driving Schedule (HWFET), respectively. Used oil analysis suggested that the IL-additized low-viscosity oils produced less wear than the commercial baselines. The gained fundamental understanding and demonstrated FEI in this work pave the way for future development and implementation of the ionic liquid technology.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Available Drawdowns for Each Oil Storage Cavern in the Strategic Petroleum Reserve (2021 Annual Report)

The Department of Energy maintains an up-to-date documentation of the number of available full drawdowns of each of the caverns owned by the Strategic Petroleum Reserve (SPR). This information is important for assessing the SPRs ability to deliver oil to domestic oil companies expeditiously if national or world events dictate a rapid sale and deployment of the oil reserves. Sandia was directed to develop and implement a process to continuously assess and report the evolution of drawdown capacity, the subject of this report. A cavern has an available drawdown if after that drawdown, the long-term stability of the cavern, the cavern field, or the oil quality are not compromised. Thus, determining the number of available drawdowns requires the consideration of several factors regarding cavern and wellbore integrity and stability, including stress states caused by cavern geometry and operations, salt damage caused by dilatant and tensile stresses, the effect of enhanced creep on wellbore integrity, and the sympathetic stress effect of operations on neighboring caverns. A consensus has now been built regarding the assessment of drawdown capabilities and risks for the SPR caverns (Sobolik et al., 2014; Sobolik 2016). The process involves an initial assessment of the pillar - to - diameter (P/D) ratio for each cavern with respect to neighboring caverns. A large pillar thickness between adjacent caverns should be strong enough to withstand the stresses induced by closure of the caverns due to salt creep. The first evaluation of P/D includes a calculation of the evolution of P/D after a number of full cavern drawdowns. The most common storage industry standard is to keep this value greater than 1.0, which should ensure a pillar thick enough to prevent loss of fluids to the surrounding rock mass. However, many of the SPR caverns currently have a P/D less than 1.0 or will likely have a low P/D after one or two full drawdowns. For these caverns, it is important to examine the structural integrity with more detail using geomechanical models. Finite-element geomechanical models have been used to determine the stress states in the pillars following successive drawdowns. By computing the tensile and dilatant stresses in the salt, areas of potential structural instability can be identified that may represent red flags for additional drawdowns. These analyses have found that many caverns will maintain structural integrity even when grown via drawdowns to dimensions resulting in a P/D of less than 1.0. The analyses have also confirmed that certain caverns should only be completely drawn down one time. As the SPR caverns are utilized and partial drawdowns are performed to remove oil from the caverns (e.g., for occasional oil sales , purchases, or exchanges authorized by the Congress or the President), the changes to the cavern caused by these procedures must be tracked and accounted for so that an ongoing assessment of the caverns drawdown capacity may be continued. A proposed methodology for assessing and tracking the available drawdowns for each cavern was presented in Sobolik et al. (2018). This report is the latest in a series of annual reports, and it includes the baseline available drawdowns for each cavern, and the most recent assessment of the evolution of drawdown expenditure for several caverns .

02 PETROLEUM↗

DOE OSTI2022

Available Drawdowns for Each Oil Storage Cavern in the Strategic Petroleum Reserve (2022 Annual Report)

The Department of Energy maintains an up-to-date documentation of the number of available full drawdowns of each of the caverns owned by the Strategic Petroleum Reserve (SPR). This information is important for assessing the SPR's ability to deliver oil to domestic oil companies expeditiously if national or world events dictate a rapid sale and deployment of the oil reserves. Sandia was directed to develop and implement a process to continuously assess and report the evolution of drawdown capacity, the subject of this report. A cavern has an available drawdown if after that drawdown, the long-term stability of the cavern, the cavern field, or the oil quality are not compromised. Thus, determining the number of a vailable drawdowns requires the consideration of several factors regarding cavern and wellbore integrity and stability, including stress states caused by cavern geometry and operations, salt damage caused by dilatant and tensile stresses, the effect of enhanced creep on wellbore integrity, and the sympathetic stress effect of operations on neighboring caverns. A consensus has now been built regarding the assessment of drawdown capabilities and risks for the SPR caverns (Sobolik et al., 2014; Sobolik 2016). The process involves an initial assessment of the pillar-to-diameter (P/D) ratio for each cavern with respect to neighboring caverns. A large pillar thickness between adjacent caverns should be strong enough to withstand the stresses induced by closure of the caverns due to salt creep. The first evaluation of P/D includes a calculation of the evolution of P/D after a number of full cavern drawdowns. The most common storage industry standard is to keep this value greater than 1.0, which should ensure a pillar thick enough to prevent loss of fluids to the surrounding rock mass. However, many of the SPR caverns currently have a P/D less than 1.0 or will likely have a low P/D after one or two full drawdowns. For these caverns, it is important to examine the s tructural integrity with more detail using geomechanical models. Finite - element geomechanical models have been used to determine the stress states in the pillars following successive drawdowns. By computing the tensile and dilatant stresses in the salt, areas of potential structural instability can be identified that may represent "red flags" for additional drawdowns. These analyses have found that many caverns will maintain structural integrity even when grown via drawdowns to dimensions resulting in a P/D of less than 1.0. The analyses have also confirmed that certain caverns should only be completely drawn down one time. As the SPR caverns are utilized and partial drawdowns are performed to remove oil from the caverns (e.g., for occasional oil sales , purchases, or exchanges authorized by the Congress or the President), the changes to the cavern caused by these procedures must be tracked and accounted for so that an ongoing assessment of the cavern's drawdown capacity may be continued. A proposed methodology for assessing and tracking the available drawdowns for each cavern was presented in Sobolik et al. (2018). This report is the latest in a series of annual reports, and it includes the baseline available drawdowns for each cavern, and the most recent assessment of the evolution of drawdown expenditure for several caverns.

02 PETROLEUM↗

DOE OSTI2023

A Systems Approach to Increasing Carbon Flux to Seed Oil for Biofuels and Bioproducts Production in Camelina sativa (Final Report)

To combat climate change and alleviate the dependency of the United States on fossil fuels, the transition to biofuel crops has long been proposed as a crucial part of the long-term solution. Camelina sativa has emerged as one of the leading commercially viable options for biofuel and bioproduct production for the U.S. Camelina has the advantages of low agronomic inputs and natural resistance to diverse biotic and abiotic stresses relative to other oilseed crops, and Camelina oil-based blends have been tested and approved as liquid transportation fuels. A major limitation in the widespread adoption of Camelina as a viable industrial oilseed crop is its modest oil yields. This project directly investigated possible paths towards increasing oil, by employing tissue-specific and whole plant systems approaches to identify major regulatory bottlenecks. We developed a new high-throughput method for the identification of multi-gene transformants in polyploid species like Camelina sativa and used this to determine that, contrary to what mathematical models suggested, introduction of the microbial Entner-Doudoroff (ED) pathway into Camelina sativa did not result in significant seed oil increases. We developed flux maps providing accurate and statistically robust models of central carbon metabolism in Camelina, including of cultured Camelina embryos. This knowledge was used in the capacitation of a number of junior researchers in gaining knowledge on approaches used for quantitative flux map analyses. We identified several novel Camelina transcription factor genes regulating fatty acid biosynthesis that showed variable effects on seed oil accumulation in transgenic plants. Among a number of community resources, we also developed a knowledge base web resource (CamRegBase) to integrate Camelina gene regulatory information. Together, research outcomes from this project have contributed to a much better understanding of the regulation and bottlenecks to engineer seed oil production in Camelina.

09 BIOMASS FUELS↗