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Developing methanogenic microbial consortia from diverse coal sources and environments

Biogenic gas production is a promising alternative or supplement to conventional methane extraction from coalbeds. Adsorbed and free gas, generated over geologic time, can be supplemented with biogenic gas during short-term engineering operations. There are two generic protocols for doing this. The first is to contact the coal with nutrients to support native bacterial development. The second approach is to inject appropriately cultured ex-situ consortia into subsurface coal accumulations. Research has mainly focused on the former: in-situ stimulation of native microbial communities with added nutrients. Relatively few studies have been conducted on the strategies for enriching ex-situ microbial populations under initial atmospheric exposure for subsequent injection into coal seams to stimulate biodegradation, and methanogenesis. In order to evaluate the feasibility of ex-situ cultivation, natural microbial populations were collected from various hydrocarbon-rich environments and locations characterized by natural methanogenesis. Different rank coals (i.e., lignite, sub-bituminous, bituminous), complex hydrocarbon sources (i.e., oil shale, waxy crude), hydrocarbon seeps, and natural biogenic environments were incorporated in the sampling. Three levels of screening (down-selection to high grade the most productive consortia) allowed selection of microbial populations, favorable nutrient amendments, sources of the microbial community, and quantification of methane produced from various coal types. Incubation periods of up to twenty-four weeks were evaluated at 23 °C. Headspace concentrations of CH 4 and CO 2 were analyzed by gas chromatography. After a two-week incubation period of the most promising microbes, generated headspace gas concentrations reached 873,400 ppm (154 sft 3 /ton or 4.8 scm 3 /g) for methane and 176,370 ppm (31 sft 3 /ton or 0.9 scm 3 /g) for carbon dioxide. Rudimentary statistical assessments – variance analysis (ANOVA) of a single factor - were used to identify trends and levels of significance or impact of the consortia enrichment. We then demonstrated that microbial communities from coal and lake sediments can be enriched and adapted to effectively generate methane under initial atmospheric exposure. The development and enrichment of these methanogenic consortia is described.

01 COAL, LIGNITE, AND PEAT↗

Internal Domains of Natural Porous Media Revealed: Critical Locations for Transport, Storage, and Chemical Reaction

Internal pore domains exist within rocks, lithic fragments, subsurface sediments and soil aggregates. These domains, which we term internal domains in porous media (IDPM), contain a significant fraction of their porosity as nanopores, dominate the reactive surface area of diverse porous media types, and are important locations for chemical reactivity and hydrocarbon storage. Traditionally difficult to interrogate, advances in instrumentation and imaging methods are providing new insights on the physical structures and chemical attributes of IDPM. In this review we: discuss analytical methods to characterize IDPM, evaluate what has been learned about their size distributions, connectivity, and extended structures; determine whether they exhibit unique chemical reactivity; and assess potential for their inclusion in reactive transport models. Three key findings are noteworthy. 1) A combination of methods now allows complete characterization of the porosity spectrum of natural materials and its connectivity; while imaging microscopies are providing three dimensional representations of the interconnected pore network. 2) Chemical reactivity in pores <10 nm is expected to be different from micro and macropores, yet research performed to date is inconclusive on the nature, direction, and magnitude of effect. 3) Existing continuum reactive transport models treat IDPM as a sub-grid feature with average, empirical, scale-dependent parameters; and are not formulated to include detailed information on pore networks. Overall we find that IDPM are key features controlling hydrocarbon release from shales in hydrofracking systems, organic matter stabilization and recalcitrance in soil, weathering and soil formation, and long term inorganic and organic contaminant behavior in the vadose zone and groundwater. We conclude with an assessment of impactful research opportunities to advance understanding of IDPM, and to incorporate their important effects in reactive transport models for improved environmental simulation and prediction.

58 GEOSCIENCES↗

Utah FORGE: Well 9-1 Logs and Data from Roosevelt Hot Springs Area

This is a compilation of logs and data from Well 9-1 in the Roosevelt Hot Springs area in Utah. This well is also in the Utah FORGE study area. The file is in a compressed .zip format and there is a data inventory table (Excel spreadsheet) in the root folder that is a guide to the data that is accessible in subfolders.

15 GEOTHERMAL ENERGY↗

Subtask 1.1 – Advanced Characterization of Unconventional Oil and Gas Reservoirs to Enhance CO2 Storage Resource Estimates

The Energy & Environmental Research Center (EERC) developed methods and approaches for advanced characterization of unconventional oil and gas reservoirs to enhance CO2 storage resource estimates using samples collected from organic-rich shales of the Bakken Formation. The project was funded under U.S. Department of Energy (DOE) Cooperative Agreement No. DE-FE0024233, with nonfederal cost share provided by Hitachi High Technologies America. The project participants included the EERC, Hitachi High Technologies America, the team at the National Energy Technology Laboratory’s (NETL’s) computed tomography (CT) scanning laboratory in Morgantown, West Virginia, and several NETL staff who have worked on CO2 storage resource estimation. Investigations on the use of subsurface geologic formations for CO2 storage have been ongoing for many years. In the last decade, improvements in directional drilling technology and hydraulic fracturing of organic-rich shale and other tight rock formations have opened new opportunities for CO2 storage, with the potential cobenefit of enhancing gas and oil recovery. Gas-bearing, organic-rich shales have been of particular interest as a carbon storage target because their ability to store large volumes of CO2 is implied by their ability to store methane; however, estimating the CO2 storage resource of organic-rich shales and other unconventional reservoirs is challenging because of the lack of detailed geologic and petrophysical data that are needed to develop improved volumetric equations. According to NETL’s method for estimating regional-scale CO2 storage resources, the key factors that control CO2 storage in geologic formations include void space within induced fractures, natural fractures and matrix pores, as well as the occurrence and distribution of organic matter (OM) and clay minerals. A key goal of this effort was to use field emission scanning electron microscopy (FESEM) analysis of fine-grain unconventional reservoir rocks coupled with advanced image analysis and machine learning techniques to quantify the occurrence and distribution of porosity, OM, and clay minerals. By better understanding the potential migration pathways of CO2 within tight rocks and quantifying the occurrence of sorptive components (OM and clays) along potential flow pathways, methods to estimate the CO2 storage resource of such rocks can be refined. The Bakken petroleum system (Bakken) was used as the source of rock samples for this effort because it includes organic-rich shales with contrasting degrees of thermal maturity as well as tight, nonshale clastic rocks with varying clay mineral content. To better understand the key components of interest in tight rock samples, the EERC worked closely with Hitachi to optimize the FESEM settings necessary to resolve the sample mineralogy, porosity and OM content at micro- to nanoscale resolution. The EERC also worked closely with Hitachi to apply and improve its advanced mineral identification and characterization system (AMICS) software so that it is better suited for mineral identification at the high resolution necessary to resolve features of interest in fine-grained rocks such as organic-rich shales. The EERC also applied advanced image analysis software packages, including Ilastik, to classify and quantify the key components of interest within the samples using FESEM imagery. These advanced techniques allowed for quantification and differentiation of the void space within fractures, pores and OM, as well as a technique to determine and quantify the key mineral and OM components surrounding pore spaces. Being able to better quantify the void space and the potential accessibility of CO2 to sorptive minerals or OM within tight rocks allows for improved estimation of the CO2 storage resource potential of organic-rich shales and other unconventional formations. The information derived from the image analysis techniques was used to refine NETL’s method for estimating regional-scale CO2 storage resources in collaboration with staff from NETL. An additional goal of this work was to better understand rates of CO2 permeation, flow pathways, and sorption in organic-rich shales and nonshale reservoir rocks and to evaluate potential changes in CO2 flow over time. The EERC conducted long-duration (several weeks) CO2 flow-through testing at reservoir conditions using Bakken shale and nonshale samples to assess CO2 permeation rates and retention/sorption within core plugs to represent bulk matrix behavior. Conventional isothermal adsorption testing over a range of pressure conditions was also performed on pulverized Bakken samples to better assess potential maximum sorptive capacity of the samples. The results of this testing illustrated the higher sorptive capacity of the Bakken shales when compared to the sorptive capacity of the nonshale reservoir rock, which contains very little OM when compared to the Bakken shales. The results also illustrate the differences in permeation behavior as a function of fracture flow versus matrix flow. In an attempt to visualize CO2 permeation and flow behavior in Bakken shale samples over time, the EERC collaborated with NETL’s CT Lab in Morgantown, West Virginia. A variety of tests were performed at the NETL lab on unfractured and fractured samples of the Bakken shale. The unfractured Bakken shale samples did not result in CO2 migration within the samples over the testing duration; thus imagery of CO2 migration pathways within the matrix of Bakken samples was not obtained. The results of the flow-through testing within fractured samples illustrate changes in CO2 permeation rates over time, with a trend of decreasing CO2 flow over time. The results of this effort suggest that FESEM analysis coupled with advanced image analysis and machine learning techniques are effective in characterizing and quantifying the mineralogy, porosity, fractures, and OM content of 2-D imagery at the high resolution needed to identify features of interest in tight rocks. In addition, the image analysis techniques allow for identification and quantification of different porosity types as well as the key mineral components and/or OM that CO2 would contact in the reservoir as it migrates through pores and fracture networks. This is key information needed to better estimate the CO2 storage resource potential of organic-rich shales and other tight reservoirs. Additional work is needed to determine the sorptive capacity of the individual sample components (OM and clay minerals) at reservoir conditions so that this approach and the refined CO2 storage resource equation can be applied to other shale and unconventional reservoirs. In addition, subsequent work should be performed to better understand the number of images needed to use stereological approaches to estimate the volume of sample components using 2-D imagery, to explore machine learning techniques to differentiate between induced vs. natural fractures, and to estimate the connectivity of pores and fracture networks using 2-D imagery. Being able to derive this information at the microscale would facilitate scaling up of the sample characterization data used for reservoir modeling and simulation to estimate the CO2 storage resource potential of tight formations.

03 NATURAL GAS↗

Water-related Issues Affecting Conventional Oil and Gas Recovery and Potential Oil-Shale Development in the Uinta Basin, Utah

Saline water disposal is one of the most pressing issues with regard to increasing petroleum and natural gas production in the Uinta Basin of northeastern Utah. Conventional oil fields in the basin provide 69 percent of Utah's total crude oil production and 71 percent of Utah's total natural gas, the latter of which has increased 208% in the past 10 years. Along with hydrocarbons, wells in the Uinta Basin produce significant quantities of saline water – nearly 4 million barrels of saline water per month in Uintah County and nearly 2 million barrels per month in Duchesne County. As hydrocarbon production increases, so does saline water production, creating an increased need for economic and environmentally responsible disposal plans. Current water disposal wells are near capacity, and permitting for new wells is being delayed because of a lack of technical data regarding potential disposal aquifers and questions concerning contamination of freshwater sources. Many companies are reluctantly resorting to evaporation ponds as a short-term solution, but these ponds have limited capacity, are prone to leakage, and pose potential risks to birds and other wildlife. Many Uinta Basin operators claim that oil and natural gas production cannot reach its full potential until a suitable, long-term saline water disposal solution is determined. The enclosed project was divided into three parts: 1) re-mapping the base of the moderately saline aquifer in the Uinta Basin, 2) creating a detailed geologic characterization of the Birds Nest aquifer, a potential reservoir for large-scale saline water disposal, and 3) collecting and analyzing water samples from the eastern Uinta Basin to establish baseline water quality. Part 1: Regulators currently stipulate that produced saline water must be disposed of into aquifers that already contain moderately saline water (water that averages at least 10,000 mg/L total dissolved solids). The UGS has re-mapped the moderately saline water boundary in the subsurface of the Uinta Basin using a combination of water chemistry data collected from various sources and by analyzing geophysical well logs. By re-mapping the base of the moderately saline aquifer using more robust data and more sophisticated computer-based mapping techniques, regulators now have the information needed to more expeditiously grant water disposal permits while still protecting freshwater resources. Part 2: Eastern Uinta Basin gas producers have identified the Birds Nest aquifer, located in the Parachute Creek Member of the Green River Formation, as the most promising reservoir suitable for large-volume saline water disposal. This aquifer formed from the dissolution of saline minerals that left behind large open cavities and fractured rock. This new and complete understanding the aquifer's areal extent, thickness, water chemistry, and relationship to Utah's vast oil shale resource will help operators and regulators determine safe saline water disposal practices, directly impacting the success of increased hydrocarbon production in the region, while protecting potential future oil shale production. Part 3: In order to establish a baseline of water quality on lands identified by the U.S. Bureau of Land Management as having oil shale development potential in the southeastern Uinta Basin, the UGS collected biannual water samples over a three-year period from near-surface aquifers and surface sites. The near-surface and relatively shallow groundwater quality information will help in the development of environmentally sound water-management solutions for a possible future oil shale and oil sands industry and help assess the sensitivity of the alluvial and near-surface bedrock aquifers. This multifaceted study will provide a better understanding of the aquifers in Utah's Uinta Basin, giving regulators the tools needed to protect precious freshwater resources while still allowing for increased hydrocarbon production.

02 PETROLEUM↗

Treatment of Chlorinated Solvents in Groundwater Beneath an Occupied Building at the Young-Rainey STAR Center, Pinellas, FL

Groundwater contamination, consisting of two dissolved-phase plumes originating from chlorinated solvent source areas, in the southeastern portion of the Young- Rainey Star Center (also known as the Pinellas County, Florida, Site) in Largo, Florida, has migrated beyond the property boundary, beneath the roadways, and beneath adjacent properties to the south and east. Groundwater contamination will persist as long as the onsite contaminant source remains. The origin of the contamination appears to be multiple long-term point sources beneath Building 100, a 4.5 ha (11 acre) building that housed manufacturing facilities during US DOE operations at the site. The site is now owned by Pinellas County, and most of the space inside the building is leased to private companies, so DOE chose not to conduct characterization or remediation through the floor of the building, instead choosing to conduct all work from outside the building. Injection of emulsified soybean oil and a microbial culture has been used at other areas of the site to accelerate naturally occurring bacterial processes that degrade groundwater contaminants to harmless compounds, and that same approach was chosen for this task. The technical approach consisted of installing horizontal wells from outside the building footprint, extending through and around the identified subsurface treatment areas, and terminating beneath the building. Two 107 m (350 ft) long wells, two 122 m (400 ft) long wells, and four 137 m (450 ft) long wells have been installed to intersect the inferred source areas and confirmed contaminant plumes beneath the building. DOE then injected emulsified vegetable oil and a microbial culture into the horizontal wells at each of several target areas beneath the building where the highest groundwater contaminant concentrations have been detected. The target areas are the northwest corner of the building between the old drum storage pad locations and monitoring well PIN12-S35B, the vicinity of former monitoring well PIN12-S57B, and hydraulically upgradient from the south plume and the east plume at the points where they exit from beneath the building. We describe the details of designing and constructing horizontal injection wells for bioremediation beneath a large, occupied industrial production facility, including lessons learned; technical, logistical, and environmental challenges; community relations; and regulatory relations. Because of the expected lag in biological acclimation and response, distance between the treatment areas and associated monitoring points, and low groundwater velocity, it will likely be years before the full impact of the project will be realized.

54 ENVIRONMENTAL SCIENCES↗

Treatment of Chlorinated Solvents in Groundwater Beneath an Occupied Building at The Young - Rainey STAR Center (Science, Technology, and Research Center) - 16342

Groundwater contamination, consisting of two dissolved-phase plumes originating from chlorinated solvent source areas, in the southeastern portion of the Young- Rainey Star Center (also known as the Pinellas County, Florida, Site) in Largo, Florida, has migrated beyond the property boundary, beneath the roadways, and beneath adjacent properties to the south and east. Groundwater contamination will persist as long as the onsite contaminant source remains. The origin of the contamination appears to be multiple long-term point sources beneath Building 100, a 4.5 ha (11 acre) building that housed manufacturing facilities during US DOE operations at the site. The site is now owned by Pinellas County, and most of the space inside the building is leased to private companies, so DOE chose not to conduct characterization or remediation through the floor of the building, instead choosing to conduct all work from outside the building. Injection of emulsified soybean oil and a microbial culture has been used at other areas of the site to accelerate naturally occurring bacterial processes that degrade groundwater contaminants to harmless compounds, and that same approach was chosen for this task. The technical approach consisted of installing horizontal wells from outside the building footprint, extending through and around the identified subsurface treatment areas, and terminating beneath the building. Two 107 m (350 ft) long wells, two 122 m (400 ft) long wells, and four 137 m (450 ft) long wells have been installed to intersect the inferred source areas and confirmed contaminant plumes beneath the building. DOE then injected emulsified vegetable oil and a microbial culture into the horizontal wells at each of several target areas beneath the building where the highest groundwater contaminant concentrations have been detected. The target areas are the northwest corner of the building between the old drum storage pad locations and monitoring well PIN12-S35B, the vicinity of former monitoring well PIN12-S57B, and hydraulically up-gradient from the south plume and the east plume at the points where they exit from beneath the building. We describe the details of designing and constructing horizontal injection wells for bioremediation beneath a large, occupied industrial production facility, including lessons learned; technical, logistical, and environmental challenges; community relations; and regulatory relations. Because of the expected lag in biological acclimation and response, distance between the treatment areas and associated monitoring points, and low groundwater velocity, it will likely be years before the full impact of the project will be realized. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Atomic intercalation to measure adhesion of graphene on graphite

The interest in mechanical properties of layered and 2D materials has reemerged in light of device concepts that take advantage of flexing, adhesion and friction in such systems. Here we provide an effective measurement of the nanoscale elastic adhesion of a graphene sheet atop highly ordered pyrolytic graphite (HOPG) based on the analysis of atomic intercalates in graphite. Atomic intercalation is carried out using conventional ion sputtering, creating blisters in the top-most layer of the HOPG surface. Scanning tunneling microscopy coupled with image analysis and density functional theory are used to reconstruct the atomic positions and the strain map within the deformed graphene sheet, as well as to demonstrate subsurface diffusion of the ions creating such blisters. To estimate the adhesion energy we invoke an analytical model originally devised for macroscopic deformations of graphene. This model yields a value of 0.221 ± 0.011 J/m -2 for the adhesion energy of graphite, which is in surprisingly good agreement with reported experimental and theoretical values. This implies that macroscopic mechanical properties of graphene scale down to at least a few nanometers length. The simplicity of our method, compared to the macroscale characterization, enables analysis of elastic mechanical properties in two-dimensional layered materials and provides a unique opportunity to investigate the local variability of mechanical properties on the nanoscale.

36 MATERIALS SCIENCE↗

Opto-nanomechanical spectroscopic material characterization

Cellulosic ethanol is a biofuel of considerable potential in the search for sustainable and renewable bioenergy [1,2]. However, while rich in carbohydrates [3], the plant cell walls exhibit a natural resistance to complex phenotype treatments such as enzymatic microbial deconstruction, heat and acid treatments that can remove the lignin polymers from cellulose before hydrolysis [5]. Noninvasive physical and chemical characterization of the cell walls and the effect of such treatments on biomass are challenging but necessary to understand and overcome such resistance [6]. Although lacking chemical recognition in their traditional forms, the various emerging modalities of nano-mechanical [7] and opto-nano-mechanical [8] force microscopies [9,10] provide a superb window into the needed nanoscale material characterization [6]. Infrared absorption spectroscopy is a powerful, non- destructive and ultra-sensitive technique that can provide the needed molecular fingerprinting but the photothermal channel is delocalized and thus lacks spatial resolution. Utilizing the emerging dynamic concepts of mode synthesizing atomic force microscopy (MSAFM) [11] and virtual resonance [12], we introduce a hybrid photonic and nanomechanical force microscopy (hp-MSAFM) with molecular recognition and characterize the extraction, holopulping and acid treatment of biomass. We present spatially and spectrally resolved cell wall images that reveal both the morphological and the compositional alterations of the cell walls. The measured biomolecular traits are in agreement with chemical maps obtained with infrared and confocal Raman micro-spectroscopies of the same samples. The presented findings should prove highly relevant in fields such as cancer research [13], nanotoxicity [14], energy storage and production [15], where morphological, chemical and subsurface studies of nanocomposites [16], nanoparticle uptake by cells [14], and nanoscale quality control [17] are in demand.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

2015 Groundwater Monitoring Report Project Shoal Area: Subsurface Correction Unit 447

The Project Shoal Area in Nevada was the site of a 12-kiloton-yield underground nuclear test in 1963. Although the surface of the site has been remediated, investigation of groundwater contamination resulting from the test is still in the corrective action process. Annual sampling and hydraulic head monitoring are conducted at the site as part of the subsurface corrective action strategy. The corrective action strategy is currently focused on revising the site conceptual model (SCM) and evaluating the adequacy of the monitoring well network. Some aspects of the SCM are known; however, two major concerns are the uncertainty in the groundwater flow direction and the cause of rising water levels in site wells west of the shear zone. Water levels have been rising in the site wells west of the shear zone since the first hydrologic characterization wells were installed in 1996. Although water levels in wells west of the shear zone continue to rise, the rate of increase is less than in previous years. The SCM will be revised, and an evaluation of the groundwater monitoring network will be conducted when water levels at the site have stabilized to the agreement of both the U.S. Department of Energy Office of Legacy Management and the Nevada Division of Environmental Protection.

54 ENVIRONMENTAL SCIENCES↗

The Kimberlina synthetic multiphysics dataset for CO 2 monitoring investigations

Abstract We present a synthetic multi‐scale, multi‐physics dataset constructed from the Kimberlina 1.2 CO 2 reservoir model based on a potential CO 2 storage site in the Southern San Joaquin Basin of California. Among 300 models, one selected reservoir‐simulation scenario produces hydrologic‐state models at the onset and after 20 years of CO 2 injection. Subsequently, these models were transformed into geophysical properties, including P‐ and S‐wave seismic velocities, saturated density where the saturating fluid can be a combination of brine and supercritical CO 2 , and electrical resistivity using established empirical petrophysical relationships. From these 3D distributions of geophysical properties, we have generated synthetic time‐lapse seismic, gravity and electromagnetic responses with acquisition geometries that mimic realistic monitoring surveys and are achievable in actual field situations. We have also created a series of synthetic well logs of CO 2 saturation, acoustic velocity, density and induction resistivity in the injection well and three monitoring wells. These were constructed by combining the low‐frequency trend of the geophysical models with the high‐frequency variations of actual well logs collected at the potential storage site. In addition, to better calibrate our datasets, measurements of permeability and pore connectivity have been made on cores of Vedder Sandstone, which forms the primary reservoir unit. These measurements provide the range of scales in the otherwise synthetic dataset to be as close to a real‐world situation as possible. This dataset consisting of the reservoir models, geophysical models, simulated time‐lapse geophysical responses and well logs forms a multi‐scale, multi‐physics testbed for designing and testing geophysical CO 2 monitoring systems as well as for imaging and characterization algorithms. The suite of numerical models and data have been made publicly available for downloading on the National Energy Technology Laboratory's (NETL) Energy Data Exchange (EDX) website.

58 GEOSCIENCES↗

Origin of water masses in Floridan Aquifer System revealed by 81 Kr

Groundwater in coastal aquifers serves as an essential resource in densely populated areas throughout the world. However, hydrological connection to the ocean leaves it at risk of salinization via changes in climate and hydrological cycles. Therefore, an accurate hydrological characterization of coastal aquifers is of the utmost importance. Although localized salinization of shallow aquifers has commonly been studied, geochemical constraints on the time scale of regional freshwater and seawater in coastal aquifers are limited especially in carbonate aquifers. Such information is not only crucial for water resource management, but also for understanding solute flux over the land-ocean boundary and for interpreting the geochemical signatures that each water mass carries. Toward this goal, we report tracer-based, subsurface residence times of groundwater in the Floridan Aquifer System in southern Florida, which is one of the most productive aquifers on Earth. The first application of Kr 81-an emerging tracer of old groundwater-to this aquifer has identified freshwater recharge during the last glacial period as anticipated from previous studies using other geochemical tools including radiocarbon, stable isotopes and noble gas concentrations. Moreover, freshwater of Holocene age was also detected at 100 km-distance from the recharge area, suggesting the possibility of an active flow system in the upgradient region. A contribution of fossil seawater that predates the last glacial maximum was locally identified, suggesting slow seawater circulation and limited but significant solute flux from the ocean into the aquifer for dolomitization. This also implies that the deep saline coastal groundwater can potentially serve as a paleo-seawater archive.

58 GEOSCIENCES↗

Deep Unsaturated Zone Contributions to Carbon Cycling in Semiarid Environments

Understanding terrestrial carbon cycling has relied primarily on studies of topsoils that are typically characterized to depths shallower than 0.5 m. At a semiarid site instrumented down to 7 m, here we measured seasonal- and depth-resolved carbon inventories and fluxes and groundwater and unsaturated zone flow rates. Measurements showed that ~30% of the CO 2 efflux to the atmosphere (60% in winter) originates from below 1 m, contrary to predictions of less than 1% by Earth System Model land modules. Respiration from deeper roots and deeper microbial communities is supported by favorable subsurface temperatures, moisture, and oxygen availability. Below 1 m, dissolved organic carbon fluxes from the overlying soil and C from deep roots and exudates are expected to be important in sustaining microbial respiration. Finally, because these conditions are characteristic of semiarid climate regions, we contend that Earth System Model land modules should incorporate such deeper soil processes to improve CO 2 flux predictions.

54 ENVIRONMENTAL SCIENCES↗

Intermediate-Scale Hydraulic Fracturing in a Deep Mine - kISMET Project Summary 2016

In support of the U.S. DOE SubTER Crosscut initiative, we established a field test facility in a deep mine and designed and carried out in situ hydraulic fracturing experiments in the crystalline rock at the site to characterize the stress field, understand the effects of rock fabric on fracturing, and gain experience in monitoring using geophysical methods. The project also included pre- and post-fracturing simulation and analysis, laboratory measurements and experiments, and we conducted an extended analysis of the local stress state using previously collected data. Some of these activities are still ongoing. The kISMET (permeability (k) and Induced Seismicity Management for Energy Technologies) experiments meet objectives in SubTER’s “stress” pillar and the “new subsurface signals” pillar. The kISMET site was established in the West Access Drift of SURF 4850 ft (1478 m) below ground (on the 4850L) in phyllite of the Precambrian Poorman Formation. We drilled and cored five near-vertical boreholes in a line on 3 m spacing, deviating the two outermost boreholes slightly to create a five-spot pattern around the test borehole centered in the test volume at ~1528 m (5013 ft). Laboratory measurements of core from the center test borehole showed P-wave velocity heterogeneity along each core indicating strong, fine-scale (~1 cm or smaller) changes in the mechanical properties of the rock. The load-displacement record on the core suggests that the elastic stiffness is anisotropic. Tensile strength ranges between 3-7.5 MPa and 5-12 MPa. Permeability measurements are planned, as are two types of laboratory miniature hydraulic fracturing experiments to investigate the importance of rock fabric (anisotropy and heterogeneity) on near-borehole hydraulic fracture generation. Pre-fracturing numerical simulations with INL’s FALCON discrete element code predicted a fracture radius of 1.2 m for a corresponding injection volume of 1.2 L for the planned fractures, and negligible microseismicity. Field measurements of the stress field by hydraulic fracturing showed that the minimum horizontal stress at the kISMET site averages 21.7 MPa (3146 psi) pointing approximately N-S (356 degrees azimuth) and plunging slightly NNW at 12°. The vertical and horizontal maximum stress are similar in magnitude at 42-44 MPa (6090-6380 psi) for the depths of testing which averaged approximately 1530 m (5030 ft). Hydraulic fractures were remarkably uniform suggesting core-scale and larger rock fabric did not play a role in controlling fracture orientation. Monitoring using ERT and CASSM in the four monitoring boreholes, and passive seismic accelerometer-based measurements in the West Access Drift, was carried out during the generation of a larger fracture (so-called stimulation test) at a depth of 40 m below the invert. ERT was not able to detect the fracture created, nor were the accelerometers in the drift, but microseismicity was detected for first (deepest) hydraulic-fracturing stress measurement. The CASSM data have not yet been analyzed. Analytical solutions suggest fracture radius of the large fracture (stimulation test) was more than 6 m, depending on the unknown amount of leak-off. The kISMET results for stress state are consistent with large-scale mid-continent estimates of stress. Currently we are using the orientation of the stress field we determined to interpret a large number of borehole breakouts recorded in nearby boreholes at SURF to generate a more complete picture of the stress field and its variations at SURF. The efforts on the project have prompted a host of additional follow-on studies that we recommend be carried out at the kISMET site.

02 PETROLEUM↗

Improved Three-Dimensional Resistivity Data Acquisition Capabilities at the Hanford Site

The recent 3D electrical resistivity characterization at 241-U Tank Farm represents the first full-farm true 3D environmental resistivity deployment in the world. Technological and manufacturing developments by the vendor resulted in a data acquisition system that far surpasses the ability of the previous off-the-shelf systems. The new data acquisition system allows for 180 channels, which enables the full-farm 3D acquisition without the inaccuracies associated with combining multiple datasets. This ultimately leads to a more accurate model of the subsurface and a better understanding of moisture and contaminant distribution within the vadose zone. Additionally, advancements in electrical noise filters and increased output power resulted in better quality data than previously acquired at the site, reducing the amount of poor quality data by more than half. Ultimately, the new, improved system increased the speed of data acquisition and quality of the final results. The system allowed a reduction in field labor and field work duration to half the field budget estimates, resulting in a 25% reduction in overall project costs. The new resistivity data acquisition system represents technological advancements resulting in a greater quantity of data with decreased project costs.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Science Serving the Nation: The Impact of Basic Research

Impacts: The BES program supports basic research that underpins a broad range of energy technologies. Research in materials sciences and engineering leads to the development of materials that improve the efficiency, economy, environmental acceptability, and safety of energy generation, conversion, transmission, storage, and use. For example, advances in superconductivity have been introduced commercially in a number of demonstration projects around the country. Improvements in alloy design for high temperature applications are used in commercial furnaces and in green technologies such as lead-free solder. Research in chemistry has led to advances such as efficient combustion systems with reduced emissions of pollutants; new solar photoconversion processes; improved catalysts for the production of fuels and chemicals; and better separations and analytical methods for applications in energy processes, environmental remediation, and waste management. Research in geosciences results in advanced monitoring and measurement techniques for reservoir definition and an understanding of the fluid dynamics of complex fluids through porous and fractured subsurface rock. Research in the molecular and biochemical nature of photosynthesis aids the development of solar photo-energy conversion. The BES program also plays a major role in enabling the nanoscale revolution. The importance of nanoscience to future energy technologies is clearly reflected by the fact that all of the elementary steps of energy conversion (e.g., charge transfer, molecular rearrangement, and chemical reactions) take place on the nanoscale. The development of new nanoscale materials, as well as the methods to characterize, manipulate, and assemble them, create an entirely new paradigm for developing new and revolutionary energy technologies.

Source record↗

Drake passage and central american seaway controls on the distribution of the oceanic carbon reservoir

A coupled carbon/climate model is used to explore the impact of Drake Passage opening and Central American Seaway closure on the distribution of carbon in the global oceans. We find that gateway evolution likely played an important role in setting the modern day distribution of oceanic dissolved inorganic carbon (DIC), which is currently characterized by relatively low concentrations in the Atlantic ocean, and high concentrations in the Southern, Indian, and Pacific oceans. In agreement with previous studies, we find a closed Drake Passage in the presence of an open Central American Seaway results in suppressed Atlantic meridional overturning and enhanced southern hemispheric deep convection. Opening of the Drake Passage triggers Antarctic Circumpolar Current flow and a weak Atlantic meridional overturning circulation (AMOC). Subsequent Central American Seaway closure reinforces the AMOC while also stagnating equatorial Pacific subsurface waters. These gateway-derived oceanographic changes are reflected in large shifts to the global distribution of DIC. An initially closed Drake Passage results in high DIC concentrations in the Atlantic and Arctic oceans, and lower DIC concentrations in the Pacific/Indian/Southern oceans. Opening Drake Passage reverses this gradient by lowering mid-depth Atlantic and Arctic DIC concentrations and raising deep Pacific/Indian/Southern Ocean DIC concentrations. Central American Seaway closure further reinforces this trend through additional Atlantic mid-depth DIC decreases, as well as Pacific mid-depth DIC concentration increases, with the net effect being a transition to a modern distribution of oceanic DIC.

54 ENVIRONMENTAL SCIENCES↗