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DOE Award No.: DE-FE0023919 Phase 3 Scientific/Technical Report

This is the Phase 3 Report for the ‘Deepwater Methane Hydrate Characterization and Scientific Assessment or Genesis of Methane Hydrates in the Gulf of Mexico (GOM2)’ research project (DOE Award No. DE-FE0023919). The report summarizes activities from January 16, 2018 to September 30, 2019. The project is led by the University of Texas at Austin (UT). The objective is to gain insight into the nature, formation, occurrence and physical properties of methane hydrate-bearing sediments for the purpose of methane hydrate resource appraisal through the planning and execution of drilling, coring, logging, testing and analytical activities that assess the geologic occurrence, regional context, and characteristics of marine methane hydrate deposits in the Gulf of Mexico outer continental shelf (OCS). We determined that it would not be possible to pursue the project with the International Ocean Discovery Program (IODP) and then developed a revised science and operations plan to maximize the science using a commercial vessel within the budget that is available. We improved the scientific capability of the UT pressure core center by adding the ability to X-ray pressure cores, and the ability to cut and store multiple core samples for experimental analysis. We transferred pressure cores to peer institutions, including the National Energy Technology Lab (NETL) the United States Geological Survey (USGS Woods Hole). We made advances in understanding the composition and source of gasses locked in the methane hydrate from Green Canyon 955 (GC-955). We developed approaches to determine the in-situ salinity of hydrate-bearing samples, revealing that the in situ salinity of the GC 955 reservoir is just above that of seawater. We determined that the GC-955 hydrate reservoir is composed of sandy silt with a high concentration of hydrate interbedded with clayey silt with no hydrate present. We determined that some or all of the intervals bounding the hydrate reservoir are composed of material similar to the reservoir (sandy silt with hydrate and clayey silt with no hydrate), but with a lower net to gross. We determined that the reservoir effective permeability at a hydrate saturation of ~80-90 % is ~0.1 mD (or 1.0×10-16 m2) to ~0.5 mD (or 5.0×10-16 m2) and the intrinsic permeability is ~12 mD (or 1.2×10-14 m2). The GC-955 reservoir in-situ porosity of sandy silt is 0.38 to 0.40 and is largely independent of effective stress, and that the porosity of clayey silt is 0.33 at an in situ effective stress of 3.8 MPa to ~0.37 at zero effective stress. We developed a systematic, repeatable approach to studying hydrate reservoir properties by reconstituting individual lithofacies from dissociated pressure cores. We determined index properties of GC-955 reservoir, including liquid limit and plasticity, porosity, capillary behavior, and particle size distribution. We developed a more robust pressure coring technology. We finalized and published the UT-GOM2-1 Expedition Volume and we finalized a dedicated volume on the UT-GOM2-1 expedition that will be published in the American Association of Petroleum Geologists Bulletin (AAPG) in spring 2020.

03 NATURAL GAS↗

Laboratory Electrical Conductivity of Marine Gas Hydrate

Methane hydrate was synthesized from pure water ice and flash frozen seawater, with varying amounts of sand or silt added. Electrical conductivity was determined by impedance spectroscopy, using equivalent circuit modeling to separate the effects of electrodes and to gain insight into conduction mechanisms. Silt and sand increase the conductivity of pure hydrate; we infer by contaminant NaCl contributing to conduction in hydrate, to values in agreement with resistivities observed in well logs through hydrate–saturated sediment. The addition of silt and sand lowers the conductivity of hydrate synthesized from seawater by an amount consistent with Archie's law. Here, all samples were characterized using cryogenic scanning electron microscopy and energy dispersive spectroscopy, which show good connectivity of salt and brine phases. Electrical conductivity measurements of pure hydrate and hydrate mixed with silt during pressure–induced dissociation support previous conclusions that sediment increases dissociation rate.

58 GEOSCIENCES↗

Characterizing Baselines and Change in Gas Hydrate Systems using EM Methods

The objective of this project was to advance our understanding of gas hydrate systems in nature by characterizing their electrical properties in the field and in the laboratory. In the laboratory measurements, methane hydrate was synthesized from pure water ice and flash frozen seawater, with varying amounts of sand or silt added. Electrical conductivity was determined by impedance spectroscopy, using equivalent circuit modeling to separate the effects of electrodes and to gain insight into conduction mechanisms. Silt and sand increase the conductivity of pure hydrate, inferred to be contaminant NaCl contributing to conduction in hydrate, to a peak conductivity in agreement with peak resistivities observed in well logs through massive hydrate (3,000--10,000 Ωm). The addition of silt and sand lowers the conductivity of hydrate synthesized from seawater, by an amount consistent with Archie's Law. All samples were characterized using cryogenic scanning electron microscopy and energy dispersive spectroscopy, which shows good connectivity of salt and brine phases. Electrical conductivity measurements of pure hydrate and hydrate mixed with silt during pressure-induced dissociation supports previous conclusions that sediment increases dissociation rate. In order to characterize gas hydrate systems in the field, we collected 360 line kilometers of controlled-source electromagnetic data on Walker Ridge 313, Orca Basin (WR100), Mad Dog (GC781), and Green Canyon 955 in the Gulf of Mexico, all areas with known or seismically inferred gas hydrate deposits and which have be drilled or targeted for future drilling. We deep-towed an EM transmitter that generates an alternating electric field which propagates through the seafloor geology. Data were recorded on 6 receivers towed behind the transmitter at distances between 550 and 1550 m. In the presence of conductive geology, the electric fields will be attenuated, and conversely, in resistive geology the fields will be preserved. Our data were inverted using a 2D inversion method that first optimizes the model-data misfit, then finds the smoothest model fitting the data. This ensures that resistivity structures present in the final model are likely necessary. At each of the proposed drilling sites we found increased resistivity, interpreted as increased hydrate concentrations. However, not only were the primary drilling sites not always more resistive than the alternate sites, at WR313 the strongest resistors were not at the locations targeted for drilling.

03 NATURAL GAS↗

Predicting the mineral composition of dust aerosols – Part 2: Model evaluation and identification of key processes with observations

A global compilation of nearly sixty measurement studies is used to evaluate two methods of simulating the mineral composition of dust aerosols in an Earth system model. Both methods are based upon a Mean Mineralogical Table (MMT) that relates the soil mineral fractions to a global atlas of arid soil type. The Soil Mineral Fraction (SMF) method assumes that the aerosol mineral fractions match the fractions of the soil. The MMT is based upon soil measurements after wet sieving, a process that destroys aggregates of soil particles that would have been emitted from the original, undisturbed soil. The second method approximately reconstructs the emitted aggregates. This model is referred to as the Aerosol Mineral Fraction (AMF) method because the mineral fractions of the aerosols differ from those of the wet-sieved parent soil, partly due to reaggregation. The AMF method remedies some of the deficiencies of the SMF method in comparison to observations. Only the AMF method exhibits phyllosilicate mass at silt sizes, where they are abundant according to observations. In addition, the AMF quartz fraction of silt particles is in better agreement with measured values, in contrast to the overestimated SMF fraction. Measurements at distinct clay and silt particle sizes are shown to be more useful for evaluation of the models, in contrast to the sum over all particles sizes that is susceptible to compensating errors, as illustrated by the SMF experiment. Model errors suggest that allocation of the emitted silt fraction of each mineral into the corresponding transported size categories is an important remaining source of uncertainty. Evaluation of both models and the MMT is hindered by the limited number of size-resolved measurements of mineral content that sparsely sample aerosols from the major dust sources. In conclusion, the importance of climate processes dependent upon aerosol mineral composition shows the need for global and routine mineral measurements.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Predicting the Mineral Composition of Dust Aerosols: Model Evaluation and Identification of Key Processes with Observations - Part 2

A global compilation of nearly sixty measurement studies is used to evaluate two methods of simulating the mineral composition of dust aerosols in an Earth system model. Both methods are based upon a Mean Mineralogical Table (MMT) that relates the soil mineral fractions to a global atlas of arid soil type. The Soil Mineral Fraction (SMF) method assumes that the aerosol mineral fractions match the fractions of the soil. The MMT is based upon soil measurements after wet sieving, a process that destroys aggregates of soil particles that would have been emitted from the original, undisturbed soil. The second method approximately reconstructs the emitted aggregates. This model is referred to as the Aerosol Mineral Fraction (AMF) method because the mineral fractions of the aerosols differ from those of the wet-sieved parent soil, partly due to reaggregation. The AMF method remedies some of the deficiencies of the SMF method in comparison to observations. Only the AMF method exhibits phyllosilicate mass at silt sizes, where they are abundant according to observations. In addition, the AMF quartz fraction of silt particles is in better agreement with measured values, in contrast to the overestimated SMF fraction. Measurements at distinct clay and silt particle sizes are shown to be more useful for evaluation of the models, in contrast to the sum over all particles sizes that is susceptible to compensating errors, as illustrated by the SMF experiment. Model errors suggest that allocation of the emitted silt fraction of each mineral into the corresponding transported size categories is an important remaining source of uncertainty. Evaluation of both models and the MMT is hindered by the limited number of size-resolved measurements of mineral content that sparsely sample aerosols from the major dust sources. The importance of climate processes dependent upon aerosol mineral composition shows the need for global and routine mineral measurements.

aerosols↗

Stormwater Pollution Prevention Plan (SWPPP) for Coal Storage Area Stabilization Project

The scope of this project is to stabilize the abandoned coal storage area and redirect the storm water runoff from sanitary sewer system to the storm drain system. Currently, the existing storm water runoff is directed to a perimeter concrete drainage swale and collected in a containment basin. The collected water is then pumped to a treatment facility and after treatment, is discharged to the Y-12 sanitary sewer system. The existing drainage swale and collection basin along with silt fencing will be used during aggregate placement and grading to provide erosion and sediment control. Inlet protection will also be installed around existing structures during the storm water diversion construction. This project scope will include the installation of a non-woven geotextile fabric and compacted mineral aggregate base (paving optional) to stabilize the site. The geotextile specifications are provided on the vendor cut sheets in Appendix B. The installation of a storm water collection/retention area will also be installed on the southern side of the site in accordance with EPA Technical Guidance on Implementing the Stormwater Runoff Requirements for federal Projects under Section 438 of the Energy Independence and Security Act. The total area to be disturbed is approximately 2.5 acres. The order of activities for this Stormwater Pollution Prevention Plan (SWPPP) will be: (1) post notice of coverage (NOC) in a prominent display near entrance of the site; (2) install rain gauge on site or contact Y-12 Plant Shift Superintendent daily for Met tower rain gauge readings; (3) install stabilized construction exit on site; (4) install silt fencing along perimeter as indicated on the attached site plan; (5) regrade site; (6) install geotextile fabric and compacted mineral aggregate base; (7) install catch basin inlet protection where required; (8) excavate and lower existing catch basin tops, re-grade and asphalt to drain; and (9) when all disturbed areas are re-stabilized, remove silt fencing and any other temporary erosion control.

01 COAL, LIGNITE, AND PEAT↗

Eddy‐driven sediment transport in the A rgentine B asin: Is the height of the Z apiola R ise hydrodynamically controlled?

Abstract In this study, we address the question whether eddy‐driven transports in the Argentine Basin can be held responsible for enhanced sediment accumulation over the Zapiola Rise, hence accounting for the existence and growth of this sediment drift. To address this question, we perform a 6 year simulation with a strongly eddying ocean model. We release two passive tracers, with settling velocities that are consistent with silt and clay size particles. Our experiments show contrasting behavior between the silt fraction and the lighter clay. Due to its larger settling velocity, the silt fraction reaches a quasisteady state within a few years, with abyssal sedimentation rates that match net input. In contrast, clay settles only slowly, and its distribution is heavily stratified, being transported mainly along isopycnals. Yet, both size classes display a significant and persistent concentration minimum over the Zapiola Rise. We show that the Zapiola Anticyclone, a strong eddy‐driven vortex that circulates around the Zapiola Rise, is a barrier to sediment transport, and hence prevents significant accumulation of sediments on the Rise. We conclude that sediment transport by the turbulent circulation in the Argentine Basin alone cannot account for the preferred sediment accumulation over the Rise. We speculate that resuspension is a critical process in the formation and maintenance of the Zapiola Rise.

58 GEOSCIENCES↗

Bench-scale electrokinetic remediation for cesium-contaminated sediment at the Hanford Site, USA

Electrokinetic (EK) remediation has been applied to extract various contaminants such as radionuclides, heavy metals, and organic compounds from contaminated sediment and soil using electric currents. We conducted a laboratory experiment to investigate the efficiency of EK remediation method for Hanford sediment (76% sand and 24% silt-clay) after artificial contamination with nonradioactive 133Cs (0.01 M CsNO3) as a surrogate for radioactive 137Cs. The initial 133Cs concentration in the bulk sediment was 668 mg kg-1, with a higher 133Cs concentration for the silt-clay fraction (867 mg kg-1) than for the sand fraction (83 mg kg-1). A significant removal of cationic 133Cs from the sediment occurred from the cathode side (-), whereas the removal was negligible from the anode side (+) during the EK remediation process for 68 days. Based on microwave-assisted total digestion, 312 mg kg-1 of 133Cs was removed from the bulk sediment, which corresponds to the removal efficiency of 47%. The EK method was significantly more efficient for the silt-clay fraction than for the sand fraction. X-ray diffraction (XRD) and scanning electron microscopy-electron dispersive spectroscopy (SEM-EDS) analyses indicate that change in major crystalline mineral phases was insignificant during the EK remediation and the removal of 133Cs from the Hanford sediment by the EK method is attributed mainly to cation exchange with K in clay minerals. The experimental results suggest that the EK method can effectively remove radioactive Cs from the surface or subsurface sediment contaminated by radioactive materials in the Hanford Site, Washington, USA.

Cation exchange↗

Comparison of Forest Soil Carbon Dynamics at Five Sites Along a Latitudinal Gradient

Carbon stocks, and C:N ratios, were measured in the forest floor, mineral soil, and two mineral soil fractions (particulate and mineral-associated organic matter, POM and MOM, respectively) at five forest sites, ranging from 60 to 100 years old, along a latitudinal gradient in the eastern United States. Sampling at four sites was replicated over two consecutive years. For many measurements (like forest floor carbon stocks, cumulative soil organic carbon stocks to 20 cm, and the fraction of whole soil carbon in POM), there was no significant difference between years at each site despite the use of somewhat different sampling methods. With one exception, forest floor and mineral soil carbon stocks increased from warm, southern, sites (with fine-textured soils) to northern, cool, sites (with more coarse-textured soils). The exception was a northern site, with less than 10% silt-clay content, that had a soil organic carbon stock similar to those measured at southern sites. Soil carbon at each site was partitioned into two pools (labile and stable) on the basis of carbon measured in the forest floor and POM and MOM fractions from the mineral soil. A two-compartment steady-state model, with randomly varying parameter values, was used in probabilistic calculations to estimate the turnover time of labile soil organic carbon (MRTU) and the annual transfer of labile carbon to stable carbon (k2) at each site in two different years. Based on empirical data, the turnover time of stable soil carbon (MRTS) was determined by mean annual temperature and increased from 30 to 100 years from south to north. Moving from south to north, MRTU increased from approximately 5 to 14 years. Consistent with prior studies, 13C enrichment factors ( ) from the Rayleigh equation, that describe the rate of change in 13C through the soil profile, were an indicator of soil carbon turnover times along the latitudinal gradient. Consistent with its role in stabilization of soil organic carbon, silt-clay content along the gradient was positively correlated (r = 0.91; P 0.001) with parameter k2. Mean annual temperature was indicated as the environmental factor most strongly associated with south to north differences in the storage and turnover of labile soil carbon. However, soil texture appeared to override the influence of temperature when there was too little silt-clay content to stabilize labile soil carbon and thereby protect it from decomposition. Irrespective of latitudinal differences in measured soil carbon stocks, each study site had a relatively high proportion of labile soil carbon (approximately 50% of whole soil carbon to a depth of 20 cm). Depending on unknown temperature sensitivities, large labile pools of forest soil carbon are potentially at risk of depletion by decomposition in a warming climate, and losses could be disproportionately higher from coarse textured forest soils.

54 ENVIRONMENTAL SCIENCES↗

Influence of living grass Roots and endophytic fungal hyphae on soil hydraulic properties

Soil hydraulic properties are often estimated based on laboratory data or pedotransfer functions dependent on soil physical properties, which often do not consider potential impacts of soil roots or fungal hyphae. Here, we first review current knowledge of how these soil biotic components affect hydraulic properties, then we conducted laboratory experiments to specifically test if the presence of roots and mycorrhizal fungi had a significant effect on the hydraulic properties of two soils with contrasting textures: Flint sand and Hamblen silt loam. Soil cores were seeded with (Panicum virgatum) and grown in a greenhouse over three separate growth periods. The endophytic fungus Serendipita indica was injected as liquid inoculant into designated mycorrhizal cores. Saturated hydraulic conductivity (K sat ) measurements were made with a constant head permeameter, and soil water retention curves were obtained by the evaporation method, supplemented at the dry end for Hamblen silt loam with water activity meter data. Retention curve parameters were obtained by fitting the van Genuchten equation to the resulting measurements. Mean root volume ratios were higher in the mycorrhizal inoculated treatment than in the uninoculated treatment for both soils. For Flint sand, analysis of variance revealed that K sat was reduced by the presence of roots as compared to bare soil. This was likely due to roots clogging soil pores. Results also indicated the presence of roots changed the shape of the water retention curve for Flint sand by increasing water content at saturation and by reducing the slope of the curve. These changes suggested roots created additional porosity and broadened the pore-size distribution. The presence of mycorrhizal fungi accentuated the root effects. The influence of roots and mycorrhizal fungi on hydraulic properties was less obvious for the Hamblen silt loam, as none of the treatments differed from each other at p < 0.05. The results highlight the necessity to consider the impact of root and fungal structures on models of soil hydraulic properties.

59 BASIC BIOLOGICAL SCIENCES↗

UT-GOM2-2 Preliminary Report: Terrebonne Basin Northern Gulf of Mexico, 30 July-28 September 2023

In the summer and fall of 2023, the Gulf of Mexico Deepwater Hydrate Coring Expedition (UT-GOM2-2) drilled, cored, made downhole measurements, and analyzed samples from the seafloor to the base of the gas hydrate stability zone in one location (Site H, WR313) in the Terrebonne basin, deepwater Gulf of Mexico. Analyses of data and samples from the expedition will inform biological, geochemical, and geomechanical models to constrain the role of gas hydrates in the carbon cycle and the potential for gas hydrates as an energy resource. Pressure and conventional cores were collected continuously to a depth of 155.1 meters below the seafloor (mbsf). At deeper depths, cores were taken periodically from hydrate-bearing sands and their bounding muds to a total depth of 861.3 mbsf. 162.6 m of conventional core and 54.8 m of pressure core were obtained. Twelve temperature measurements were made between 27.1 and 144.5 mbsf to determine the geothermal gradient. At the seafloor, more than 4 m of sandy silt of unknown origin was encountered. Beneath this sand, to a depth of ~200 mbsf, the section was composed of interbedded mud and biogenic carbonate ooze. The biogenic ooze correlated to low density and high porosity intervals observed in the previously acquired logging while drilling (LWD) data and as measured. Calcareous nannofossil biostratigraphy constrains the entire record to the Pleistocene (< 0.91 million years) with a pronounced increase in sedimentation rate with depth. Beneath 200 mbsf, the section was predominantly composed of mud with two thicker, hydrate-bearing coarse-grained intervals, which are commonly known as the Blue and Orange sands. The dissolved gas concentration was quantified from pressure cores. In the shallow section, dissolved methane concentration increased below the sulfate-methane transition zone (SMTZ) and reaches saturation (the limit of solubility for methane) at 147 mbsf. Gas expansion was very common in conventional and depressurized pressure (conventionalized) cores below the SMTZ. At deeper depths, the methane concentration within muds bounding the Blue and Orange reservoirs was generally found to be less than saturation. The dissolved and hydrate gas composition is consistent with a microbial source, containing greater than 99.99% methane and only trace concentrations of ethane, propane, and butane. The methane to ethane ratio (C 1 /C 2 ) and the methane to ethane plus propane (C 1 /(C 2 +C 3 )) decrease with depth down to at least 678 mbsf, mainly driven by the increase in ethane with depth. It is unclear if this trend continues through the Orange sand interval. The δ 13 C isotopic signature of methane ranges between -69.9 and -78.5 ‰ Vienna Pee Dee Belemnite (VPDB). Pressure core recovery of all sandy intervals was poor. However, pressure core logs of the Orange sand show intervals of low density and high velocity, which are indicative of high hydrate saturation. One core from within the Orange sand was composed of interbedded graded sandy silt and mud. The sandy silts from this core are composed of mainly quartz and feldspar with some lithics. Most of the recovered pressure core samples are maintained at near in-situ pressure and temperature (within the hydrate stability field) at the University of Texas Pressure Core Center awaiting analysis. In the shallow section, samples will be used to determine the flux of organic carbon through the basin system, find the rate at which that carbon was consumed, and understand the microbial population responsible for these processes. In the deeper section, samples from in and around the hydrate reservoirs will be used to determine the petrophysical properties of the reservoir and bounding seals in these systems.

03 NATURAL GAS↗

Expedition UT-GOM2-2 Site H

Pressure and conventional cores were collected at Site H of the Walker Ridge Protracted Area Block 313 in the Terrebonne Basin, deepwater Gulf of America (Gulf of Mexico) during the University of Texas (UT) Deepwater Hydrate Coring Expedition (UT-GOM2-2). Pressure and conventional cores were collected continuously to a depth of 155.1 meters below the seafloor (mbsf). At deeper depths, cores were taken periodically from hydrate-bearing sands and their bounding muds to a total depth of 861.3 mbsf. 162.6 m of conventional core and 54.8 m of pressure core were recovered. Twelve temperature measurements were made between 27.1 and 144.5 mbsf to determine the geothermal gradient. At the seafloor, more than 4 m of sandy silt of unknown origin was encountered. Beneath this sand, to a depth of about 200 mbsf, the section was composed of interbedded mud and biogenic carbonate ooze. The ooze correlated to low density and high porosity intervals observed in the previously acquired logging while drilling (LWD) data and as measured. These ooze intervals also correspond to lighter sediment color, increased Ca content based on X-ray florescence (XRF) core scanning, and increased calcareous nannofossil abundance. Calcareous nannofossil biostratigraphy constrains the entire record to the Pleistocene (< 0.91 million years), with a pronounced increase in sedimentation rate with depth. Below 200 mbsf, the section was predominantly composed of mud with two thicker, hydrate-bearing coarse-grained intervals, which are commonly known as the Blue and Orange sands. The dissolved gas concentration was quantified from pressure cores. In the shallow section, dissolved methane concentration increased below the sulfate-methane transition zone (SMTZ) and reaches saturation (the limit of solubility for methane) at 147 mbsf. Gas expansion was very common in conventional and depressurized pressure (conventionalized) cores below the SMTZ. At deeper depths, the methane concentration within muds bounding the Blue and Orange reservoirs was generally found to be less than saturation. The dissolved and hydrate gas composition is consistent with a microbial source, containing greater than 99.99% methane and only trace concentrations of ethane, propane, and butane. The methane to ethane ratio (C1 /C2 ) and the methane to ethane plus propane (C1 /(C2 +C3 )) decrease with depth down to at least 678 mbsf, mainly driven by the increase in ethane with depth. It is unclear if this trend continues through the Orange sand interval. The δ13C isotopic signature of methane ranges between -69.9 and -78.5 ‰ relative to the Vienna Pee Dee Belemnite (VPDB) standard. Pressure core recovery in sandy intervals was poor. However, pressure core logs of the Orange sand show intervals of low density and high velocity, which are indicative of high hydrate saturation. One pressure core was degassed and the average hydrate saturation in the core was determined to be 24%. One core from within the Orange sand was composed of interbedded graded sandy silt and mud. The sandy silts from this core are composed of mainly quartz and feldspar with some lithics. Most of the recovered pressure core samples are maintained at near in-situ pressure and temperature (within the hydrate stability field) at the University of Texas Pressure Core Center awaiting analysis. In the shallow section, samples will be used to determine the flux of organic carbon through the basin system, find the rate at which that carbon was consumed, and understand the microbial population responsible for these processes. In the deeper section, samples from in and around the hydrate reservoirs will be used to determine the petrophysical properties of the reservoir and bounding seals in these systems.

03 NATURAL GAS↗

Comprehensive analysis of Shuttle Orbiter leeside surface infrared imagery obtained during atmospheric entry

The thermographic analysis techniques developed for processing of data from the Shuttle Infrared Leeside Temperature Sensing (SILTS) experiment are discussed. The SILTS experiment will obtain high-spatial-resolution infrared images of the leeside of the Space Shuttle Orbiter during atmospheric entry by means of a scanning infrared radiometer located atop the orbiter's vertical stabilizer. Comprehensive analysis of the SILTS thermography requires accurate consideration of all those factors (such as geometry of the observed surfaces, local surface emissivity, solar radiation, and other potential sources of image degradation) which may potentially affect the output of the infrared radiometer. An overview of the entire data processing procedure and brief descriptions of the data processing algorithms are presented.

Myrick, D. L.↗

Dust deposits on Mars: The 'parna' analog

Parna is an Autralian aboriginal word meaning 'sandy dust'. It has been applied to deposits of clay, silt, and sand which were initially transported by the wind as aggregates, or pellets, of sand size. Parna is distinguished by its silt and clay content, which in some cases exceeds 85% of the total volume of the deposit. Much of the fine-grained playa silt and clay is incorporated into the parna as sand-sized aggregates, which greatly facilitate their transportation and reworking by the wind. Rain following aggregate emplacement can cause their disintegration, rendering the parna immobile by the wind, yet some pellets can survive several wetting/drying episodes. Parna deposits on Earth occur both as dune forms and as sheet deposits which mantle older terrains. In both cases the deposits are typically derived from lacustrine (lake) beds, such as playas. There is substantial evidence to suggest that bodies of water existed on Mars in the past. Thus, the potential is high for lacustrine deposits and the formation of parna on Mars. Although no parna dunes have been identified, it is suggested that the deposits derived from White Rock (-8 deg, 335 deg W), near Mamers Valles (34 deg, 343 deg W), and elsewhere on Mars may represent sheet parna. Data obtained from Mars-94/96 missions and potential landed spacecraft may provide additional evidence for the existence of parna on Mars.

Greeley, Ronald↗

Bioremediation of a Large Chlorinated Solvent Plume, Dover AFB, DE

Bioremediation of a Large Chlorinated Solvent Plume, Dover AFB, DE Aleisa Bloom, (Oak Ridge National Laboratory, Oak Ridge, Tennessee, USA) Robert Lyon (bob.lyon@aecom.com), Laurie Stenberg, and Holly Brown (AECOM, Germantown, Maryland, USA) ABSTRACT: Past disposal practices at Dover Air Force Base (AFB), Delaware, created a large solvent plume called Area 6 (about 1 mile long, 2,000 feet wide, and 345 acres). The main contaminants are PCE, TCE, and their degradation products. The remedy is in-situ accelerated anaerobic bioremediation (AAB). AAB started in 2006 and is focusing on source areas and downgradient plume cores. Direct-push injections occurred in source areas where contamination is typically between 5 and 20 feet below ground surface. Lower concentration dissolved-phased contamination is present downgradient at 35 and 50 feet below ground surface. Here, permanent injection/extraction wells installed in transects perpendicular to the flow of groundwater are used to apply AAB. The AAB substrate is a mix of sodium lactate, emulsified vegetable oil, and nutrients. After eight years, dissolved contaminant mass within the main 80-acre treatment area has been reduced by over 98 percent. This successful application of AAB has stopped the flux of contaminants to the more distal portions of the plume. While more time is needed for effects to be seen in the distal plume, AAB injections will soon cease, and the remedy will transition to natural attenuation. INTRODUCTION Oak Ridge National Laboratory Environmental Science Division (ORNL) and AECOM (formerly URS Corporation) have successfully implemented in situ accelerated anaerobic bioremediation (AAB) to remediate chlorinated solvent contamination in a large, multi-sourced groundwater plume at Dover Air Force Base (AFB). AAB has resulted in significant reductions of dissolved phase chlorinated solvent concentrations. This plume, called Area 6, was originally over 1 mile in length and over 2,000 feet wide (Figure 1). It originated from at least four separate source areas that comingled in the subsurface to form the large plume. The major contaminants of concern (COCs) are tetrachloroethene (PCE), trichloroethene (TCE), and 1,1,1-trichloroethane (1,1,1-TCA), which were historically used for degreasing operations in the maintenance of aircraft and support vehicles. Relatively small areas of elevated PCE, TCE, and 1,1,1-TCA were delineated in the shallow portion of the water table aquifer by direct-push groundwater sampling. Focused direct-push AAB treatment occurred in March 2006 at these source areas (Figure 1). Downgradient of the these areas and deeper in the aquifer, AAB treatment was implemented using rows of extraction/injection wells oriented perpendicular to groundwater flow to create multiple reductive zones across the plume cores, defined as areas where more than 1,000 micrograms per liter (ug/L) total solvent concentrations were present. Initial indications of successful degradation were observed within 6 months of starting injections. FIGURE 1. Dover AFB Area 6 plume. This paper describes the AAB implementation and progress of remediation after 8 years of treatment and periodic groundwater monitoring. SITE LITHOLOGY Contamination at the site is limited to the surficial aquifer, which consists of 35 to 50 feet (ft) (11 to 15 meters [m]) of unconsolidated Pleistocene deposits of the Columbia Formation. The Columbia Formation consists of fine to coarse sand with silt and clay lenses and less common gravel lenses. Silts and silty sands are generally encountered to a depth of 10 to 12 ft (3.05 to 3.65 m) below ground surface (bgs) and grade to medium- and coarse-grained sands to a depth of 35 to 50 ft (11 to 15 m) bgs. There is a clay and silt unit (part of the Calvert Formation) below the surficial aquifer that acts as an aquitard to the downward migration of contaminants. The depth to the water table varies across the site but usually ranges from 8 to 15 ft (2.4 to 4.5 m) bgs in the treatment area. REMEDIAL APPROACH AND OPERATIONS Because the Columbia Aquifer is used as a source of potable water off base, the remedial goal is to restore the aquifer to usable condition, i.e., reduce all chemicals of concern to below drinking water maximum contaminant levels (MCLs). To achieve this goal, AAB was selected as the best remedial alternative to reduce the solvent contamination. Source areas with high solvent concentrations were present in the shallow portion of the aquifer. From the source areas, dissolved solvents migrated downgradient and deeper in the aquifer with the flow of groundwater. In the deeper portion of the aquifer, the individual plumes comingle to form the larger Area 6 Plume, which covers approximately 345 acres. Types of Substrate. Previous AAB pilot tests at Dover AFB used either sodium lactate or emulsified vegetable oil (EVO) as substrates to stimulate microbial growth. The best results were obtained with...

Bloom, Aleisa C↗

Interpreting Temperature Strain Data from Meso-Scale Clathrate Experiments

Gas hydrates are important in global climate change, carbon sequestra- tion, and seafloor stability. Currently, formation and dissociation pathways are poorly defined. We present a new approach for processing large amounts of data from meso-scale experiments, such as the LUNA distributed sensing system (DSS) in the seafloor process simulator (SPS) at Oak Ridge National Laboratory. The DSS provides a proxy for temperature measurement with a high spatial resolution allowing the heat of reaction during gas hydrate formation/dissociation to aid in locating clathrates in the vessel. The DSS fibers are placed in the sediment following an Archimedean spiral design and then the position of each sensor is solved by iterating over the arc length formula with Newtons method. The data is then gridded with 1 a natural neighbor interpolation algorithm to allow contouring of the data. The solution of the sensor locations is verified with hot and cold stimulus in known locations. An experiment was preformed with a vertically split column of sand and silt. The DSS system clearly showed hydrate forming in the sand first, then slowly creeping into the silt. Similar systems and data processing techniques could be used for monitoring of hydrates in natural environments or in any situation where a hybrid temperature/strain index is useful. Further ad- vances in fiber technology allow the fiber to be applied in any configuration and the position of each sensor to be precisely determined making practical applications easier.

54 ENVIRONMENTAL SCIENCES↗

Biochars impact on soil moisture storage in an Ultisol and two Aridisols

Biochar additions to soils can improve soil water storage capability, however, there is sparse information identifying feedstocks and pyrolysis conditions that maximize this improvement. Nine biochars were pyrolyzed from five feedstocks at two temperatures and their physical and chemical properties were characterized. Biochars were mixed at 2% wt w{sup -1} into a Norfolk loamy sand (Fine-loamy, kaolinitic, thermic Typic Kandiudult), a Declo silt loam (Coarse-loamy, mixed, superactive, mesic xeric Haplocalcid), or a Warden silt loam (Coarse-silty, mixed, superactive, mesic xeric Haplocambid). Untreated soils served as controls. Soils were laboratory incubated in pots for 127 days and were leached about every 30 days with deionized water. Soil bulk densities were measured before each leaching event. For six days thereafter, pot holding capacities (PHC) for water were determined gravimetrically and were used as a surrogate for soil moisture contents. Water tension curves were also measured on the biochar treated and untreated Norfolk soil. Biochar surface area, surface tension, ash, C, and Si contents, in general, increased when produced under higher pyrolytic temperatures ({ge}500 C). Both switchgrass biochars caused the most significant water PHC improvements in the Norfolk, Declo and Warden soils compared to the controls. Norfolk soil water tension results at 5 and 60 kPa corroborated that biochar from switchgrass caused the most significant moisture storage improvements. Significant correlation occurred between the PHC for water with soil bulk densities. In general, biochar amendments enhanced the moisture storage capacity of Ultisols and Aridisols, but the effect varied with feedstock selection and pyrolysis temperature.

54 ENVIRONMENTAL SCIENCES↗

Determination of Water Saturation in Relatively Dry Porous Media Using Gas-phase Tracer Tests

Soil desiccation (drying), involving water evaporation induced by dry air injection and extraction, is a potentially robust remediation process to slow migration of inorganic or radionuclide contaminants through the vadose zone. The application of gas-phase partitioning tracer tests has been proposed as a means to estimate initial water volumes and to monitor the progress of the desiccation process at pilot-test and field sites. In this paper, tracer tests have been conducted in porous medium columns with various water saturations using sulfur hexafluoride as the conservative tracer and tricholorofluoromethane and difluoromethane as the water-partitioning tracers. For porous media with minimal silt and/or organic matter fractions, tracer tests provided reasonable saturation estimates for saturations close to zero. However, for sediments with significant silt and/or organic matter fractions, tracer tests only provided satisfactory results when the water saturation was at least 0.1 - 0.2. For dryer conditions, the apparent tracer retardation increases due to air – soil sorption, which is not included in traditional retardation coefficients derived from advection-dispersion equations accounting only for air – water partitioning and water – soil sorption. Based on these results, gas-phase partitioning tracer tests may be used to determine initial water volumes in sediments, provided the initial water saturations are sufficiently large. However, tracer tests are not suitable for quantifying moisture content in desiccated sediments.

54 ENVIRONMENTAL SCIENCES↗