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At least 55 records · Page 3

Strontium and oxygen isotope study of M-1, M-3 and M-4 drill core samples from the Manson impact structure, Iowa: Comparison with Haitian K-T impact glasses

Strontium and oxygen isotope analyses were performed on 8 samples from the M-1, M-3, and M-4 cores recently drilled at the Manson impact structure. The samples were three elastic sedimentary rocks (of probable Cretaceous age) which occurred as clasts within the sedimentary clast breccia, two samples of crystalline rock breccia matrix, and three samples of dolomite and limestone. The Sr-87/Sr-86 (corrected to 65 Ma) ratios were much higher than those in impact glasses from the Haitian Cretaceous-Tertiary (K-T) boundary. Isotope mixing calculations demonstrate that neither the silicate or carbonate rocks analyzed from the Manson crater, or mixtures of these rocks are appropriate source materials for the Haitian impact glasses. However, the Sr-87/Sr-86 (65Ma) ratio and delta O-18 value of the Ca-rich Haitian glasses are well reproduced by mixtures of Si-rich Haitian glass with platform carbonate of K-T age.

Blum, Joel D.↗

Assessment of In-situ Proppant Placement in SRV Using Through-Fracture Core Sampling at HFTS

The primary aim of this study was to develop robust methods aimed at detecting and quantifying the subsurface proppant distribution as it relates to the completed wells in both the upper and the middle Wolfcamp formations at the HFTS site. There were two sources of proppant deemed useful for this task. The first source was the actual scrapings from the fracture faces that were collected during the core description work. The second sample source was the scrapings and sludge from the cut core tubes collected during core handling. This study highlights the analysis done on the second set of sludge samples. Apart from developing a method for detection and quantification of proppant and other particles contained within this sludge, the study was aimed at the following broad objectives: Determine the spatial distribution of proppant in the created SRV along the cored interval, including size distribution and proppant concentration. Determine if pay zones of interest are sufficiently propped/ stimulated. Determine if fracture and cluster spacing is optimal for thorough lateral reservoir coverage. Determine if well spacing is optimal based on propped SRV length.

Maity, Debotyam↗

Methane, ethane, and propane production in Greenland ice core samples and a first isotopic characterization of excess methane

Air trapped in polar ice provides unique records of the past atmospheric composition ranging from key greenhouse gases such as methane (CH 4 ) to short-lived trace gases like ethane (C 2 H 6 ) and propane (C 3 H 8 ). Recently, the comparison of CH 4 records obtained using different extraction methods revealed disagreements in the CH 4 concentration for the last glacial in Greenland ice. Elevated methane levels were detected in dust-rich ice core sections measured discretely, pointing to a process sensitive to the melt extraction technique. To shed light on the underlying mechanism, we performed targeted experiments and analyzed samples for methane and the short-chain alkanes ethane and propane covering the time interval from 12 to 42 kyr. Here, we report our findings of these elevated alkane concentrations, which scale linearly with the amount of mineral dust within the ice samples. The alkane production happens during the melt extraction step of the classic wet-extraction technique and reaches 14 to 91 ppb of CH 4 excess in dusty ice samples. We document for the first time a co-production of excess methane, ethane, and propane, with the observed concentrations for ethane and propane exceeding their past atmospheric background at least by a factor of 10. Independent of the produced amounts, excess alkanes were produced in a fixed molar ratio of approximately 14 : 2 : 1, indicating a shared origin. The measured carbon isotopic signature of excess methane is (-47.0 ± 2.9) ‰ and its deuterium isotopic signature is (-326 ± 57) ‰. With the co-production ratios of excess alkanes and the isotopic composition of excess methane we established a fingerprint that allows us to constrain potential formation processes. This fingerprint is not in line with a microbial origin. Moreover, an adsorption–desorption process of thermogenic gas on dust particles transported to Greenland does not appear very likely. Instead, the alkane pattern appears to be indicative of abiotic decomposition of organic matter as found in soils and plant leaves.

54 ENVIRONMENTAL SCIENCES↗

Spatial and temporal baseline of perfluorooctanesulfonic acid retained in sediment core samples from Puget Sound, Washington, USA

Per- and poly-fluorinated alkyl substances (PFAS) are a group of highly persistent synthetic chemicals utilized in many industrial and consumer products, and — most significantly toward introduction to the marine environment — in fire-fighting foams. Recently, PFAS have been linked to adverse health effects, prompting the need to understand transport and fate. Puget Sound’s main basin, hosting densely populated urban and industrial areas, is known to be contaminated with various persistent organic pollutants and provides a central focus for ecosystem monitoring. Perfluorooctanesulfonic acid, a manufactured PFAS and biodegradation product, partitions to marine sediments and thus can be used as a primary indicator toward regulatory efforts. The current study offers a spatial and temporal analysis of the Puget Sound from cores collected adjacent, Tacoma and Seattle, WA, as well as cores from central Hood Canal and Carr Inlet.

Per- and poly-fluorinated alkyl substances (PFAS),↗

Diffusive Properties of UNESE Core Samples via Continuously Monitored Mass Spectroscopy

The transport properties of porous geological media are of fundamental importance when modeling the migration of chemical and radiological species in subterranean systems. Due to their relatively high mobility, short-lived noble gas species are of particular interest as detection of these species at the surface is a tell-tale indicator of recent nuclear activity. However, determining the diffusivity of these species is challenging due to their inert and transparent nature, requiring chemically insensitive techniques, such as mass spectroscopy, to quantify noble gas concentrations. The work described herein details recent advances in the methodology for determining diffusivity on porous media and results obtained on samples relevant to the UNESE project.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Evaluating Surface Exposure Timescales Derived From Solar Energetic Particle Track Densities for Grains From Apollo 17 Core Sample 73002

Space weathering causes the surface soils of airless bodies like the Moon to be morphologically, microstructurally, and chemically altered due to micrometeoroid bombardment and solar wind exposure. These processes produce a multitude of microstructural and chemical changes that accumulate on individual soil grains that are continuously exposed on the surface. One characteristic is the formation of solar wind damaged rims on grains which develop from low energy solar wind particles penetrating <100 nm in depth. Also present are solar energetic particle (SEP) tracks, which are nanoscale streaks of irradiation damage in grain interiors formed by heavy, high energy ions (predominantly Fe group nuclei) originating from solar energetic particles (SEPs) that penetrate millimeters below the surface.

J. A. McFadden↗

Diesel Particulate Filter Durability Performance Comparison Using Metals Doped B20 vs. Conventional Diesel Part II: Chemical and Microscopic Characterization of Aged DPFs

This project's objective was to generate experimental data to evaluate the impact of metals doped B20 on diesel particle filter (DPF) ash loading and performance compared to that of conventional petrodiesel. The effect of metals doped B20 vs. conventional diesel on a DPF was quantified in a laboratory controlled accelerated ash loading study. The ash loading was conducted on two DPFs - one using ULSD fuel and the other on B20 containing metals dopants equivalent to 4 ppm B100 total metals. Engine oil consumption and B20 metals levels were accelerated by a factor of 5, with DPFs loaded to 30 g/L of ash. Details of the ash loading experiment and on-engine DPF performance evaluations are presented in the companion paper (Part I). The DPFs were cleaned, and ash samples were taken from the cleaned material. X-ray Fluorescence (XRF), X-Ray Photoelectron Spectroscopy (XPS) and X-Ray Diffraction (XRD) were conducted on the ash samples. Core samples were taken from the cleaned DPF and were subjected to scanning electron microscope energy dispersive x-ray spectroscopy (SEM-EDS) and XRF analysis. A comparison of the data from the two DPFs is presented. The XRD and XPS analysis showed that the compounds present in the ash from the two DPFs were nearly identical, though differing in concentrations. CaSO4 was the biggest component of the ash from both DPFs. The metals doped B20 fuel resulted in ash with similar characteristics to that deposited by the lube oil and did not appear to have any deleterious physical effects on the DPF substrate (did not penetrate the substrate).

ADVANCED PROPULSION SYSTEMS,BIOMASS FUELS↗

Investigation of Thermolytic Hydrogen Generation Rate in Tank 44 Dissolved Saltcake Samples

Saltcake core samples collected from Tank 44 in 2006 were dissolved to provide material for HGR measurements applicable to F-Area dissolved saltcake material. Additionally, characterization was performed on the Tank 44 saltcake material. The following are key results from the Tank 44 saltcake characterization. The Tank 44 Upper Saltcake Composite, corresponding to the 171 to 285 inch tank level, contained by mass approximately 69% sodium nitrate, 11% sodium carbonate, 8% sodium nitrite, smaller amounts of other salts and components, and 9% unquantified (which includes water, water of hydration, oxygen/hydrogen content of oxides and hydroxides, and uncertainty). The Tank 44 Lower Saltcake Composite, corresponding to the 76 to 114 inch tank level, contained by mass approximately 49% sodium carbonate, 18% sodium nitrate, smaller amounts of other salts, at least 8% sludge, and 9% unquantified (see above). The dissolved saltcake contained free hydroxide less than quantifiable (<0.01 M) due to the limited quantity of material that could be removed from the Shielded Cells based on the sample radioactivity. Measurement by pH paper provided an approximate pH of 12. The following are key results from the Tank 44 HGR testing. During boiling at 106.7 °C, HGR for Tank 44 dissolved saltcake without added glycolate was 7.2×10 -8 ft 3 h -1 ga l-1 . During boiling at 106.9 °C, HGR for Tank 44 dissolved saltcake with 1000 mg/L of added glycolate was 8.2×10 -8 ft 3 h -1 gal -1 . ∙ For the test without added glycolate, the first several HGR measurements at 70, 85, and 100 °C gave indication of the release of dissolved hydrogen and should not be used to represent the sustained thermolytic HGR for those temperatures. The measurements at boiling are the best representation of thermolysis in this testing. Carbon dioxide was observed at concentrations up to 6 vol% in the flow-system offgas for the test at boiling. ∙ Methane generation was observed at 100 °C and boiling. Methane concentration in the total gas generated during testing remained well below the lower flammability limit for methane in air. The addition of 1000 mg/L of glycolate did not have a significant impact on the hydrogen generation rates measured during this testing. The low hydroxide concentration in the Tank 44 dissolved saltcake likely influenced the relatively low thermolytic HGR and high carbon dioxide release observations in this testing. Based on the observation that methane was generated or released upon heating SRS radioactive Tank 44 waste samples to 100 °C and above, we recommend gaining a greater understanding of the cause and mechanism of its generation. First, the applicable literature should be reviewed to reveal the thermolytic methane generation mechanisms of possible methane generating species in the SRS CSTF. If warranted, a plan should be developed for simulant tests with methylated siloxanes and other applicable compounds in order to gain a better mechanistic understanding of methane generation in the SRS CSTF.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Investigation of Thermolytic Hydrogen Generation Rate in Tank 44 Dissolved Saltcake Samples

Saltcake core samples collected from Tank 44 in 2006 were dissolved to provide material for HGR measurements applicable to F-Area dissolved saltcake material. Additionally, characterization was performed on the Tank 44 saltcake material. The following are key results from the Tank 44 saltcake characterization. The Tank 44 Upper Saltcake Composite, corresponding to the 171 to 285 inch tank level, contained by mass approximately 69% sodium nitrate, 11% sodium carbonate, 8% sodium nitrite, smaller amounts of other salts and components, and 9% unquantified (which includes water, water of hydration, oxygen/hydrogen content of oxides and hydroxides, and uncertainty). The Tank 44 Lower Saltcake Composite, corresponding to the 76 to 114 inch tank level, contained by mass approximately 49% sodium carbonate, 18% sodium nitrate, smaller amounts of other salts, at least 8% sludge, and 9% unquantified (see above). The dissolved saltcake contained free hydroxide less than quantifiable (<0.01 M) due to the limited quantity of material that could be removed from the Shielded Cells based on the sample radioactivity. Measurement by pH paper provided an approximate pH of 12. The following are key results from the Tank 44 HGR testing. During boiling at 106.7 °C, HGR for Tank 44 dissolved saltcake without added glycolate was 7.2×10 -8 ft 3 h -1 gal -1 . During boiling at 106.9 °C, HGR for Tank 44 dissolved saltcake with 1000 mg/L of added glycolate was 8.2×10 -8 ft 3 h -1 gal -1 . For the test without added glycolate, the first several HGR measurements at 70, 85, and 100 °C gave indication of the release of dissolved hydrogen and should not be used to represent the sustained thermolytic HGR for those temperatures. The measurements at boiling are the best representation of thermolysis in this testing. Carbon dioxide was observed at concentrations up to 6 vol% in the flow-system offgas for the test at boiling. Methane generation was observed at 100 °C and boiling. Methane concentration in the total gas generated during testing remained well below the lower flammability limit for methane in air. The addition of 1000 mg/L of glycolate did not have a significant impact on the hydrogen generation rates measured during this testing. The low hydroxide concentration in the Tank 44 dissolved saltcake likely influenced the relatively low thermolytic HGR and high carbon dioxide release observations in this testing. Based on the observation that methane was generated or released upon heating SRS radioactive Tank 44 waste samples to 100 °C and above, we recommend gaining a greater understanding of the cause and mechanism of its generation. First, the applicable literature should be reviewed to reveal the thermolytic methane generation mechanisms of possible methane generating species in the SRS CSTF. If warranted, a plan should be developed for simulant tests with methylated siloxanes and other applicable compounds in order to gain a better mechanistic understanding of methane generation in the SRS CSTF.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Analysis of Monolith Cores from an Engineering Scale Demonstration of a Prospective Cast Stone Process

The primary disposition path of Low Activity Waste (LAW) at the DOE Hanford Site is vitrification. A cementitious waste form is one of the alternatives being considered for the supplemental immobilization of the LAW that will not be treated by the primary vitrification facility. Washington River Protection Solutions (WRPS) has been directed to generate and collect data on cementitious or pozzolanic waste forms such as Cast Stone. This report documents the coring and leach testing of monolithic samples cored from an engineering-scale demonstration (ES Demo) with non-radioactive simulants. The ES Demo was performed at SRNL in October of 2013 using the Scaled Continuous Processing Facility (SCPF) to fill an 8.5 ft. diameter x 3.25 ft. high container with simulated Cast Stone grout. The Cast Stone formulation was chosen from the previous screening tests. Legacy salt solution from previous Hanford salt waste testing was adjusted to correspond to the average LAW composition generated from the Hanford Tank Waste Operation Simulator (HTWOS). The dry blend materials, ordinary portland cement (OPC), Class F fly ash, and ground granulated blast furnace slag (GGBFS or BFS), were obtained from Lafarge North America in Pasco, WA. In 2014 core samples originally obtained approximately six months after filling the ES Demo were tested along with bench scale molded samples that were collected during the original pour. A latter set of core samples were obtained in late March of 2015, eighteen months after completion of the original ES Demo. Core samples were obtained using a 2” diameter x 11” long coring bit. The ES Demo was sampled in three different regions consisting of an outer ring, a middle ring and an inner core zone. Cores from these three lateral zones were further segregated into upper, middle and lower vertical segments. Monolithic core samples were tested using the Environmental Protection Agency (EPA) Method 1315, which is designed to provide mass transfer rates (release rates) of inorganic analytes contained in monolithic material under diffusion controlled release conditions as a function of leaching time. Compressive strength measurements and drying tests were also performed on the 2015 samples. Leachability indices reported are based on analyte concentrations determined from dissolution of the dried samples.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

A Viable Path Forward to Carbon Capture and Storage in Wyoming, USA

The State of Wyoming, USA, benefits from favorable geologic, regulatory, and infrastructure attributes that promote efficient and sustainable carbon capture and storage (CCS). Two research sites in Wyoming exhibit high potential for the underground geologic storage of greater than 50 million metric tons of carbon dioxide (CO 2 ) over 25 years. Funded by the U.S. Department of Energy’s (DOE) Carbon Storage Assurance and Facility Enterprise (DOE CarbonSAFE) Phase I prefeasibility initiative, studies of both sites indicate promising capture, transport, utilization, and storage characteristics. The Dry Fork site is located near Gillette, in northeast Wyoming. Four storage reservoir/seal pairs have been identified at the Dry Fork site that provide excellent prospects for stacked storage of CO 2 . All four reservoirs lie at sufficient depths to maintain supercritical CO 2 and all four seals exhibit favorable characteristics for stratigraphic confinement. The reservoir with the highest expected significance is the Pennsylvanian/Permian Minnelusa Formation, which consists of near-shore dunes and shoreline sands, as well as shale and carbonate layers. The Minnelusa resides at a depth of ~2,900 m below the land surface and is ~45 m thick in the study area. Average porosity for samples from core within 10 km of the study area is 9%, with permeability values as high as 169 mD (n=6). The Permian Opeche Formation seals the Minnelusa and consists of redbed shales with minor fine-grained siltstones and evaporite deposits. Entry pressures as high as ~4700 psia were measured by mercury injection capillary pressure (MICP) analysis on core samples from the Opeche. A CarbonSAFE Phase II feasibility proposal at the Dry Fork site has recently been selected by DOE for negotiation leading to award. The second proposed site is located at the Rock Springs Uplift (RSU) in southwest Wyoming. Four reservoir/seal pairs have been studied at the RSU, all of which present promising geologic attributes for the stacked storage of CO 2 . The two deepest reservoirs (Mississippian Madison Limestone and Pennsylvanian/Permian Weber Formation) and their seals were studied previously under the auspices of the Wyoming Carbon Underground Storage Project (WY-CUSP), which was funded by DOE and the State of Wyoming. For the more recent CarbonSAFE initiative, two shallower reservoir/seal pairs were studied in detail. The highest priority of these reservoirs is the Triassic/Jurassic Nugget Formation, which consists of eolian sands and minor fluvial and interdune deposits. The Nugget lies at a depth of ~2,800 m and is ~140 m thick in the study area. Average measured porosity for samples from core within 40 km of the study site is 9%, with permeability values as high as 91 mD (n=10). The Nugget is sealed by the overlying Jurassic Gypsum Spring and Morrison Formations, as well as a thick (~1,700 m) regional Upper Cretaceous seal that includes shales from multiple geologic units. Entry pressures as high as 1120 psia were measured by MICP for shales within this regional confining unit. Overall, the State of Wyoming provides an advantageous climate to develop sustainable integrated CCS projects based on the following considerations: (1) well-characterized and favorable geology; (2) some of the largest deposits of economically recoverable coal in the USA; (3) an existing CO 2 -enhanced oil recovery industry, including CO 2 pipeline infrastructure; (4) supportive commercial enterprises, including utilities and the oil and gas industry; (5) supportive policymakers; (6) a favorable legal and regulatory environment; (7) proximity to carbon-constrained markets such as the State of California; (8) large CO 2 emission sources, including coal-fired power plants; and (9) backing for carbon capture, storage, and management related research and development, specifically implementation of the Integrated Test Center at Dry Fork Station, which is hosting the coal-track of the NRG/COSIA Carbon XPrize® competition.

Phillips, Erin↗