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At least 37 records · Page 2

I-129/I-127 variations among enstatite chondrites

The iodine isotopic compositions and corresponding I-Xe ages were obtained for eight enstatite chondrites, bringing the total number of enstatite chondrites examined by the I-Xe technique to 11. Iodine isotopic compositions of these 11 chondrites indicate a well-defined hiatus correlated with the hiatus in chemical composition defining the two distinct enstatite groups: EH(4,5) and EL(6). Judging by the I-129/I-127 ratios and assuming that both the EH and EL groups originated from a reservoir with a uniform initial iodine isotopic composition, the EH(4,5) chondrites were estimated to be about 4 mln older than the El chondrites.

Kennedy, B. M.↗

STS 129 Return Samples: Assessment of Air Quality aboard the Shuttle (STS-129) and International Space Station (ULF3)

Reports on the air quality aboard the Space Shuttle (STS-129), and the International Space station (ULF3). NASA analyzed the grab sample canisters (GSCs) and the formaldehyde badges aboard both locations for carbon monoxide levels. The three surrogates: (sup 13)C-acetone, fluorobenzene, and chlorobenzene registered 109, 101, and 109% in the space shuttle and 81, 87, and 55% in the International Space Station (ISS). From these results the atmosphere in both the Space Shuttle and the International Space Station (ISS) was found to be breathable.

James, John T.↗

In situ reductive dissolution to remove Iodine-129 from aquifer sediments

The use of an aqueous reductant (Na-dithionite) with pH buffer (K-carbonate, pH 12) was evaluated in this laboratory study as a potential remedial approach for removing Fe oxide associated iodine and enhancing pump-and-treat extraction from iodine-contaminated sediments in the unconfined aquifer in the 200 West Area of the Hanford site. X-ray fluorescence data of untreated sediment indicated that iodine was largely associated with Fe (i.e., incorporated into Fe oxides), however, XANES data was inconclusive as to valence state. During groundwater leaching, aqueous and adsorbed iodine was quickly released, then additional iodine was slowly released potentially from dissolution of one or more surface phases. The Na-dithionite treatment removed greater iodine mass (2.9x) at a faster rate (1 to 4 orders of magnitude) compared to leaching with groundwater alone. Iron extractions for untreated and treated sediments showed a decrease in Fe(III)-oxides, which likely released iodine to aqueous solution. Solid phase inorganic carbon and aqueous Ca and Mg analysis further confirmed that significant calcite dissolution did not occur in these experiments meaning these phases did not release significant iodine. Although it was expected that, after treatment, 127 I concentrations would eventually be lower than untreated sediments, leaching experiments showed continued, elevated iodine concentrations for treated samples over 750 hours. Stop flow events during 1-D column leaching suggested that some iodide precipitated within the first few pore volumes. In the survey of metals during leaching, some silver was detected which could have been solubilized by the elevated pH of initial Na-dithionite injection. Then, silver (or other metals) could have subsequently precipitated with iodide during the initial stop flow event forming a slowly dissolving source. Although significantly greater iodine is removed with treatment, the long-term leaching needs to be investigated further as it may limit dithionite treatment at the field scale.

54 ENVIRONMENTAL SCIENCES↗

Process optimization of caustic scrubber and iodine-129 immobilization in sodalite-based waste forms

Caustic scrubbers are proposed to remove vaporized iodine from nuclear fuel reprocessing plants. Resulting caustic slurries of radioactive iodine ( 129 I) and other anions can be captured and immobilized into the cage structures of sodalite-type minerals. Here, mixed anion sodalites were hydrothermally synthesized from a simulated caustic scrubber solution containing hydroxide/water, carbonate, chlorine, bromine, iodine, nitrate, and nitrite ions with added kaolinite. Experiments were conducted with twenty-five different sets of process conditions. Resulting powders were characterized by quantitative X-ray diffraction (XRD) and multi-functional thermal analysis, including gravimetry, calorimetry, and mass spectrometry. Using statistical analysis, process variables were tailored to maximize conversion of kaolinite into cage silicates, immobilize caustic scrubber anions, and minimize amorphous content. Further, chemical analysis showed the incorporation of all the targeted ions into the solids. Detailed investigation of a batch characterized after washing (creating secondary waste) and one without washing but subsequent calcination is given. This work contributes to defining the constraints required for subsequent consolidation process steps of the waste form to avoid volatilization.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Computed Tomography Scanning and Geophysical Measurements of UW Enterprises LP 1-250512-129 Well in Southwestern Indiana

The computed tomography (CT) facilities and the Multi-Sensor Core Logger (MSCL) at the National Energy Technology Laboratory (NETL) in Morgantown, West Virginia, were used to characterize Illinois Basin core of the Upper Devonian-Early Mississippian New Albany Shale Formation from Posey County, Indiana. The primary impetus of this work is a collaboration between Indiana Geological and Water Survey at Indiana University Bloomington, NETL, and Woolsey Operating Company LLC to characterize and make publicly available core information from the New Albany Shale of the Illinois Basin. Core characterization of this unconventional oil/gas well will aid in understanding the lithology changes and the fracture complexity of the New Albany Shale. There is a potential for this formation to be developed in the future for critical mineral and rare earth element (CM/REE) extraction. The resultant datasets are presented in this report and can be accessed from NETL's Energy Data eXchange (EDX) online system using the following link: https://edx.netl.doe.gov/dataset/uw-enterprises. All equipment and techniques used were non-destructive, enabling future examinations and analyses to be performed on this core. None of the equipment used was suitable for direct visualization of the pore space in the fine-grained structures studied; however, fractures, discontinuities, and millimeter-scale features were readily detectable with the methods tested. Imaging with the NETL medical CT scanner was performed on the entire core. Targeted higher resolution CT scanning of select sections was performed with NETL’s industrial and micro-CT scanner. Qualitative analysis of the medical CT images, coupled with X-ray fluorescence (XRF), P-wave, and magnetic susceptibility measurements from the MSCL were useful in identifying zones of interest for more detailed analysis. The ability to quickly identify key areas for more detailed study with higher resolution will save time and resources in future studies. The combination of methods used provides a multi-scale analysis of the core; the resulting macro and micro descriptions are relevant to many subsurface energy related examinations traditionally performed at NETL.

58 GEOSCIENCES↗

Radiogenic Xenon-129 in Silicate Inclusions in the Campo Del Cielo Iron Meteorite

Iron meteorites present a challenge for the I-Xe dating technique because it is usually the inclusions, not metal, that contain radiogenic xenon and iodine. Silicate inclusions are frequent in only types IAB and IIE, and earlier studies of irons have demonstrated that I-Xe system can survive intact in these inclusions preserving valuable age information. Our previous studies of the I-Xe record in pyroxene grains from Toluca iron suggested an intriguing relationship between apparent I-Xe ages and (Mg+Fe)/Fe ratios. The I-Xe system in K-feldspar inclusions from Colomera (IIE) had the fingerprint of slow cooling, with an indicated cooling rate of 2-4 C/Ma. Here we present studies of the iodine-xenon system in a silicate-graphite-metal (SiGrMet) inclusion of the IA Campo del Cielo iron meteorite from the collection of the Museum of Natural History in Vienna.

Meshik, A.↗

Characterization of Contaminants and Mobility in WMA A-AX Boreholes D0006 and D0008

This study was initiated to determine if subsurface contaminants in the A-AX vadose zone at the Hanford site (boreholes D0006 and D0008) caused corrosion of nearby stainless steel well casings (299-E-24-19, 299-E25-46, and 299-E25-236) and, based on the type and distribution of contaminants, determine if contaminants are from one or more sources including a) the A-104 and/or A-105 tanks, b) the 242A evaporator, and c) the 200-E-286 ditch. A tiered approach was used for characterizing contaminants in vadose zone sediments starting with mobile and total contaminant concentrations (Tier 1), characterizing contaminant speciation (Tier 2), and measuring contaminant leaching (Tier 3). Total and mobile contaminant measurements at seven depths showed elevated sulfate and nitrate in all samples (130 to 280 ft depth), elevated chloride in five depths, and no elevated radionuclides except I-129 in D0006 at 206 to 208 ft depth. If these contaminants were initially acidic, stainless-steel corrosion would occur. However, because sediments likely have a high acid neutralization capacity, an acidic spill would have been neutralized within tens of feet, so casing corrosion would likely occur in shallow sediments. GEL labs data also shows low (but above natural) chromate from shallow to 170 ft depth, then higher chromate to 280 ft, suggesting a surface Cr spill or casing corrosion. GEL labs data also showed evidence of more than one plume, with deep nitrate, sulfate, and chloride migration, but only shallow tritium migration. Tritium should migrate nearly unretarded in the subsurface like nitrate and chloride. Elevated aqueous cations and anions in the D0006 206 to 208' depth pore water (SO 4 2- , NO 3 - , Na + , K + , Ca 2+ , Mg 2+ , Si) could be the result of acid disposal and calcite dissolution at shallow depth, with deeper migration of SO 4 2- , NO 3 - from acids and Ca 2+ and Mg 2+ from calcite. Elevated Si (160 mg/L) indicates dissolution of clays or other silicates, which can also occur in acids. Acid extractable metals did show elevated Cr (but not Fe, Ni, Mo, and Mn) above natural levels, which may indicate stainless-steel well corrosion or transport of metals from a shallow spill. The elevated I-129 in D0006 at 206 to 208' depth was low with 0.34 μg/g in pore water and 1.5 μg/g total extractable I-129 in the sediment, which indicates significant fraction of I-129 was bound in one or more precipitates. Although total I-129 was below detection limits in most extractions due to high molybdate interference, I-127 analysis provided some insight into potential precipitate phases. Total I-127 was mainly extracted by acetate or acetic acid (67%), which may be iodine in calcite. Inorganic carbon measurement identified 1.65% calcite, and total organic carbon (TOC) was below detection limits, so iodine was not associated with organic matter. Nearly all the I-127 was present as iodide. In 1-D leach experiments, I-127 as iodide leached from the sediment within 2 pore volumes. Due to high and dynamic molybdate leaching from the sediment and interference with I-129 analysis, there were few quantifiable I-129 measurements. The calculated molybdate release rates from the sediment suggested Mo was being released from the same precipitate phase, such as molybdate incorporated into calcite. Overall, because there was little radioactive contamination measured in D0006 and D0008 boreholes, potential releases from A-104 and A-105 did not reach this location south of the A tank farm. Elevated cations and anions found in D0006 and D0008 at depth as the result of acidic disposal could cause shallow stainless steel casing corrosion. The nearby 242A evaporator generally contained alkaline waste and tritium, but the nearby 200-E-286 ditch generally contained high Cl - liquid effluent, so these are unlikely to be acidic sources.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Iodine Flowsheet Status Report

A simplified flowsheet was developed to evaluate the impact of varied assumptions of I-129 decontamination factors on the overall I-129 material balance in the Direct Feed Low-Activity Waste (DFLAW) facility. The flowsheet allows inputs for I-129 feed and Decontamination Factors (DFs) for multiple DFLAW unit operations and provides information on I-129 partitioning to output streams. A series of 6 DFs were evaluated, including baseline DFs from a prior Waste Treatment and Immobilization Plant (WTP) study and refined values based on a Savannah River National Laboratory (SRNL) review. The Microsoft Excel flowsheet spreadsheet will be provided to WRPS to allow further evaluation of the impact of DF assumptions on output streams. The spreadsheet is not specific to iodine, the partitioning of any species can be estimated by entering the assumed DFs for each unit operation. Flowsheet outputs matched results from the prior WTP study and show that different assumptions for the DFs can greatly impact iodine partitioning to primary and secondary waste streams. Results from SRNL's baseline DF values suggest less than 50% of I-129 would be retained in glass versus the 96% when using the BNI DF values. In addition, the flowsheet demonstrated that more than 5 DFLAW operational cycles are required to achieve a steady-state of I-129 to the primary waste stream. It is not possible with the data available to determine whether the BNI approach or the approach taken in this study will be a better match for the iodine partitioning once the LAW facility begins operation.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Nucleogenic noble gas components in the Cape York iron meteorite

The paper reports data on neutron capture products of the secondary cosmic ray component, the inferred proton and neutron fluences, and the identification of double beta decay of Se-82 in heavily shielded samples of the Cape York iron meteorite. One purpose of this study is to develop a new chronometer for cosmic ray exposure, based on the nuclides I-129 (16 My half-life) and Xe-129 from low energy cosmic ray reactions on Te. The abundance ratio of these two nuclides permits the determination of an (effective) exposure age of 93 + or - 16 My, which represents the first exposure age datum of Cape York. The very small concentrations of spallogenic Ar-38 = 6.5 x 10 to the -10th cu cm STP/g in the metal and troilite (per g Fe) document the heavily shielded locations of the sample. An excess of Xe-129 in the troilite is shown to be entirely due to the decay of cosmic-ray-produced I-129. On the other hand, an inclusion in the troilite reveals the presence of Xe-129 from extinct I-129 and documents its about 4.5 Gy formation age. Mono-isotopic excess of Kr-82 is identified as due to beta-beta-decay of Se-82 with an inferred half-life of 1.0 x 10 to the 20th y. This represents the first beta-beta-decay product observed in a meteorite.

Murty, S. V. S.↗

Early outgassing of Mars supported by differential water solubility of iodine and xenon

The Martian atmosphere has a high X-129/Xe-132 ratio compared to the Martian mantle. As Xe-129 is the daughter product of the extinct nuclide I-129, a means of fractionating iodine from xenon early in Martian history appears necessary to account for the X-129/Xe-132 ratios of its known reservoirs. A model is presented here to account for the Marian xenon data which relies on the very different solubilities of xenon and iodine in water to fractionate them after outgassing. Atmospheric xenon is lost by impact erosion during heavy bombardment, followed by release of Xe-129 produced from I-129 decay in the crust.

Musselwhite, Donald S.↗

Impact of UV-light and pH on the Fate of Tc, I, and U in Wetlands at Savannah River Site - 20230

The Savannah River Site (SRS) is one of the major nuclear facilities owned by the U.S Department of Energy. During the Cold War, these facilities produced large amounts of radioactive and hazardous waste. On site, three unlined seepage basins in the F-Area received approximately 1.8 billion gallons of low-level waste containing nitric acid, radionuclides, and dissolved metals due to plutonium and tritium production operations. The acidic nature of the waste created a source of relatively mobile radionuclides below the basins. Radionuclides previously disposed of within the F-Area, including uranium isotopes (U), technetium-99 (Tc-99), and iodine-129 (I-129), are moving with groundwater towards Four Mile Branch Wetland, where they are subsequently upwelling and interacting with natural organic matter (NOM). Many environmental factors including redox conditions, porewater composition, pH, light, and temperature affect the degradation of organic matter as well as interactions with Tc-99, U, and I-129. In particular, the high concentrations of nitrate from the acidic waste may increase the formation of reactive oxygen species (ROS) that impact both degradation of NOM and behavior of contaminants. In the presence of sunlight, I-129, Tc-99, and U speciation and complexation behavior may be affected by ROS and NOM degradation products in addition to the factors generally considered in subsurface systems in the absence of light. This research aims to determine whether the interactions between radionuclides, NOM, and nitrate affect the fate of I-129, Tc-99, and U and which processes are controlling their behavior. Experiments were conducted at variable pH in the presence of NaNO{sub 3} in order to determine the impact of light and pH on NOM degradation and to evaluate the impact on the fate of contaminants of concern. Soil samples high in NOM collected from two sites in the Southeastern United States (Savannah River Site and the Everglades) were studied. Batch experiments were conducted with NOM and the following aqueous contaminants, U, I-129, Tc-99 with exposure to ultraviolet (UV) light in an environmental chamber. This study was conducted in a sterile environment in order to exclude the potential for microbial degradation of organic matter. Results indicated photodegradation of NOM and significant interaction of radionuclides with NOM. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

I-Xe Ages and Trapped Xe Compositions

I-Xe isochrons are mixing lines between a single trapped and a single iodine derived component. The slope of this line establishes initial iodine and hence the I-Xe age. One end of the isochron is fixed by the composition of the trapped Xe component, which should be representative of the Xe that was present in the early solar system (Q-Xe or OC-Xe). Because the I/Xe ratio in the solar nebular was ~1, and the I-129/I-127 was about 10-4, the Xe-129 in trapped Xe cannot evolve appreciably with decay of I-129. While it may be possible for Xe in a closed system with elevated I/Xe ratios to evolve producing trapped components with higher Xe-129/Xe-132 ratios, trapped Xe compositions with lower (sub-planetary) Xe-129/Xe-132 ratios seem implausible.

Hohenberg, C. M.↗

Review of recent developments in iodine wasteform production

Radioiodine capture and immobilization is not only important to consider during the operation of reactors (i.e., I-131), during nuclear accidents (i.e., I-131 and I-129) or nuclear fuel reprocessing (i.e., I-131 and I-129), but also during disposal of nuclear wastes (i.e., I-129). Most disposal plans for I-129-containing waste forms (including spent nuclear fuel) propose to store them in underground repositories. Here, iodine can be highly mobile and, given its radiotoxicity, needs to be carefully managed to minimize long-term environmental impacts arising from disposal. Typically, any process that has been used to capture iodine from reprocessing or in a reactor is not suitable for direct disposal, rather conversion into a wasteform for disposal is required. The objectives of these materials are to use either chemical immobilization or physical encapsulation to reduce the leaching of iodine by groundwaters. Some of the more recent ideas have been to design capture materials that better align with disposal concepts, making the industrial processing requirements easier. Research on iodine capture materials and wasteforms has been extensive. This review will act as both an update on the state of the research since the last time it was comprehensively summarized, and an evaluation of the industrial techniques required to create the proposed iodine wasteforms in terms of resulting material chemistry and applicability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Predictive Contaminant Transport Simulation with the P2R Model for the Composite Analysis Inventory Sensitivity Case

The Plateau to River (P2R) Model is a groundwater flow and contaminant fate and transport (F&T) simulation model used to support remedial activities conducted by the Central Plateau Cleanup Company (CPCCo) at the Hanford Site in Washington State. The model simulates contaminants of concern within the saturated zone of the uppermost aquifer beneath the Central Plateau and downgradient to the Columbia River. The overall objective of the saturated zone modeling effort is to provide a basis for making informed remedial action decisions based on descriptions of current and expected future contaminant concentrations in groundwater at decision points within and downgradient of the Central Plateau of the Hanford Site. Specifically, the purpose of this environmental calculation file (ECF) is to describe an inventory sensitivity case of the CA base case. The inventory sensitivity case implements a change in the activity contribution from the vadose zone in the A Trenches Area model (for tritium (H-3) and iodine-129 (I-129)), BC Cribs and Trenches model (for I-129 and technetium-99 (Tc-99)), and the PUREX Area model (for H-3 and I-129). All other simulated inventories are identical to the CA base case. The simulation of F&T of contaminants reported in this case will support dose predictions as part of the Hanford Site CA.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Predictive Contaminant Transport Simulation with the P2R Model for the Composite Analysis Recharge Sensitivity Case

The Plateau-to-River (P2R) model is a groundwater flow and contaminant fate and transport (F&T) simulation model used to support remedial activities conducted by the Central Plateau Cleanup Company (CPCCo) at the Hanford Site in south-central Washington State. The overall objective of the saturated zone modeling effort is to provide a basis for making informed remedial action decisions based on descriptions of current and expected future contaminant concentrations in groundwater at decision points within and downgradient of the Central Plateau of the Hanford Site. Specifically, the purpose of this environmental calculation file (ECF) is to describe a recharge sensitivity case of the CA base case. The recharge sensitivity case implements a change in the activity contribution from the vadose zone in the A Trenches Area model (for tritium [H-3] and iodine-129 [I-129]), BC Cribs and Trenches model (for I-129 and technetium-99 [Tc-99]), or the Plutonium Uranium Extraction (PUREX) Area model (for H-3 and I-129). All other simulated inventories are identical to the CA base case. The simulation of fate and transport of contaminants reported in this case will support dose predictions as part of the updated Hanford Site CA.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Live 129I-129Xe dating

A technique of cosmic ray exposure age dating using cosmic ray produced I-129 and Xe-129 components is discussed. The live I-129 - Xe-129 method provides an ideal monitor for cosmic ray flux variations on the 10(7)y - 10(8)y time-scale. It is based on low-energy neutron reactions on Te, and these data, when coupled to those from other methods, may facilitate the detection of complex exposure histories.

Marti, K.↗