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At least 163 records · Page 9

Iodine Air Sampling: Installation and Preliminary Results

The F-Area wetlands are a known sink for radioiodine generated at the Savannah River Site (SRS). Wastewater containing iodine-129 ( 129 I) was discharged into the F-Area Seepage Basins for disposal, but the acidity of the wastewater mobilized some of the contaminants from the basin soil through the vadose zone and into the groundwater; ultimately creating a groundwater plume that extends towards Fourmile Branch and its associated wetland areas. Dissolved radioiodine specifically has migrated to the nearby F-Area wetlands, where it persists as a contaminant of concern. Accumulation and resurfacing of 129 I in the wetlands and nearby areas creates a potential secondary source zone where changes in biogeochemical conditions could result in the release of this sequestered 129 I to the air. Monitoring data has indicated that 129 I has a seasonal behavior at several surface water stations, with high concentrations during summertime and low concentrations during wintertime. Still, it is not known which factors control the seasonal behavior of 129 I. Further, it has been reported that 129 I contributed approximately 23% to the 2019 SRS offsite air pathway dose to the representative person for that year (SRNS, 2020), but air measurements of 129 I have never been taken in the F-Area wetlands. Because air emissions of 129 I from the wetlands have never been investigated, it is not known if this could be a potential release pathway that needs to be included in the site conceptual model. To address these unknowns, the Savannah River National Laboratory (SRNL) has an applied research task to investigate whether 129 I in the wetlands is emitted to the air and, if so, whether air concentrations exhibit seasonal variation. This report presents information about the system recently installed in the F-Area wetlands for measuring 129 I, as well as analysis results for samples collected June through August 2023. Quantification of this constituent will provide a better understanding of the contribution of airborne 129 I from the F-Area wetlands to the offsite dose and better inform ongoing and future remedial actions.

54 ENVIRONMENTAL SCIENCES↗

Roadmap to Iodine and Mercury Abatement Materials Selection in Nuclear Waste Processing Off-Gas Streams

This work provides a guide for candidate mercury (Hg) and iodine-129 (129I) abatement material identification, screening, evaluation, technical gap identification, and bench-scale testing prioritization while also conceptualizing a materials deployment roadmap for implementation of new materials in the Hanford Waste Treatment and Immobilization Plant (WTP) Low-Activity Waste (LAW) Facility at Hanford in Richland, Washington, and elsewhere in the U.S. Department of Energy (DOE) complex for similar applications. The study was prompted by the need to replace the Kombisorb BAT-37 due to uncertainties in Hg and 129I capture performance and future availability for use in the WTP LAW Facility secondary off-gas system, specifically the Carbon Adsorber units. However, replacement of this material could also mitigate two other issues with Kombisorb BAT-37 (and its successor BAT II 37): (1) fire safety risk due to exothermic heat generated by adsorption reactions between the carbon material and Hg and (2) the risk of low retention of 129I in glass and subsequent downstream impacts on secondary liquid waste treatment at the Effluent Treatment Facility.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Preparation of iodine-bearing waste forms for hot isostatic pressing

Oak Ridge National Laboratory (ORNL) has prepared a new set of iodine-bearing sorbents. The sorbent materials used for this activity were supplied by IONEX (NexSorb-99) or C&CS (AC6120-7%). Metal canisters were previously prepared by ORNL in 2022. They are 2 in. long by 1.5 in. in diameter and are made of 316 stainless steel.

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Structural Assessment of Fluorine, Chlorine, Bromine, Iodine, and Hydroxide Substitutions in Lead Arsenate Apatites (Mimetites)–Pb 5 (AsO 4 ) 3 X

Five lead-arsenate apatites (mimetites)-Pb 5 (AsO 4 ) 3 X—where X denotes fluorine (F), chlorine (Cl), bromine (Br), iodine (I), and hydroxide (OH)—were synthesized via precipitation from aqueous solutions. The crystal structures were determined through Rietveld refinement of powder synchrotron X-ray data. All the compounds crystallized in the hexagonal class symmetry (space group P6 3 /m). The Rietveld refinement indicated that mimetite-Cl, -Br, -I, and -OH had an anion deficiency at position X. Substitution of halogens in a mimetite structure brought about systematic changes in unit-cell parameters, interatomic distances, and metaprism twist angles φ, proportional to the substituted halogen’s ionic radius. Mimetite-OH did not follow the linear correlations determined within the series. Twist angle φ, a useful device for monitoring changes in apatite topology, ranged from 20.34° for mimetite-F to 11.42° for mimetite-I. The geometric method has been proposed for determining the diameter of hexagonal channels hosting halogens in apatites. A comparison of the results with halogenated pyromorphites showed similar systematic trends: the substitutions in mimetites have comparable effect on the interatomic distances as in their phosphorous analogues.

58 GEOSCIENCES↗

Sorption of Anionic Iodine and Molybdenum to Multi-sorbing Barrier (MSB) Materials - 20030

A multi-sorbing barrier (MSB) material containing sodium bentonite (NaB), organoclay, and anion resin is being evaluated for containment of anionic radionuclides. Batch tests on the MSB were conducted using two non-radioactive analog isotopes ({sup 127}I, {sup 95}Mo) as surrogates for {sup 129}I and {sup 99}Tc due to their similar valence and molecular weight relative to the radionuclides. Tests were conducted on the organoclay, anion resin, and NaB individually and on NaB-resin blends with resin contents of 1% and 5% by mass. The anion resin exhibits very strong sorption of {sup 127}I and {sup 95}Mo relative to the other materials. The organoclay exhibited modest sorption of {sup 95}Mo and {sup 127}I, and NaB little sorption. The sorption isotherms follow a linear model for NaB, a Freundlich model for the organoclay, and a Langmuir model for the anion resin and NaB-resin mixtures. Combining resin with NaB significantly enhances sorption relative to NaB alone, with a larger resin fraction yielding greater sorption. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Removal of fission product tellurium and iodine from recently irradiated HEU using copper metal

Gamma detection of select fission products or activation products such as 153 Sm and 239 Np in a fission sample is difficult due to gamma interferences from radiotellurium and radioiodine. To aid in the detection of these difficult-to-detect nuclides, the radiotellurium and radioiodine were removed using Cu metal turnings. This method is highly effective at the removal of the interfering radionuclides removing > 98% of the radiotellurium and radioiodine. A mechanistic study was conducted. Determining the deposition mechanism, using a number of techniques including XANES and electrochemistry providing an understanding of the electrochemical path for the Te deposition. Initial work focused on the use of stable Te, further expanding into activated TeO 2 , and a fresh fission sample. Importantly, this method presents a rapid method for the direct detection of select fission products that could have a significant impact on nuclear related fields including nuclear forensics.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Iodine Electrochemistry Dictates Voltage‐Induced Halide Segregation Thresholds in Mixed‐Halide Perovskite Devices

Abstract Owing to straightforward stoichiometry–bandgap tunability, mixed‐halide perovskites are ideal for many optoelectronic devices. However, unwanted halide segregation under operational conditions, including light illumination and voltage bias, restricts practical use. Additionally, the origin of voltage‐induced halide segregation is still unclear. Herein, a systematic voltage threshold study in mixed bromide/iodide perovskite devices is performed and leads to observation of three distinct voltage thresholds corresponding to the doping of the hole transport material (0.7 ± 0.1 V), halide segregation (0.95 ± 0.05 V), and degradation (1.15 ± 0.05 V) for an optically stable mixed‐halide perovskite composition with a low bromide content (10%). These empirical threshold voltages are minimally affected by composition until very Br‐rich compositions, which reveals the dominant role of iodide/triiodide/iodine electrochemistry in voltage‐induced Br/I phase separation and transport layer doping reactions in halide perovskite devices.

36 MATERIALS SCIENCE↗

Impact of oxidation and carbonation on the release rates of iodine, selenium, technetium, and nitrogen from a cementitious waste form

Evaluation of the long-term retention mechanisms and potential release rates for the primary constituents of potential concern (COPCs) (i.e., Tc, I, Se, and nitrate) is necessary to determine if Cast Stone, a radioactive waste form, can meet performance objectives under near-surface disposal scenarios. In this work, a mineral and parameter set accounting for the solubility of I and Se in Cast Stone was developed based on pH-dependent and monolithic diffusion leaching test results, to extend a geochemical speciation model previously developed. The impact of oxidation and carbonation as environmental aging processes on the retention properties of Cast Stone for primary COPCs was systematically estimated. Physically, the effective diffusion coefficients of 4 COPCs in Cast Stone were increased after carbonation and/or oxidation, reflecting an increase in permeability to diffusion. Chemically, i) pH & pe conditions in the original Cast Stone were favorable for the stabilization of Tc, but not for I, Se, and N; ii) oxidation (with/without carbonation) of Cast Stone changed the pe & pH conditions to be detrimental for Tc stabilization; and iii) carbonation (with/without oxidation) of Cast Stone modified the pH & pe conditions to be beneficial for the stabilization of I (in system with Ag added) and Se.

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