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DOE OSTI2025

Development of a Robust Reference Electrode in Aggressive Chemical and Radiation Environments in the Hanford Waste Tanks

The Hanford site stores more than 200 million liters of radioactive and chemically hazardous wastes from the production of weapons materials. The wastes are stored in 177 underground carbon-steel storage tanks, separated between 149 single shell tanks (SSTs) and 28 double shell tanks (DSTs). The DSTs provide critical retrieval and interim storage before the waste is vitrified in the Waste Treatment and Isolation Plant (WTP). The tanks will need to remain in-service far beyond the initial 40-year design life, and effective corrosion control practices must remain in force to extend the tanks’ lifespans. This effort includes direct measurements of corrosion rate (e.g., ultrasonic measurements and corrosion coupons) and electrochemical processes (e.g., linear polarization measurements and open circuit potential measurements). The Hanford site began monitoring the corrosion potential in select DSTs in 2008. Of the 45 reference electrodes that have been installed, 29 have failed and 6 others provided unreliable results. DOE-EM is supporting a 3-year program to develop a chemical and radiation resistant reference electrode for application in the Hanford tanks. The first year of the program focused on understanding the failure mechanism for the reference electrodes and identification of candidate construction materials that would mitigate degradation of the electrodes in the waste environment. During the second year of the program, the objectives were to: 1) test candidate materials under simulated waste conditions, 2) design components that will extend the service life of the electrode, 3) fabricate materials for prototype reference electrodes, and 4) assemble prototype reference electrodes for accelerated testing. The reference electrode is constructed of four principal parts: 1) junction, 2) casing, 3) inner chamber backfill materials, and 4) the sensing wire. Principally, improvements of the junction, casing, and inner chamber backfill materials are being pursued. The junction material at the interface between the waste and the inner chamber of the reference electrode was identified as a critical component in the failure of the reference electrodes. Nine candidate replacement junction materials were tested under simulated waste conditions to evaluate permeation rate. These materials included a variety of polymeric and ceramic materials, some of which were 3-D printed. Thus far, porous polyvinylidene fluoride materials have performed satisfactorily and are being considered for prototype development. The commercial electrode casing materials in general have performed well. Additionally, 3-D printing of chemically and mechanically stable materials is being investigated as a means for further improvement in fabrication consistency. SRNL has also investigated altering the reference electrode design to extend the service life. The new design of the interior of the reference electrode casing creates a longer, more tortuous path between the junction material and the electrode sensing wire. A finite element model was used to optimize the design without adversely impacting the circuit resistance of the electrode during the measurements, thus preserving the measurement accuracy while enhancing the service life. The inner chamber back fill materials are also critical to the performance of the reference electrode. Materials that are resistant to intruding tank waste and provide a conductive path to the sensing wire were investigated. Gel and powder materials that are interspersed with a conductive chloride bearing material were tested for their influence on diffusion and electrode resistance. All the investigated materials and components will be assembled, with collaboration from commercial vendors, to fabricate the initial prototypes. Accelerated testing of the prototypes will be initiated in Year 2 of the program and will be completed in Year 3. A recommendation on the materials of construction and the design of the new robust reference electrode will be presented to the Hanford tank farm facility.

Sykes, Kiana [Savannah River National Laboratory (↗

NASA NTRS2006

Water Vapor Sensors Go Sky-High to Assure Aircraft Safety

JPL used a special tunable diode laser, which NASA scientists could tune to different wavelengths, like a radio being tuned to different frequencies, to accurately target specific molecules and detect small traces of gas. This tunable diode laser was designed to emit near-infrared light at wavelengths absorbed by the gas or gases being detected. The light energy being absorbed by the target gas is related to the molecules present. This is usually measured in parts per million or parts per billion. Multiple measurements are made every second, making the system quick to respond to variations in the target gas. NASA scientists developed this technology as part of the 1999 Mars Polar Lander mission to explore the possibility of life-giving elements on Mars. NASA has since used the tunable diode laser-based gas sensor on aircraft and on balloons to successfully study weather and climate, global warming, emissions from aircraft, and numerous other areas where chemical gas analysis is needed. SpectraSensors, Inc., was formed in 1999 as a spinoff company of JPL, to commercialize tunable diode laser-based analyzers for industrial gas-sensing applications (Spinoff 2000). Now, the San Dimas, California-based firm has come back to the market with a new product featuring the NASA-developed instrument for atmospheric monitoring. This instrument is now helping aircraft avoid hazardous weather conditions and enabling the National Weather Service to provide more accurate weather forecasts.

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NASA NTRS1992

HAZBOT - A hazardous materials emergency response mobile robot

The authors describe the progress that has been made towards the development of a mobile robot that can be used by hazardous materials emergency response teams to perform a variety of tasks including incident localization and characterization, hazardous material identification/classification, site surveillance and monitoring, and ultimately incident mitigation. In September of 1991, the HAZBOT II vehicle performed its first end-to-end demonstration involving a scenario in which the vehicle: navigated to the incident location from a distant (150-200 ft.) deployment site; entered a building through a door with thumb latch style handle and door closer; located and navigated to the suspected incident location (a chemical storeroom); unlocked and opened the storeroom's door; climbed over the storeroom's 12 in. high threshold to enter the storeroom; and located and identified a broken container of benzene.

Stone, H. W.↗

NASA NTRS1975

Current aspects of occupational chemical carcinogenesis

The history of measures to control occupational exposure to carcinogenic substances is reviewed. Health hazards associated with exposure to a certain chemical substance must be considered not only from the aspects of its acute or chronic toxicity, but also from its potential to produce tumors (latent effect). There can be no clear distinction between classic toxicity and oncogenesis until the mechanisms of both are completely understood for a given chemical substance. The assessment of carcinogenic potential for a specific substance must include the consideration of published information, monitoring and control data from the affected industry, and the in-depth epidemiologic experience of affected employees.

Lassiter, D.↗

NASA NTRS1983

Comet nucleus sample return mission

A comet nucleus sample return mission in terms of its relevant science objectives, candidate mission concepts, key design/technology requirements, and programmatic issues is discussed. The primary objective was to collect a sample of undisturbed comet material from beneath the surface of an active comet and to preserve its chemical and, if possible, its physical integrity and return it to Earth in a minimally altered state. The secondary objectives are to: (1) characterize the comet to a level consistent with a rendezvous mission; (2) monitor the comet dynamics through perihelion and aphelion with a long lived lander; and (3) determine the subsurface properties of the nucleus in an area local to the sampled core. A set of candidate comets is discussed. The hazards which the spacecraft would encounter in the vicinity of the comet are also discussed. The encounter strategy, the sampling hardware, the thermal control of the pristine comet material during the return to Earth, and the flight performance of various spacecraft systems and the cost estimates of such a mission are presented.

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NASA NTRS2012

Histogrammatic Method for Determining Relative Abundance of Input Gas Pulse

To satisfy the Major Constituents Analysis (MCA) requirements for the Vehicle Cabin Atmosphere Monitor (VCAM), this software analyzes the relative abundance ratios for N2, O2, Ar, and CO2 as a function of time and constructs their best-estimate mean. A histogram is first built of all abundance ratios for each of the species vs time. The abundance peaks corresponding to the intended measurement and any obfuscating background are then separated via standard peak-finding techniques in histogram space. A voting scheme is then used to include/exclude this particular time sample in the final average based on its membership to the intended measurement or the background population. This results in a robust and reasonable estimate of the abundance of trace components such as CO2 and Ar even in the presence of obfuscating backgrounds internal to the VCAM device. VCAM can provide a means for monitoring the air within the enclosed environments, such as the ISS (International Space Station), Crew Exploration Vehicle (CEV), a Lunar Habitat, or another vehicle traveling to Mars. Its miniature pre-concentrator, gas chromatograph (GC), and mass spectrometer can provide unbiased detection of a large number of organic species as well as MCA analysis. VCAM s software can identify the concentration of trace chemicals and whether the chemicals are on a targeted list of hazardous compounds. This innovation s performance and reliability on orbit, along with the ground team s assessment of its raw data and analysis results, will validate its technology for future use and development.

Mandrake, Lukas↗

NASA NTRS1990

FTIR Monitoring Of Curing Of Composites

Infrared-sensing optical fiber system developed to monitor principal infrared absorption bands resulting from vibrations of atoms and molecules as chemical bonds form when resin cured. System monitors resin chemistry more directly. Used to obtain Fourier transform infrared (FTIR) spectrum from graphite fiber/polyimide matrix resin prepreg. Embedded fiber optic FTIR sensor used to indicate state of cure of thermosetting composite material. Developed primarily to improve quality of advanced composites, many additional potential applications exist because principal of operation applicable to all organic materials and most inorganic gases. Includes monitoring integrities of composite materials in service, remote sensing of hazardous materials, and examination of processes in industrial reactors and furnaces.

Druy, Mark A.↗

NASA NTRS1979

Water Quality Monitor

In the photo above, the cylindrical container being lowered into the water is a water quality probe developed by NASA's Langley Research Center for the Environmental Protection Agency (EPA) in an applications engineering project. It is part of a system- which also includes recording equipment in the helicopter-for on-the-spot analysis of water samples. It gives EPA immediate and more accurate information than the earlier method, in which samples are transported to a lab for analysis. Designed primarily for rapid assessment of hazardous spills in coastal and inland waters, the system provides a wide range of biological and chemical information relative to water pollution.

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DOE OSTI2026

Microbial inoculants for soil restoration: A Risk-Proportional Stewardship Framework Integrating Strain-Resolved Genomics and Adaptive Governance

Global soil degradation and increasing reliance on chemical inputs threaten agricultural sustainability, driving interest in microbial inoculants as tools for soil restoration. These biological products have the potential to enhance nutrient cycling, improve soil structure, and support plant resilience, but their environmental release raises important safety and stewardship considerations. Here, we propose a risk-proportional framework for the responsible deployment of microbial inoculants grounded in release-based stewardship. The framework integrates genome-resolved strain identification, exclusionary hazard screening, bioassay-based risk triage, ecological testing under realistic conditions, and monitored field deployment. Drawing on evidence from microbial ecology and invasion biology, we highlight how inoculants can alter resident microbial communities, influence ecosystem function, and, in some cases, facilitate gene flow, underscoring the need for risk assessment. We further outline a federated, genome-informed data infrastructure to support traceability, cross-jurisdiction learning, and adaptive management. Together, this approach provides a scalable and scientifically grounded pathway to balance innovation and safety, enabling microbial technologies to contribute to soil restoration and climate-resilient agriculture.

Edlund, Anna [OATH Inc]↗

NASA NTRS1990

The effects of the space environment on two aramid materials

Two aramid fibers having closely related chemical structures were chosen for important roles in the first tether to be used to connect pairs of orbiting vehicles. The protective outer jackets of the tethers will consist of woven fibers of poly(m-phenylene isophthalamide), commercially available from du Pont as Nomex. A cylindrical sheath of woven Kevlar 29, whose principal constituent is poly(p-phenylene terephthalamide), will be the load-bearing component for the tethers. Orbiting tethers will be in a hostile environment in which short wavelength electromagnetic radiation and energetic charged particles degrade exposed organic materials. At lower orbiting altitudes atomic oxygen is an especially serious hazard. Studies on the effects of ultraviolet radiation and atomic oxygen on fibers and films of Kevlar and Nomex are in progress. In an experiment to simulate the effects of atomic oxygen in space, small tows of Kevlar and Nomex were mounted in a commercial ashing device filled with oxygen at low pressure. An RF discharge in the instrument dissociated the molecular oxygen producing a strongly oxidizing atmosphere containing O(3P)(sup 4). Erosion was measured in terms of mass loss. Kevlar films were exposed to UV radiation in an apparatus consisting of a small vacuum chamber, 23 cm in diameter, into which a mass spectrometer and a quartz window were incorporated. Samples were exposed under vacuum with a 1000 watt xenon-arc lamp. Volatile products could be monitored with the mass spectrometer during the exposures. Transmission infrared spectra were taken before and after exposure to monitor chemical changes in the films.

Kiefer, Richard L.↗

NASA NTRS1990

Flame Detector

Scientific Instruments, Inc. has now developed a second generation, commercially available instrument to detect flames in hazardous environments, typically refineries, chemical plants and offshore drilling platforms. The Model 74000 detector incorporates a sensing circuit that detects UV radiation in a 100 degree conical field of view extending as far as 250 feet from the instrument. It operates in a bandwidth that makes it virtually 'blind' to solar radiation while affording extremely high sensitivity to ultraviolet flame detection. A 'windowing' technique accurately discriminates between background UV radiation and ultraviolet emitted from an actual flame, hence the user is assured of no false alarms. Model 7410CP is a combination controller and annunciator panel designed to monitor and control as many as 24 flame detectors. *Model 74000 is no longer being manufactured.

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NASA NTRS1975

Selenium in soils of the Lower Wasatch Formation, Campbell County, Wyoming: Geochemistry, distribution, and environmental hazards

The author has identified the following significant results. Seleniferous Shingle series soils and sandstone outcrops of section 27, T 48 N, R 71 W, Wyoming are mapped on aerial photography by their association with Astragalus bisulcatus. Chemical leachate analyses and atomic absorption methods reveal all studied Samsil and Shingle soils to contain acid, base, and water soluble selenium compounds, and that water extractions showed varied concentration behavior due to soil pH. Acid-soluble selenium is found to be associated with smectite. Statistical analyses confirm that A. bisulcatus presence has a weak influence on soil-lens organic selenium concentration, and determine the importance of other geobotanical factors for convertor presence. Environmental procedures of high selenium lens burial, convertor plant eradication, and revegetated site monitoring are recommended. Usage of density analysis and photographic enlargement are used to successfully produce both a control area and a Campbell County, Wyoming regional map of A. bisulcatus supportive soils and outcrops using Skylab photography.

Kolm, K. E.↗

DOE OSTI2026

Predicting multiphase flow and tracer transport for an underground chemical explosive test

Detecting radionuclide gas seepage from clandestine underground nuclear tests is central to nonproliferation explosion monitoring research. Yet, early-time (<6 day) gas transport driven by the explosive pressure wave remains poorly constrained due to scarcity of field data. We simulate multi-phase gas transport in the vadose zone using pre-shot data from a recent chemical explosion in P-Tunnel at the Nevada National Security Site, USA. Despite using a simplified 2D-radial model, predictions of tracer arrival matched observations within one order-of-magnitude. Our results show how transient blast forcing rapidly mobilizes gases from the cavity into surrounding rock – critical for optimizing sensor placement and test planning. This unique integration of field data and modeling represents a significant improvement in our ability to predict gas migration from underground explosions. More broadly, it offers insights into the coupled dynamics of pressure waves and contaminant transport in the vadose zone, with implications for monitoring and hazard assessment.

54 ENVIRONMENTAL SCIENCES↗

NASA NTRS2002

Microgravity Compatible Reagentless Instrumentation for Detection of Dissolved Organic Acids and Alcohols in Potable Water

The Organic Acid and Alcohol Monitor (OAAM) program has resulted in the successful development of a computer controlled prototype analyzer capable of accurately determining aqueous organic acids and primary alcohol concentrations over a large dynamic range with high sensitivity. Formic, acetic, and propionic acid were accurately determined at concentrations as low as 5 to 10 micrograms/L in under 20 minutes, or as high as 10 to 20 mg/L in under 30 minutes. Methanol, ethanol, and propanol were determined at concentrations as low as 20 to 100 micrograms/L, or as high as 10 mg/L in under 30 minutes. Importantly for space based application, the OAAM requires no reagents or hazardous chemicals to perform these analyses needing only power, water, and CO2 free purge gas. The OAAM utilized two membrane processes to segregate organic acids from interfering ions. The organic acid concentration was then determined based upon the conductiometric signal. Separation of individual organic acids was accomplished using a chromatographic column. Alcohols are determined in a similar manner after conversion to organic acids by sequential biocatalytic and catalytic oxidation steps. The OAAM was designed to allow the early diagnosis of under performing or failing sub-systems within the Water Recovery System (WRS) baselined for the International Space Station (ISS). To achieve this goal, several new technologies were developed over the course of the OAAM program.

Akse, James R.↗

DOE OSTI2022

2021 Annual Site Environmental Report

This report provides the U.S. Department of Energy (DOE) and the public with information on the level of radioactive and non-radioactive pollutants (if any) that are added to the environment as a result of Princeton Plasma Physics Laboratory’s (PPPL) operations. The results of PPPL’s 2021 environmental surveillance and monitoring program are presented and discussed. The report also summarizes environmental initiatives, assessments, and community involvement programs that were undertaken in 2021. PPPL’s on-site operations were significantly curtailed in 2021 due to the global coronavirus pandemic. PPPL has engaged in fusion energy research since 1951. The Laboratory’s mission is to develop the scientific knowledge and advanced engineering to enable fusion to power the U.S. and the world, and to developing the understanding of plasmas from the nano- to the astrophysical scale. PPPL’s primary experiment, the National Spherical Torus Experiment-Upgrade (NSTX-U) is a collaboration among national laboratories, universities, and national and international research institutions and is a major element in the US Fusion Energy Sciences Program. Its design tests the physics principles of spherical torus (ST) plasmas, playing an important role in the development of smaller, more economical fusion reactors. Due to previous operational issues, NSTX-U did not operate in 2021. PPPL is engaged in a project to replace key NSTX-U components and systems to enable operation of this international fusion user facility. In 2021, PPPL’s radiological environmental monitoring program measured tritium in the air at the NSTX-U Stack and at onsite sampling stations. Using highly sensitive air monitors, PPPL is capable of detecting small changes in the ambient levels of tritium. The operation of an in-stack monitor located on D-site is used to demonstrate compliance with the National Emission Standard for Hazardous Air Pollutants (NESHAPs) regulations. Also included in PPPL’s radiological environmental monitoring program, are water monitoring – ground, surface, and waste waters. PPPL’s radiological monitoring program characterized the background levels of tritium in the environment and those data are presented in this report. Ground water monitoring continued under New Jersey Department of Environmental Protection’s (NJDEP) Site Remediation Program regulations. PPPL monitored for non-radiological contaminants, mainly volatile organic compounds (components of common degreasing solvents). In 2021, PPPL complied with permit limits for surface and sanitary discharges. PPPL was honored with awards for EPEAT-certified electronics purchasing and use of peracetic acid as an alternative water treatment chemical in its non-potable process water systems an NJDEP recycling award.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2020

Field Test Bed for Vadose-Zone Monitoring Approaches - 20404

In the Central Plateau at the U.S. Department of Energy Hanford Site, a large inventory of contaminants resides in unsaturated sediments within the approximately 100-meter-thick vadose zone, posing a potential continuing risk to groundwater. Vadose zone remedies used to address these contaminants will require performance monitoring to provide feedback during implementation and for long-term verification that remedial action objectives have been met. Passive approaches may also need long-term monitoring to demonstrate that the flux of contaminants from the vadose zone to the groundwater are below thresholds established to meet groundwater protection goals. Collection of physical (e.g., groundwater or sediment) samples is a common method for identifying contaminant concentration distributions, but this approach is limited by the number of locations and the frequency with which data can be collected. In situ vadose zone measurements have evolved over the past few years to include key measurements of water content, soil water pressure, temperature, and chemical concentration. However, the current generation of sensors is designed for relatively short-term use in near-surface soils or sediments. Geophysical methods have been evolving but are also limited in that they have not been designed for the specific long-term vadose zone monitoring needs at the Hanford Site. Overall, monitoring under unsaturated conditions can be difficult due to the need to install and maintain instrumentation over a large area and depth and the need to identify preferential flow pathways due to geologic and chemical heterogeneities over long periods. Thus, a vadose zone monitoring test bed was initiated to address these challenges and identify cost-effective approaches for implementation and postclosure monitoring of the deep vadose zone. The monitoring test bed is expected to provide valuable field-scale information for the design of vadose zone monitoring systems. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2020

The Challenges of Air Monitoring at a Soil Remediation Project in a Suburban Setting - 20448

Air monitoring during soil excavation at a chemically and radiologically impacted site in a suburban setting presents unique challenges. Site activities were conducted in a manner that minimized the release of airborne particulates of concern, principally radionuclides of concern (ROC). Dust and air monitoring were performed to ensure the public was not being exposed to the soil contaminants. The project team collected representative air and dust data while being mindful to not impose on the lives of residents in the area. Due to the close proximity to the public, there was a high level of oversight from the client and regulatory agencies. The challenges involved with air sampling at this soil remediation site located in a suburban setting included the number of contaminants, the ranges of risks and hazards presented by the contaminants and the method of remediation, the concerns of the regulators and the public, and the perception of risk from the public. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2020

Novel Foaming Solutions for High Level Waste (HLW) Processing - 20195

Foaming occurs during treatment of high level waste (HLW) at Savannah River Site's Defense Waste Processing Facility (DWPF) in the Chemical Process Cell (CPC) due to high gas generation from process steam and chemical offgas products [1]. The presence of amphiphilic particles in the waste slurry stabilizes the foam [2], [3]. Efficient processing of HLW requires foam control, as foam-overs lead to lower productivity and potential radioactive contamination of condensate streams. DWPF currently employs Siovation Antifoam 747, a surfactant produced by Momentive Performance Materials, as an antifoaming agent during waste treatment. Despite its ability to control foam generation, processing issues have arisen from its use [4]. During DWPF chemical processing, a chemical antifoam agent must be effective at temperatures up to 103 deg. C between pH 3-13. Antifoam 747 is effective at pH 7 but degrades as pH deviates [5]. Antifoam 747 is 90% by weight Momentive{sup TM} L77 and 10% by weight Momentive{sup TM} Y-17580. These ingredients are trisiloxane products, which are especially vulnerable to attack in acidic and caustic environments. Since Antifoam 747 readily degrades, periodic addition is required. Several processing concerns related to Antifoam 747 have affected DWPF operation. Its overuse warranted concern of potential flammable melter offgas under upset conditions due to the generation of carbon dioxide and hydrogen. As a result, a Potential Inadequacy in the Safety Analysis (PISA) was declared [6]. Antifoam contribution has been included in the melter offgas flammability strategy and the quantity of antifoam is monitored to ensure limits are not exceeded. Testing at Savannah River National Laboratory (SRNL) determined that propanal, tri-methylsilanol, and hexamethyldisiloxane are generated as Antifoam 747 degrades, leading to a second PISA [7]. The formation of these byproducts poses additional flammability risks. Furthermore, the methyl and ethyl groups of these compounds may be responsible for the formation of the methyl and ethyl mercury discovered in DWPF [8], [9]. The formation of organomercury has specifically been called out by DOE as a need for increased research. The effectiveness of non-chemical methods for foam control and the efficiency of alternative antifoam agents were evaluated as part of an effort to improve HLW treatment operations at DWPF and to reduce, or eliminate, the flammability hazards associated with Antifoam 747 currently in use. Foaming of high-level waste (HLW) slurries is an issue at the Defense Waste Processing Facility (DWPF) Chemical Process Cell (CPC) which is currently mitigated with a chemical antifoam agent. The effectiveness of non-chemical methods for foam control and the efficiency of alternative antifoams were examined to improve HLW treatment at DWPF and to eliminate the flammability hazards associated with Siovation Antifoam 747 currently in use. Non-chemical foam control methods were deemed unviable for chemical processing at DWPF, as the spray/mist technique requires too much water and space limitations make installation and implementation of headspace agitators unfeasible. The use of ultrasonic energy thickened and further stabilized the foam. Two suitable alternative defoaming agents, Momentive{sup TM} Y- 17112 and Evonik Surfynol{sup R} MD-20, were identified. Both defoamers control foam over a pH range of 4- 13 at boiling, with no flammable degradation products, and only minimal quantities (100-200 mg/kg) are required under glycolic acid conditions. In order to validate the effectiveness of these defoaming agents, SRNL recommends irradiation testing and laboratory scale SRAT/SME experiments with actual radioactive waste. (authors)

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