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At least 19 records

Investigation of Mercury Compound Partitioning Through the Solvent Extraction System

Savannah River National Laboratory (SRNL) has been requested by Savannah River Mission Completion (SRMC)/ Salt Waste Processing Facility (SWPF) personnel to investigate the potential routes for titanium and mercury accumulations within the SWPF Flowsheet. This report documents work performed to examine how various forms of mercury can migrate through the multiple flowsheets of a solvent extraction system. This entailed 29 single stage distribution tests, a multi-stage Extraction-Scrub-Strip (ESS) test, and a detailed speciation analysis of several salt batch feed samples.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

High-resolution imaging of Hg/Se aggregates in the brain of small Indian mongoose, a wild terrestrial species: insights into intracellular Hg detoxification

Human activities result in the emission of 2000 metric tons of mercury compounds annually. Mercury (Hg) biomagnification has been characterized in marine mammals and predatory fish; however, little is known about mercury accumulation in brains of wild terrestrial species. Elevated Hg content, of 1.27 μg/g wet wt.—found in the brain of wild small Indian mongoose, prompted us to use synchrotron X-ray fluorescence imaging for simultaneous, quantitative mapping of biologically relevant and neurotoxic elements with high spatial resolution. X-ray fluorescence combined with immunohistochemistry revealed ~0.5–1.9 micron Hg-rich aggregates in cells of the choroid plexus and astrocytes of the subventricular wall in the mongoose brain. Hg content within aggregates correlated with selenium. Hg aggregates did not co-localize with lysosomes. The low Hg density inside aggregates indicated diffuse Hg binding to a Se-containing biomolecule, rather than much denser HgSe nanoparticles proposed to form in other species. Our data show the susceptibility of the small Indian mongoose population to Hg pollution and highlight the vulnerability of the brain as an organ targeted by mercury. Data also provide evidence on the adaptation in the form of a Se-based detoxification mechanism sequestering Hg into intracellular aggregates.

36 MATERIALS SCIENCE↗

Critical Design Elements for an On-Site Mercury Concentration and Holding Facility - 20175

Administrative changes and funding issues have delayed the Department of Energy (DOE) from establishing and commissioning a National Repository for mercury as required under the Mercury Export Ban Act (MEBA) of 2008. In the interim, a few hazardous waste Treatment, Storage, and Disposal Facilities (TSDFs) have been authorized to accept mercury classified as a hazardous waste as under Subtitle C of the Resource Conservation and Recovery Act (RCRA). Waste generators are charged (either by weight or by volume) for the waste they manifest to these TSDFs. In many cases, mercury and mercury compounds have chemically sorbed to (or physically lodged into) the interstitial spaces of a substrate material. This almost always causes the amount of waste generated to be unnecessarily large, due to the extra volume (or weight) of the accompanying, non-mercury materials. Depending on a multitude of factors, it could be financially beneficial for waste generators to take greater control of their mercury affairs by separating these substrate materials from the mercury and mercury compounds that have become associated with them. Building and operating an on-site mercury Concentration and Holding Facility (CHF) could help relieve a waste generator's overall cost burden. The purpose of such CHFs is not to treat or dispose of mercury, but to recover and concentrate mercury from bulky mercury-laden materials to the extent that the host substrate to which the mercury may have previously been sorbed could pass a Toxicity Characteristic Leaching Procedure (TCLP) test and either be disposed of at a conventional landfill, or be disposed of at a hazardous waste landfill, but absent additional restrictions specifically for mercury. A CHF represents a way for waste generators to save money by separating mercury from common host materials, concentrating it, and then safely storing it until transportation to an authorized TSDF takes place This paper focuses on the critical design elements waste generators should consider when designing and operating a mercury CHF. (authors)

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Vapor-Liquid Partitioning of Methylmercury Compounds: Fundamental Data to Support the Savannah River Site Liquid Waste System: Henry's Law, Solubility and Vapor Pressure Determination for Representative Methylmercury Compounds

The Savannah River Site (SRS) Liquid Waste System (LWS) contains approximately 66 tons of mercury within the liquids, salts, and sludges that are currently being processed into final wasteforms for disposal. Mercury concentrations within the system exceed those typically experienced in environmental or industrial systems; thus, management of mercury compounds continues to be a priority for SRS. In the LWS, waste is vitrified into a borosilicate glass wasteform that contains most of the radioactivity, while the lower activity solutions are dispositioned in a low-level grout wasteform, or “saltstone”. The alkaline, high ionic strength caustic wastes are pumped, evaporated, and otherwise managed throughout the LWS and Defense Waste Processing Facility (DWPF) as they are stored and prepared for conversion to the final wasteforms. Because of the complexity of this system, a key component of effective mercury management in the LWS requires analysis of mercury in various physical phases. The high concentration of mercury within the SRS LWS has the potential to generate vapor-phase contamination. Elemental mercury (Hg 0 ), dimethylmercury ((CH 3 ) 2 Hg), and methylmercury (CH 3 Hg + ) are among species known or suspected to contribute to the flux of mercury from liquid to vapor phase (Iverfeldt and Lindquist, 1982). Chemical speciation affects not only mercury behavior in LWS operations but may also affect the performance of mercury treatment and removal technologies in the LWS.

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Ecological Traits of Fish for Mercury Biomonitoring: Insights from Compound-Specific Nitrogen and Stable Mercury Isotopes

Here we coupled compound-specific isotopic analyses of nitrogen (N) in amino acids (δ 15 N Glu , δ 15 N Phe ) and mercury stable isotopes (δ 202 Hg, Δ 199 Hg) to quantify ecological traits governing the concentration, variability, and source of Hg in largemouth bass (LB) and pike gudgeon (PG) across four rivers, South Korea. PG displayed uniform Hg concentration (56–137 ng/g), trophic position (TP corrected ; 2.6–3.0, n = 9), and N isotopes in the source amino acid (δ 15 N Phe ; 7–13‰), consistent with their specialist feeding on benthic insects. LB showed wide ranges in Hg concentration (45–693 ng/g), TP corrected (2.8–3.8, n = 14), and δ 15 N Phe (1.3–16‰), reflecting their opportunistic feeding behavior. Hg sources assessed using Hg isotopes reveal low and uniform Δ 199 Hg in PG (0.20–0.49‰), similar to Δ 199 Hg reported in sediments. LB displayed site-specific δ 202 Hg (-0.61 to -0.04‰) and Δ 199 Hg (0.53–1.09‰). At the Yeongsan River, LB displayed elevated Δ 199 Hg and low δ 15 N Phe , consistent with Hg and N sourced from the atmosphere. LB at the Geum River displayed low Δ 199 Hg and high δ 15 N Phe , both similar to the isotope values of anthropogenic sources. Our results suggest that a specialist fish (PG) with consistent ecological traits and Hg concentration is an effective bioindicator species for Hg. When accounting for Hg sources, however, LB better captures site-specific Hg sources.

59 BASIC BIOLOGICAL SCIENCES↗

Human perturbations to mercury in global rivers

Mercury compounds are potent neurotoxins that pose threats to human health, primarily through fish consumption. Rivers, critical for drinking water and food supply, have seen rapid increases in mercury concentrations and export to coastal margins since the Industrial Revolution (~1850). However, patterns of these changes remain understudied, limiting assessments of environmental policies. Here, we develop a global model to simulate preindustrial riverine total mercury and assess human perturbations by comparing it to present-day conditions. We find that global rivers transported ~390 megagrams annually of mercury to the oceans in the preindustrial era, with spatial variability. Human activities have elevated riverine mercury budgets by two to three times in the present day. Establishing a baseline riverine mercury level, our findings reveal rapid responses of riverine mercury to human perturbations and could be used to inform targets for global riverine mercury restoration. Total riverine mercury concentrations could also be used as indicators to comprehensively understand the effectiveness of mercury pollution governance.

Science & Technology - Other Topics↗

Speciation of Mercury in Sludge Solids: Unwashed Sludge

The objective of this applied research task is to study the type and concentration of mercury compounds found within the contaminated Savannah River Site Liquid Waste System (SRS LWS). A method of selective sequential extraction (SSE), originally developed by (Eurofins) Frontier Global Sciences (FGS) and adapted by the Savannah River National Laboratory (SRNL), utilizes an extraction procedure divided into seven separate tests for different species of mercury. In the SRNL’s modified procedure four of these tests were applied to an unwashed sample of high-level radioactive waste sludge.

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A Mercury Lander Mission Concept Study for the Next Decadal Survey

Mariner 10 provided our first closeup reconnaissance of Mercury during its three flybys in 1974 and 1975. MESSENGER’s 2011–2015 orbital investigation enabled numerous discoveries, several of which led to substantial or complete changes in our fundamental understanding of the planet. Among these were the unanticipated, widespread presence of volatile elements (e.g., Na, K, S); a surface with extremely low Fe abundance whose darkening agent is likely C; a previously unknown landform—hollows— that may form by volatile sublimation from within rocks exposed to the harsh conditions on the surface; a history of expansive effusive and explosive volcanism; substantial radial contraction of the planet from interior cooling; offset of the dipole moment of the internal magnetic field northward from the geographic equator by ~20% of the planet’s radius; crustal magnetization, attributed at least in part to an ancient field; unexpected seasonal variability and relationships among exospheric species and processes; and the presence in permanently shadowed polar terrain of water ice and other volatile materials, likely to include complex organic compounds. Mercury’s highly chemically reduced and unexpectedly volatile-rich composition is unique among the terrestrial planets and was not predicted by earlier hypotheses for the planet’s origin. As an end-member of terrestrial planet formation, Mercury holds unique clues about the original distribution of elements in the earliest stages of the Solar System and how planets (and exoplanets) form and evolve in close proximity to their host stars. The BepiColombo mission promises to expand our knowledge of this planet and to shed light on some of the mysteries revealed by the MESSENGER mission. However, several fundamental science questions raised by MESSENGER’s pioneering exploration of Mercury can only be answered with in situ measurements from the planet’s surface.

Ernst, C. M.↗

Results of The Solvent Hold Tank Disposal Sample

Multiple samples from the Solvent Hold Tank (SHT) at the Modular Caustic-Side Solvent Extraction Unit (MCU) were delivered to SRNL and composited for comprehensive analysis in support of a disposal pathway for this organic liquid. A suite of radiochemical and nonradiochemical analyses show that the solvent composition is as expected with respect to the solvent components. The radiochemical analyses confirm the assumption that very few radioactive species are associated with the solvent (other than cesium) and those that have measurable values are typically a few tens of pCi/mL in activity concentration. The solvent has a total activity of ≤1.99E- 08 Ci/g, or ≤6.27E-05 Ci/gal. The cesium in the solvent has an activity of ≤1.76E-08 Ci/g, or ≤5.55E-05 Ci/gal. For the non-radiochemical analyses, the results are as anticipated. The solvent shows no or minimal propensity to take up Resource Conservation Recovery Act (RCRA) metals, except for mercury, likely due to uptake of methyl-mercury compounds known to be in the feed stream.

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Finding Of Adverse Effect and Proposed Mitigation for the Removal of Joshua Trees at Building 23-210, Mercury, Area 23, Nevada National Security Site, Nye County, Nevada

The U.S. Department of Energy (DOE), National Nuclear Security Administration Nevada Field Office (NNSA/NFO) recently removed two fallen Joshua trees that were part of an Accessory Resource (AR) to the former Department of Defense (DOD) Motor Pool Maintenance Compound in Mercury (Nevada State Historic Preservation Office [SHPO] Resource No. C307) on the Nevada National Security Site (NNSS) in Nye County, Nevada (Figure 1). The Joshua trees were part of AR3, a landscaped feature at the entrance to the compound. There are two remaining Joshua trees at risk of falling which may require removal in the future. The NNSA/NFO is proactively consulting with the SHPO regarding the potential removal of the remaining two trees. The purpose of the undertaking is to ensure that dead or dying Joshua trees do not cause damage to the remaining landscape elements, nor injury to NNSS employees. The NNSA/NFO will implement this undertaking in accordance with the Programmatic Agreement between the National Nuclear Security Administration Nevada Field Office and the Nevada State Historic Preservation Officer Regarding Modernization and Operational Maintenance of the Nevada National Security Site, at Mercury in Nye County, Nevada, hereafter referred to as the Mercury PA. Building 23-210 was the DOD’s motor vehicle maintenance compound constructed in 1951. The compound included its own repair shop and fuel station. The town of Mercury and the immediate surrounding area have been formally determined eligible for listing in the National Register of Historic Places (National Register, NRHP) as the Mercury Historic District (MHD, SHPO Resource No. D230) under Criteria A and C for their importance in supporting nuclear testing and scientific research from 1951 through 1992. The former DOD Motor Pool Compound was identified as a contributing element to the MHD in a 2018 architectural survey of the district (Reno et al. 2018) and recorded on a Nevada Architectural Resource Assessment (ARA) form (Reno et al. 2017). The foundation for Building 23-210 was also identified in Appendix C of the Mercury PA as a Category III contributing element with three contributing ARs. Category III properties are those that may include elements for which there are several representatives in the MHD, such as foundations, and those elements which possess characteristics that are not unique to the MHD and are commonly found in other non-NNSS facilities. The former DOD compound, which is identified by the foundation for the Building 23-210 and its ARs, is a historic property for the purposes of compliance with Section 106 of the National Historic Preservation Act (NHPA) and subject to the stipulations of the Mercury PA.

54 ENVIRONMENTAL SCIENCES↗

Proof-of-Concept Experiments on a Gallium-Based Ignitron for Pulsed Power Applications

Ignitrons are electrical switching devices that operate at switching times that are on the order of microseconds, can conduct high currents of thousands of amps, and are capable of holding off tens of thousands of volts between pulses. They consist of a liquid metal pool within an evacuated tube that serves both the cathode and the source of atoms and electrons for an arc discharge. Facing the liquid metal pool is an anode suspended above the cathode, with a smaller ignitor electrode tip located just above the surface of the cathode. The ignitron can be charged to significant voltages, with a potential difference of thousands of volts between anode and cathode. When an ignition pulse is delivered from the ignitor electrode to the cathode, a small amount of the liquid metal is vaporized and subsequently ionized, with the high voltage between the anode and cathode causing the gas to bridge the gap between the two electrodes. The electrons and ions move rapidly towards the anode and cathode, respectively, with the ions liberating still more atoms from the liquid metal cathode surface as a high-current plasma arc discharge is rapidly established. This arc continues in a self-sustaining fashion until the potential difference between the anode and cathode drops below some critical value. Ignitrons have been used in a variety of pulsed power applications, including the railroad industry, industrial chemical processing, and high-power arc welding. In addition, they might prove useful in terrestrial power grid applications, serving as high-current fault switches, quickly shunting dangerous high-current or high-voltage spikes safely to ground. The motivation for this work stemmed from the fact that high-power, high-reliability, pulsed power devices like the ignitron have been used for ground testing in-space pulsed electric thruster technologies, and the continued use of ignitrons could prove advantageous to the future development and testing of such thrusters. Previous ignitron designs have used mercury as the liquid metal cathode, owing to its presence as a liquid at room temperatures and a vapor pressure of 10 Pa (75 mtorr) at room temperature. While these are favorable properties, there are obvious environmental and personal safety concerns with the storage, handling, and use of mercury and its compounds. The purpose of the present work was to fabricate and test an ignitron that used as its cathode an alternate liquid metal that was safe to handle and store. To that end, an ignitron test article that used liquid gallium as the cathode material was developed and tested. Gallium is a metal that has a melting temperature of 29.76 C, which is slightly above room temperature, and a boiling point of over 2,300 C at atmospheric pressure. This property makes gallium the element with the largest relative difference between melting and boiling points. Gallium has a limited role in biology, and when ingested, it will be subsequently processed by the body and expelled rather than accumulating to toxic levels. The next section of this Technical Memorandum (TM) provides background information on the development of mercury-based ignitrons, which serves as the starting point for the development of the gallium-based variant. Afterwards, the experimental hardware and setup used in proof-of-concept testing of a basic gallium ignitron are presented. Experimental data, consisting of discharge voltage and current waveforms as well as high-speed imaging of the gallium arc discharge in the gallium ignitron test article, are presented to demonstrate the efficacy of the concept. Discussion of the data and suggestions on improvements for future iterations of the design are presented in the final two sections of this TM.

Ali, H. K.↗

Feasibility of Metal Oxide Glasses and Polymer Membranes as Sorbents for Gaseous Oxidized Mercury

Mass spectrometry methods are currently under development by the atmospheric mercury (Hg) research community to elucidate the identity of atmospheric oxidized mercury (Hg II ) compounds. Due to high instrument detection limits, materials that can quantitatively preconcentrate atmospheric Hg II without facilitating compound-altering chemical reactions are needed to support these methods. Cation exchange membranes (CEM) and nylon membranes are currently used to preconcentrate ambient Hg II for concentration measurements and Hg II compound estimation, respectively. However, CEM and nylon membranes are poor candidates for observations by mass spectrometry methods due to release of interfering compounds upon heating; glasses do not have this problem. Here, three metal oxide glasses were explored as potential alternatives for Hg II preconcentration for future use with mass spectrometry methods: calcium phosphate (CaP), iron phosphate (FeP), and calcium aluminate (CaAl). The glasses demonstrated quantitative selective capture of HgBr 2 without capture of Hg 0 . Under ambient conditions, the CaP, FeP, and CaAl sorbed 36.4 ± 12.6% of the total HgII as the CEM. However, when Hg concentrations were normalized to surface area, CaP, FeP, and CaAl sorbed more HgBr 2 in the laboratory and ambient HgII compared to CEM. The CEM and CaP retained similar concentrations of HgBr 2 when preloaded samples were deployed in the field. Additionally, a permeation tube-based calibrator was used to load sorbents with HgBr 2 for investigation of HgII retention on CEM and thermal desorption profile changes on nylon membranes during active sampling. Nylon membranes were purchased from three vendors and used to compare HgBr 2 retention; a different HgBr 2 thermal desorption profile was achieved for each vendor’s nylon membrane.

Amides↗

Optical Characteristics of Radiated Multifunctional Optical Materials

The performance of optical and electronic materials, and devices are affected significantly in space due to exposure from high energy radiations. We have been investigating the effect of -ray radiations on multifunctional binary and ternary selenide and halide crystals. These materials have shown excellent performance for the wavelength conversion in MWIR and LWIR regions, acousto-optics, and great potential for radiation detection. Crystals with high Z materials such as thallium, mercury and lead based compounds have great potential for the development of a variety of devices and components suitable for space applications. We will report on the characteristics of several halides including mercurous halides (Hg2X2, X= Cl, Br, I), Thallium mercury iodide (Tl4HgI4) and thallium arsenic selenide and thallium gallium selenide, and ternary selenides. These crystals, synthesized with high purity source materials, will be evaluated by studying optical characteristics and measuring resistivity after exposure to a 137Cs -ray source.

Radiation↗

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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