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All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Recommended Updates to Solubility Controls for Modeling Leaching of Technetium, Uranium, Neptunium, Plutonium, and Iodine from the Residual Waste Layer of Closed Savannah River Site High Level Waste Tanks

The objective of this report is to relate waste leaching experiments by the Savannah River National Laboratory (SRNL) to performance assessment modeling of release of several radionuclides from residual waste in closed high-level waste tanks. SRNL leached residual waste from Tanks 18F and 12H with solutions simulating the modeled evolution of pore fluids in residual waste layers of closed tanks through various stages of grout degradation. Tc-99, uranium isotopes, Np-237, plutonium isotopes, and I-129 were analyzed in the leachate multiple times over 90 days.

07 ISOTOPE AND RADIATION SOURCES↗
DOE OSTI2020

History of Ultrasonic Inspection of High-Level Waste Tanks at SRS - 20220

The Liquid Waste Disposition Projects (LWDP) Structural Authority and Inspection Engineering Support Group has teamed with the Materials Science and Technology Non-destructive Evaluation Group of Savannah River National Laboratory (SRNL) to implement a comprehensive In-Service Inspection (ISI) program for the High-Level Waste (HLW) tanks in the sites tank farms. The purpose of this program is to demonstrate the structural and leak integrity of the tanks to maintain the function of waste containment throughout the desired service life. Four types of waste tanks were constructed at Savannah River Site (SRS) from 1951 thru 1981 to store radioactive nuclear waste from the separations process. The Type I, II and III are carbon steel cylindrical tanks with varying degrees of access to the side walls and very limited access to the tank bottom. The tanks contain 750,000 to 1.3 million gallons of waste and are buried or backfilled with soil. The tanks are 75'-85' in diameter and 24'-33' from tank bottom to the tank roof. Inspection of the HLW tanks is made difficult by radiation, contamination, and small access openings. Through the years these challenges have been overcome by progressive improvements to programs and equipment resulting in the sophisticated wall crawler Ultrasonic Testing (UT) technology of today. A formal inspection program was developed and put in service in 1972. UT thickness measurements were first made in 1967 and 1969 of selected waste tanks using an analog-type instrument to measure the thickness of the carbon steel walls. Routine inspections for thinning were performed from 1972-1985 and then discontinued because no thinning had been observed and this technique could not detect pitting or cracking. UT inspections resumed in 1994 using a sophisticated robotic wall crawler with UT technology capable of detecting thinning, cracking and pitting. The current program focuses on the newer Type III tanks that are used primarily for storage. The program was upgraded in 2003 to include selected regions of the tank wall, secondary wall and annulus floor on a 7 to 10-year frequency. The facility is currently in its third cycle of tank inspections. Thus far, there have been no reportable indications of service induced degradation. This result provides assurance that the chemistry control program has been effective at mitigating corrosion and that the tanks remain structurally sound even after more than 40 years of service. This paper will present the UT technology first used at SRS and the evolution to the current systems and their capabilities. Additionally, plans for equipment upgrades that will improve the extent of inspection will be discussed. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2020

Savannah River Site High Level Radioactive Waste Tank Sample Thermolytic Hydrogen Generation - 20346

To support the revision of flammability calculations and controls for the Savannah River Site (SRS) High-Level Radioactive Waste (HLW) tanks, Savannah River National Laboratory (SRNL) conducted laboratory measurements with the goal of quantifying hydrogen produced in HLW by non-radiolytic chemical reactions (i.e., thermolysis). Testing was performed with HLW tank supernate samples that represented a cross section of types of waste at SRS, including tanks that store typical evaporator concentrate, dissolved salt-cake, dilute recycle stream from the Defense Waste Processing Facility (DWPF), evaporator concentrate of the recycle stream from DWPF, fresh waste from the canyon separations facility, and waste that has been through salt processing cesium removal. Non-radioactive simulant testing included the classes of organic compounds historically introduced into the HLW tanks that were recently shown to be the most active toward the thermolytic generation of hydrogen. The reaction rate equations developed for thermolytic hydrogen generation from each class of organic compound showed direct proportionality to organic compound concentration and hydroxide concentration. Simulant testing identified that highly concentrated waste with high hydroxide concentration had the highest rates of thermolytic hydrogen generation. Using the radioactive tank sample thermolysis measurements at high temperatures and the mechanistic salt dependence of the simulant models, a global model was developed for tank waste thermolytic hydrogen generation as a function of total organic carbon content of SRS HLW. Through the primary functionality of the global model (organic carbon and free hydroxide concentration), the relative reactivity of the organic carbon in the waste was quantified. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2026

Using Best Basis Inventory Data to Direct Strategies for Real Time Monitoring of Hanford High Level Waste – 26226

The potential to accelerate the processing of low- and high-level tank waste by applying real-time monitoring (RTM) of chemical and physical properties has prompted research into the suitability of multiple analytical methods for that purpose. The broad variety of waste stream properties and the large number of analytes of interest (as evidenced by Waste Acceptance Criteria (WAC) and Process Control Limit (PCL) lists) lead to an overwhelming set of possible analytical scenarios. This report describes the use of Best Basis Inventory (BBI) data to find the most relevant analytical targets for the specific case of monitoring the blending of High Level Waste from multiple tanks prior to introduction into a vitrification facility. Campaigns for blending this waste to minimize the risk of exceeding WACs and PCLs have been proposed. However, the predicted compositions of the blended materials do not incorporate any uncertainties that may be associated with the representativeness of the waste layer samples or the laboratory analyses that generated the BBI data. Also, they do not include any uncertainty associated with the precision of collecting highly specific fractions of the layers during a blending campaign or any inhomogeneities that may exist in those layers. Monte Carlo methods are used to apply uncertainties to the compositions of the individual layers specified in the campaign recipes. The resulting variations in the compositions of the blended materials allow estimation of the risks of exceeding WACs and PCLs for each campaign. A critical subset of WACs/PCLs – NOx, NaK, AlFeZr, and S – are especially at risk of being exceeded in multiple campaigns. These analytes should be the focus of instrument development. We also have extracted the expected solid/supernate distribution for these analytes, which establishes important performance criteria for individual analytical methods. The BBI data also permits an understanding of the different chemical forms in which the analytes appear. Thus, the need to establish instrumental sensitivity to these forms can be gainfully addressed. Although concentrating on one specific application – the blending of tank waste - this approach should be generalizable for the analysis of other possible RTM applications for waste processing.

Lascola, Robert [Savannah River National Laborator↗
DOE OSTI2024

STATISTICAL ANALYSIS OF IN-SERVICE ULTRASONIC INSPECTION DATA OF WASTE TANKS AT THE SAVANNAH RIVER Site-25021

Liquid radioactive waste has been stored in large, underground carbon steel tanks of 4.92-million-liter capacity at the United States Department of Energy's Savannah River Site (SRS) in Aiken, South Carolina since the 1950s. The In-service inspection of the Savannah River Site High Level Waste tanks will be reviewed as well as Ultrasonic testing (UT) for detecting for general wall thinning, pitting and interface attack through accessible regions of the tanks. In-service inspection [1] of the Savannah River Site (SRS) High Level Waste (HLW) tanks is an essential element of a comprehensive structural integrity program. Inspection confirmed the effectiveness of chemistry and temperature controls used to preclude localized and general corrosion of the tanks. Ultrasonic testing is used to detect general wall thinning, pitting and interface attack, as well as vertically oriented cracks through inspection of a 21.59 cm (8.5-in.) wide strip extending over the accessible height of the primary tank wall.

Harris, Stephen P.↗
DOE OSTI2025

Using Best Basis Inventory Data to Direct Strategies for Real-Time Monitoring of Hanford High Level Waste

The proposed Direct Feed High Level Waste (DFHLW) approach for processing high-level tank waste at Hanford is intended to reduce processing time by bypassing the Pretreatment Facility and transferring waste directly from the tank farm to the WTP HLW vitrification facility. This processing strategy could reduce or eliminate the washing and leaching steps that would have occurred in the Pretreatment facility. Operation of the vitrification facility is subject to chemical and radiological limits protecting safety (e.g. Waste Acceptance Criteria, or WACs) and process quality (e.g. Process Control Limits, or PCLs). Without washing and leaching, there is a greater risk of exceeding the WACs and PCLs. Hanford process engineers have devised blending strategies based on known chemical and radiological composition, volumes, and solids loadings of individual layers within each waste tank. These blending campaigns succeed in predicting a processing strategy that does not exceed the WACs and PCLs. However, the calculations do not ascribe uncertainties to the tank analysis data, quantities of material taken from the tanks to make the blend, or potential for mixing of layers within tanks. In order to confirm that a process strategy is working, it would be advantageous to have inline or at-line analytical instrumentation installed in the processing facilities that deliver measurement results in real time.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2025

Reactions of Studtite UO 4 ·4H 2 O in Alkali Hydroxides: Isolation of Single-Crystal Uranate Phases under Mild Hydrothermal Conditions

Uranyl peroxide complexes, particularly studtite (UO 4 ·4H 2 O), are important phases within the nuclear fuel cycle, forming through radiolysis-induced reactions on the surfaces of spent fuel and in waste environments. Studtite has been identified in Hanford’s irradiated fuel storage basins, Chornobyl’s corium lavas, and is anticipated on Fukushima’s fuel debris. While its formation and stability have been extensively studied, the reactivity of UO 4 ·4H 2 O in highly alkaline environments such as those encountered in high-level nuclear waste remains underexplored. These environments contain molar concentrations of [OH - ] and present a chemically dynamic and reactive environment where actinide behavior is not well understood. Reported here are investigations of uranium reactions in concentrated alkali hydroxides under mild hydrothermal conditions (<200 °C) that have resulted in the isolation of the alkali metal uranates Li 2 UO 4 , α-Na 2 UO 4 , γ-Na 2 U 2 O 7 , and K 2 U 2 O 7 . In contrast to conventional solid-state methods (>800 °C) that typically yield polycrystalline powders, our approach enables the isolation of these uranates as single crystals, allowing us to provide single-crystal structure solutions of certain uranates for the first time. Our findings match the results of high-level waste tank sampling, confirming that sodium diuranate (Na 2 U 2 O 7 ) is the most persistent uranium phase, potentially forming through reactions of uranyl peroxide intermediates with NaOH under radiolytic and highly alkaline conditions.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2020

99 TcO 4 - removal from legacy defense nuclear waste by an alkaline-stable 2D cationic metal organic framework

Removal of 99 TcO 4 - from legacy defense nuclear tank waste at Savannah River Site is highly desirable for the purpose of nuclear safety and environmental protection, but currently not achievable given the extreme conditions including high alkalinity, high ionic strength, and strong radiation field. Herein, we present a potential solution to this long-term issue by developing a two-dimensional cationic metal organic framework SCU-103, showing ultrahigh stability in alkaline aqueous media and great resistance to both β and γ radiation. More importantly, it is very effective for 99 TcO 4 - separation from aqueous media as demonstrated by fast exchange kinetics, high sorption capacity, and superior selectivity, leading to the successful removal of 99 TcO 4 - from actual Savannah River Site high level tank waste for the first time, to the best of our knowledge. In addition, the uptake mechanism is comprehensively elucidated by molecular dynamics simulation and density functional theory calculation, showing a unique chemical recognition of anions with low charge density.

98 NUCLEAR DISARMAMENT, SAFEGUARDS, AND PHYSICAL P↗
DOE OSTI2026

Tank 11H Low Temperature Aluminum Dissolution and Inhalation Dose Potential Analyses at Savannah River Site – 26018

Currently, there is approximately 34 million gallons of high-level radioactive tank waste in the Tank Farm at the Savannah River Site (SRS). The ultimate goal of operations at the Tank Farm is to remove the high level waste (HLW) from the tanks followed by stabilization of the waste through vitrification of the HLW into glass or grouting the decontaminated waste into saltstone. After bulk removal of the HLW consisting of sludge, saltcake, and supernatant, further efforts are made to reduce the residual waste present in the tank in order to declare preliminary cease waste removal (PCWR) signifying completion of HLW removal. These reduction efforts can include tank washing to remove soluble salts and radioisotopes and dissolution of solids including aluminum. Aluminum in the form of gibbsite and boehmite is relatively insoluble in water. Through addition of aqueous sodium hydroxide, the aluminum can be dissolved at mild temperatures. In order for the waste tank to meet closure mode requirements of the Concentration, Storage, and Transfer Facilities (CSTF), which includes the Tank Farm, Documented Safety Analysis (DSA), a component of the safety basis, the inhalation dose potential (IDP) and the radiolytic hydrogen generation rate of the stored waste must be demonstrated to be lower than their respective designated limits. These parameters are calculated from measured radiochemical analyses of isotopes that emit a high amount of radioactivity including Cs-137, Sr-90, Pu-238, Pu-239, Pu-240, Pu-241, Am-241, and Cm-244. Following the low temperature aluminum dissolution (LTAD) process, Tank 11H slurry samples were pulled from the tank and sent to Savannah River National Laboratory (SRNL) to measure the extent of aluminum dissolution, hydroxide concentration, densities of slurry and supernatant, weight percent solids analyses, and radionuclide activities. The analyses of the composite sample found that approximately 90% of the total aluminum in the slurry was dissolved, indicating successful reduction of the insoluble aluminum in the waste tank. Additionally, the weight percent insoluble solids (slurry basis) measurement of the composite sample was found to be approximately 1%, demonstrating that minimal solids still remain in the tank. Finally, the radiochemical analyses of the composite sample determined that the waste contents of the tank met the IDP and radiolytic hydrogen generation rate requirements of the CSTF DSA. These measurements have shown that the LTAD process in Tank 11H was successful in waste reduction efforts and a positive step towards declaring PCWR and tank closure at SRS.

Dekarske, John [Savannah River National Laboratory↗
DOE OSTI2020

Savannah River Site Composite Analysis (FY2019 Annual Review)

The Savannah River Site (SRS) is a Department of Energy (DOE) site encompassing approximately 310 square miles in South Carolina. It is bounded on the southwest by the Savannah River (SR) and is situated approximately 12 miles south of Aiken, South Carolina, and 15 miles southeast of Augusta, Georgia. Construction of and subsequent operations at the SRS began in 1951 under the direction of the Atomic Energy Commission. The primary mission of the SRS was to produce tritium and plutonium for the national nuclear weapons complex. Between 1953 and 1955, SRS brought five reactors and various support facilities into operation in support of its primary mission. Support facilities included two chemical separations plants, a heavy water extraction plant, a nuclear fuel and target fabrication facility, a tritium extraction facility and waste management facilities. With the declining need for a large nuclear weapons stockpile since the end of the Cold War, many SRS facilities no longer produce or process nuclear materials. All reactors were shut down by 1993. However, the SRS Tritium Extraction Facility continues to supply DOE with tritium. Additionally, operations at the K-Area Complex currently provide interim safe storage for much of DOE’s excess plutonium (Pu) and high enriched uranium, in a building which formerly housed K Reactor. As the SRS mission has changed, many surplus facilities are being dispositioned safely and economically. SRS has completed extensive decommissioning activities in D-Area, M-Area, P-Area, R-Area, and T-Area, with groundwater (GW) remediation ongoing. High-level waste tanks continue to be emptied and closed.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2024

Deployment of Low Temperature Aluminum Dissolution (LTAD) Technology to Retrieve H-Modified (HM) Sludge in SRS Tank 15 – 25672

Tank 15 is a 4,234,000-liter (1,118,500-gallon) Type 2 high-level waste storage tank located in H Tank Farm at the Savannah River Site. It was put into service in 1960 to receive high-activity, H-Modified (HM) waste from H Canyon. Between June 1964 and November 1972, the waste tank was filled six times, and supernate was decanted five times, leaving behind the sludge solids. Tank 15 also received a mixture of high-activity and low-activity HM waste from Tank 16. Tank 15 has more recently undergone several mixing campaigns to remove much of the sludge waste; however, the effectiveness of suspending the sludge heel via mechanical mixing has significantly diminished. Low Temperature Aluminum Dissolution (LTAD) is a process developed for the dissolution of suspended aluminum solids in a large waste storage tank. Originally intended for deployment during the preparation of sludge batches in H Tank Farm for the Defense Waste Processing Facility (DWPF), the process involves maintaining the waste storage tank at a slightly elevated temperature and highly alkaline chemistry to facilitate dissolution of aluminum solids. As mechanical heel removal efforts diminished in effectiveness in Tank 15, LTAD was selected to both reduce the volume of sludge solids remaining in the heel and to modify the sludge rheology to facilitate the suspension of additional solids using the installed mixing devices.

Campbell, Seth G.↗
DOE OSTI2020

Rheology and Flow Evaluation of Neutralized Sodium Reactor Experiment Fuel with Manganous Nitrate

H-Canyon is preparing the Sodium Reactor Experiment (SRE) solutions in Tanks 16.3 and 16.4 for discard to the Savannah River Site (SRS) High Level Waste (HLW) Tanks into Sludge Batch (SB) 10. To meet HLW's criticality requirements, manganese will be added to the SRE solutions. The addition of manganese to the existing thorium and uranium in the SRE solution raised concerns with the flow of this neutralized material as it is discharged from H-Canyon through the gravity drain system to the H-Area Pump Pit (HPP). A neutralized Mn adjusted SRE stream will produce primarily Mn, Th, and U solids that can deter transfer. A 2012 rheology study was completed as part of the flowsheet development.1 However, the initial rheology study did not include the addition of manganous nitrate as a poison. Therefore, H-Canyon Engineering requested Savannah River National Laboratory (SRNL) to determine if the neutralized, Mn-adjusted SRE solutions will flow through the waste header to the HPP. The H-Canyon Technical Task Request (TTR) specified a target of 80 to 1 to bound the uncertainty in Mn target. Parallel studies were being performed to ensure that freshly precipitated Mn did not have a solubility that would result in challenging the DWPF WAC requirements of 70 to 1. This task was requested via a TTR and is governed by a Task Technical and Quality Assurance Plan (TTQAP).

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2026

Online Alpha Monitoring of High Cs-137 Hanford and SRS High Level Waste with Tensioned Metastable Fluid Detectors

The Department of Energy’s Hanford and Savannah River Sites maintain millions of gallons of caustic supernate and salt high activity waste in their high-level waste (HLW) tank farm inventories. The Savannah River Site is currently treating this waste with a calixarene-based solvent extraction of Cs-137 to reduce these inventories. Hanford is employing an at-tank crystalline silico titanate (CST) based solid phase extraction methodology to reduce their liquid HLW inventories. Due to the high solubility of Cs-137 and the relative insolubility of the actinides in these caustic waste forms, the beta to alpha radioactivity ratio can often exceed six orders of magnitude in the feed solutions to these treatment processes. This unique characteristic leads to significant technical challenges in making rapid gross alpha measurements in the presence of the overwhelming beta, gamma, as well as dissolved sodium salt in these HLW matrices. Conventional radioanalytical techniques, such as liquid scintillation analysis or gas flow proportional counting require significant radiochemistry preparation prior to the radiometric measurements for gross alpha activity. These required pretreatments render these technologies untenable for rapid quantification of gross alpha activity that could be required to support on or at-line measurements ensuring a waste stream will meet regulatory requirements. The radiation measurement properties of Tensioned Metastable Fluid Detectors (TMFDs) have been studied by Purdue University’s Taleyarkhan research group for well over a decade. Fluids tensioned to the appropriate degree will rupture when struck by radiation, resulting in a measurable cavitation event. The negative pressure generating this tension can be adjusted by centrifugal rotation or by acoustic means in such a way that these cavitation events can be generated from alpha radiation but will not be generated by beta or gamma radiation. Purdue University and the Savannah River National Laboratory are currently collaborating to develop a gamma/beta blind, spectroscopic alpha measurement system based on the Tensioned Metastable Fluid Detector technology to provide a potential solution for performing rapid gross alpha measurements on these high gamma/beta sample matrices. Measurements using the Indirect Drive Acoustically Tensioned Metastable Fluid Detectors developed as part of this collaboration were performed with an alpha emitting radionuclide. Successful determination of gross alpha activity was observed, indicating a potential pathway for rapid gross alpha measurements in remote-handled shielded cells or in process situations requiring online alpha monitoring. Measurements using this system have been conducted on high beta activity solutions, demonstrating the beta blind capability of this system. Measurements are currently underway to test the system’s capability to measure gross alpha activity on Savannah River Site high level waste high Cs-137 samples that have been measured by the SRNL radiochemistry team. This work was supported by the DOE EM Technology Development program.

DiPrete, David [Savannah River National Laboratory↗
DOE OSTI2020

Reduced Neutralization Feasibility Study for H-Canyon Accelerated Basin De- Inventory (ABD) Program

An alternative approach to Spent Nuclear Fuel (SNF) and Nuclear Material Processing was developed for future H-Canyon (HCAN) and L-Area operations that involves a paradigm shift from current HCAN, Concentrate, Storage, and Transfer Facility (CSTF), and Defense Waste Processing Facility (DWPF) operations. The alternative, referred to as Accelerated Basin De-inventory (ABD), requires that all Domestic and Foreign Research Reactor SNF currently at the Savannah River Site (SRS) will be dissolved, stored, and then transferred to CSTF without recovery of Highly Enriched Uranium (HEU). Concentrated nitric acid is utilized to dissolve aluminum spent nuclear fuel (ASNF) in HCAN. The vessels and piping in HCAN are fabricated from 304L stainless steel and are ideally suited to handle the acidic waste stream. However, as the waste is transferred to the CSTF and DWPF, it will contact the carbon steel waste tanks in CSTF. In order to prevent corrosion of the carbon steel, the acidic waste is neutralized (i.e., pH adjusted over 11) by the addition of sodium hydroxide (NaOH). The NaOH is added until the final solution contains 1.2 M excess -OH. Additionally, if the waste is not neutralized to a pH greater than 11, then aluminum hydroxide (Al(OH) 3 ) would form, and solids may form in the piping as it is transferred to CSTF. This document presents an analysis of the influence of reducing the excess caustic that is added to the neutralization tanks on the corrosion protection scheme primarily for the CSTF waste tanks. The implications to HCAN and DWPF were also assessed.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2024

Refinement of Pitting Factor Basis to Evaluate Minimum Nitrite Requirement in Dilute Waste Chemistries

Considering that chloride concentrations are an order of magnitude lower at SRS than the maximum chloride previously tested to evaluate pitting susceptibility of carbon steel, it has been proposed that the Pitting Factor methodology be refined to determine if a reduction in the minimum nitrite requirement is warranted in more dilute solutions and those with chloride concentrations more indicative of waste tank chemistries at SRS. Through the use of cyclic potentiodynamic polarization, the susceptibility of A537 carbon steel to pitting corrosion was evaluated. The Pitting Factor was shown to accurately predict pitting susceptibility throughout the chemistry envelope evaluated. In addition, it was shown that nitrite is not required for inhibition of pitting corrosion in tank conditions with chloride concentrations observed at SRS and up to 4 M nitrate. Based upon these findings, new control limits were proposed that removed the minimum nitrite requirement within the chemistry envelope evaluated up to 50 °C.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Benzenesulfonamide Derivatives as Complexants and Extractants for Addressing the Mercury Problem at the Savannah River Site

Mercury (Hg) is a major global pollutant arising from both natural and anthropogenic sources. Its widespread use in medicinal and industrial applications makes it a common chemical exposure and environmental pollutant. It can exist in several forms which include: Metallic mercury (Hg{sup 0}), mercurous (Hg{sub 2}{sup 2+}), mercuric salts (Hg{sup 2+}), and organic mercury (e.g. CH{sub 3}Hg{sup +}), with the latter being the most toxic of all the species. Due to mercury's high toxicity, new approaches towards its detection has received significant attention in the scientific community. Mercury exposure at the Savannah River Site (SRS) has been a recent concern especially with increasing amounts of organic mercury in the saltstone. It originates mainly from its use as an acidic dissolution catalyst of aluminum cladding from target fuels within the uranium and plutonium processing operations [1]. It is present to an amount of about 60 metric tons in the high-level waste (HLW) tanks. Organic Mercury species have been found in low activity waste (LAW) at the site that eventually ends up in the saltstone. Therefore, there is a need for: i) Converting organic mercury to other less toxic forms and ii) Complexation and removal of Hg prior of disposal of LAW in saltstone. Various methods have been developed for selective sensing of mercury in the presence of other toxic metals. These methods include using ligands that can form organo-soluble metal complexes with different optical and spectroscopic properties that can be used for toxic metal sensing. In 2005, our group pioneered an ion-exchange extraction method, in which o-phenylenediamine-derived disulfonamides were used to complex and selectively extract and sense Pb{sup 2+} from aqueous solutions into an organic phase [2,3]. Herein, a disulfonamide and a bis-dansylamide have been shown to extract, complex and sense Hg(II). Ligand 1: The crystal structure of the disulfonamide-Hg complex confirms the complexation of Hg(II) with the ligand. Complexation was corroborated by the {sup 1}H-NMR spectra obtained after contacting solutions of various concentrations of Hg{sup 2+} with 2 mM ligand in chloroform. Distinct resonances are observed at Hg/L ratio of 0.5 that are also observed for the isolated 1:2 complex. In the presence of excess mercury, new resonances, as well as the movement of Et{sub 3}N resonances indicate the formation of a different Hg-sulfonamide-triethylamine complex, presumably having 1:1 Hg:L stoichiometry. The electronic spectra of aqueous phases after extraction show that there was no free ligand absorption at 0.5 eq of Hg, indicating a complete complexation. Complexation was also confirmed by the UV-visible titrations with Hg{sup 2+} at constant ligand concentration. pH-dependent extraction carried out shows that extraction of Hg(II) by ligand 1 was over 90% for most alkaline pHs. Ligand 2: The crystal structure of the Ligand 2 complex formed with Hg(OAc){sub 2} shows a remarkable coordination pattern with 4:2 metal:ligand stoichiometry. The fluorescent bis-dansyl disulfonamide derivative was found to complex and sense HgCl{sub 2} and Hg(OAc){sub 2} by demonstrating fluorescence quenching upon Hg(II) addition in comparison with other metals (Zn(II), Cd(II), Pb(II)). No were observed for Cu(II), Ag(I) and Co(II). We have shown the complexation of Hg(II) by a disulfonamide and a bis-dansyl disulfonamide ligand using several spectroscopic methods. Ligand 1 was able to extract mercury into chloroform and form a complex in the presence of excess mercury by synergistic complexation with triethylamine acting as a co-ligand. X-ray and NMR both confirm a 1:2 HgL{sub 2} stoichiometry. Ligand 2 can be used for sensing of Hg(II) as fluorescence quenching was observed after addition of Hg(II)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗