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Organomercury Measurements from Sludge Batch 10 Simulant Studies

Researchers at the Savannah River National Laboratory have recently performed testing to evaluate the Sludge Batch 10 flowsheet using simulated sludge waste. In the course of this testing several samples were taken to determine the concentration of organomercury species resulting from sludge batch processing. These samples were submitted to the Savannah River National Laboratory Sensing and Metrology department quantitation using a mercury analyzer. The signal amplifier used to perform organomercury quantitation in the mercury analyzer experienced a malfunction in the course of analysis, leading to uncertainty of organomercury concentrations observed. Seventy-three organomercury samples from six project submissions to the Savannah River National Laboratory Sensing and Metrology department have been critically reviewed.

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Mercury speciation using microcolumns with a direct mercury analyzer (DMA). Development of analytical method for the Savannah River Site liquid system

Mercury in the Savannah River Site (SRS) Liquid Waste System (LWS) exists in various forms, including: a) ionic inorganic mercury, organomercury (e.g., methyl Hg), and other less abundant species dissolved in LWS fluids, b) mercury solids such as oxides, hydroxides, amalgams, sulfides, and sorbed mercury, c) accumulations of dense liquid elemental mercury, and d) vapor phase elemental and organomercury mercury in tank headspace gas and in evaporators. Strategic and proactive management of the estimated 60,000 Kg mercury in the LWS requires deployment of efficient and effective paradigms for sampling and analysis of the total quantity of mercury in the various physical-chemical forms. Scoping tests of selective gas-phase sorbents for mercury speciation were performed to support LWS objectives. This research specifically focused on developing and testing streamlined methods to obtain high-quality analytical results for gaseous mercury species. The proposed methods are straightforward, using small columns (microcolumns) filled with materials that selectively sorb one or more target forms of mercury. Simple differentiation of mercury species and quantification is then achieved using an efficient thermal-desorption-based total mercury analyzer as the final step. Benefits associated with transitioning from multistep procedures such as EPA Methods 245.1, 1630 and 1631to streamlined microcolumn approaches include reduced analysis time, labor, and waste generation. Such transitioning would maximize the value of the current deployment of direct mercury analysis (EPA Method 7473) at SRS. This work has two target end uses: 1) simplifying the analysis steps and reducing costs for liquid samples (e.g., developing a total organic mercury (TOM) method), and 2) providing options for high-quality onsite analysis and rapid turnaround for gas samples in support of SRS LWS industrial hygiene (IH) objectives.

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Methanotrophic-Mediated Methylmercury Transformation: Characterization of Products, Mechanism, and Environmental Significance (Final Technical Report)

Previous work in the laboratories of the PIs found that methanotrophs, through the production of a novel metal chelator called methanobactin (MB), can bind inorganic mercury (Hg[II]). By doing so, methanotrophs substantially reduce Hg[II] toxicity. We have also recently shown that MB can bind a much more toxic form of mercury, the neurotoxin methylmercury (MeHg). MeHg bioaccumulates and biomagnifies in biota such as fish, and is of significant concern. Further, certain methanotrophs expressing MB are able to demethylate significant amounts of MeHg despite lacking merB, the organomercurial lyase. Further, unlike the canonical organomercurial lyase, methanotrophs take up and degrade MeHg at environmentally relevant pH and Hg concentrations (i.e., picomolar to nanomolar), suggesting that methanotrophs likely play a critical role in controlling net MeHg production and toxicity in situ. However, although MB is necessary for methanotrophic-mediated MeHg degradation, it is not sufficient as purified MB binds, but does not degrade MeHg. That is, MB appears to serve as binding device leading to demethylation of MeHg by an as yet unknown mechanism. The major goals of this project were to extend this initial work and characterize the mechanism of methanotrophic-mediated MeHg demethylation and how methanobactin production may affect net methylmercury production in situ.

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Innovative mercury treatment technology options for the liquid waste system at the Savannah River Site: scoping studies

The Savannah River Site (SRS) Liquid Waste System (LWS) contains liquids, salts and sludges that are currently being processed into final wasteforms for disposition, specifically, waste glass for sludges, solids and liquids containing high levels of radioactivity, and saltstone grout for low activity decontaminated liquid solutions. The LWS also contains approximately 60,000 kg of mercury present in the following physical and chemical forms, specifically: a) ionic inorganic mercury, organomercury (e.g., methylmercury), and other minor components found in LWS fluids b) mercury solids such as oxides, hydroxides, amalgams sulfides and sorbed mercury, c) accumulations of dense liquid elemental mercury, and d) vapor phase elemental and organomercury mercury found in tank headspace gas and in evaporators. An effective and proactive management strategy of the mercury present in the LWS is needed to support processing of LWS wastes into glass and saltstone. Sustainable processing of the LAWS to completion requires mercury removal from the LWS at a rate of approximately 2,900 kg/yr. This removal can be accomplished through existing mercury treatment systems or newly implemented LWS “purge points”. The chemical speciation of mercury has emerged as the key factor that controls mercury behavior in the LWS. For example, past studies demonstrated that mercury speciation is adversely impacting the performance of existing removal systems so that significant levels of mercury are recycled from the Defense Waste Processing Facility (DWPF) back to the tank farm. Consequently, mercury concentrations have slowly increased in the LWS tank fluids over time. The presence of organo-mercury has also been identified as the cause of increased mercury leaching from saltstone. In response to these challenges, the Department of Energy (DOE) Office of Environmental Management (EM-TD) Technology Development Program has supported a series of scoping studies predicated on manipulating or controlling mercury speciation and mercury behaviors within the constraints of LWS waste chemistry and safety conditions. The intent of these studies was to rapidly triage potential technology options and develop a technically based go / no go recommendation for further work. This composite report presents the results of three scoping studies: 1) advanced photooxidation processes, 2) chemical reduction, and 3) mercury getters.

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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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